(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
(19) World Intellectual Property
Organization
International Bureau
(43) International Publication Date
6 February 2014 (06.02.2014) PO
(51) International Patent Classification: Not classified
(21) International Application Number:
PCT/IB2013/056335
(22) International Filing Date:
2 August 2013 (02.08.2013)
(25) Filing Language: English
(26) Publication Language: English
(30) Priority Data:
2012/09098 3 August 2012 (03.08.2012) TR
(71) Applicant: KORDSA GLOBAL ENDUSTRIYEL IP¬
LIK VE KORD BEZI SANAYI VE TICARET ANON-
IM SIRKETI [TR/TR]; Alikahya Fatih Mahallesi, Sanayi
Caddesi No: 90, Izmit, 413 10 Kocaeli (TR).
(72) Inventors: BAS, Serkan; Kordsa Global Endustriyel Iplik
ve Kord Bezi Sanai ve Ticaret Anonim Sirketi, Alikahya
Fatih Mahallesi Sanayi Caddesi No: 90, Izmit, 4 1310
Kocaeli (TR). ERGUN, Burak; Kordsa Global Endustriyel
Iplik ve Kord Bezi Sanai ve Ticaret Anonim Sirketi,
Alikahya Fatih Mahallesi Sanayi Caddesi No: 90, Izmit,
41310 Kocaeli (TR).
(74) Agent: ANKARA PATENT BUREAU LIMITED; Be-
stekar Sokak No: 10, Kavaklidere, 06680 Ankara (TR).
(54) Title: A METHOD FOR PRODUCING FIBER REINFORCED RUBBER COMPRISING UNSATURATED BONDS
o
o
o
(10) International Publication Number
WO 2014/020570 A2
PCT
(81) Designated States (unless otherwise indicated, for every
kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KN, KP, KR,
KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC,
SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
(84) Designated States (unless otherwise indicated, for every
kind of regional protection available): ARIPO (BW, GH,
GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, ΓΓ , LT, LU, LV,
MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).
Published:
— without international search report and to be republished
upon receipt of that report (Rule 48.2(g))
(57) Abstract: The present invention relates to a method for
producing fiber or fiber compositions comprising unsatur
ated bonds. These fibers eliminate dipping and curing pro
cess in producing fiber reinforced rubber and the need for
the chemicals used during dipping process. These novel
yarns, thus, decrease the costs of producing fiber reinforced
rubber. The objective of the present invention is to produce
fiber comprising unsaturated bonds which do not require
treatment with RFL solution and activating chemicals in the
fiber reinforced rubber materials. Reinforced rubber produc
tion will have lower production, processing and investment
costs and will be more environmental friendly since RFL
solution and activating chemicals are not used. Fibers with
good fatigue and elongation properties can be produced
without needing high twisting levels since the unsaturated
fibers have higher elongation than the saturated fibers.
 A METHOD FOR PRODUCING FIBER REINFORCED RUBBER
COMPRISING UNSATURATED BONDS

Field of the Invention

The present invention relates to a method for producing rubber reinforced with a
fiber comprising unsaturated bonds which eliminates dipping process performed
in producing fiber reinforced rubber and the need for the chemicals used during
dipping process, and thus decreases the costs of producing fiber reinforced rubber.

Background of the Invention

Reinforced rubber production has been performed with the same methods for
almost 70 years. The first step of this production is producing fibers such as
polyester, nylon 6.6, nylon 6, rayon, aramide, dipping this material with an
adhesive dipping solution and curing this material in a rubber composition. Before
the rubber is reinforced with the fibers, the fibers are subjected to dipping process
in conventional resorcinol-formaldehyde-latex (RFL) solution. Initially, the
synthesis of resorcinol-formaldehyde was performed which provides functional
groups to hold onto the surface of the fiber and provide strength to the interface of
fiber and rubber. Resorcinol-formaldehyde is then blended with latex (styrene-
butadiene-vinyl pyridine terpolymer) which forms sulfur crosslinking with the
styrene-butadiene rubber present in the rubber compound by means of the
unsaturated bonds during vulcanization process. For this reason the current fibers
in the market necessitate dipping with RFL.

