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Polyesters
Polyesters are polymers formed from a dicarboxylic acid and a

diol. They have many uses, depending on how they have been produced and the
resulting orientation of the polymer chains.
Uses of polyesters
Polyesters are extremely important polymers. Their most familiar applications are in
clothing, food packaging and plastic water and carbonated soft drinks bottles.
The most used of the polyesters has the formula:
Being an ester, it is made from an acid, benzene-1,4-dicarboxylic acid (terephthalic acid),

and an alcohol, ethane-1,2-diol.
It is often known by its trivial name, polyethylene terephthalate (PET).

The annual world wide production of PET is approximately 40 million tonnes and is growing
at ca 7% per year. Of this, about 65% is used to make fibres, 5% for film and 30% for
packaging.
Another useful polyester is produced from benzene-1,4-dicarboxylic acid and propane-1,3-
diol (which replaces ethane-1,2-diol). It is known by its trivial name, polytrimethylene
terephthalate.
The different uses of polyesters depend on their structure. The benzene rings in the
molecular chain give them a rigid structure, leading to high melting points (over 500 K) and
great strength. They do not discolour in light.
In PET fibres, the molecules are mainly arranged in one direction, in film, they are in two
directions and for packaging, they are in three directions (Figure 1).
Figure 1 Diagram to show the arrangement of PET molecules in PET fibres, films and packaging.
As fibres
The polyester is produced as small granules. These are melted and squeezed through fine
holes and the resulting filaments spun to form a fibre. This fibre, commonly known as
Terylene or Dacron, is widely used in clothing (for example, in suits, shirts and skirts) either
alone or in blends with other manufactured or natural fibres, principally cotton.
It is also used for filling anoraks and bedding duvets to give good heat insulation. Other
uses include car tyre cords, conveyor belts and hoses, where its strength and resistance to
wear are paramount.
Figure
2 Polyesters are
often used to make
the suits and
parachutes for sky
divers.
By kind permission of
Gayle Pook.
As films
The polyester can also be made into thin films which can be used in food packaging, audio
and video tapes, electrical insulation, and X-ray films.
As packaging
A relatively newer use is for packaging, for example for bottles (see Figure 3). The small
granules of the polyester are heated to about 500 K and further polymerization takes place.
This heating is sometimes called solid-state polymerizing. The polymer is melted, moulded
and then stretched. The molecules are now orientated in three directions giving the plastic
great strength.
Figure 3 For beverage

packaging the barrier
properties of the PET to
certain gases, the excellent
mass to strength ratio and
the recyclability of the final
product are very important
features influencing the
choice of PET over other
plastics or more traditional
packaging materials.
By kind permission of APPE
Packaging.
Annual production of PET

World 53.3 million tonnes
Europe 3.9 million tonnes
North America 7.2 million tonnes
US 7.0 million tonnes
FSU 1.9 million tonnes
China 18.9 million tonnes
Rest of Asia 16.4 million tonnes

(Japan) (1.5 million tonnes)
Manufacture of PET
(a) The production of the monomer
Ethane-1,2-diol is reacted with benzene-1,4-dicarboxylic acid (sometimes known as
terephthalic acid), or its dimethyl ester, in the presence of a catalyst, to produce initially the
monomer and low molecular mass oligomers (containing up to about 5 monomer units).
Using the acid provides a direct esterification reaction, while the dimethyl ester reaction
involves ester interchange. The dimethyl ester route requires the use of an acid catalyst
whereas direct esterification is self-catalysed by the carboxylic acid groups.
The dimethyl ester route was originally preferred because the ester could be purified more
readily than the acid. Very pure acid is now available in large commercial quantities; the
modern processes therefore start from the acid.
(i) Starting from the acid: Direct Esterification Reaction
The acid reacts directly with ethane-1,2-diol:
(ii) Starting from the dimethyl ester: Ester Interchange Reaction

The acid reacts with methanol to form the dimethyl ester, with manganese(II) ethanoate
being commonly used as the catalyst.
The dimethyl ester is then reacted with ethane-1,2-diol, by a process known as
transesterification, in which one alcohol (ethane-1,2-diol) exchanges for another
(methanol):
Figure 4 Granules of
PET from both batch
and continuous
processes are used as
feedstocks for
extrusion and
moulding machines
for the production of
film and some
moulded articles.
By kind permission of Shell
International Ltd.
(b) Polymerization of the monomer

The monomer then undergoes polycondensation with the elimination of ethane-1,2-diol, a
condensation reaction:
The polycondensation stage requires a catalyst, antimony(lll) oxide, and is carried out at
high temperatures (535-575 K) when the monomer and polymer are molten. Low
pressures are used to favour product formation. Ethane-1,2-diol is recycled.
Polyester production can be carried out using both batch and continuous processes. In the
production of polyester fibre, the products of a continuous process can be fed directly into
melt-spinning heads. This removes the casting, chipping, blending and drying stages that
are necessary with batch processing.
Benzene-1,4-dicarboxylic acid
Benzene-1,4-dicarboxylic acid is manufactured by oxidation of 1,4-dimethylbenzene
(commonly known as para-xylene).
One method is to pass air into the liquid hydrocarbon dissolved in ethanoic acid under
pressure, in the presence of cobalt(ll) and manganese(ll) salts as catalysts, at about 500 K:
The pure acid used in PET production is obtained from the crude product by further
processing to remove colour-forming impurities, and then by crystallization, washing and
drying stages.
The manufacture of 1,4-dimethylbenzene (para-xylene) is described in the unit Benzene
and methylbenzenes. A recent development is the production of bio-based 1,4-
dimethylybenzene which means that bio-based polyesters can be manufactured.
Date last amended: 25th August 2016
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1. Chemistry
2. Pl-Pr
3. Polyesters - Chemistry Encyclopedia
Polyesters
Photo by: lefebvre_jonathan
Polyesters are long chain synthetic polymers that have ester linkages. Polyester
materials are used as fibers, plastics, and films; in composites and elastomers; and as
coatings. They are truly versatile materials.
In the late 1920s American chemist Wallace Carothers and his research group at
DuPont began to investigate the formation of polymers from the reaction of aliphatic
diacids (having two acid groups) with diols (having two alcohol groups), in search of
materials that would give them fibers. At first they were able to form only syrupy
mixtures. But the Carothers group did make polyester fibers. They investigated a wide
array of dialcohols, diacids, and w-hydroxy acids for use as starting points. Some of the
polyesters that they achieved were solids, but they had rather low melting points and
thus were not useful as fiber materials. The lack of success was due to the fact that the
researchers had used only aliphatic diacids. In order to form long polymer chains, the
reactive groups of the reactants must be present in approximately equal amounts. This
is easily achieved via the use of amines and the subsequent formation of amine salts.
(Diols do not easily form salts.) Carothers's group understood the principle of "driving"
an equilibrium reaction and so sought to remove water from their amine salt mixtures,
thus forcing the reaction toward ester formation. For this they developed a so-called
molecular still, which involved heating the mixture and applying a vacuum coupled with
a "cold-finger" that allowed evacuated water to condense and be removed from the
reaction system. Even with this understanding and lots of hard work, they achieved
polymer chains with fewer than 100 repeat units. (See Figure 2.)
The DuPont research team turned from the synthesis of polyesters to tackle, more
successfully, the synthesis of polyamides. The experience with polyesters was put to
use in the making of polyamides.
Initial polyester formation actually occurred much earlier and is attributed to Gay Lussac
and Théophile-Jules Pelouze in 1833 and Jöns Jakob
Figure 2. Wallace Carothers attempted to form polymers from the reaction of ethylene glycol (a diol) and apidic
acid (an aliphatic diacid).
Figure 3. Glyptal polyester formation.
Berzelius in 1847. They did not realize what they had discovered, however, and so
moved on to other work.
Glyptal polyesters were first produced in 1901 by heating glycerol and phthalic
anhydride. (See Figure 3.) Because the secondary hydroxyl is less active than the
terminal, primary hydroxyl in glycerol, the initial product formed is a linear polyester. A
cross-linked product is produced by further heating through reaction the third alcohol.
Related compounds, alkyds, were synthesized by Kienle in the 1920s from trifunctional
alcohols and dicarboxylic acids. Unsaturated oils (alcohols and anhydrides containing
double bonds) were also reacted with phthalic anhydride, yielding polyesters that
contained a double bond, which could be further reacted to produce cross-linked
products. The extent of cross-linking or "drying" depends on the amount of unsaturated
oil present.
Today, the term alkyd is often used to describe all polyesters produced from the
reaction of a diacid or anhydride and a diol or triol resulting in a product that contains a
double bond that can be further reacted, giving a cross-linked product. (See Figure 4.)
These polyesters are called unsaturated polyesters. They are mainly used in the
production of reinforced plastics (composites) and nonreinforced filled products for the
marine, automotive, and other industries.
These glyptal and alkyd polyesters are useful as coating materials but not for fiber or
plastic production. The first commercially available polyesters were made by GE in the
1920s. Called Glyptals ™ , they were used as sealing waxes. Out of the Glyptal™
research came alkyd paints. Although these reactions had low fractional conversions,
they formed high molecular weight materials because they had functionalities (i.e., a
number of reactive groups on a single reactant) greater than 2, resulting in cross-linking.
Figure 4. Reaction of an anhydride and a diol result in a double bonded product that can be further reacted to
produce a cross-linked product called unsaturated polyester.
The heat resistance of Carothers's polyesters was not sufficient to withstand the
temperature of the hot ironing process. Expanding on the work of Carothers and his
coworkers on polyesters, Whinfield and Dickson, in England, overcame the problems of
the Carothers group by using aromatic acids, especially terephthalic. This classic
reaction, which produces plastics and fibers that are sold under a variety of tradenames,
including Dacron, Fortrel, Trevira, and Terylene, and films sold under a variety of trade
names that includes Mylar, is shown in Figure 5. All new plants now use pure acid for
this reaction.
Methyl alcohol, or methanol, is lower boiling than water (65 ° C compared with 100 ° C)
and is thus more easily removed, allowing the reaction to be forced toward polymer
formation more easily. Although this poly(aryl ester), produced by Whinfield and
Dickson, poly(ethylene terephthalate) or PET, met the specifications for a useful
synthetic fiber, because of inferior molding machines and inadequate plastic technology,
it was not possible to use it in injection molds. Until more recently PET was not a widely
used plastic or film material.
Although aromatic polyesters had been successfully synthesized from the reaction of
ethylene glycol with various aromatic diacids (almost always terephthalic acid or its
ester), commercialization of polyester synthesis awaited an inexpensive source of
aromatic diacids. In 1953 an inexpensive process for the separation of the various
xylene isomers by crystallization was discovered. The availability of inexpensive xylene
isomers enabled the formation of terephthalic acid through the air oxidation of the p-
xylene isomer. Du Pont, in 1953, produced polyester fibers from melt spinning, but it
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 Saturated Polyesters
UNSATURATED POLYESTERS
PROPERTIES
Unsaturated polyesters are the third-largest class of thermoset molding resins. They are
produced by the condensation of a diol with a blend of saturated and unsaturated
anhydrides. The condensation products (reactive resins) form very durable structures
and coatings when cross-linked with reactive vinyl monomers such as styrene.
The properties of the cross-linked resin depend on the types of anhydrides and glycols
used and their relative amounts. The majority of commercial unsaturated polyester
resins (UPR) are derived from phthalic and maleic anhydride as the saturated and
unsaturated component and 1,2-propylene glycol as the diol in the polymer. Many other
glycols and acids or anhydrides can be used to taylor the properties of unsaturated
polyesters. For example, isophthalic acid (IPA) and terephthalic acid (TA) are
sometimes chosen to achieve better thermal and chemical resistance, whereas long-
chain aliphatic acids, such as adipic or succinic acid, improve the flexibility but reduce
the chemical and heat resistance. Similar improvements in flexibility can be achieved
with ether glycols such as diethylene glycol and polypropylene glycol. Monofunctional
acids and bases can be employed to tie off excess of hydroxyl and carboxyl groups and
to reduce the molecular weight of the final prepolymer. The anhydrides and acids can
also be condensed with epoxy resins such as epichlorhydrin or bisphenol A diglycidyl
ether. The oxirane rings of the epoxy compounds act as difunctional glycols, that is,
they can replace all or some of the polyols. In some cases, carboxylated unsaturated
polyesters are caped with glycidyl methacrylates. These resins are sometimes
employed in UV curable coating formulations.

A relative new class of vinyl esters are dicyclopentadiene (DCPD) modified resins.
These resins were introduced commercially in the 1980s and have gained significant
market share due to their low shrinkage and low styrene content1 DCPD can be reacted
with any dicarboxylic acid or anhydride. For example, in the presence of water,
dicyclopentadiene and maleic anhydride form dicyclopentadiene maleate. DCPD can
also be converted to cyclopentadiene, its monomeric form, which is reacted with the
double bond of maleic anhydride via Diels-Alder addition. Both intermediates can be
further esterified (polymerized) with a diol such as propylene glycol. These resins
provide enhanced thermooxidative resistance, improved processability and low linear
shrinkage when crosslinked.
Unsaturated polyesters are typically low-molecular-weight prepolymers. To fully cure
them, they are dissolved in a vinyl monomer (and occasionally a solvent 2) together with
an appropriate organic peroxide3 and poured, sprayed, or molded into the final product
and then converted into a thermoset by heating. Many resins can also be room
temperature cured when a reducing agent such as a cobalt salt (naphthenate or
octoate) or an aromatic tertiary amine is added to the sytem. This compound is often
called accelerator or activator. Resin products with an activator are typically two-pack
systems whereas heat curable UPRs are typically one-part systems. The cure time and
pot-life will depend on the initiator system, its concentration as well as on the type of
resin and vinyl monomer and cure temperature.

