3,087,920

United States Patent Office Patented Apr. 30, 1963

2
C., for a period of time varying from 20 hours to a few
3,087,920 minutes, in inverse proportion to the temperature, prior
COLD-WATER-SOLUBLE POLYWNYL ALCOHOL to mixing with the other components.
Hideo Suzumura and Hisao Miyahara, Ku rashiki City, When a finely-divided powder of partially-Saponified
Japan, assignors to Kurashiki Rayon Co., Ltd., a cor polyvinyl alcohol is dissolved in water, it is important to
poration of Japan prevent the formation of undissolved powder lumps and
No Drawing. Filed Oct. 7, 1960, Ser. No. 61,081 to effect complete dissolution quickly. In doing so, the
Claims priority, application Japan Oct. 12, 1959 individual polyvinyl alcohol particles must be prevented
7 Claims. (C. 260-93) from adhering to one another so that each particle will be
The invention relates to cold-water-soluble partially 0 free to dissolve smoothly.
saponified polyvinyl alcohol and to a method for pro However, partially-Saponified polyvinyl alcohol often
ducing it, and the invention is more particularly con exhibits the formation of undissolved powder lumps be
cerned with a cold-water-soluble partially-Saponified poly cause of its property of rapid swelling. Therefore, pre
vinyl alcohol in finely-divided, e.g. powder, form. vention of the formation of undissolved powder lumps
may be achieved by retarding this swelling. We have
Polyvinyl alcohol has recently come to be used ex 15 conducted a series of experiments involving the heating
tensively as a base for various types of adhesives and of partially-saponified polyvinyl alcohol and we have
finishing agents for woven fabrics because of the bind found that this procedure is effective for this purpose but
ing powder of its aqueous solutions, and because of the we have also observed that the solubility drops upon
tenacity, gloss, agreeable feel, and like desirable char 20 Such heat-treatment, as shown in the following table.
acteristics of film obtained from aqueous solutions of
polyvinyl alcohol. However, known polyvinyl alcohols
generally require the use of heat to put them into solu Temperature, C. Time, Min. Solubility,
Percent
tion in water or they are, at best, dissolved in cold Water
without difficulty. No heating---------------------------------------------- 97.2
As is well known, an aqueous solution of fully saponi 25 50----- 1,200 94.6
fied polyvinyl alcohol can not be obtained unless dissolu 70----- 100.
1,200
60
94.0
94.4
tion is effected by heating. Accordingly, in seeking a 120--------- 6 88.9
polyvinyl alcohol of cold-water-solubility, partially-sa 50---------------------------------------- 5 87.6
ponified polyvinyl alcohol has been produced.
For example, when 2.5 parts of polyvinyl alcohol of a 30 in the foregoing table, the partially-saponified poly
degree of polymerization of 1700 and partially saponi vinyl
fied to the extent of 87.42 mol percent are mixed with degreealcohol was 88 mol percent saponified and had a
100 parts of water at 20° C., 85.9% goes into solution in each solution was 2% andofdissolution
of polymerization 1700. The concentration of
was effected at 40
30 minutes. In this case, however, it is necessary to in 35 C. during the course of 60 minutes with agitation at the
part to the mixture of water and polyvinyl alcohol a rela rate of 300 revolutions per minute.
tively violent agitation of more than 300 revolutions per It will be understood that it is not desirable to effect
minute. When such agitation is not provided, or when excessive heat-treatment since it retards the cold water
the agitation is mild, the paritally-saponified polyvinyl solubility. However, heat-treatment to the above speci
alcohol will rapidly swell in the water as it comes into 40 fied extent is useful in preventing the formation of un
contact with the water, with the resultant formation of dissolved powder lumps.
gels which enclose and trap undissolved polyvinyl alco Thus, heat-treatment of the partially-saponified poly
hol particles, giving rise to undissolved powder lumps. vinyl alcohol used in accordance with this invention is
When such undissolved powder lumps form, further dis advantageous, but we have found that complete solution
solution is greatly retarded. There has existed, therefore,
an unfilled need for a polyvinyl alcohol which is freely 45 can be effected in a very short period of time merely with
mild agitation in cold water when use is made of a par
soluble in cold water without need for violent agitation tially-Saponified polyvinyl alcohol having admixed with
and like special techniques. - ..