The dipping solution is an emulsion of activating chemicals such as blocked

polyisocyanate and epoxy resin and/or the composition of water based resorcinol,
formaldehyde and latex (RFL). The polyester fiber treated with the said dipping
solutions respectively is cured at high temperature and high tension. The polyester
yarns have a smooth surface and low reactivity. Therefore, polyester yarns cannot
be completely adhered to the rubber without using adhesion promoters. The low
surface activity of the yarns stems from the low polarity and low reactivity of
polyester. In addition, polyester yarns have short residence time in the dipping
solution. Because of the low surface activity, smoothness, short residence time of
yarns in the adhesive dipping solution, it is hard to coat the surface of polyester
with the activating solution and RFL. These parameters reduce the adhesion
performance of polyester yarns coated with RFL. Since the physical and chemical
bonding is too low between the reinforcement material and the rubber, adhesion
activators are used in the interface to improve adhesion performance. Adhesion
activators are expensive epoxy or blocked polyisocyanate or blocked
polyurethane. Additionally, for better adhesion, the adhesive amount in the
dipping solution should be increased. All these increase the cost of the dipping
solution and thus the dipped reinforcement material.

In the literature, unsaturated polyesters were formulated with glass fiber, acrylic
copolymer and styrene monomer. The said formulation is cured with peroxide and
used for applications of composite material (C. H . Kroekel, US Patent 3,701,748,
Jul 20, 1966). Another study discloses polyester production with high molecular
weight (E. Takiyama, Y. Hatano, US Patent 5,198,529, Nov 18, 1991). In another
study, unsaturated nylon 6 and 18 polymers are synthesized by using diacid
monomers comprising unsaturated bonds in the center of the molecule (C.
Bennett, L . J . Mathias, Macromolecular Chemistry and Physics, 205, 18, 2438-
2442, 2004). However, none of these polymers in the state of the art are used to
produce fibers or used as a rubber reinforcement material. With the present
invention, by producing unsaturated fibers, the production time and cost of rubber
materials reinforced with fiber can be reduced.

Summary of the Invention

The objective of the present invention is to produce fiber comprising unsaturated
bonds. The unsaturated fibers in this invention do not require treatment with RFL
solution and activating chemicals in the production of fiber reinforced rubber.
Another objective of the present invention is to provide a fiber comprising
unsaturated bonds which has lower production, processing and investment costs
since the RFL solution and activating chemicals are not used.

A further objective of the present invention is to provide a production process

which is more environmental friendly since RFL solution and activating
chemicals are not needed.

A further objective of the present invention is to provide a production process

which is improved in terms of worker's health and work safety since RFL solution
and activating chemicals are not used.

High twisting of yarns is needed to have high elongation properties. Another

objective of the present invention is to provide a method for producing fiber
comprising unsaturated bonds which has the required fatigue and elongation
properties without needing high twisting levels since the elongation of unsaturated
fibers is higher than the saturated fibers.

Detailed Description of the Invention

The inventive fiber comprising unsaturated bonds forms the rubber-fiber
composite structure by crosslinking with the sulfur during vulcanization by means
of the unsaturated bonds therein without need RFL solution and activators.

In one embodiment of the invention, the fibers used for reinforcement are the
"nylon fibers" which is synthesized through a condensation reaction between
diamines and dicarboxylic acids wherein water is by-product.

In one embodiment of the invention, the fibers used for reinforcement are the
"polyester fibers" which is synthesized through a condensation reaction between
diamines and dihydroxyl acids wherein water is by-product.
In the novel yarns, dicarboxylic acids comprising unsaturated bonds can be cyclic
4-cyclohexene- 1,2-dicarboxylic anhydride; 2-cyclohexene- 1,2-dicarboxylic
anhydride; l-cyclohexene-l,2-dicarboxylic anhydride; 3,5-cyclohexene-l,2-
dicarboxylic anhydride and 2,6-cyclohesene-l,2-dicarboxylic anhydride.. The use
of cyclic acid makes it possible to produce fibers having higher modulus than the
linear dicarboxylic acids. The linear dicarboxylic acids used in production of
fibers having unsaturated bonds are selected from a group comprised of
unsaturated linear diacids which can be itaconic, citraconic, mesaconic, cis-/trans-
glutaconic acid, maleic acid and fumaric acid and/or dianhydrides but not limited
with these monomers.