The most common vinyl monomer is styrene. It functions as a reactive diluent and as a
crosslinking agent. When polymerized in the presence of unsaturated polyester, it
reacts with the double bonds of the prepolymer but also undergoes
homopolymerization. The degree of homo- and co-polymerization depends on the
reaction conditions, monomer content, and miscibility of the two resins. In some cases,
vinyl cure can lead to the formation of a (semi-)interpenetrating network.4
Due to growing health concern5, styrene has been replaced in many resin systems by
other less toxic vinyl monomers such as vinyl toluene, vinyl acetate, methyl
methacrylate and allyl ethers as well as by difunctional vinyl monmers such as
diacrylates and dimethacrylates. The type of reactive diluent will effect both the cure
and the final properties of the polyester.
Ansaturated
Saturated Acids
Polyols (Glycols) Acids Vinyl Monomers
/ Anhydrides
/ Anhydrides
Phthalic
Propylene glycol Maleic anhydride Styrene
anhydride
Ethylene glycol Isophthalic acid Fumaric anhydride α-Methylstyrene
Methyl
Diethylene glycol Terephthalic acid Methacrylic acid
methacrylate
Epichlorhydrin Adipic acid Acrylic acid Vinyl toluene
Bis A diglycidyl
Succinic acid Itaconic acid Vinytl acetate
ether
Ethylene glycol
1,4-Butanediol Azelaic acid DCPD Maleate
diacrylate
COMMERCIAL UNSATURATED POLYESTERS
Unsaturated polyester resins are produced on a large scale by a large number of
companies including Ashland, Reichhold, and Royal DSM. They are typically sold in
liquid form in an unsaturated and reactive solvent, normally styrene. Grades with
different viscosities, unsaturation and cure speed are available. DCPD modified resins
are produced by Deltech, Polynt, and Dow and others.
APPLICATIONS
Unsaturated polyester resins are mainly used in the production of fiber reinforced
plastics and filled plastic products, including sanitary-ware, tanks, pipes, gratings, and
high performance components for the marine and transportation industry such as
closure and body panels, fenders, boat hulls/ decks and other large glass fiber
reinforced plastic articles. Unsaturated polyester resins also find uses in coatings and
adhesives.
References and Notes

1. Unsaturated polyester resins have been described in US patent 3,347,806 (Chemische Werke
Albert) and 4,029,848 (Dow Chremical).
2. In some cases, conventional solvents such as xylenes are also used. However, most are
prepared solely with reactive vinly type monmomers.
3. Common initiators include methyl ethyl ketone peroxide (MEKP), benzoyl peroxide (BPO), and
acetylacetone peroxide (AAP).
4. An Interpenetrating polymer network (IPN) consists of two or more polymers which are at least
partially interlaced on a microscopic scale but are not covalently bonded to each other. At least
one of the polymers is crosslinked in the immediate presence of the other(s). Due to the
crosslinking, IPNs can swell, but do not dissolve in solvents, and creep and flow is strongly
suppressed.
5. Acute (short-term) exposure to styrene can cause mucous membrane, skin, and eye irritation,
whereas chronic (long-term) exposure can effect the central nervous system (CNS) resulting in
headache, fatigue, weakness, etc. Styrene is also suspected to cause cancer. 5
6. The Department of Occupational Medicine at Aarhus University in Denmark concluded that
styrene may cause cancer in humans.
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was not until the 1970s that these polyester fibers became commercially available.
Figure 5. The classic reaction for producing plastics and fibers. New plants use pure acid for this reaction.
John Travolta and Karen Lynn Gorney in the 1970s hit film Saturday Night Fever. Polyester was a popular
fabric used in clothing in the 1970s.
In 2000 about 3,900 million pounds of polyester fiber were used in the United States,
making it the largest single fiber group material. As with nylon, polyester fibers are
comparable to and/or surpass common natural fibers such as cotton and wool in heat
stability, wash-and-wear properties, and wrinkle resistance. Textiles blended from
polyester, cotton, and wool (in varying combinations) can also be made to be
"permanent press" and wrinkle resistant. The fibers are typically formed from melt or
solvent spinning. Chemical and physical modification can generate fibers of differing
fiber appearances from the same basic fiber material. Self-crimping textiles are made by
combining materials that have differing shrinkage properties. Different shaped dyes
produce materials with varying contours and properties, including hollow fibers.
Along with the famous polyester suits and slacks, polyester fibers are widely used in
undergarments, permanent press shirts, tire cord, and felts.
Figure 6. Poly(butylene terephthalate), or PBT, has a lower melting point than PET, and it crystallizes more
rapidly.
Because the ease of processing and fabricating polyesters is related to the number of
methylene groups (–CH 2 –) in the repeat units, scientists turned to the use of diols with
additional methylene units. Whereas PET is difficult to mold because of its high melting
point, Tm 240 ° C, poly(butylene terephthalate), or PBT, because of its two additional
methylene units in the diol-derived portion (see Figure 6), is lower melting with a Tg of
about 170 ° C. PET also crystallizes relatively slowly, so extra care must be exercised to
insure that PET molded products become fully crystallized. Otherwise, the partially
crystallized portions will be preferred sites for cracking, crazing, shrinkage, and so on.
By comparison, PBT melts at a lower temperature (as noted above), crystallizes more
rapidly, and is often employed as a molding compound. PBT has properties that
represent a balance between those of nylons and acetals. It is characterized by low
moisture absorption, good fatigue resistance, good solvent resistance, extremely good
self-lubrication, and good maintenance of its physical properties even at relatively high
use temperatures. Fiber-reinforced PBT molding compound is sold under the trade-
name Celanex. Another PBT molding compound was first sold under the tradename
Valox. Today, there are many PBT molding compounds available.
In 2000 worldwide production of PET was 30 million tons. The manufacture of PET
textiles is increasing at 5 percent a year, of PET bottles at 10 percent a year. China
produces the most polyesters. PET is now used extensively as bottling material for soft
drinks instead of glass because it is shatterproof and lightweight. Carbon dioxide
permeability decreases with increasing film thickness and crystallinity. Glass has better
CO 2 impermeability than PET in these respects. Therefore, to achieveoptimal
crystallinity, partially crystalline PET is employed in the stretch blow molding process,
carried out to promote further crystalline formation. It is also used for molded automobile
parts. Over 500,000 tons of polyester engineering plastics are produced annually in the
United States.
Poly(dihydroxymethylcyclohexyl terephthalate) was introduced by Eastman Kodak as
Kodel in 1958. Here, the insertion of the cyclohexyl moiety gives a more hydrophobic
material (in comparison to PET and PBT) as well as a more moldable product that can
very readily be injected-molded. (See Figure 7.) The polymer's sole raw material is
dimethyl terephthalate. Reduction of dimethyl terephthalate yields the dialcohol,
cyclohexanedimethanol. Kodel, along with its blends and mixtures, is often extruded into
film and sheeting for packaging. Kodel-type materials are used to package
Figure 7. Materials made from Poly(dihydroxy methylcyclohexyl terephthalate) are used in shampoo and
detergent bottles.
hardware and other heavy items; they are also blow-molded to produce packaging for
shampoos, liquid detergents, and so on.
Du Pont and Shell have developed a new polyester, poly(trimethylene terephthalate), or
PTT, with the trademarks Sorona (Du Pont) and Corterra (Shell). It is structurally similar
to poly(ethylene terephthalate), PET, except that 1,3-propanediol (PDO) is used as a
reactant in place of ethylene glycol. (See Figure 8.) The extra methylene (CH 2 ) in PTT
allows the fiber to be more easily colored, giving a material that is also softer to the
touch and with greater stretch for textile use. Further, PTT offers good wear and stain
resistance for carpet use. The ready availability of the monomer PDO is a major
consideration, with current efforts underway to create PDO from the fermentation of
sugar through the use of biocatalysts for this conversion. Corterra and Lycra blends
have already been successfully marketed. Corterra is also targeted for use as a resin
and film.
Du Pont first introduced microfibers in 1989. Microfibers have diameters that are less
than typical fibers; they are about half the diameter of fine silk fiber, one-quarter the
diameter of fine wool, and one hundred times finer than human hair. Denier, the weight
in grams of 9,000-meter length of a fiber, is the term used to define the diameter or
fineness of a fiber. Microfibers have a denier that is 0.9 denier or less. In comparison,
nylon stockings are knit from 10– to 15– denier fiber.
Microfibers allow a fabric to be woven that is lightweight and strong. They can be tightly
woven so that wind, rain, and cold do not easily penetrate. Rainwear manufactures use
microfibers for this reason. They also have the ability to allow perspiration to pass
through them. In addition, microfibers are very flexible because their small fibers can
easily slide back and forth on one another. The first fabric made from microfiber was
Ultrasuade, in which short polyester microfibers were imbedded into a polyurethane
base. Today, microfibers are manufactured primarily from
Figure 8. The extra methylene in poly(trimethylene terephthalate) (PTT) provides material that is easily colored
and soft to the touch.
polyesters, nylon, and acrylic fibers. They are used under various tradenames to make
a variety of products, such as clothing, hosiery, bedding, and scarves.
SEE ALSO Polymers, Synthetic .
Charles E. Carraher Jr.
Bibliography
Internet Resources
"The Macrogalleria: A Cyberworld of Polymer Fun." University of Southern Mississippi
Department of Polymer Science. Available from http://www.psrc.usm.edu/marcrog .
"Polymers: Molecular Giants." Chemical Heritage Foundation. Available from
http://www.chemheritage.org/explore/explore.html .
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Polyester production method, polyester
composition, and polyester fiber
Abstract
translated from
In a polyester production method, a titanium compound having a radical selected from a

carbonyl group, a carboxyl group, or an ester group, and a phosphorous compound having a
structure illustrated in Formula (I), are added.
This yields a polyester composition which does not exhibit increased filter pressure when
forming, which has excellent filament and film forming properties, and which has a polymer
color tone superb to that of conventional products.
Classifications
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Google has not performed a legal analysis and makes no representation as to the accuracy of the
classifications listed.
C CHEMISTRY; METALLURGY
C08 ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR
CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08G MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY
REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
C08G63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in
the main chain of the macromolecule
C08G63/78 Preparation processes
C08G63/82 Preparation processes characterised by the catalyst used
C08G63/83 Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold,
zinc, cadmium, mercury, manganese, or compounds thereof
C08G63/85 Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium,
vanadium, niobium, tantalum, or compounds thereof
C08G63/87 Non-metals or inter-compounds thereof
D TEXTILES; PAPER
D01 NATURAL OR ARTIFICIAL THREADS OR FIBRES; SPINNING
D01F CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS,
THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR
THE MANUFACTURE OF CARBON FILAMENTS
D01F6/00 Monocomponent artificial filaments or the like of synthetic polymers; Manufacture
thereof
thereof from homopolycondensation products
thereof from homopolycondensation products from polyesters
C08G63/66 Polyesters containing oxygen in the form of ether groups
C08G63/668 Polyesters containing oxygen in the form of ether groups derived from
polycarboxylic acids and polyhydroxy compounds
C08G63/68 Polyesters containing atoms other than carbon, hydrogen and oxygen
C08G63/688 Polyesters containing atoms other than carbon, hydrogen and oxygen containing
sulfur
C08G63/6884 Polyesters containing atoms other than carbon, hydrogen and oxygen containing
sulfur derived from polycarboxylic acids and polyhydroxy compounds
Y GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL
TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL
SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC
CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y10 TECHNICAL SUBJECTS COVERED BY FORMER USPC
Y10T TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
Y10T428/00 Stock material or miscellaneous articles
Y10T428/249921 Web or sheet containing structurally defined element or component
Y GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL
TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL
SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC
CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y10 TECHNICAL SUBJECTS COVERED BY FORMER USPC
Y10T TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
Y10T428/00 Stock material or miscellaneous articles
Y10T428/29 Coated or structually defined flake, particle, cell, strand, strand portion, rod,
filament, macroscopic fiber or mass thereof
Y10T428/2913 Rod, strand, filament or fiber
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EP1491572A1
European Patent Office
Publication of application with search report

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Other languages
German
French
Inventor
Keisuke Honda
Kunihiro Morimoto
Masatoshi Aoyama
Tatsuya Nagano
Minoru Fujimori
Current Assignee
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accuracy of the list.
Toray Industries Inc
Worldwide applications
2003 JP
Application number: JP2003182227A
Filing date: 2003-06-26
Legal status: Expired - Fee Related
2004 TW
Application number: TW93118019A
Legal status:
US
Application number: US10/875,557
Legal status: Active
MY
Application number: MYPI20042497A
Legal status:
KR
Application number: KR1020040048444A
Legal status: IP Right Grant
CN
Application number: CN 200410059452
Legal status: IP Right Grant
EP
Application number: EP20040253857
Legal status: Withdrawn
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completeness of the events listed.
2003-06-26
Priority to JP2003182227
2003-06-26
Priority to JP2003182227A
2004-06-28
Application filed by Toray Industries Inc
2004-12-29
Publication of EP1491572A1
2019-04-22
Application status is Withdrawn
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Patent citations (11)
Non-patent citations (4)
Cited by (20)
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Description
translated from
BACKGROUND OF THE INVENTION 1. Field of the Invention
 [0001]
The present invention relates to a polyester production method, a polyester composition,

and a polyester fiber.
2. Description of the Related Art
 [0002]
Polyester is employed in a wide variety of uses due to the usefulness of the functions
thereof, such as in clothing, material, medical, and other applications.
 [0003]
Generally, in the production of polyester, antimony compounds are widely used as a

polymerization catalyst in industrial processes for manufacturing high-molecular-weight
polymers. However, polymers containing antimony compounds have several undesirable
properties, as follows.
 [0004]
For example, at the time of melt-spinning of polyester obtained with antimony

compounds as a polymerization catalyst, there is residual antimony compound which
accumulates around the spinneret. This accumulation of the residual antimony compound
is thought to be due to the antimony compound being denaturized near the spinneret, of
which a part vaporizes and dissipates, leaving a component which is primarily antimony
at the spinneret. Progression of this accumulation leads to defective filament, and
accordingly must be periodically removed.
 [0005]
Also, residual antimony compounds readily form relatively large pieces of foreign matter.
This is undesirable since it can cause increased pressure at the filter in the forming
process, thread breakage during spinning, film damage in formation of films, and so
forth, and has been a factor in reduced operation capabilities. Due to such reasons, there
is the need for a polyester containing little or no antimony.
 [0006]
An known example thereof is employing a germanium compound instead of an antimony

compound as the polymerization catalyst, but there is little germanium deposited which
can be mined and germanium is rare, so general-purpose application thereof is not
practical.
 [0007]
Also, a technique for using titanium complexes formed of titanium compounds and
phosphorous compounds as a polymerization catalyst are disclosed in PCT Japanese
Translation Patent Publication No. 2001-524536, PCT Japanese Translation Patent
Publication No. 2002-512267, Japanese Unexamined Patent Application Publication No.
2002-293909, Japanese Unexamined Patent Application Publication No. 2003-40991,
and Japanese Unexamined Patent Application Publication No. 2003-40994. While this
method allows the amount of pieces of foreign matter to be reduced, the color tone of the
obtained polymer is not quite suitable for actual use.
 [0008]
Further, Japanese Unexamined Patent Application Publication No. 2003-147060

discloses a technique for producing a copolymerized polyester having phenylene
dioxydiacetic acids as a copolymerization component, wherein polycondensation is
carried out under the presence of a polymerization catalyst and an organic phosphite
compound. However, this Publication makes no mention of the specific chemical
structure of the titanium compound. Also, the only polymerization catalyst described in
the Embodiments of this Publication is an antimony compound, and accordingly does not
lead to solving the cause of increased pressure at the filter in the forming process, thread
breakage during spinning, and film damage in formation of films.
SUMMARY OF THE INVENTION
 [0009]
The present invention has been made in light of the above-described problems of the
conventional art, and accordingly, it is an object of the present invention to provide a
polyester compound which does not lead to increased filter pressure at the time of
formation, having excellent fiber and film formation properties, and having superb color
tone of polymer over conventional products.
 [0010]
To this end, a first aspect of the present invention is a polyester production method
wherein a titanium compound having a radical selected from a carbonyl group, a carboxyl
group, or an ester group, and a phosphorous compound having a structure illustrated in
Formula (I) are added;
in which R1 represents hydrogen, a hydrocarbon radical comprising 1 to 50