It is thus an object of this invention to provide poly it small but effective amounts of a diamino-stilbene opti
vinyl alcohol which will rapidly dissolve in cold water 50 cal bleaching agent and of a surface active agent as
described above.
without need for violent agitation and without the forma To combine the several components by means of a
tion of lumps. Solvent, 100 parts by weight of the crushed partially
It is another object of the invention to provide a proc Saponified polyvinyl alcohol described above, but prefer
ess of producing polyvinyl alcohol of high cold-water ably having a particle size of 100 mesh or below, are
solubility. 55 mixed with 100 parts by weight of a solvent, e.g. meth
In accordance wtih the invention, partially saponified anol, containing 0.5 to 3 parts of a diamino-stilbene
polyvinyl alcohol is combined with diamino-stilbene optical bleaching agent and 1 to 3 parts of a surface
compounds of the type used as optical bleaching agents
and with surface-active agents. The components may be active agent, the entire composition being homogeneously
mixed. The mixture is then left at 35 to 45° C. for 30.
combined in solid form or in solution. Thus, to pre 60 60 minutes, and the solvent, e.g. methanol is separated,
pare a composition from these components in solid form, e.g. by evaporation.
partially-Saponified polyvinyl alcohol is crushed to a pow The product thus obtained is white in color and dis
der of 50-120 mesh size, and there are combined with Solves freely and easily in cold water in a short period
100 parts by weight of this powder 0.5 to 5 parts by
weight of an optical bleaching agent of the diamino 65 ofAlternatively,
time with only mild stirring.
the partially saponified polyvinyl alcohol
stilbene type and 1 to 3 parts by weight of a surface is produced by conventional saponification of polyvinyl
active agent, such as a fatty acid ester of a polyoxyethyl
enesorbitan, the several components being homogene acetate in a methanol solution containing an optical
ously mixed. The product thus obtained melts smoothly bleaching agent of the diamino-stilbene type dissolved
in it in the relative relationships described above. The
and easily in cold water, e.g. at a temperature of 25 C. 70 Surface active agent may also be present in the saponifi
and below, in a short period of time with only light stir cation solution
ring. Advantageously, the powdered partially-saponi in the relativelyorrelationships it may be mixed after saponification
specified above. The re
fied polyvinyl alcohol is heat-treated, e.g. at 50° to 120°
 3,087,920
3 4.
Sulting product exhibits the same solubility characteristics lution in water in 5 to 8 minutes upon light stirring by
as the products previously described.
The partially-Saponified polyvinyl alcohol used in ac hand to form aqueous solutions of 2 to 5% concentration.
cordance with this invention to prepare cold-water Example 2
Soluble polyvinyl alcohol is produced by conventional One hundred parts of 88% partially-saponified poly
techniques from polyvinyl esters, such as polyvinyl ace vinyl alcohol having a degree of polymerization of 2000
tate, by known saponification procedures as described, were pulverized to a particle size of about 80 mesh and
of example, in Scott et al. U.S. Patent No. 2,266,996 then mixed with 0.1 part of a fatty acid containing
and Bryant et al. U.S. Patent No. 2,668,809. As is 1% of a polyoxyethylenealkyl ether and 2.3% of a poly
known in the art, a "partially-Saponified' polyvinyl alco O oxyethylenealkyl ester, and with 2 parts of polyoxy
hol is the product of the hydrolysis of a polyvinyl ester, ethylenesorbitan laurate, while heating at 70° C. Then
e.g. polyvinyl acetate, in which less than all of the ester 1 part of the diamino-Stilbene optical bleaching agent
groups, e.g. acetate groups, have been converted to described in Example 1 was uniformly intermixed with
hydroxyl groups. As explained in Scott et al. 2,266,996, the foregoing composition. The resultant product dis
the Saponification or hydrolysis reaction is stopped by 5 solved
neutralizing the actalyst when the desired percentage con to formfreely and completely in water in 6 to 10 minutes
solutions of 2 to 5% concentration and very little
version has occurred. The partially-saponified polyvinyl foaming was observed.