The diamines used in the production of nylon fibers can be ethylenediamine,

propylenediamine, 2,2-dimethylpropylene diamine, tetramethylene diamine,
hexamethylene diamine, octamethylene diamine, nonamethylene diamine,
decemethylene diamine, dodecamethylene diamine, 4,4'-
diaminodicyclohexylmethane, xylene diamine, bis(aminomethyl)cyclohexane,
para- and meta-phenylenediamine, oxybis(aniline), thiobis (aniline),
sulfonilbis (aniline), diaminobenzophenone, methylenebis(aniline), benzydine,
1,5-diaminonaphtaline, oxybis(2,methylaniline), thiobis(2-methylainiline), 1,6-
diamino-2-hexene, l,6-diamino-3-hexene, 2,7-diamino-2,7-dimethyl-4-octene,
bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) methane and
2,2-bis(4-aminocyclohexyl)propane but not limited with these monomers.

The dihydroxyls used with dicarboxylic acids in the production of polyester fibers
can be l-propenediol-2,3, 2-propenediol-l,3, l-butenediol-1,4, 2-butenediol-l,4,
2-butenediol-l,3, l-butenediol-3,4, 2-pentenediol-3,5, 2,4-pentadienediol-3,5, 2,4-
heptadienediol-1,4, 2,6-octadienediol-3,5, 3-pentenediol-l,4, 3-pentenediol-2,5, 1-
hexenediol-3,6, 2,4-hexadienediol-3,5, ethylene glycol, propylene glycol,
glycerol, trimethylolethane but not limited with these monomers.
Synthesis and spinning of unsaturated nylon and polyester fiber can be performed
similar to the conventional nylon and polyester fiber production process. The
polymers disclosed in the said invention have tendency to gelling since they carry
double bonds. This may cause the polymers of the invention to become gel at
polymerization or processing temperature (150-300 °C). For this reason free
radical inhibitors should be used. The said inhibitors can be added to the polymer
in the range of 0.001-1% by weight. The said stoppers can be the chemicals
selected from p-t-butyl hydroxytoluene, p-t-butyl hydroxyanisol, distearyl
tiodipropionate, dilauryl tiodipropionate.

In the inventive fiber reinforced rubber comprising unsaturated bonds, at least one
of the unsaturated functional groups (only dicarboxylic or only diamine or only
diol) or two unsaturated monomers is used for unsaturated polyester or nylon
fiber. Thus the unsaturation degree of the fiber can be adjusted. The unsaturation
degree is important since the unsaturated bonds crosslink with the rubber through
sulfur bonds during vulcanization. The unsaturation degree can be adjusted with
the mixture of saturated and unsaturated monomers (dicarboxylic acids, diamines
or dihydroxyls) in polymer chain as well as the polymers comprising unsaturated
bonds can be mixed with the saturated polymers (Nylon 6.6, polyethylene
teraphthalate (PET) etc.). The said degree can be in the range of 1-100 wt% of
unsaturated polymer.

The cross-sections of the rubbers reinforced with conventional nylon and

polyester fiber dipped with RFL are shown below (Figure 1,2). Conventional
nylon 6.6 fiber is used in Figure 1, the said fiber is dipped with RFL and used as a
reinforcement material for rubber. Here, the fiber which is a reinforcing material,
resorcinol-formaldehyde resin, vinyl pyridine latex and rubber are shown
respectively. Sulfur (Sg) is present in a certain concentration in rubber
formulation. During the vulcanization of the rubber, the cyclic sulfur opens, and
the vinyl pyridine latex in RFL and the styrene-butadiene rubber present in the
rubber compound are reacted to each other through sulfur covalent bonds. The
said bonds are important to form a stable composite structure. In the said
composite structure, the resorcinol-formaldehyde resin also forms covalent bonds
by reacting with the nylon. The bonding mechanism of the conventional polyester
fiber to the rubber is shown in figure 2 . Here, since the surface activity of the
polyester is very low, activators such as epoxy and polyisocyanate are also used.
The said components form thermoset polyurethane after reacting. Besides, the
said activators form covalent bonds with the polyester; they mainly form
secondary bonds (such as hydrogen and van der Waals). Here, the vinyl pyridine
latex present in the RFL is cured with rubber during the vulcanization.