carbon atoms, a hydroxyl group, or a hydrocarbon radical comprising 1 to 50 carbon
atoms and including an alkoxy group, of which two or more may be included with regard
to the benzene ring; R2 and R3 independently represent a hydrocarbon radical comprising
1 to 50 carbon atoms, a hydroxyl group, or a hydrocarbon radical comprising 1 to 50
carbon atoms and including an alkoxy group, and may be an alkoxy group of -OR2 or -
OR3 as to the phosphorous atom; L + M + N = 3 wherein L is an integer of 1 through 3,
and M and N are integers between 0 and 2; and R2 and R3 may form a ring.
 [0011]
The titanium compound may include a radical selected from a group of functional groups
represented by the following Formulas (II) through (VI);
in which R4 through R12 independently represent hydrogen, a hydrocarbon radical
comprising 1 to 30 carbon atoms, or a hydrocarbon radical comprising 1 to 30 carbon
atoms and including an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl
group, a carboxyl group, an ester group, or an amino group.
 [0012]
The titanium compound may include a radical selected from a group of functional groups
represented by the Formulas (II) through (IV), in which R4 through R9 independently
represent a hydrocarbon radical comprising 1 to 30 carbon atoms and including a
carbonyl group, a carboxyl group, or an ester group.
 [0013]
The phosphorous compound may contain a six-membered ring structure or higher

including phosphorous atoms, and further, the phosphorous compound may include that
represented by Formula (VII);
in which R13 and R14 independently correspond to R1 in Formula (I).
 [0014]
0.5 to 150 ppm of titanium compound may added as to the amount of polyester to be
generated, in terms of titanium atoms, or 0.1 to 400 ppm of phosphorous compound may
added as to the amount of polyester to be generated, in terms of phosphorous atoms.
 [0015]
The ratio of addition of titanium compound and phosphorous compound may be 0.1 to 20
in terms of molecular ratio Ti/P of titanium atoms and phosphorous atoms. Also, 1 to 400
ppm of a manganese compound may be added as to the amount of polyester to be
generated, in terms of manganese atoms, wherein the ratio of addition of manganese
compound as to the phosphorous compound is 0.1 to 200 in terms of molecular ratio
Mn/P of manganese atoms and phosphorous atoms. Further, a blue organic color
adjusting agent and/or a red organic color adjusting agent may be added. Moreover,
polymerized polyester which has then been depolymerized may be used as a material.
 [0016]
A polyester composition is produced by the polyester production method. The amount of
antimony compound contained in the polyester composition may be 30 ppm or less in
terms of antimony atoms as to the polyester.
 [0017]
A polyester fiber includes the polyester composition. The polyester composition may
include 0.5 to 7.0% by weight of titanium dioxide particles.
 [0018]
The polyester of the polyester composition may be produced by copolymerization of 0.1

to 10 mol% of an isophthalic acid component containing a metal sulfonate radical and 0.1
to 5.0% by weight of a polyoxy alkylene glycol component having a number average
molecular weight of 400 to 6000. This polyester composition may include 0.5 to 7.0% by
weight of titanium dioxide particles.
 [0019]
An industrial polyester fiber includes the polyester composition, wherein the intrinsic
viscosity of the polyester is 0.85 or higher, the toughness T·E½, defined by the product of
the strength T(cN/dtex) and the square root of the elongation E(%) of the fiber, is 28 or
higher, and the dimensional stability represented by the sum of intermediate elongation
and dry-heat shrinkage is 12% or lower.
 [0020]
A polyester fiber for sewing machine thread includes the polyester composition, wherein
the strength is 7.1 to 8.5 cN/dtex and elongation is 14 to 24%.
 [0021]
A polyester nonwoven fabric includes the polyester composition, wherein the polyester is
produced by copolymerization of 0.1 to 20 mol% of an isophthalic acid component.
 [0022]
According to the present invention, a polyester can be produced which does not lead to
increased filter pressure at the time of forming, having excellent fiber and film formation
properties, and having superb color tone of polymer over conventional products.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
 [0023]
Polyester is a polymer synthesized from dicarboxylic acid or an ester-forming derivative
thereof and diol or an ester-forming derivative thereof. The polyester produced according
to the present invention is preferably used in formed articles such as fabrics, films,
bottles, and so forth.
 [0024]
Examples of such polyester include polyethylene terephthalate, polytrimethylene

terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene
terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polyethylene-1,2-bis (2-
chlorophenoxy)ethane-4,4'-dicarboxylate, and so forth.
 [0025]
Also, compounds which may be copolymerized with these polyesters as a

copolymerization component other than diethylene glycol are: adipic acid, isophthalic
acid, sebacic acid, phthalic acid, naphthalene dicarboxylic acid, 4,4'-diphenyl
dicarboxylic acid, cyclohexane dicarboxylic acid and like dicarboxylic acids and ester-
forming derivatives thereof; and polyethylene glycol, hexamethylene glycol, heopentyl
glycol, polypropylene glycol, cyclohexane dimethanol and like dioxy compounds; p-(β-
oxyethoxy) benzoate and like oxycarboxylates and ester-forming derivatives thereof.
 [0026]
The polyester production method according to the present invention is suitable for
producing polyethylene terepthalate which is the most commonly and widely used form,
or polyester copolymers including primarily ethylene terepthalate units.
 [0027]
The polyester production method according to the present invention employs a titanium
compound as a polymerization catalyst, since employing a titanium compound as a
polyerization catalyst instead of an antimony compound suppresses residue and foreign
matter originating from the antimony compound.
 [0028]
The polymerization catalyst in producing the polyester contributes to promoting a part of

the elementary reactions described in the following (1) through (3) or all reactions, in the
process wherein polyester is synthesized from dicarboxylic acid or an ester-forming
derivative thereof and diol or an ester-forming derivative thereof.
o (1) Esterification reaction, which is reaction between the dicarboxylic acid

component and the diol component.
o (2) Ester interchange reaction, which is reaction between the ester-forming
derivative of the dicarboxylic acid component and the diol component.
o (3) Polycondensation, wherein a low polymer obtained by the reaction (1) or (2) is
high-polymerized by removing the diol component out of the reaction system.
 [0029]
It is crucial with the present invention that the titanium compound used as the
polymerization catalyst have a radical selected from a carbonyl group, a carboxyl group,
or an ester group, since using employing such a titanium compound enables the color
tone of the polyester to be polymerized with the titanium compound to be improved.
 [0030]
It should be noted that catalysts such as conventionally-known tetraisopropoxy titanium

and tetrabuthoxy titanium do not contain the carbonyl group, carboxyl group, or ester
group.
 [0031]
As for a titanium compound having a radical selected from a carbonyl group, a carboxyl
group, or an ester group, one including a radical selected from a group of functional
groups represented by the following Formulas (II) through (VI) is preferably employed.
 [0032]
In Formulas (II) through (VI), R4 through R12 independently represent hydrogen, a

hydrocarbon radical comprising 1 to 30 carbon atoms, or a hydrocarbon radical
comprising 1 to 30 carbon atoms and including an alkoxy group, a hydroxyl group, a
carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group.
 [0033]
Of these, those having radicals selected from functional groups indicated by Formula (II)
and Formula (V) are preferable from the perspective of thermal stability of the polymer
and color tone thereof.
 [0034]
Also, those having radicals selected from functional groups indicated by Formula (II)
through Formula (IV) are preferable from the perspective of ease of synthesis. Here, R4
through R9 independently represent a hydrocarbon radical comprising 1 to 30 carbon
atoms and including a carbonyl group, a carboxyl group, or an ester group.
 [0035]
Examples of the functional group indicated by formula (I) include hydroxy polyvalent
carboxylic compounds such as lactic acid, malic acid, tartaric acid, citric acid, and so
forth.
 [0036]
Examples of the functional group indicated by formula (II) include acetyl acetone and
like β-diketone compounds, methyl acetoacetate, ethyl acetoacetate, and like ketoester
compounds.
 [0037]
Examples of the functional group indicated by formula (III) include those of phenoxy,
cresylate, salicyl, and the like.
 [0038]
Examples of the functional group indicated by formula (IV) include acylate groups such
as lactate, stearate, and so forth; polyvalent carboxylic acid compounds such as phthalic
acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid,
malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric
acid, cyclohexane dicarboxylic acid, or anhydrates thereof; and nitrogenous polyvalent
carboxylic acid compounds such as ethylene diamine tetra-acetic acid, nitrilo tripropionic
acid, carboxy iminodiacetic acid, carboxymethyl iminobipropionic acid,
diethylenetriamino pentaacetic acid, triethylenetetramino hexaacetic acid, iminodiacetic
acid, iminobipropionic acid, hydroxyethyl iminodiacetic acid, hydroxyethyl
iminobipropionic acid, methoxyethyl iminodiacetic acid, and so forth.
 [0039]
Examples of the functional group indicated by formula (V) include aniline, phenylamine,
diphenylamine, and so forth.
 [0040]
Also, titanium compounds containing two or more substituents of Formula (I) through
Formula (V) are preferable, examples thereof being titanium isopropoxy bis-
acetylacetonate including the functional group of Formula (II) and Formula (III), titanium
triethanolaminate isopropoxide including the functional group of Formula (II) and
Formula (VI), and so forth.
 [0041]
Note that titanium dioxide particles, which are commonly used as a delustering agent for
fabrics essentially have no'catalytic effects, and are to be distinguished from titanium
compounds used as polymerization catalysts
 [0042]
The amount of titanium compound (excluding titanium dioxide particles) used is

preferably 0.5 to 150 ppm in terms of titanium atoms as to the amount of polyester to be
generate, more preferably 1 to 100 ppm, and even more preferably 3 to 50 ppm. Inclusion
of 0.5 ppm or more yields the actual effects as a polymerization catalyst, and 150 ppm or
less yields excellent thermal stability and color tone of the polyester produced.
 [0043]
Also, with the polyester producing method according to the present invention, it is crucial
that the phosphorous compound illustrated in Formula (I) is added along with the
titanium compound.
 [0044]
Here, R1 represents hydrogen, a hydrocarbon radical comprising 1 to 50 carbon atoms, a

hydroxyl group, or a hydrocarbon radical comprising 1 to 50 carbon atoms and including
an alkoxy group, of which two or more may be included with regard to the benzene ring.
In this case, the hydrocarbon radical may include an alicyclic structure such as
cyclohexyl, or the like, an aliphatic branch structure, or an aromatic ring structure such as
phenyl or naphthyl or the like. R2 and R3 independently represent a hydrocarbon radical
comprising 1 to 50 carbon atoms, a hydroxyl group, or a hydrocarbon radical comprising
1 to 50 carbon atoms and including an alkoxy group, and may be an alkoxy group of -
OR2 or -OR3 as to the phosphorous atom. Here, the hydrocarbon radical may include an
alicyclic structure such as cyclohexyl, or the like, an aliphatic branch structure, or an
aromatic ring structure such as phenyl or naphthyl or the like. Also, L + M + N = 3 holds,
wherein L is an integer of 1 through 3, and M and N are integers between 0 and 2.
Moreover, R2 and R3 may form a ring structure.
 [0045]
Adding the phosphorous compound of Formula (I) yields the effects of improved color
tone and thermal stability of the polymer produced, and this phosphorous compound is
further advantageous among phosphorous compounds that polymerization is not delayed.
 [0046]
Examples of the phosphorous compound of Formula (I) include ester phosphite, diallyl
phosphinous alkyl, diallyl phosphinous allyl, allyl phosphonous dialkyl, allyl
phosphonous diallyl, and so forth, and ester phosphite is particularly preferable from the
perspective of thermal stability and color tone improvement.
 [0047]
As for ester phosphites not having a ring structure, examples wherein L = 3, M = 0, and
N = 0 in formula (I) include triphenyl phosphite, tris(4-monononyl phenyl) phosphite,
tri(monononyl/dinonyl phenyl) phosphite, tris(2,4-tert-butyl phenyl) phosphite indicated
by Formula (VIII), and so forth.
 [0048]
Examples wherein L = 2, M = 1, and N = 0 include monooctyldiphynyl phosphite,

monodecyldiphynyl phosphite, bis [2,4-bis(1,1-dimethylethtyl)-6-methylphenyl]
ethylphosphite, tetrakis(2, 4-di-tert-butylpheriyl)4,4'-biphenylene diphosphite. Examples
wherein L = 1, M = 1, and N = 1 include dioctylmonophenyl phosphite,
didecylmonophenyl phosphite, and so forth.
 [0049]
Of these, the tris (2,4-tert-butyl phenyl) phosphite indicated by Formula (VIII) is

particularly preferable. This compound can be obtained as ADEKASTAB 2112
(manufactured by Asahi Denka Co., Ltd.) or as IRGAFOS168 (manufactured by Ciba
Specialty Chemicals).
 [0050]
The phosphorous compound of Formula (I) preferably has a six-membered ring structure
or higher including phosphorous atoms, from the perspective of thermal stability and
color tone improvement.
 [0051]
As for ester phosphites having a six-membered ring structure or higher, examples

wherein L = 1, M = 1, and N = 1 include bis(2,6-di-tert-butyl-4-methylphenyl)
pentaerithritol-di-phosphite indicated by Formula (IX),
bis (2,4-di-tert-butylphenyl) pentaerithritol-di-phosphite indicated by Formula