alcohols which are suitably used in accordance with this
invention are at most 90 percent saponified or hydrolyzed Example 3
but they are are sufficiently saponified to be water-soluble 20 One hundred parts of 80% partially-saponified poly
which, according to Bryant et al. 2,668,809, requires the vinyl alcohol having a degree of polymerization of 1700
conversion of at least about 75% of the ester groups were pulverized to a particle size of about 80 mesh and
into hydroxyl groups. Their degree of polymerization, Were mixed with 1 part of the optical bleaching agent
upon which viscosity is dependent, may vary widely of
and is selected in relation to the use to which the poly 25 withthe0.2diamino-stilbene
part of the oil
type described in Example 1,
preparation described in Ex
vinyl alcohol is to be put, as known in the art and as ample 2, and with 100 parts of methanol containing in
discussed in Scott et al. and Bryant et al. solution 2 parts of the surface active agent, viz. poly
While the reason for the surprising action of the oxyethylene sorbitan laurate. All of the components
diamino-stilbene compound and the surface-active agent were thoroughly mixed and then the methanol was
is not fully understood, it is believed that the particles 30
of the partially-saponified polyvinyl alcohol become dis evaported in the course of 30 minutes by application of
heat. The product thus obtained was pure white in color
persed in Water by the action of the surface active agent and attractive in appearance and water solutions of 2
and that they then react instantaneously with the diamino to 5% concentration were readily prepared in 5 to 10
stilbene optical bleaching agent, forming a three-dimen minutes.
Sional bridge, thereby assuming a gel form. The sur Example 4
faces of the polyvinyl alcohol particles thus gelled are
deficient in mutual adhesiveness, and the individual par In 1400 parts of a methanol solution of polyvinyl ace
ticles do not coagulate, but remain individually suspended tate (15% concentration), 1.5 part of an optical bleach
in the water even after absorbing water and after swell ing agent of the diamino-stilbene type, viz. the compound
ing. Meanwhile, it is believed that water permeates 40 described in Example 1, was dissolved, and the poly.
through the surface of the particles and becomes dis vinylacetate was Saponified in conventional manner to
persed inside the particles in a short period of time, produce an 88% partially-saponified polyvinyl alcohol
with the result that complete solution thus occurs. having a degree of polymerization of 1700. This poly
The cold-water-soluble polyvinyl alcohol composition vinyl alcohol was homogeneously mixed with 2 parts
produced in accordance with this invention is particularly 45 of polyoxyethylenesorbitan laurate. The mixture was
useful for all purposes for which a water-soluble poly then dried and pulverized. This product readily formed
vinyl alcohol is desired, e.g. in adhesives, and in finishing 2minutes.
to 5% aqueous Solutions by simply mixing in 5 to 10
agent for fabrics, but it is by no means limited to such
uses. The cold-water-soluble polyvinyl alcohol composi Diamino-silbene compounds of the type employed as
tion may be combined with fillers and pigments such as optical bleaching agents which are employed in accord
clay, kaolin, and the like in conventional manner. ance with the present invention are well-known com
A polyvinyl alcohol solution sometimes has a tendency pounds and are described, for example, by F. G. Vil
to foam and is somewhat difficult to handle in that case. laume in The Journal of the American Oil Chemists' So
In order to check this foaming, the use of 0.05 to 0.3
part by weight of a fatty acid, e.g. stearic acid admixed 55 ciety, vol. XXXV, No. 10 (October 1958), pp. 558
566. In general, these compounds are classified as tri
with a polyoxyethylene alkyl ether or ester per 100 parts azinyldiaminostilbenes, as exemplified in FIG. 11 of Vil
of partially-saponified polyvinyl alcohol is highly effective. laume, and aroyldiaminostilbenes, as exemplified in FIG.