Figures 3 and 4 show the vulcanization of rubber reinforced with novel nylon and
polyester fibers with unsaturated bonds through sulfur. By means of the said
fibers having unsaturated bonds, the rubber can be reacted with the fiber with
sulfur bonds without any interface such as RFL or epoxy and polyisocyanate. By
means of the new fibers in the invention, the production rate of fiber reinforced
rubber material can be accelerated. Therefore, production, processing and
investment costs decrease.
Through the inventive fiber with unsaturated bonds, the RFL solution becomes
redundant and the costs of the reinforced rubber materials decrease significantly in
the rubber reinforcement. Eliminating RFL dipping process will reduce the
factory and business investment costs. Furthermore many expensive chemicals
used in conventional methods will not be needed in the present invention, and the
rubber materials reinforced with fiber and the production process will be more
environmental friendly. Through the inventive fiber with unsaturated bonds, the
dipping process will be completely eliminated. The fibers can be twisted and
weaved.. Therefore, production efficiency and capacity will increase significantly.

Twisting process is performed to improve the fatigue properties of yarn in the

fiber reinforced rubber. The increase in twisting level of the fiber to a certain level
improves the fatigue resistance and the elongation of the twisted fiber before
rupture. Besides, it is known that the elongation of unsaturated fibers is higher
than the saturated fibers. For this reason, by using the inventive fibers, necessary
fatigue and elongation properties can be acquired without needing high twisting
levels. By decreasing the twisting levels the cost of the twisting process (energy,
labor etc.) decreases. Additionally, the use of RFL is eliminated by using said
fibers. RFL is a hard coating which leads to a high heat build-up and therefore
poor fatigue properties. Through the use of inventive fibers, heat build-up on the
fibers will be eliminated and therefore the lifetime of fibers and fiber-reinforced
rubber can be extended.

The conventional dipping and curing processes will be eliminated by the fibers in
the present invention and the product costs of the reinforcement materials
decreases. Furthermore the expensive chemicals used in conventional dipping and
curing processes will not be used with the present invention, and the rubber
materials reinforced with fiber and the production process thereof will be more
environmental friendly. By means of the new reinforcement materials in the
present invention, a similar adhesion performance to the rubber will be acquired
as in the conventional dipping solutions. Besides, friction and heat build-up is
eliminated and the lifetime of the reinforced rubber material increases since the
RFL interface is eliminated. Conventional dipping processes require high
investment cost (factory, labor, substructure, energy etc.). By means of the
inventive fiber reinforced rubber comprising unsaturated bonds, all substructure,
unit and labor required by the dipping process will be eliminated.
 CLAIMS

A method for producing nylon fiber reinforced rubber which do not

require dipping solutions and activators such as RFL dipping solution and
epoxy and/or polyisocyanate, and characterized by the steps of spinning
fiber with unsaturated bonds synthesized by the condensation reaction of
diamine and dicarboxylic acid and the unsaturated bonds within the fiber
crosslinking with styrene -butadiene through the sulfur in the rubber during
vulcanization.

A method for producing nylon fiber reinforced rubber, according to claim

1, characterized in that the fiber with unsaturated bonds is spun after
synthesizing polymer comprising at least one unsaturated bonds such as the
reaction of cyclic dicarboxylic acid with diamine.

A method for producing nylon fiber reinforced rubber according to claim 2,

characterized by a cyclic dicarboxylic acid which is selected from a
monomer group comprising 4-cyclohexene-l,2-dicarboxylic anhydride; 2-
cyclohexene- 1,2-dicarboxylic anhydride; 1-cyclohexene- 1,2-dicarboxylic
anhydride; 3,5-cyclohexene-l,2-dicarboxylic anhydride and 2,6-
cyclohesene- 1,2-dicarboxylic anhydride

A method for producing nylon fiber reinforced rubber , according to claim

1, characterized in that the fiber with unsaturated bonds is spun after
synthesizing polymer comprising at least one unsaturated bonds such as the
reaction of the linear dicarboxylic acids with diamine.