(X),
and 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5]

undecane, phenyl-neopentyleneglycol-phosphite, and so forth.
 [0052]
Examples wherein L = 2, M = 1, and N = 0 include the 2,2-methylene bis (4,6-di-tert-
butylphenyl) octylphosphite indicated by Formula (XI), and so forth.
 [0053]
Particularly, that of Formula (VII), such as the bis(2,6-di-tert-butyl-4-methylphenyl)

pentaerithritol-di-phosphite of Formula (IX), the bis (2,4-di-tert-butyphenyl)
pentaerithritol-di-phosphite of Formula (X), and so forth, are preferable from the
perspective of thermal stability and color tone improvement.
 [0054]
In Formula (VII), R13 and R14 independently correspond to R1 in Formula (I).
 [0055]
Moreover, the 2,2-methylene bis(4,6-di-tert-butylphenyl) octylphosphite of Formula (XI)

is also preferable.
 [0056]
The bis(2,6-di-tert-butyl-4-methylphenyl) pentaerithritol-di-phosphite of Formula (IX)

can be obtained as ADEKASTAB PEP-36 (manufactured by Asahi Denka Co., Ltd.).
 [0057]
The bis(2,4-di-tert-butylphenyl) pentaerithritol-di-phosphite of Formula (X) can be

obtained as ADEKASTAB PEP-24G (manufactured by Asahi Denka Co., Ltd.), or as
IRGAFOS126 (manufactured by Ciba Specialty Chemicals).
 [0058]
The 2,2-methylene bis(4,6-di-tert-butylphenyl) octylphosphite of Formula (XI) can be

obtained as ADEKASTAB HP-10 (manufactured by Asahi Denka Co., Ltd.).
 [0059]
Any one type of these phosphorous compounds may be used independently, or may be
used along with other phosphorous compounds.
 [0060]
Further, phosphorous compounds other than the phosphorous compound of Formula (I)
may be used as well. Examples of such phosphorous compounds which can be used
include phosphoric acids, phosphorous acids, phosphonic acids, phosphinic acids,
phosphin oxides, phosphonous acids, phosphinous acids, phosphines, and so forth.
 [0061]
Examples of phosphoric acids include phosphoric acid, trimethyl phosphate, triethyl

phosphate, triphenyl phosphate, and so forth.
 [0062]
Examples of phosphorous acids include phosphorous acid, trimethyl phosphite, triethyl

phosphite, triphenyl phosphite, and so forth.
 [0063]
Examples of phosphonic acids include methylphosphonic acid, ethylphosphonic acid,
propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid,
phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic
acid, biphenylphosphonic acid, naphtylphosphonic acid, anthrylphosphonic acid, 2-
carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-
carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-
dicarboxyphenylphosphonic acid, 2,5-dicarboxyphenylphosphonic acid, 2.6-
dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-
dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2,3,5-
tricarboxyphenylphosphonic acid, 2.3.6-tricarboxyphenylphosphonic acid, 2,4,5-
tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, dimethylester
methylphosphonate, diethylester methylphosphonate, dimethylester ethylphosphonate,
diethylester ethylphosphonate, dimethylester phenylphosphonate, diethylester
phenylphosphonate, diphenylester phenylphosphonate, dimethylester benzylphosphonate,
diethylester benzylphosphonate, diphenylester benzylphosphonate, lithium (3,5-di-tert-
butyl-4-ethyl hydroxybenzylphosphonate), sodium (3,5-di-tert-butyl-4-ethyl
hydroxybenzylphosphonate), magnesium bis(3,5-di-tert-butyl-4-ethyl
hydroxybenzylphosphonate), calcium bis(3,5-di-tert-butyl-4-ethyl
hydroxybenzylphosphonate), diethyl phosphonoacetate, methyl diethylphosphonoacetate,
ethyl diethylphosphonoacetate, and so forth.
 [0064]
Examples of phosphinic acids include hypophosphorous acid, sodium hypophosphite,

methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic
acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xylylphosphinic
acid, biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid,
diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid,
dibutylphosphinic acid, ditolylphosphinic acid, dixylylphosphinic acid,
dibiphenylylphosphinic acid, naphtylphosphinic acid, anthrylphosphinic acid, 2-
carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-
carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid, 2,4-
dicarboxyphenylphosphinic acid, 2,5-dicarboxyphenylphosphinic acid, 2,6-
dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-
dicarboxyphenylphosphinic acid, 2,3,4-tricarboxyphenylphosphinic acid, 2,3,5-
tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-
tricarboxyphenylphosphinic acid, 2,4,6-tricarboxyphenylphosphinic acid, bis(2-
carboxyphenyl) phosphinic acid, bis(3-carboxyphenyl) phosphinic acid, bis(4-
carboxyphenyl) phosphinic acid, bis (2,3-dicarboxyphenyl) phosphinic acid, bis(2,4-
dicarboxyphenyl) phosphinic acid, bis(2,5-dicarboxyphenyl) phosphinic acid, bis(2,6-
dicarboxyphenyl) phosphinic acid, bis(3,4-dicarboxyphenyl) phosphinic acid, bis(3,5-
dicarboxyphenyl) phosphinic acid, bis(2,3,4-tricarboxyphenyl) phosphinic acid, bis
(2,3,5-tricarboxyphenyl) phosphinic acid, bis(2,3,6-tricarboxyphenyl) phosphinic acid,
bis (2, 4, 5-tricarboxyphenyl) phosphinic acid, bis(2,4,6-tricarboxyphenyl) phosphinic
acid, methylester methylphosphinate, methylester dimethylphosphinate, ethylester
methylphosphinate, ethylester dimethylphosphinate, methylester ethylphosphinate,
methylester diethylphosphinate, ethylester ethylphosphinate, ethylester
diethylphosphinate, methylester phenylphosphinate, ethylester phenylphosphinate,
phenylester phenylphosphinate, methylester diphenylphosphinate, ethylester
diphenylphosphinate, phenylester diphenylphosphinate, methylester benzylphosphinate,
ethylester benzylphosphinate, phenylester benzylphosphinate, bis-methylester
benzylphosphinate, bis-ethylester benzylphosphinate, bis-phenylester benzylphosphinate,
and so forth.
 [0065]
Examples of phosphin oxides include trimethylphosphin oxide, triethylphosphin oxide,

tripropylphosphin oxide, triisopropylphosphin oxide, tributylphosphin oxide,
triphenylphosphin oxide, and so forth.
 [0066]
Examples of phosphonous acids include methylphosphonous acid, ethylphosphonous

acid, propylphosphonous acid, isopropylphosphonous acid, butylphosphonous acid,
phenylphosphonous acid, and so forth.
 [0067]
Examples of phosphinous acids include methylphosphinous acid, ethylphosphinous acid,

propylphosphinous acid, isopropylphosphinous acid, butylphosphinous acid,
phenylphosphinous acid, dimethylphosphinous acid, diethylphosphinous acid,
dipropylphosphinous acid, diisopropylphosphinous acid, dibutylphosphinous acid,
diphenylphosphinous acid, and so forth.
 [0068]
Examples of phosphines include methylphosphine, dimethylphosphine,

trimethylphosphine, ethylphosphine, diethylphosphine, triethylphosphine,
phenylphosphine, diphenylphosphine, triphenylphosphine, and so forth.
 [0069]
The amount of phosphorous compound added is preferably 0.1 to 400 ppm in terms of
phosphorous atoms as to the amount of polyester to be generated, more preferably 1 to
200 ppm, and even more preferably 3 to 100 ppm. Inclusion of 0.1 ppm or more yields
the actual effects of thermal stability and color tone of the polyester produced, and 400 or
less prevents delay of polymerization.
 [0070]
The ratio of addition of titanium compound and phosphorous compound is preferably 0.1
to 20 in terms of molecular ratio Ti/P of titanium atoms and phosphorous atoms, more
preferably 0.2 to 10, and even more preferably 0.3 to 5. 0.1 or greater improves
polymerization effectiveness, and 20 or less yields excellent thermal stability and color
tone of the polyester produced.
 [0071]
Also preferable is adding a manganese compound 1 to 400 ppm in terms of manganese

atoms as to the amount of polyester to be generated, with the molecular ratio Mn/P of the
manganese atoms of the manganese compound and phosphorous atoms of the
phosphorous compound of 0.1 to 200. Manganese atoms of 1 ppm or more with a
molecular ratio Mn/P of 0.1 or more allows deterioration of polymerization activity to be
suppressed, and also, keeping the manganese atoms to 400 ppm or lower with a
molecular ratio Mn/P of 200 or less enables the advantages of improving the color tone of
the polymer due to the phosphorous compound to be maintained. Examples of the
manganese compound include manganese chloride, manganese bromide, manganese
nitrate, manganese carbonate, manganese acetylacetonate, manganese acetate
tetrahydrate, manganese acetate dihydrate, and so forth.
 [0072]
Other polymerization catalysts or polymerization assistants which can be added include

alkali metal compounds such as lithium compounds, alkaline-earth metal compounds
such as calcium compounds, magnesium compounds and so forth, or aluminum
compounds, zinc compounds, tin compounds, and so forth.
 [0073]
As for a method of obtaining a titanium compound which can be used as a

polymerization compound, a polymerization catalyst can be synthesized by mixing a
titanium alcoxide compound to serve as the center of the polymerization with a
compound having a radial selected from the group of functional groups of Formulas 2
through 6 described earlier (hereafter referred to as "ligand compound").
 [0074]
Examples of the titanium alcoxide compound to be used include titanium

tetraisopropoxide and titanium tetrabutoxide.
 [0075]
As a method for synthesizing a polymerization catalyst by mixing the titanium alcoxide

compound and the ligand compound, a concentrate or diluted solution of the ligand
compound can be delivered by drops into a solution of the titanium alcoxide compound,
to carry out the reaction.
 [0076]
Or, a concentrate or diluted solution of the titanium alcoxide compound can be delivered
by drops into a solution of the ligand compound, and mixed to carry out the reaction.
 [0077]
Also, a phosphorous compound may be mixed beforehand into the solution into which
the other compound is to be delivered by drops, or, a concentrate or diluted solution of
the phosphorous compound can be delivered by drops.
 [0078]
Examples of a solvent used for synthesizing the polymerization catalyst include water,
methanol, ethanol, ethylene glycol, propanediol, butanediol, benzene, xylene, and so
forth, one of which may be used independently, or multiple kinds may be used together.
 [0079]
Also, adding the phosphorous compound at the point of synthesizing the titanium
compound used as the polymerization catalyst is also preferable. In this case, preparation
is preferably made in a solvent of pH 4 to 6, and hydrochloric acid, sulfuric acid, nitric
acid, p-toluenephosphonic acid, and like acid compounds, MES (pH of 5.6 to 6.8), ADA
(pH of 5.6 to 7.5), and like Good's buffers, and so forth.
 [0080]
As for the. reaction temperature and reaction time for the reaction for synthesizing the
polymerization catalyst, 1 minute or longer at 0 to 200°C is preferable, and more
preferable is 2 to 100 minutes at 20 to 100°C.
 [0081]
Further, carrying out the reaction while stirring is also preferable, and in this case 1
minute or longer at 0 to 200°C is preferable, and more preferable is 2 to 60 minutes at 10
to 100°C.
 [0082]
There are no restrictions on the reaction pressure of the reaction for synthesizing the
polymerization catalyst, i.e., room pressure is sufficient.
 [0083]
As described earlier, the polyester production process can be divided into the three of
o (1) esterification reaction,

o (2) ester interchange reaction, and
o (3) polycondensation, wherein a low polymer obtained by the reaction (1) or (2) is
high-polymerized.
 [0084]
While esterification reaction will proceed without a catalyst, a titanium compound is

preferably added as a catalyst from the perspective of promoting reaction.
 [0085]
With ester interchange reaction, a manganese compound, calcium compound, magnesium

compound, zinc compound, lithium compound, or the like, or a titanium compound is
preferably used as a catalyst to carry out the reaction. Also, after the ester interchange
reaction has essentially ended, a phosphorous compound is preferably added to deactivate
the catalyst used for the reaction.
 [0086]
With polycondensation reaction, using a titanium compound having a radical selected

from a carbonyl group, carboxyl group, or ester group, as a catalyst as descried above, is
preferable from the perspective of achieving the object of the present invention, which is
a substitute for an antimony compound.
 [0087]
The polymerization catalyst of the titanium compound produced as described above is

added into the polyester reaction system either with the solvent for synthesizing the
catalyst remaining or removed, but an arrangement wherein a solution or slurry using a
solvent including polyester diols such as ethylene glycol or propylene glycol or the like
has the low-boiling-point components such as alcohol and so forth removed and then
added to the reaction system is preferable, since formation of foreign matter in the
polymer can be suppressed even further.
 [0088]
Further, additional adding of a phosphorous compound is preferable form the perspective

of thermal stability and improved color tone. For this, there are methods for suppressing
deactivation such as additional addition in a different reaction vat, setting a 1 to 15
minute interval between addition of the polymerization catalyst and the phosphorous
compound in the same reaction vat, and distancing the positions for adding the two one
from another.
 [0089]
In the event of adding the phosphorous compound at this stage, the phosphorous
compound is preferably dissolved or dispersed in a diol component of ethylene glycol or
the like in a slurry.
 [0090]
Also preferably is adding, at an optional timing in the above reaction, particles such as
titanium dioxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin,
Carbon Black, etc., cobalt compounds, coloration inhibitors, stabilizers, phenol
antioxidants, and so forth.
 [0091]
Examples of cobalt compounds include cobalt chloride, cobalt nitrate, cobalt carbonate,
cobalt acetylacetonate, cobalt naphthenate, cobalt acetate tetrahydrate, and so forth.
 [0092]
Also, an organic color tone adjusting agent is preferably added at an optional point in the
above reaction, or after the polycondensation reaction has essentially ended. A color tone
adjusting agent is a dye used for resins and the like. Adding a color tone adjusting agent
suppresses the yellow color of the polyester, and enables a color tone to be provided
which is desired by users. Also, adding the color tone adjusting agent at the stage of
producing the polyester composition allows for a color tone suitable for lightly-colored
dyeing as well.
 [0093]
Specific examples of organic color tone adjusting agents by Color Index Generic Name
are as follows. For blues, there are Solvent Blue 104, Solvent Blue 122, Solvent Blue 45,
and so forth, for reds, Solvent Red 111, Solvent Red 179, Solvent Red 195, Solvent Red
135, Pigment Red 263, Vat Red 41, and so forth, and for violets, there are Disperse
Violet 26, Solvent Violet 13, Solvent Violet 37, Solvent Violet 49, and so forth. Of these,
organic color tone adjusting agents which do not contain halogens which readily become
a factor for device corrosion, have relatively excellent thermal resistance at high
temperatures, and have excellent coloration are preferable, Solvent Blue 104, Solvent
Blue 45, Solvent Red 179, Solvent Red 195, Solvent Red 135, and Solvent Violet 49
meeting these conditions.
 [0094]
One or multiple types of these color tone adjusting agents can be used according to
application or the demands of the user. Particularly, including a blue color tone adjusting
agent and/or a red color tone adjusting agent is preferable since color tone can be
adjusted finely. Here, the term "and/or" means that only one of the two, or both, may be
used. In this case, in the event that the ratio of blue color tone adjusting agent is 50% by
weight or more of the entire amount of organic color tone adjusting agent used in the
stage of producing the polyester composition, the color tone of the obtained polyester is
particularly excellent, and accordingly is preferable.
 [0095]
As for the amount of adding the organic color tone adjusting agent, 30 ppm or less as to
the polyester is preferable, since this maintains the transparency of the polyester, and
suppresses matte coloration. In the event of using the following master chip, the amount
of addition to the total amount of polyester following blending should be considered.
 [0096]
Methods for adding the organic color tone adjusting agent following polycondensation
reaction include a method for direct melt kneading using a uniaxial or biaxial extruder,
and a method for preparing polyester having the color tone adjusting agent at a high
concentration as a master chip beforehand and separately blending the master chip with a
chip not containing the color tone adjusting agent so as to adjust the color.
 [0097]
Also, as for the type of process for producing the polyester according to the present
invention, batch, semi-batch, or flow models, or the like, may be applied.
 [0098]
Also preferable for the polyester producing method according to the present invention is
to use a material which has been polymerized as polyester once and then depolymerized.
Sources for the once-polymerized polyester include, for example, fiber, film, bottles, and
so forth. For example, chemical recycling methods for depolymerizing polyethylene
terephthalate include a method wherein the polyethylene terephthalate is depolymerized
with ethylene glycol to yield bis(2-hydroxyethyl)terephthalate, which is then refined, a
method wherein the bis(2-hydroxyethyl)terephthalate obtained by depolymerization is
subjected to ester interchange reaction with methanol, and the obtained crude dimethyl
terephthalate is refined by recrystallizing or distilling, thereby obtaining dimethyl
terephthalate, and further a method wherein the dimethyl terephthalate is subjected to
hydrolysis under high temperature and pressure, thereby obtaining terephthalic acid.
Applying the present invention in the process of performing repolymerization using the
bis(2-hydroxyethyl)terephthalate, dimethyl terephthalate, and terephthalic acid, obtained
by depolymerizing once-polymerized polyester, allows a polymer with a color tone
superb to that of conventional produces to be obtained, with no formation of foreign
matter due to antimony compounds, and with excellent fiber and film formation
properties.
 [0099]
The polyester composition according to the present invention is produced with the
polyester production method according to the present invention.
 [0100]
The polyester composition according to the present invention preferably has 30 ppm or
less of an antimony compound included as to the polyester, more preferably 10 ppm or
less, and even more preferably none at all. Keeping the amount of antimony compound
included to 30 ppm or less enables soiling of the spinneret during spinning and so forth to
be reduced. Also, a relatively inexpensive polymer can be obtained.
 [0101]
The polyester resin according to the present invention contains the polyester composition
according to the present invention, whereby a fiber with excellent color tone can be
obtained.
 [0102]
Examples of the fiber-forming polyester include polyethylene terephthalate,