The invention will be further understood from the 12 of Villaume.
following specific examples of practical application. The Surface-active agents which are employed in com
However, it will be understood that these examples are 60 bination with the diamino-stilbene compounds to pro
not to be construed as limiting the scope of the present duce the cold-water-soluble partially-saponified polyvinyl
invention in any manner. In these examples, all parts alcohol of this invention are, in general, any of the many
are by weight, unless otherwise indicated. known anionic, non-ionic, and cationic surface-active
Example 1 agents such as Sodium Stearate (anionic), polyoxyethyl
65 enedodecyl ether (non-ionic), and dodecyltrimethyl am
One hundred parts of 90% partially-Saponified poly monium chloride (cationic). By surface-active agents
vinyl alcohol having a degree of polymerization of 1700 are meant generally those compounds possessing a hydro
were crushed to a particle size of 50 to 100 mesh, and carbon group which is hydrophobic and a soluble group
heat-treated at 120° C. for 6 minutes. Then 2 parts of which is hydrophylic. The nature of the solubilizing
70 group determines the classification of the surface-active
4,4'-diaminostilbene-2,2'-disulfonic acid sodium salt, sold agent as anionic, cationic, and non-ionic. The sodium
under the trade-name "Kaycoll BA,' and 2 parts of salts of the fatty acids (soaps) and the corresponding
polyoxyethylenesorbitan laurate were uniformly mixed alcohol Sulfonates, sulfates, phosphates, and thiosulfates
with the polyvinyl alcohol. are typical of the anionic class whose aqueous dispersions
The product thus obtained underwent complete disso 75 are negatively charged. Surface-active agents in which

.
 3,087,920
5 6
the appended claims. It is
cations act as the solubilizing groups are those in which matter contained in the foregoing intended, therefore, that all
the solubilizing action depends on amino or ammonium interpreted description shall be
groups. Cetyl pyridinium chloride is a typical example invention. as illustrative only and not as limitative of the
of a cationic surface-active agent, the aqueous disper We claim:
sions of which are positively charged. The non-ionic 1. A cold-water-soluble polyvinyl alcohol which com
Surface agents do not form salts with acids of bases, and, prises an intimate admixture of 100 parts by weight of
under normal conditions, their dispersions do not carry a partially saponified polyvinyl alcohol having a hydrol
electrical or ionic charges. Solubilization of this class ysis of 75 to 90 percent and a particle size not exceed
of agents is achieved by a series of hydroxyl ether groups, 0. ing 100 mesh, 0.5 to 5 parts by weight of 4,4'-diamino
and the hydroxyl polyethylene ether of diamylphenol, is stilbene-2,2'-disulfonic acid sodium salt, and 1 to 3 parts
a commercial example of another non-ionic surface-active by weight of a Surface active agent.
agent. As other suitable surface-active agents, refer 2. The process of producing a polyvinyl alcohol hav
ence may also be made to anionic surface-active agents ing improved cold-water-solubility which comprises com
of the alkylaryl sulfonate type such as Nacconol. NRFS 5 bining 100 parts by weight of a partially saponified poly
and Santomerse D, and alcohol sulfates such as sodium vinyl alcohol having a hydrolysis of 75 to 90 percent
lauryl sulfate and triethanolamine lauryl sulfate. The and a particle size not exceeding 50 mesh with 0.5 to 5
alkyl phosphate salts are also suitable anionic surface parts by weight of 4,4'-diaminostilbene-2,2'-disulfonic
active agents for the purposes of this invention. Included acid sodium salt and 1 to 3 parts by weight of surface
among cationic surface-agents are the sulfosuccinamates 20 active agent.