A method for producing nylon fiber reinforced rubber , according to claim

4, characterized by at least one linear dicarboxylic acid selected from a
monomer group itaconic, citraconic, mesaconic, cis-/trans-glutonic acid,
maleic acid and fumaric acid .
A method for producing nylon fiber reinforced rubber , according to any
one of the preceding claims, characterized in that at least one diamine
monomer selected from a monomer group comprising ethylenediamine,
propylenediamine, 2,2-dimethylpropylene diamine, tetramethylene
diamine, hexamethylene diamine, octamethylene diamine, nonamethylene
diamine, decemaethylene diamine, dodecamethylene diamine, 4,4'-
diaminodicyclohexylmethane, xylene diamine,
bis(aminomethyl)cyclohexane, para- and meta-phenylenediamine,
oxybis(aniline), thiobis(aniline), sulfonilbis(aniline),
diaminobenzophenone, methylenebis(aniline), benzydine, 1,5-
diaminonaphtaline, oxybis(2,methylaniline), thiobis(2-methylainiline), 1,6-
diamino-2-hexene, 1,6-diamino-3-hexene, 2,7-diamino-2,7-dimethyl-4-
octene, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)
methane and 2,2-bis(4-aminocyclohexyl)propane is reacted with
dicarboxylic acid and spun as a nylon with unsaturated bonds.

A method for producing polyester fiber reinforced rubber without needing

dipping solution such as RFL dipping solution and epoxy and/or
polyisocyanate on polyester fiber surface, and characterized by the steps
of synthesizing fiber with unsaturated bonds as a result of the condensation
of dihydroxyl with dicarboxylic acid and crosslinking the unsaturated
bonds of rubber through sulfur bonds during vulcanization.

A method for producing polyester fiber reinforced rubber, according to

claim 7, characterized in that the fiber with unsaturated bonds is spun
after synthesizing polymer comprising at least one unsaturated bonds such
as the reaction of the cyclic dicarboxylic acids with dihydroxyls.
A method for producing polyester fiber reinforced rubber according to
claim 8, characterized by a cyclic dicarboxylic acid which is selected from
a monomer group comprising 4-cyclohexene-l,2-dicarboxylic anhydride;
 8-cyclohexene- 1,2-dicarboxylic anhydride; 1-cyclohexene- 1,2-dicarboxylic
anhydride; 3,5-cyclohexene-l,2-dicarboxylic anhydride and 2,6-
cyclohesene- 1,2-dicarboxylic anhydride.

10. A method for producing polyester fiber reinforced rubber, according to

claim 7, characterized in that the fiber with unsaturated bonds is spun
after synthesizing polymer from monomers comprising at least one
unsaturated bonds such as the reaction of the linear dicarboxylic acids with
dihydroxyls.

11. A method for producing polyester fiber reinforced rubber, according to

claim 10, characterized by at least one linear dicarboxylic acid selected
from a monomer group comprising itaconic, citraconic, mesaconic, cis-
/trans-glutonic acid, maleic acid and fumaric acid.

12. A method for producing polyester fiber reinforced rubber, according to any
one of the claims 7-11, characterized in that at least one dihydroxyl
monomer selected from a monomer group comprising l-propenediol-2,3, 2-
propenediol-1,3, l-butenediol-1,4, 2-butenediol-l,4, 2-butenediol-l,3, 1-

butenediol-3,4, 2-pentenediol-3,5, 2,4-pentadienediol-3,5, 2,4-

heptadienediol-1,4, 2,6-octadienediol-3,5, 3-pentenediol-l,4, 3-
pentenediol-2,5, l-hexenediol-3,6, 2,4-hexadienediol-3,5, ethylene glycol,
propylene glycol, glycerol, trimethylolethane is reacted with dicarboxylic
acid and the polyester fibers are spun from a material synthesized after the
reaction of said hydroxyls and dicarboxylic acids.

13. A method for producing fiber reinforced rubber according to any one of the
preceding claims, characterized in that the fiber spinning of the
synthesized polyester or nylon fibers is performed by using free radical
inhibitors in the range of 0.001-1% by weight and thus gelation during
process is prevented.
14. A method for producing fiber reinforced rubber according to any one of the
preceding claims, characterized in that the nylon or polyester fibers are
the nylon or polyester fibers are placed inside the rubber material.

15. A method for producing fiber reinforced rubber according to any one of the
preceding claims, characterized in that produced unsaturated fibers is
used to produce fiber reinforced rubber material.