polytrimethylene terephthalate, polytetramethylene terephthalate, and so forth. For
clothing in particular, primarily using polyethylene terephthalate, which is highly
versatile, is preferable.
 [0103]
Also, the polyester fiber according to the present invention may be compound or blend
spun, assuming that the fiber includes the polyester composition according to the present
invention. Examples of compound fibers include core-sheath, core-sheath hollow, island-
in-sea, composite, and so forth.
 [0104]
Including at least 3% by weight of the polyester composition according to the present

invention as to the polyester fiber according to the present invention is preferable in
yielding the effects of the present invention.
 [0105]
As one form of polyester fiber according to the present invention, including 0.5 to 0.7%
by weight of titanium dioxide particles is preferable. Including titanium dioxide particles
within this range, which is a relatively large amount, provides the polyester fiber with a
sensation of dryness and with light-shielding properties. Also, the sensation of dryness
can be manifested by coarsening the surface of the fiber by alkali processing or the like.
Also, as described above, the polyester composition according to the present invention is
suitable for this form containing a great amount of titanium dioxide particles, since the
formation of foreign matter near the spinneret owing to antimony compounds can be
suppressed and fiber forming properties can be improved.
 [0106]
As for the size of the titanium dioxide particles which the polyester fiber according to the
present invention is to include, an average secondary particle size of 1.0 µm or less, and
an integration percentage of particles 2.0 µm or greater in frequency distribution of 5% or
less, are preferable from the point of reducing friction against guides and the like in the
process of passing the yarn.
 [0107]
Also, the polyester fiber according to the present invention includes the polyester
composition according to the present invention, and the polyester is preferably
copolymerized with 0.1 to 10 mol% of an isophthalic acid component having a metal
sulfonate group, and 0.1 to 5.0% by weight of a polyoxy alkylene glycol component
having a number average molecular weight of 400 to 6000.
 [0108]
The isophthalic acid component having the metal sulfonate group serves as a dyeing seat
for kation dye, yielding bright coloration which cannot be realized with disperse dyes.
Also, the copolymerization of polyoxy alkylene glycol enables suppression of increasing
melting viscosity of the polymer due to copolymerization with the isophthalic acid
component having the metal sulfonate group. Conventionally, with these
copolymerization component combinations, deterioration in spinning properties due to
formation of foreign matter at the spinneret was marked, but the polyester composition
according to the present invention allows formation of foreign matter near the spinneret
owing to antimony compounds to be suppressed and spinning properties can be
improved. Accordingly, the polyester composition according to the present invention is
suitable for this form wherein a third component is copolymerized.
 [0109]
Examples of isophthalic acid component having a metal sulfonate group include alkali
metal salts of sulfoisophthalic acid such as 5-sodiumsulfoisophthalic acid, 5-
lithiumsulfoisophthalic acid; ester-forming derivatives of alkali metal salts of
sulfoisophthalic acid such as dimethyl 5- sodiumsulfoisophthalate, dimethyl 5-
lithiumsulfoisophthalate, 5-sodiumsulfo-bis(2-hydroxyethyl)isophthalate, and 5-
lithiumsulfo-bis.(2-hydroxyethyl)isophthalate; phosphonium salts of sulfoisophthalic acid
such as 5-(tetraethyl)phosphoniumsulfoisophthalic acid and 5-
(tetrabutyl)phosphoniumsulfoisophthalic acid; and ester-forming derivatives of
phosphonium salts of sulfoisophthalic acid such as dimethyl 5-(tetraethyl)
phosphoniumsulfoisophthalate, dimethyl 5-(tetrabutyl) phosphoniumsulfoisophthalate, 5-
(tetraethyl) phosphoniumsulfo-bis(2-hydroxyethyl)isophthalate, 5-
(tetrabutyl)phosphoniumsulfo-bis(2-hydroxyethyl)isophthalate, and so forth. Of these,
dimethyl 5- sodiumsulfoisophthalate and 5-sodiumsulfo-bis(2-hydroxyethyl)isophthalate
are preferable from the point of dyeing properties.
 [0110]
Arranging the copolymerization amount of the isophthalic acid component having the
metal sulfonate group so as to be 0.1 mol% or more yields excellent dyeing properties,
and keeping this to 10 mol% or less suppresses increase of viscosity when molten,
thereby suppressing the increased pressure at the filter to within a permissible range. A
range of 0.6 to 5 mol% is more preferable, and 1.0 to 2.0 mol% is even more preferable.
 [0111]
Examples of the polyoxy alkylene glycol component include polyethylene glycol,

polypropylene glycol, polybutylene glycol and so forth, and of these, polyethylene
glycol, which is highly versatile, is preferable.
 [0112]
For the polyoxy alkylene glycol, a number average molecular weight of 400 or more
yields excellent dyeing properties, and 6000 or less prevents lumps from forming in the
polyester. 2000 to 5000 is even more preferable.
 [0113]
Arranging for the amount of copolymerization of the polyoxy alkylene glycol to be 0.1%
by weight or more allows excellent dyeing properties to be obtained, and 5.0% by weight
or less allows excellent heat resistance and polymer color tone to be maintained. 0.5 to
2.0% by weight is even more preferable.
 [0114]
Examples of the kation dye for dyeing the polyester fiber of this form include the product
groups Aizen Cathilon (manufactured by Hodogaya Chemical Co, Ltd.), Kayacryl
(manufactured by Nippon Kayaku Co., Ltd.), Estrol and Sumiacryl (manufactured by
Sumitomo Chemical Co, Ltd.), Diacryl (manufactured by Mitsubishi Chemical
Corporation), Maxilon (manufactured by Ciba-Geigy), Astrazon (manufactured by Bayer
Japan), and so forth. Disperse kation dyes may be used as well.
 [0115]
Also, the polyester fiber according to the present invention contains the polyester
composition according to the present invention, with the polyester preferably
copolymerizing 0.1 to 10 mol% of an isophthalic acid component having a metal
sulfonate group, and 0.1 to 5.0% by weight of a polyoxy alkylene glycol component
having a number average molecular weight of 400 to 6000, and further preferably with
the polyester composition containing 0.5 to 7.0% by weight of titanium dioxide particles.
 [0116]
Also, the polyester fiber according to the present invention is preferably an industrial
polyester fiber. Industrial polyester fibers require high strength values, and the polyester
composition according to the present invention is suitable to this application since
excellent mechanical properties can be obtained due to little foreign matter therein.
 [0117]
The intrinsic viscosity of the polyester composition according to the present invention is
preferably 0.85 or higher from the perspective of strength, toughness, and durability, and
more preferably 0.90 or higher. Further, from the perspective of thread formation, 1.3 or
lower is preferable.
 [0118]
With the industrial polyester fiber according to the present invention, the toughness
defined by the product of the strength T and the square root of the elongation E of the
fiber is preferably 28 or higher, with 30 or higher being even more preferable. Toughness
of 28 or higher yields sufficiently satisfactory strength and durability.
 [0119]
Also, with the industrial polyester fiber according to the present invention, the
dimensional stability represented by the sum of intermediate elongation (elongation
corresponding to strength of 4.0 cN/dtex) and dry-heat shrinkage is 12% or lower,
preferably 10% or lower, and even more preferably 8% or lower. With shrinkage is 12%
or lower, cords can be obtained which are satisfactory as a material for reinforcing rubber
with balanced strength, toughness, and durability, as well as maintaining the uniformity
of tires when forming tires. Dimensional stability of 8% or less enables substituting for
rayon in forming tires.
 [0120]
In addition to tire cords, the industrial polyester fiber according to the present invention
can also be applied to the following uses. For example, using in energy absorbing belts
such as seatbelts and the like allows greater shock to be absorbed than with conventional
textile of the same amount, or the same shock absorbing capabilities can be obtained with
textile that is thinner and more readily stored than conventional textiles. Also, use in
protective mesh sheets for construction work and the like allows reduction in weight and
consequently ease of work, since the amount of fabric used is less than conventional
articles. Further, use as a belt reinforcing material yields a belt with excellent durability
which is not as easily broken or damaged by shock or biting foreign objects. Other
examples of products to which the industrial polyester fiber according to the present
invention is advantageously applied includes conveyer belts, safety belts, safety nets,
sheets for civil engineering, seepage control sheets, ropes, fishing nets, tent fabric, heavy
fabric, flexible containers, sailcloth, airbag fabric, hose reinforcing material, and so forth.
 [0121]
Also, the polyester fiber according to the present invention is preferably used as a sewing
machine thread, due to the aforementioned excellent mechanical properties due to little
foreign matter therein. The polyester fiber for sewing machine thread according to the
present invention should have strength of 7.1 to 8.5 cN/dtex. Strength of 7.1 cN/dtex or
higher yields strength satisfactory for sewing machine thread. Strength of 8.5 cN/dtex is
sufficient, so 8.5 cN/dtex or lower is preferable from the perspective of plant operations
and facility maintenance.
 [0122]
The'polyester fiber for a sewing machine thread according to the present invention has
elongation of 14 to 24%. Elongation of 14% or higher yields fiber effectively, and 24%
or less yields satisfactory dimensional stability.
 [0123]
The polyester composition or polyester fiber according to the present invention is

preferably used as a polyester nonwoven fabric. The polyester composition according to
the present invention has little foreign matter, and accordingly allows a nonwoven cloth
having excellent yarn-disintegration properties and excellent uniformity to be provided,
while suppressing thread breakage.
 [0124]
With a type wherein the fibers are fused to each other to form a nonwoven cloth, the
polyester composition according to the present invention is produced by
copolymerization of 0.1 to 20 mol% of an isophthalic acid component as to the entire
acid component. Copolymerization of 0.1 mol% or more of the isophthalic acid
component as to the entire acid component yields a fusibility sufficient for forming
nonwoven cloth. Also, 20 mol% is sufficient as an upper limit, and preferably is 18 mol%
or less from the perspective of thermal stability.
 [0125]
Generally, low melting point copolymerized polyester tends to exhibit soiling of the
spinneret, but with the polyester composition according to the present invention,
formation of foreign matter around the spinneret owing to antimony'compounds is
suppressed, and spinning properties are improved; accordingly, the polyester composition
according to the present invention is suitable for this form wherein a third component is
copolymerized.
 [0126]
Also, in the event of using this polyester composition as the sheath component in a core-
sheath compound fiber, the core component should have a fusing point 20 to 60°C higher
than that of the sheath component, and more preferably 25 to 50°C higher. Setting the
difference in melting point between the two to be 20°C or more enables the fusion
between fibers to be strong since thermal compression at high temperature can be
performed, thereby suppressing down from being generated, and also, setting the
difference in fusing point between the two to be 60°C or less enables filaments
discharged from the spinneret at the time of spinning to be cooled in a stable manner even
in the event that single-strand fibers are large in diameter.
Examples [Measurement methods] (1) Amount of titanium element, phosphorous

element, antimony element, and manganese element contained in the polyester
composition
 [0127]
First, in the event that titanium dioxide particles were contained in the polyester
composition, pre-processing for removing the titanium dioxide particles was performed
as follows. The polyester composition was dissolved in orthochlorophenol at a ratio of
100 g solvent to 5 g polymer, the viscosity of the solution was adjusted by adding
dichloromethane of an amount the same as the polymer solution, following which the
solution was centrifugalized for 1 hour at 18,000 rpm, thereby settling out the particles.
Subsequently, the supernatant fluid was recovered by gradient, the same amount of
acetone as the supernatant was added for reprecipitation of the polymer, which was then
filtered with a glass filter (3G3, manufactured by Iwaki Glass Co., Ltd.), that remaining
on the filter was further washed with acetone, and then dried in a vacuum for 12 hours at
room temperature to remove the acetone.
 [0128]
On the other hand, in the event that there were no titanium dioxide particles contained in
the polyester composition, such pre-processing is unnecessary, so the polymer was
analyzed as it was.
 [0129]
The polyester from which the titanium dioxide particles were removed was melted into a
plate shape, and the amount of the titanium element, phosphorous element, antimony
element, and manganese element contained was measured using an X-ray fluorescence
analyzer (model MESA-500, manufactured by Horiba, Ltd.).
(2) Intrinsic viscosity (IV) of the polymer
 [0130]
Measured at 25°C with orthochlorophenol as a solvent.