Such as n-octadecyl disodium sulfosuccinamate and the 3. A cold-water-soluble polyvinyl alcohol which com
corresponding tetrasodium sulfosuccinamate. These ma prises an intimate admixture of 100 parts by weight of a
terials are marketed by The American Cyanamid Co. partially saponified polyvinyl alcohol having a hydroly
under the trade-name Aerosol. Other suitable surface sis of 75 to 90 percent and a particle size not exceeding
active agents include the fatty amines of the type repre 50 mesh, 0.5 to 5 parts by weight of 4,4'-diaminostilbene
sented by Alkamine S.J. (marketed by Amalgamated 2,2'-disulfonic acid sodium salt, and 1 to 3 parts by weight
Chemical Company), and the hexitol oleates, such as an
hydrohexitol partial oleate marketed under the name of 4.a surface A active agent.
process of producing a polyvinyl alcohol having
Ariacel A (Atlas Powder Company). Most advanta cold-water-solubility
geously, however, and preferred over all other surface 30 parts by weight of awhich comprises combining 100
partially saponified polyvinyl al
active agents, are compounds of the polyoxyethylene cohol having a hydrolysis of 75 to 90 percent and a par
type, Such as polyoxyethylene esters and ethers as exem ticle size not exceeding 50 mesh, 0.5 to 5 parts by Weight
plified by polyoxyethylene monostearate, polyoxyethyl of a diaminostilbene disulfonic acid sodium Salt, and 1 to
ene sorbitan mono-oleate known under the names "poly 3 parts by weight of a surface active agent.
oxy 40 stearate' and "polysorbate 80,' respectively, as 35 5. A cold-water-soluble polyvinyl alcohol which com
well as the surface-active agents sold under the trade prises an intimate admixture of 100 parts by Weight of a
name "Tween,' some of which are described on page partially saponified polyvinyl alcohol having a hydrolysis
450 of Zimmerman and Lavine, "Handbook of Material of 75 to 90 percent and a particle size not exceeding 50
Trade Names.'
In the embodiment of the process of the invention 40 mesh, 0.5 to 5 parts by weight of a diaminostilbene di
sulfonic acid sodium salt, and 1 to 3 parts by Weight of
wherein the several components are mixed in Solution, a surface active agent.
any inert solvent for all of the components may be em 6. A cold-water-soluble polyvinyl alcohol which com
ployed but lower-alkyl alcohols, such as methanol, are prises an intimate admixture of 100 parts by weight of
suitably employed. When the components are mixed a partially
prior to saponification of polyvinyl ester to form poly 45 ysis 75 to saponified polyvinyl alcohol having a hydrol
vinyl alcohol, any conventional saponification procedure mesh, 0.5 to90% and a particle size not exceeding 100
5 parts by weight of 4,4'-diaminostilbene
may be employed to form the polyvinyl alcohol. In addi 2,2'-disulfonic acid sodium salt, and 1 to 3 parts by
tion to the Scott et al. and Bryant et al. patents men
tioned above, typical suitable saponification methods are 50 weight of a non-ionic surface-active agent selected from
described, for example, in Bristol U.S. Patent 2,700,035, the group consisting of polyoxyethylene ethers and poly
oxyethylene esters.
Waugh et al. U.S. Patent 2,642,419 and Germain U.S. 7. A process of producing a polyvinyl alcohol having
Patent 2,643,994, saponification being stopped in con improved cold-water-solubility which comprises combin
ventional manner, e.g. by neutralizing the catalyst, when
the desired partial degree of saponification or hydrolysis 55 ing
vinyl
100 parts by weight of a partially saponified poly
alcohol having a hydrolysis of 75 to 90% and a
has been reached.
Thus, the conditions and the relative relationships set by weightsizeofnot
particle exceeding 100 mesh with 0.5 to 5 parts
4,4'-diaminostilbene-2,2'-disulfonic acid so
forth in the examples are those preferred in carrying out dium salt, and 1 to 3 parts by weight of a surface-active
the process of this invention, but it will be understood agent.
that other conditions and relationships may be used with 60
in the scope of the invention. In general, unless other References Cited in the file of this patent
wise indicated, conventional operations and techniques UNITED STATES PATENTS
are suitably employed.
It will also be understood that various changes and 1971,662 Schmidt -------------- Aug. 28, 1934
modifications in addition to those indicated above may 65 2,362,026 Quist ------------------ Nov. 7, 1944
be made in the embodiments herein described without
departing from the scope of the invention as defined in