(3) Solution haze
 [0131]
2.0 g of a sample was dissolved in 20 ml of orthochlorophenol, and analyzed with a haze

meter (model HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.) by
integrating sphere photoelectric photometry.
 [0132]
For example, with a polyester composition not containing titanium dioxide particles, a
polymer with solution haze of 2% or less can be said to have a small percentage of
foreign matter and be a polymer with excellent spinning properties.
(4) Color tone of polymer
 [0133]
A chip sample of polyester resin was tested for the Hunter value (L, a, and b values) with
a colorimeter.(SM color computer model SM-3, manufactured by Suga Test Instruments
Co., Ltd.). C light was used as the light source, with measurement performed with an
incident angle of 45°, vertical photoreception, and a 2° field of view. The number of
samples, n, was 10.
(5) State of formation of deposit around spinneret
 [0134]
Melt spinning as performed, and the deposit at the spinneret 72 hours following spinning
fiber was observed using a long-focus microscope. The state of formation of the deposit
was determined by the following standard.
o A: Almost no deposit at all.

o B: Some deposit, but within an operable range.
o C: Deposit observed, and strand breakage occurs frequently.
(6) Percentage of yarn breakage during drawing
 [0135]
Undrawn polyester fibers were drawn to various lengths as shown in the various
examples and comparative examples, and with the number of broken fibers out of 1000
undrawn fibers as n, the percentage of breakage was calculated with the following
expression. Yarn breakage = (n/1000) × 100
(7) Strength and elongation of fiber
 [0136]
An automatic tensile tester (ASC-5Y-A/RTA-100, manufactured by Orientec Co.) was

used to obtain the weight/elongation with a sample having an initial length of 20 cm and
drawn at 20 cm/minute. The maximal point of weight on the curve was divided by the
initial fineness of the sample to obtain the strength, and the length of stretching of the
sample at the maximal point of weight on the curve was divided by the initial length of
the sample to obtain the elongation. The number of samples, n, was 10.
(8) Dye exhaustion percentage
 [0137]
A tubular fabric was woven with a 27-gauge hosiery machine (manufactured by Eiko
Industrial Co., Ltd.), the tubular fabric was then refined by boiling for 5 minutes in
boiling water containing 0.2% nonionic activator (Gran Up CS, manufactured by Sanyo
Chemical Industries, Ltd.) and 0.2% soda ash, washed in water, and dried. The tubular
fabric was then dyed for 60 minutes in a 120°C hot water solution of Malachite Green
(manufactured by Kanto Kagaku) 5% (owf), acetic acid 0.5 ml/1, and sodium acetate 0.2
g/L, with a liquor ratio of 1:100, and the dye exhaustion percentage of the tubular fabric
was obtained from the difference in dye concentration in the liquid before and after
dyeing. A value of 40% or higher indicates that the polymer has excellent dyeing
properties.
(9) Coefficient of variation
 [0138]
As a parameter indicating the non-uniformity (Coefficient of Variation) of nonwoven

cloth, 100 samples 50 mm by 50 mm were taken from various places and the weight of
each was measured, obtaining the CV values from the following expression. CV value
(%) = (standard variation of weight of sample) / (average weight of samples) × 100
 [0139]
A CV value of 5% or lower means that yarn-disintegration properties are good, and a CV

value of 4% or lower means that yarn-disintegration properties are excellent.
(10) Strength, elongation, intermediate elongation, and toughness of industrial polyester

fiber
 [0140]
A Tensilon tensile tester (manufactured by Toyo Baldwin) was used to obtain the
weight/elongation with a sample having an initial length of 25 cm and drawn at 30
cm/minute. The maximal point of weight on the curve was divided by the initial fineness
of the sample to obtain the strength, and the length of stretching of the sample at the
maximal point of weight on the curve was divided by the initial length of the sample to
obtain the elongation. Also, the elongation corresponding to the strength 4.0 cN/dtex was
taken as the intermediate elongation from the weight/elongation curve. The toughness
was obtained from the strength T (cN/dtex) and elongation E(%) by T·E½.
(11) Dry-heat shrinkage
 [0141]
A 50 cm circumference two-wind skein of multifilament was taken as a sample, and left

in a 20°C and 65% RH environment for 24 hours, following which the length L0 of the
skein under a weight equivalent to 0.1 g/dtex was measured. Next, the weight was
removed, the sample placed on 150°C oven for 30 minutes with no tension, removed
from the oven and left for four hours in the above-described environment, weighted again
in the same way, and the length L1 of the skein was measured. The dry-heat shrinkage
was calculated from L0 and L1 with the following expression. Dry-heat shrinkage (%) =
{(L 0 - L 1 ) /L 0 } × 100
(12) Dimensional stability
 [0142]
The sum of the above intermediate elongation and dry-heat shrinkage was calculated as
the dimensional stability.
(13) Strength of processed cord
 [0143]
A sample was twisted 45 times per 10 cm (first twist), multiple strands were doubled, and
then twisted 45 times per 10 cm (final twist) in the opposite direction, thereby forming a
cord. The strength of the processed cord obtained from the industrial polyester fiber was
tested in the same way as (10) above.
(14) Heat resistance of processed cord in rubber
 [0144]
The processed cord was embedded in rubber, and the tenacity maintaining percentage
was evaluated following vulcanization at 150°C for 6 hours. A tenacity maintaining
percentage of 60% or higher is determined to be excellent, 50% or higher but less than
60% is comparable to conventional products, and less than 50% is inferior to
conventional products.
(15) Fatigue endurance (GY fatigue life)
 [0145]
In accordance with ASTM-D885, the time to tube rupture was measured under the
conditions of an internal pressures of tube of 3.5 kg/cm2, rotation speed of 850 rpm, and
tube angle of 90°. Comparison was made with a conventional tire cord (1000-240-703M,
manufactured by Toray Industries) regarding the time till rupturing, and evaluated as
follows. AA: Improved 10 to 30% over conventional product.
o A: Improved 0 to 10% over conventional product.

o C: Time to rupturing shorter than conventional product.
[Example 1] (Preparing Catalyst Compound) (Preparing titanium catalyst solution)
 [0146]
Warm (50°C) water (371 g) was put into a 3 liter flask having a stirrer, condenser, and
thermometer, into which a citric acid monohydrate (532 g, 2.52 mol) was dissolved.
While stirring the solution, titanium tetraisopropoxide (288 g, 1.00 mol) was slowly
added thereto from a dropping funnel. This compound was refluxed for 1 hour under
heat, so as to generate a cloudy solution, and the isopropanol/water thereof was distilled
and removed under a vacuum. The remainder was cooled to under 70°C, and the solution
thereof was stirred while slowly adding 32 weight/weight % aqueous solution of NaOH
(380 g, 3.04 mol) from a dropping funnel. The generated product was filtered, then mixed
with ethylene glycol (504 g, 8 mol), and heated under vacuum to remove the
isopropanol/water, thereby obtaining a slightly cloudy, light-yellow product containing a
chelated titanium citrate (containing 3.85% by weight of titanium).
(Adding phosphorous compound)
 [0147]
To the titanium catalyst solution was added 85 weight/weight % aqueous solution of

phosphoric acid (114 g, 1.00 mol), thereby yielding a titanium catalyst composition
having a phosphorous compound (containing 2.49% by mass of phosphorous).
(Producing polyester composition)
 [0148]
123 kg of bis(2-hydroxyethyl) terephthalate was placed in an esterification reaction vat
beforehand and maintained at a temperature of 250°C and a pressure of 1.2 × 105 Pa, into
which was continuously supplied a slurry of 100 kg of high-purity terephthalic acid
(manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by
Nihon Shokubai) over a period of 4 hours, and following supplying, esterification
reaction was performed for 1 hour while distilling out water.
 [0149]
Next,.123 kg of the esterification reaction product was transported to a polycondensation

vat.
 [0150]
Then, an ethylene glycol slurry of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerithritol-

di-phosphite (ADEKASTAB PEP-36, manufactured by Asahi Denka Co., Ltd.) was
added so as to be 50 ppm by mass to the target production amount of polyester (5 ppm by
mass in terms of phosphorous atoms), and stirred for 5 minutes. This ADEKASTAB
PEP-36 will be referred to as "phosphorous compound 1" hereafter.
 [0151]
Next, an ethylene glycol slurry of titanium dioxide particles was added so as to be 0.3%
by mass in terms of titanium dioxide to the target production amount of polyester, and
further stirred for 5 minutes. Further, an ethylene glycol solution of cobalt acetate and
manganese acetate was added so as to be 30 ppm by mass in terms of cobalt atoms and 15
ppm by mass in terms of manganese atoms to the target production amount of polyester,
and further stirred for 5 minutes.
 [0152]
Next, the catalyst compound A was added so as to be 10ppm by mass to the target
production amount of polyester in terms of titanium atoms, the low polymer was stirred
at 30 rpm while gradually raising the temperature of the reactive system from 250°C to
285°C and lowering the pressure to 40 Pa. The speed of increasing temperature and speed
of reducing pressure were both adjusted so as to reach the final temperature and final
pressure in 60 minutes.
 [0153]
Stirring was continued at 30 rpm, and at the point that a predetermined stirring torque
was reached, the reactive system was subjected to nitrogen purging and returned to
normal pressure, thereby stopping the polymerization reaction, and discharged into cold
water in strands and immediately cut so as to obtain polymer pellets. The time from
starting pressure reduction to reaching the predetermined stirring torque was 3 hours.
 [0154]
The intrinsic viscosity of the obtained polymer was 0.66, the color tone was L = 77, a = -
1.1, and b.= 0.5, and the solution haze was 0.7%. Also confirmed by measurement was
that the amount of titanium atoms originating from the titanium catalyst measured from
the polymer was 10 ppm by mass, the amount of phosphorous atoms contained was 13
ppm by mass,'Ti/P was 0.50, and the amount of antimony atoms contained was 0 ppm by
mass.
(Melt spinning, drawing)
 [0155]
The obtained polyester was dried, supplied to a spinning machine, molten at 290°C in a
melter, measured with a gear pump, discharged at 300°C from a spinning pack, and taken
up at a speed of 2000 m/minute. The obtained undrawn strand was drawn to 2.8 times at
80°C, and then subjected to thermal setting with a 125°C roller, thereby obtaining a 75
denier (83 dtex) 36 filament drawn yarn.
 [0156]
Carried out in the same way as with Example 1.
 [0157]
To the titanium catalyst solution was added phenylphosphonic acid (158 g, 1.00 mol),
thereby yielding a titanium catalyst composition having a phosphorous compound
(containing 2.49% by mass of P).
 [0158]
A polyester composition was obtained in the same way as with Example 1 except for
using the above catalyst composition and adding the phosphorous compound 1 so as to be
1 ppm by mass to the target production amount of polyester in terms of phosphorous
atoms.
 [0159]
Carried out in the same way as with Example 1, except for using the above-described
polyester composition.
 [0160]
 [0161]
To the titanium catalyst solution was added 85 weight/weight % of an aqueous solution

of phosphoric acid (39.9 g, 0.35 mol) and phenylphosphonic acid (158 g, 1.00 mol),
 [0162]
atoms.
 [0163]
Phosphorous compound A: phosphorous compound added to titanium catalyst compound
Phosphorous compound B: phosphorous compound added to system separate from
titanium catalyst compound
Amounts in Table are in terms of metal or phosphorous atoms.
 [0164]
The color tone of the polymers obtained with each of the Examples 1 through 3 was
excellent.
 [0165]
Also, in the melt spinning process, there was hardly any deposit around the spinneret and
increased filter pressure when spinning, and there was hardly no strand breakage when
drawing. That is, all of Examples 1 through 3 were polymers with excellent formation
workability.
 [0166]
Titanium tetraisopropoxide (285 g, 1.00 mol) was put into a 2 liter flask having a stirrer,
condenser, and thermometer, into which ethylene glycol (218 g, 3.51 mol) was added
from a dropping funnel while stirring. The speed of adding was adjusted so that the
reaction temperature kept the temperature within the flask at approximately 50°C.
Following this reaction, the reaction compound was stirred for 15 minutes. Following
stirring, 85 weight/weight % of an aqueous solution of ammonium lactate (252 g, 2.00
mol) was added, thereby obtaining a transparent, light-yellow product containing a
chelated titanium lactate (containing 6.54% by weight of titanium).
 [0167]
To the titanium catalyst solution was added 85 weight/weight % aqueous solution of

phosphoric acid (114 g, 1.00 mol), thereby yielding a titanium catalyst composition
having a phosphorous compound (containing 4.23% by weight of P).
 [0168]
using the above catalyst composition.
 [0169]
 [0170]
 [0171]

 [0172]
atoms.
 [0173]
 [0174]
 [0175]

 [0176]
atoms.
 [0177]
 [0178]
The color tone of the polymers obtained with each of the Examples 4 through 6 was
excellent.
 [0179]
drawing. That is, all of Examples 4 through 6 were polymers with excellent formation
workability.
 [0180]

 [0181]
No phosphorous compound was added at this stage.
 [0182]
using the above catalyst compound, and using phenylphosphite (manufactured by Sigma-
Aldrich Co.) (phosphorous compound 2) instead of the phosphorous compound 1 so as to
be 50 ppm by mass to the target production amount of polyester in terms of phosphorous
atoms.
 [0183]
 [0184]
 [0185]
 [0186]
using the above catalyst compound, and using tris(monononylphenyl) phosphite
(manufactured by Sigma-Aldrich Co.) (phosphorous compound 3) instead of the
phosphorous compound 1 so as to be 50 ppm by mass to the target production amount of
polyester in terms of phosphorous atoms.

 [0187]

 [0188]
The color tone of the polymers obtained with both the Examples 7 and 8 was excellent.
 [0189]
drawing. That is, both Examples 7 and 8 were polymers with excellent formation
workability.

 [0190]
 [0191]
 [0192]
using the above catalyst compound, and using phosphorous compound 2 instead of the
 [0193]
 [0194]
 [0195]
 [0196]
using the above catalyst compound, and using phosphorous compound 3 instead of the
 [0197]

 [0198]
 [0199]
workability.
[Example 11] (Preparing Catalyst Compound)
 [0200]
 [0201]
using the above catalyst composition and using bis(2,4-di-tert-butylphenyl)
pentaerithritol-di-phosphite (ADEKASTAB PEP-24G, manufactured by Asahi Denka
Co., Ltd.) (phosphorous compound 4) instead of the phosphorous compound 1 so as to be
atoms.
 [0202]
 [0203]
 [0204]
To'the titanium catalyst solution was added phenylphosphonic acid (158 g, 1.00 mol),
 [0205]
using the above catalyst composition and adding the phosphorous compound 4 instead of
the phosphorous compound 1 so as to be 1 ppm by mass to the target production amount
of polyester in terms of phosphorous atoms, and further adjusting the amount of adding
the catalyst compound so as to be 15 ppm by mass in terms of titanium atoms.
 [0206]
 [0207]
 [0208]

 [0209]
the phosphorous compound 1 so as to be 300 ppm by mass to the target production
amount of polyester in terms of phosphorous atoms, and further adjusting the amount of
adding the catalyst compound so as to be 5 ppm by mass in terms of titanium atoms, the
amount of addition of manganese acetate so as to be 30 ppm by mass, and moreover,
adding antimony trioxide as another catalyst so as to be 20 ppm by mass to the target
production amount of polyester in terms of antimony atoms.
 [0210]
 [0211]
 [0212]
drawing. That is, both the Examples 11 and 12 were polymers with excellent formation
workability.
 [0213]
As for Example 13, the obtained polymer had excellent color tone, and while some
deposit around the spinneret was observed when spinning, an operable state was
maintained.
 [0214]
 [0215]
using the above catalyst composition and using the phosphorous compound 4 instead of
the phosphorous compound 1 so as to be 5 ppm by mass to the target production amount
of polyester in terms of phosphorous atoms.
 [0216]
 [0217]
 [0218]
 [0219]
using the above catalyst composition and adding 1 ppm by mass of the phosphorous
compound 4 instead of the phosphorous compound 1 to the target production amount of
polyester in terms of phosphorous atoms, and adjusting the amount of addition of the
catalyst compound so as to be 15 ppm by mass.
 [0220]
 [0221]
 [0222]

 [0223]
the phosphorous compound 1 so as to be 300 ppm by mass to the target production
amount of polyester in terms of phosphorous atoms, and further adjusting the amount of
adding the catalyst compound so as to be 5 ppm by mass in terms of titanium atoms, the
amount of addition of manganese acetate so as to be 40 ppm by mass, and moreover,
adding antimony trioxide as another catalyst so as to be 20 ppm by mass to the target
production amount of polyester in terms of antimony atoms.
 [0224]
 [0225]
 [0226]
drawing. That is, both the Examples 14 and 15 were polymers with excellent formation
workability.
 [0227]
As for Example 16, the obtained polymer had excellent color tone, and while some
deposit around the spinneret was observed when spinning, an operable state was
maintained.
 [0228]
 [0229]
using the above catalyst compound, and using 2,2-methylene bis (4,6-di-tert-butylphenyl)
octylphosphite (ADEKASTAB HP-10, manufactured by Asahi Denka Co., Ltd.)
(phosphorous compound 5), instead of the phosphorous compound 1, so as to be 50 ppm
by mass to the target production amount of polyester in terms of phosphorous atoms.
 [0230]
 [0231]
 [0232]
using the above catalyst compound, and using tris(2,4-di-tert-butylphenyl) phosphite
(ADEKASTAB 2112, manufactured by Asahi Denka Co., Ltd.) (phosphorous compound
6), instead of the phosphorous compound 1, so as to be 50 ppm by mass to the target
production amount of polyester in terms of phosphorous atoms.
 [0233]
 [0234]
 [0235]
Also, in the melt spinning process,.there was hardly any deposit around the spinneret and
workability.
 [0236]

 [0237]
using the above catalyst compound, and using the phosphorous compound 5 instead of
the phosphorous compound 1, so as to be 50 ppm by mass to the target production
amount of polyester in terms of phosphorous atoms.
 [0238]
 [0239]
 [0240]
using the above catalyst compound, and using the phosphorous compound 6 instead of
the phosphorous compound 1, so as to be 50 ppm by mass to the target production
amount of polyester in terms of phosphorous atoms.
 [0241]
 [0242]
 [0243]
workability.
[Comparative Example 1] (Producing polyester composition)
 [0244]
adding 10 ppm by mass of tetrabuthoxy titanium (manufactured by Nippon Soda Co.,
Ltd.) as a titanium catalyst so as to be 10 ppm by mass to the target production amount of
polyester in terms of titanium atoms, adding the phosphoric acid was omitted, and the
amount of addition of the phosphorous compound 1 was 100 ppm by mass to the target
production amount of polyester in terms of phosphorous atoms.
 [0245]
 [0246]
In the melt spinning process, there was hardly any deposit around the spinneret and
increased filter pressure when spinning, and there was hardly no strand breakage at the
time of drawing, with excellent formation workability as a polymer, but the color tone b
value of the polymer obtained was 10.3, which is high, and the polymer had a poor
yellow color tone.
[Comparative Example 2] (Producing polyester composition)
 [0247]
A polyester composition was obtained in the same way as with Example 1 except that a
titanium catalyst was not used, the amount of addition of the phosphoric acid was 10 ppm
by mass to the target production amount of polyester in terms of phosphorous atoms, the
amount of addition or the phosphorous compound 1 was 500 ppm, by mass to the target
production amount of polyester in terms of phosphorous atoms and antimony trioxide
(manufactured by Sumitomo Metal Mining Co., Ltd.) as a catalyst was added 400 ppm by
mass to the target production amount of polyester in terms of antimony atoms.
 [0248]
 [0249]
The polymerization reaction progressed favorably even though the catalyst was replaced,
and there was no problem with the color tone of the polymer obtained, but the haze of the
polymer was a high 3.4%, and the operation was poor in that deposition at the spinneret
was observed when spinning, which resulted in frequent strand breakage.
[Comparative Example 3] (Preparing Catalyst Compound)

 [0250]
An ethylene glycol solution including tetraisopropoxy titanium (manufactured by Nippon

Soda Co., Ltd.) and phosphoric acid was prepared.
 [0251]
omitting adding of the phosphorous compound, and the above catalyst compound was
added so as to be 10 ppm by mass to the target production amount of polyester in terms
of phosphorous atoms.
 [0252]
 [0253]
The polymerization reaction progressed favorably even though the catalyst was replaced,
and there was hardly any deposit around the spinneret and increased filter pressure when
spinning, and hardly no strand breakage at the time of drawing, with excellent formation
workability as a polymer, but the color tone b value of the polymer obtained was 13.8,
which is high, and the polymer had a poor yellow color tone.
[Example 21] (Recovering bis(2-hydroxyethyl) terepthalate)
 [0254]
Used polyethylene terepthalate (PET) products including PET bottles were pulverized
into flakes, the flakes were mixed with molten bis(2-hydroxyethyl) terepthalate, further
heated for preliminary depolymerization, and the obtained preliminarily depolymerized
product was subjected to depolymerization in ethylene glycol to form an ethylene glycol
solution of the bis(2-hydroxyethyl) terepthalate.
 [0255]
This solution was subjected to filtering out of foreign matter, decoloration with activated
carbon, and deionization by ion exchange.
 [0256]
Next, the crude bis(2-hydroxyethyl) terepthalate was separated out of the solution by
crystallization, and the separated matter was refined by molecular distillation, thereby
yielding a melt of refined bis(2-hydroxyethyl) terepthalate.
 [0257]
This melt was maintained at 120°C, and dropped onto a belt flaker maintained at 25°C at
a speed of 1 drop per second from a dropping orifice such that the weight of each drop
was 25 mg, thereby yielding bis(2-hydroxyethyl) terepthalate pellets having a meniscus
lens shape with a maximum diameter of 4 mm at the average circumference and a height
of 2 mm at the top of the convex face.
(Recovering terephthalic acid)
 [0258]
A 500 ml separable flask having 200 parts by mass of ethylene glycol was prepared
beforehand, into which were placed 1.5 parts by mass of sodium carbonate and 50 parts
by mass of used PET product flakes including PET bottles, and heated to 185°C while
stirring. This was continuously stirred for 4 hours at this temperature, whereby the used
PET product flakes were dissolved, and depolymerization was completed. The obtained
matter was concentrated by depressurization distilling, and 150 parts by mass of ethylene
glycol were recovered as distillate.
 [0259]
0.5 parts by mass of sodium carbonate and 100 parts by mass of methanol were added to
the concentrate as an ester interchange reaction catalyst, and stirred at normal pressure for
1 hour at 75°C, carrying out the ester interchange reaction.
 [0260]
The obtained mixture was cooled to 40°C, and filtered with a glass filter. 100 parts by
mass of the crude dimethyl terephthalate captured on the filter were placed in methanol,
washed by stirring while heating to 40°C, and filtered with a glass filter again. Following
this, washing by stirring in methanol was repeated again.
 [0261]
The crude dimethyl terephthalate captured on the filter was placed in a still, subjected to
depressurization distillation at a pressure of 6.65 kPa and a reflux ratio of 0.5, thereby
obtaining dimethyl terephthalate as a distill.
 [0262]
100 parts by mass of the obtained dimethyl terephthalate were mixed with 200 parts by
mass of water, stirred while maintaining at 180°C, and subsequently supplied to a
hydrolysis device. The fluid temperature in the hydrolysis device to which the mixture
was supplied as maintained at 250°C, and stirred to carry out the hydrolysis, and the
methanol generated was distilled out along with the water.
 [0263]
The mass ratio of the terephthalic acid to the water in the terephthalic acid / water slurry
was approximately 1 to 1. Also, the total amount of 4-carboxybenzaldehyde, paratoluic
acid, benzoic acid, and dimethyl 2-hydroxyterephthalate, was 1 ppm by mass or less as to
the terephthalic acid.
 [0264]
Next, 166 parts by mass of the obtained terephthalic acid / water slurry and 4150 parts by
mass of ethylene glycol were placed in a centrifuge and mixed. The ratio by mass of the
terephthalic acid / water / ethylene glycol was 1 : 1 : 50 at the point of being placed
therein, and the solvent was removed from the slurry to yield a terephthalic acid cake.
The ratio by mass of the terephthalic acid /water / ethylene glycol in the terephthalic acid
cake was approximately 83 : 0.4 : 14.3.
 [0265]
Ethylene glycol was further added to the cake and mixed, finally yielding a terephthalic
acid / ethylene glycol slurry with a mass ratio of 66 : 34.
(Preparing Catalyst Compound)
 [0266]
 [0267]
using the bis(2-hydroxyethyl) terepthalate and the terephthalic acid / ethylene glycol
slurry obtained as described above as the material for the polyester.
 [0268]

[Examples 22 through 26] (Preparing Catalyst Compound)
 [0269]
 [0270]
adding cobalt oxide, Solvent Blue 104 (Polysynthren Blue RBL, manufactured by
Clariant) (B1), and Solvent Red 135 (Polysynthren Red GFP, manufactured by Clariant)
(R1), to the Examples, in the amounts shown in Table 11.
 [0271]


 [0272]
 [0273]
changing the amount of titanium dioxide particles added to the amounts shown in Table
12.
 [0274]
Amounts in Table are in terms of metal or phosphorous atoms except for titanium
dioxide.
 [0275]
 [0276]
100 kg of bis(2-hydroxyethyl) terephthalate was placed in an esterification reaction vat

beforehand and maintained at a temperature of 250°C and a pressure of 1.2 × 105 Pa, into
which was continuously supplied a slurry of 82.5 kg of high-purity terephthalic acid
(manufactured by Mitsui Chemicals) and 35.4 kg of ethylene glycol (manufactured by
Nihon Shokubai) over a period of 4 hours, and following supplying, esterification
reaction was performed for 1 hour while distilling out water.
 [0277]
Next, 101.5 kg of the esterification reaction product was transported to a

copolymerization reaction vat.
 [0278]
Next, 5 g of silicon (TSF433 manufactured by GE Toshiba Silicones) was added into the
copolymerization reaction vat to which the esterification reaction product was
transported.
 [0279]
Next, an ethylene glycol solution of 11.5 g of cobalt acetate (30 ppm by mass in terms of
cobalt atoms as to the target production amount of polyester), 15 g of manganese acetate
(33 ppm by mass in terms of manganese atoms as to the target production amount of
polyester), 75 g of pentaerithritol-tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenol)
propionate) (Irganoxs 1010, manufactured by Ciba-Geigy), 45 g of lithium acetate, and
0.4g of B1 as a blue color tone adjusting agent, was added.
 [0280]
Also, the above catalyst compound in terms of titanium atoms was added so as to be 10
ppm by mass as to the target production amount of polyester, as well as an ethylene
glycol slurry of the phosphorous compound 1 being added so as to be 70 ppm by mass (7
ppm by mass in terms of phosphorous atoms) as to the target production amount of
polyester.
 [0281]
After stirring for 5 minutes, 1 kg of polyethylene glycol (manufactured by Sanyo

Chemical Industries, Ltd.) having a number average molecular weight of 4000 was
added.
 [0282]
After stirring another 5 minutes, an ethylene glycol solution of hydroxyethylester 5-

sodium sulfoisophthalate (ES-740, manufactured by Takemoto Oil & Fat) was added so
as to be a 1.78 mol % isophthal component as to the acid component of the polyester.
 [0283]
Next, following stirring for 5 minutes, an ethylene glycol slurry of titanium dioxide
particles was added so as to be 0.07% by mass to the target production amount of
polyester in terms of titanium dioxide particles as to the target production amount of
polyester, the low polymer was stirred at 30 rpm while gradually raising the temperature
of the reactive system from 250°C to 290°C and lowering the pressure to 40 Pa. The
speed of increasing temperature and speed of reducing pressure were both adjusted so as
to reach the final temperature and final pressure in 60 minutes.
 [0284]
Stirring was continued at 30 rpm, and at the point that a predetermined stirring torque
was reached, the reactive system was subjected to nitrogen purging and returned to
normal pressure, thereby stopping the polymerization reaction, and discharged into cold
water in strands and immediately cut so as to obtain polyethylene terephthalate pellets.
The time from starting pressure reduction to reaching the predetermined stirring torque
was 3 hours.
 [0285]
The intrinsic viscosity of the obtained polymer was 0.68, the color tone was L = 72, a = -
2.5, and b = 4.5, and the solution haze was 0.7%. Also confirmed by measurement was
that the amount of titanium atoms originating from the titanium catalyst measured from
the polymer was 10 ppm by mass, the amount of phosphorous atoms contained was 13
ppm by mass,'Ti/P was 0.50, and the amount of antimony atoms contained was 0 ppm by
mass.
 [0286]
The obtained polyester was dried, supplied to a spinning machine, molten at 285°C in a
melter, measured with a gear pump, discharged at 295°C from a spinning pack, and taken
up at a speed of 1000 m/minute. The obtained undrawn strand was drawn to 2.8 times at
80°C, and then subjected to thermal setting with a 125°C roller, thereby obtaining a 75
denier (83 dtex) 36 filament drawn yarn.
 [0287]
There was hardly any deposit around the spinneret and increased filter pressure when
spinning, and there was hardly any strand breakage when drawing. That is, Example 30
was a polymer with excellent formation workability.
 [0288]
Also, the dye exhaustion percentage was 62%, exhibiting excellent dyeing properties.
 [0289]
 [0290]
changing the amount of the isophthalic acid component having the metal sulfonate group
added, and the number average molecular weight of the polyethylene glycol component
added, as indicated in Tables 13 and 14.
 [0291]
dioxide.
dioxide.
 [0292]
 [0293]
changing the amount of the isophthalic acid component having the metal sulfonate group
added, and the number average molecular weight of the polyethylene glycol component
added, as indicated in Tables 15 and 16, and also the changing amount of adding the
titanium dioxide particles to 1.5% by mass in terms of titanium dioxide particles as to the
target production amount of the polyester.
 [0294]
dioxide.
dioxide.
 [0295]
(Producing polyester composition for core component)
 [0296]
A polyester composition was obtained in the same way as with Example 1, and used as
the core component of a core-sheath compound fiber.
(Producing polyester composition for sheath component)
 [0297]
A polyester composition was obtained in the same way as the polyester composition for
the core component above, except for using 90 kg of terephthalic acid and 10 kg of
isophthalic acid (manufactured by Mitsui Chemicals, Inc.) as a dicarboxylic acid, and
setting the amount of titanium dioxide particles added so as to be 0.1% by mass as to the
target production amount of the polyester, and this obtained polyester composition was
used for the sheath component of a core-sheath compound fiber.
 [0298]
The IV of the obtained polyester for the sheath component was 0.63, and the melting
point was 257°C. Also, the amount of titanium atoms contained owing to the titanium
catalyst was configured by measurement of the polymer to be 10 ppm by mass.
(Melt spinning and forming nonwoven cloth)
 [0299]
The above core component and sheath component were each molted at 280°C, 240
g/minute for the core component and 60 g/minute for the sheath component were
discharged from a core-sheath compound fiber spinneret having 200 orifices 0.5 mm in
diameter, the spun filaments were sucked at high speed with an air sucker pressure of
0.54 MPa and caused to collide into a collision plate along with the air flow so as to
disintegrate the filaments, which were collected on a net conveyer adjusted such that the
sheet weight was 50 g/m2. Subsequently, part of this was subjected to thermal
pressurization by an embossing roller heated to 235°C, thereby obtaining a nonwoven
cloth. The state of strand breakage in the process of manufacturing the nonwoven cloth
was observed for 180 minutes but not a single strand breakage was observed, meaning
that operating properties were excellent.
 [0300]
The obtained nonwoven cloth had an excellent CV value of 3.2%.
[Examples 45 and 46] (Preparing Catalyst Compound)
 [0301]
(Producing polyester composition for core component)
 [0302]
A polyester composition was obtained in the same way as with Example 1, and used as
the core component of a core-sheath compound fiber.
(Producing polyester composition for sheath component)
 [0303]
changing the amount of isophthalic acid as indicated in Table 17 for each Example.
(Melt spinning and forming nonwoven cloth)
 [0304]
Carried out in the same way as with Example 44, except for using the above polyester
composition.
Amounts in Table are in terms of metal or phosphorous atoms. Table 18
Example 44 Example 45 Example 46

Core component ratio (%) 80 80 80
CV value(%) 3.2 3.2 4.1
Strand breakage (times/180 minutes) 00 00 00
 [0305]
 [0306]
omitting addition of the titanium dioxide particles and setting the torque value such that
the IV was 0.72.
 [0307]
Further, the polyester composition as subjected to preliminary drying at 160°C for 5

hours, then solid-phase polymerized under conditions of 225°C and a pressure of 40 Pa,
thereby yielding a chip of a polyester composition having an IV of 1.27.
 [0308]
The a polyester composition having an IV of 1.27 was spun using an extruder type
spinning machine. Filaments discharged from discharge orifices 0.6 mm in diameter were
subjected to cold removal in a heating cylinder 300 mm in length at 300°C, then
hardened by cooling in a breeze of 18°C, and taken up at a speed of 2000 m/minute. The
undrawn strands thus obtained were subjected to change in drawing and relaxation at a
drawing temperature of 85°C and heat treatment temperature of 240°C, thereby yielding a
1000 dtex 240 filament drawn yarn.
 [0309]
There was hardly any filter pressure increase during spinning. Further breakage hardly
occurred at all when drawing, meaning that yarn formation properties were excellent.
 [0310]
The IV measured from the polyester fiber was 1.02. Also, the solution haze measured
from the drawn yarn was 0.6.
 [0311]
A processed cord formed from this drawn yarn had excellent strength of 7.1 cN/dtex, and
fatigue resistance was also superb to that of conventional products.
 [0312]
 [0313]
omitting addition of the titanium dioxide particles and setting the torque value such that
the IV was 0.72.
 [0314]
The obtained polyester was dried and then supplied to a spinning machine, molten at
290°C with a melter, measured with a gear pump, discharged at 300°C from a spinning
pack, and taken up at a speed of 1000 m/minute. The obtained undrawn strand was drawn
to 3.2 times at 90°C, further drawn at 105°C to 1.6 times, and then subjected to thermal
setting with a 210°C hot roller, thereby obtaining a 78 dtex 24 filament drawn yarn.
 [0315]
There was hardly any deposit around the spinneret and increased filter pressure when
spinning, and there was hardly any strand breakage when drawing. That is, Example 48
was a polymer with excellent formation workability.
Claims (20)
Hide Dependent
translated from
1. A polyester production method wherein
a titanium compound having a radical selected from a carbonyl group, a carboxyl group,
or an ester group, and
a phosphorous compound having a structure illustrated in Formula (I)
are added;
in which each R1 independently represents hydrogen, a hydrocarbon radical

having 1 to 50 carbon atoms and optionally including an alkoxy substituent, a hydroxyl
group, or a hydrocarbyloxy radical having 1 to 50 carbon atoms and optionally including
an alkoxy substituent, of which R1 two or more may be included with regard to the
benzene ring; each of R2 and R3 independently represents a hydrocarbon radical having 1
to 50 carbon atoms and optionally including an alkoxy substituent, a hydroxyl group, or a
hydrocarbyloxy radical comprising 1 to 50 carbon atoms, such as an alkoxy group, and
optionally including an alkoxy substituent; or R2 and R3 may, together with the
phosphorus atom, form a hydrocarbyl ring optionally interrupted by at least one hetero
atom, additional to the phosphorus atom, selected from oxygen and phosphorus, and
which hydrocarbyl ring is optionally substituted by a hydrocarbon or hydrocarbyloxy
radical having 1 to 50 carbon atoms, which hydrocarbon or hydrocarbyloxy radical
optionally includes an alkoxy substituent;
L + M + N = 3 where L is an integer of 1 to 3, and M and N are integers between 0 and 2;

and, when L is 2 or 3, respective groups R1 on adjacent benzene rings may form a
hydrocarbyl group, such as an alkylene group, linking the respective benzene rings
together.
2. A polyester production method according to Claim 1 wherein said titanium compound

includes a radical selected from a group of functional groups represented by the
following Formulae (II) to (VI);
in which each of R4 to R12 independently represents hydrogen, an alkoxy group, a
hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or
an amino group, a hydrocarbon radical having 1 to 30 carbon atoms, or a hydrocarbyloxy
radical having 1 to 30 carbon atoms and which hydrocarbon or hydrocarbyloxy group
optionally includes an alkoxy, a hydroxyl, a carbonyl, an acetyl, a carboxyl, an ester, or
an amino substituent group.
3. A polyester production method according to Claim 2 wherein said titanium compound

includes a radical selected from a group of functional groups represented by the Formulae
(II) to (IV);
in which each of R4 to R9 independently represents a carbonyl group, a carboxyl
group or an ester group or a hydrocarbon radical having 1 to 30 carbon atoms and
including a carbonyl, a carboxyl, or an ester substituent group.
4. A polyester production method according to Claim 1 wherein said phosphorous
compound contains a six-membered ring structure or higher including phosphorus atoms.
5. A polyester production method according to Claim 4 wherein said phosphorous
compound includes that represented by Formula (VII);
in which R13 and R14 independently correspond to R1 in Formula (I).
6. A polyester production method according to Claim 1 wherein 0.5 to 150 ppm of titanium
compound is added as to the amount of polyester to be generated, in terms of titanium
atoms.
7. A polyester production method according to Claim 1 wherein 0.1 to 400 ppm of
phosphorous compound is added as to the amount of polyester to be generated, in terms
of phosphorus atoms.
8. A polyester production method according to Claim 1 wherein the ratio of addition of
titanium compound and phosphorous compound is 0.1 to 20 in terms of molecular ratio
Ti/P of titanium atoms and phosphorus atoms.
9. A polyester production method according to Claim 1 wherein 1 to 400 ppm of a
manganese compound is added as to the amount of polyester to be generated, in terms of
manganese atoms, wherein the ratio of addition of manganese compound as to the
phosphorous compound is 0.1 to 200 in terms of molecular ratio Mn/P of manganese
atoms and phosphorus atoms.
10. A polyester production method according to Claim 1 wherein a blue organic color
adjusting agent and/or a red organic color adjusting agent is added.
11. A polyester production method according to Claim 1 wherein polymerized polyester
which has then been depolymerized is used as a material.
12. A polyester composition produced by the polyester production method according to
Claim 1.
13. A polyester composition according to Claim 12, wherein the amount of antimony
compound contained as to the polyester is 30 ppm or less in terms of antimony atoms.
14. A polyester fiber including the polyester composition according to either Claim 12 or 13.
15. A polyester fiber including the polyester composition according to either Claim 12 or 13,
said polyester composition including 0.5 to 7.0% by weight of titanium dioxide particles.
16. A polyester fiber including the polyester composition according to either Claim 12 or 13,
said polyester produced by copolymerization of 0.1 to 10 mol% of an isophthalic acid
component containing a metal sulfonate radical and 0.1 to 5.0% by weight of a polyoxy
alkylene glycol component having a number average molecular weight of 400 to 6000.
17. An polyester fiber including the polyester composition according to Claim 16, said
polyester composition including 0.5 to 7.0% by weight of titanium dioxide particles.
18. An industrial polyester fiber including the polyester composition according to either
Claim 12 or 13, wherein the intrinsic viscosity of the polyester is 0.85 or higher, the
toughness T·E½, defined by the product of the strength T(cN/dtex) and the square root of
the elongation E(%) of the fiber, is 28 or higher, and the dimensional stability represented
by the sum of intermediate elongation and dry-heat shrinkage is 12% or lower.
19. A polyester fiber for sewing machine thread including the polyester composition
according to either Claim 12 or 13, wherein the strength is 7.1 to 8.5 cN/dtex and
elongation is 14 to 24%.
20. A polyester nonwoven fabric including the polyester composition according to either
Claim 12 or 13, wherein the polyester is produced by copolymerization of 0.1 to 20
mol% of an isophthalic acid component.
Patent Citations (11)
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using the catalyst and it for polyester production
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Cited By (20)
Publication number Priority date Publication date Assignee Title

EP1714998A1 * 2005-04-21 2006-10-25 Mitsubishi Polyester Film GmbH Biaxially oriented
film based on titanium catalysed polyesters
EP2210910A1 * 2009-01-21 2010-07-28 Nan Ya Plastics Corporation Antimony-free PET resin
and PET polyester fiber made therefrom
EP2765149A1 * 2013-02-06 2014-08-13 Uhde Inventa-Fischer GmbH Method for the
production of a titanium containing catalyst, titanium containing catalyst, method for the
production of polyester and polyester
DE202015005969U1 2015-08-27 2015-09-28 Carl Freudenberg Kg Nonwoven fabric
comprising antimony-free polyester
EP3109271A4 * 2014-02-20 2016-12-28 Teijin Ltd Polyethylene-2,6-naphthalate composition
with excellent blow moldability, and molded product thereof
Family To Family Citations
TWI341339B * 2004-03-30 2011-05-01 Teijin Fibers Ltd Island-in-sea type composite fibers
and process for producing same
JP2007056420A * 2005-08-26 2007-03-08 Toray Ind Inc Cationic dyeability antistatic polyester
fiber
JP2007063714A * 2005-08-31 2007-03-15 Toray Ind Inc Ultrafine polyester fiber and cloth
JP2007063713A * 2005-08-31 2007-03-15 Toray Ind Inc Undrawn polyester yarn having
excellent dyeability
WO2007072893A1 2005-12-23 2007-06-28 Toray Industries, Inc. Catalyst for producing
polyester and method for producing polyester
CN101328263B 2007-06-22 2012-06-06 东丽纤维研究所（中国）有限公司 Catalyst for
producing polyester
KR20100112605A * 2008-01-08 2010-10-19 데이진 화이바 가부시키가이샤 Normal pressure
cation dyeable polyester and fiber
CN101525418B 2008-03-04 2012-01-18 东丽纤维研究所（中国）有限公司 Bright
polyethylene terephthalate
CN101555345B 2008-04-09 2012-07-25 东丽纤维研究所（中国）有限公司 Preparation
method of flame retarding phosphorus-copolyester with better color phase
JP2010180270A * 2009-02-03 2010-08-19 Nan Ya Plast Corp Pet resin not containing antimony
and polyester fiber comprising the same
JP5746684B2 * 2009-04-24 2015-07-08 ユニリーバー・ナームローゼ・ベンノートシヤープ Hair styling
composition
KR101700630B1 * 2009-09-14 2017-01-31 미쓰비시 쥬시 가부시끼가이샤 Biaxially oriented
polyester film for solar cell back surface sealing
CN102453239B * 2010-10-21 2015-08-05 东丽纤维研究所（中国）有限公司 The method of
producing the polyester composition and
KR101303819B1 * 2011-05-31 2013-09-04 웅진케미칼 주식회사 Recycled polyester filament
having low melting property and antibacterial property
TWI492959B * 2013-04-16 2015-07-21 Far Eastern New Century Corp A modified-polyester
composition for making a low-melting copolyester and a method for making the low-melting
copolyester
* Cited by examiner, † Cited by third party, ‡ Family to family citation
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Flow Chart of Polyester Fiber Production

Flow Chart of Polyester Fiber Production
Muhammad Ibrahim Khalilullah
Department of Textile Engineering
Daffodil International University
Email: ibrahim23-3123@diu.edu.bd
Polyester Fiber:
Polyester fibres are formed from synthetic polymers, manufactured by the action of
polyfunctional acids with polyfunctional alcohols. The fibre forming polymer substance is
a long linear polymer with repeating ester groups in its structure. Polyester fiber is also
known as Terylene, Terene, Dacron etc. It is a manmade fiber of high polymers which
are obtained by esterification of dicarboxylic acids, with glycols or by ester exchange
reactions between dicarboxylic acid esters and glycols.
Polyester staple fiber production
Flow Chart of Polyester Production
Preparation of raw material
(Terephthalic acid, DMT, ethylene glycol preparation)
↓
Mixing tank
↓
Polymerization in reactor
(Ester interchange and poly condensation, Temperature: 260-2800C, Time: 3-6 hours)
↓
Polymer chips
↓
Melt spinning
↓
Polyester filament produced from spinneret holes
(Monofilament, multifilament)
↓
Drawing
↓
Reeling onto a package or Texturization
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search com_search 251

Polyesters are polymers formed from a dicarboxylic acid and a

Being an ester, it is made from an acid, benzene-1,4-dicarboxylic acid (terephthalic acid),

It is often known by its trivial name, polyethylene terephthalate (PET).

Figure 3 For beverage

Annual production of PET

Europe 3.9 million tonnes

North America 7.2 million tonnes

US 7.0 million tonnes

FSU 1.9 million tonnes

China 18.9 million tonnes

Rest of Asia 16.4 million tonnes

(ii) Starting from the dimethyl ester: Ester Interchange Reaction

(b) Polymerization of the monomer

Date last amended: 25th August 2016

Figure 3. Glyptal polyester formation.

produced by the condensation of a diol with a blend of saturated and unsaturated

also be condensed with epoxy resins such as epichlorhydrin or bisphenol A diglycidyl

employed in UV curable coating formulations.

dicyclopentadiene and maleic anhydride form dicyclopentadiene maleate. DCPD can

provide enhanced thermooxidative resistance, improved processability and low linear

shrinkage when crosslinked.

Unsaturated polyesters are typically low-molecular-weight prepolymers. To fully cure

temperature cured when a reducing agent such as a cobalt salt (naphthenate or

resin and vinyl monomer and cure temperature.

crosslinking agent. When polymerized in the presence of unsaturated polyester, it

homopolymerization. The degree of homo- and co-polymerization depends on the

vinyl cure can lead to the formation of a (semi-)interpenetrating network.4

methacrylate and allyl ethers as well as by difunctional vinyl monmers such as

and the final properties of the polyester.

Ethylene glycol Isophthalic acid Fumaric anhydride α-Methylstyrene

Epichlorhydrin Adipic acid Acrylic acid Vinyl toluene

are produced by Deltech, Polynt, and Dow and others.

References and Notes

Albert) and 4,029,848 (Dow Chremical).

prepared solely with reactive vinly type monmomers.

acetylacetone peroxide (AAP).

headache, fatigue, weakness, etc. Styrene is also suspected to cause cancer. 5

6. The Department of Occupational Medicine at Aarhus University in Denmark concluded that

styrene may cause cancer in humans.

two hundred and fifty polymers

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In a polyester production method, a titanium compound having a radical selected from a

Publication of application with search report

Application EP20040253857 events

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a polyester production method, a polyester composition,

2. Description of the Related Art

Generally, in the production of polyester, antimony compounds are widely used as a

For example, at the time of melt-spinning of polyester obtained with antimony

An known example thereof is employing a germanium compound instead of an antimony

Further, Japanese Unexamined Patent Application Publication No. 2003-147060

SUMMARY OF THE INVENTION

in which R1 represents hydrogen, a hydrocarbon radical comprising 1 to 50

The phosphorous compound may contain a six-membered ring structure or higher

in which R13 and R14 independently correspond to R1 in Formula (I).

The polyester of the polyester composition may be produced by copolymerization of 0.1

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples of such polyester include polyethylene terephthalate, polytrimethylene