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Publication numberUS3121607 A
Publication typeGrant
Publication dateFeb 18, 1964
Filing dateJul 9, 1959
Priority dateJul 14, 1958
Also published asDE1129451B
Publication numberUS 3121607 A, US 3121607A, US-A-3121607, US3121607 A, US3121607A
InventorsOhno Yasuji, Tanabe Kenichi
Original AssigneeKurashiki Rayon Co, Air Reduction
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Production of polyvinyl alcohol bodies having improved dyeability
US 3121607 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

nite tates Patent 3,121,607 PRODUCTION OF PQLYVINYL ALCOHOL BODIES HAVING IMPROVED DYEABILITY Yasuji 'Uhno and Kenichi Tanahe, Kurashiki City, Japan, assignors of three-fourths to Kurashiki Rayon Co., Ltd, Okayama Prefecture, Japan, a corporation of Japan, and one-fourth to Air Reduction Qornpany Incorporated, New York, N31, a corporation of New York No Drawing. Filed Judy 9, 1959, Ser. No. 825,882

Clm'ms priority, application Japan July 14, 1958 11 Claims. (Q1. 3-4155) This invention relates to a method of improving the dyeing characteristics of shaped polyvinyl alcohol bodies, and particularly of fibers of the polyvinyl alcohol series. It relates especially to a method for improving the dyeing characteristics of animalized polyvinyl alcohol fibers which are subjected to alkaline treatment.

It is known that fibers of hydroxylated polymers such as polyvinyl alcohol or hydrolyzed copolymers of vinyl esters with minor amounts of polymerizable vinyl or vinylidene compounds may be obtained by dry or wet spinning from their aqueous solutions. But these fibers are characterized by an undesirable sensitivity to water, particularly to hot water.

In order to avoid such disadvantages, the freshly spun fibers are usually subjected to a heat treatment at a temperature of 200 C. to 250 C. and then acetalized with formaldehyde. The wet softening temperature of heat treated fibers, i.e. the temperature at which the fiber shrinks of its original length, when dipped in Water for 30 minutes, can be raised up to 60 C. to 100 C. If after heat treatment the fiber is subjected to formalization, its wet softening temperature is increased up to 100 C. to 130 C. and it is not dissolved even in hot water of 150 C. It can, therefore, be considered that the Wet heat resistance of the fiber thus treated is sufficient for practical uses.

On the other hand, the heat treated and formalized polyvinyl alcohol fibers have the disadvantage of poor dyeability. Since polyvinyl alcohol fibers do not contain basic nitrogen, they cannot be dyed with most acid and acid mordant dyestuffs, and are only somewhat stained with some of these dyes. Untreated polyvinyl alcohol fibers may have almost the same dyeability as cellulose fibers due to the presence of hydroxyl groups, but after a heat-treatment the accessible hydroxyl groups of these molecules decrease so that the affinity of the fibers to direct dyestuffs becomes the same or even a little lower than that of cotton fibers. Moreover, when the heattreated polyvinyl alcohol fibers are acetalized by formaldehyde, the dyeability usually decreases further due L to the fact that the accessible hydroxyl groups of polyvinyl alcohol molecules remaining after the heattreatrnent are substantially blocked by formaldehyde. Thus the dye-absorption of the heat-treated and then formalized polyvinyl alcohol fibers with respect to direct dyestuffs is in general about 30 to 80% of that of cotton fibers.

When polyvinyl alcohol fibers are subjected to partial formalization in an aqueous solution directly after they are spun, without intermediate heat-treatment, the affinity to direct dyes is good. This is due to the large increase of accessible hydroxyl groups by the swelling of the 3,121,607 Patented Feb. 18, 1964 fibers during formalization. Its effect overcomes the blocking of the accessible hydroxyl groups by the formalizatiou, so that the total amount of accessible hydroxyl groups increases considerably compared with fibers heattreated before formalization. As the ratio of formalization increases, the afiinity to direct dyestuffs decreases until the fibers can no longer be dyed but only stained.

In order to improve the dyeing characteristics of polyvinyl alcohol fibers animalization methods have been developed in which basic nitrogen groups are introduced into the fiber, for example, by acetalization of the fiber with aminoaldehydes containing a primary or secondary amino group. Also a mixed spinning method has been developed in which the fiber is spun from a spinning solution containing a mixture of partially aminoacetalized polyvinyl alcohol and untreated polyvinyl alcohol. The spun fiber is then heat-treated and acetalized.

The animalized fibers which contain the weakly basic amino radicals may be dyed by conventional techniques, but they lose affinity for dyestuffs in the presence of alkali. For example, when an alkalizing treatment is applied during the course of fiber production the dyeing capacity of the fiber will be lowered when it is later treated with neutral dyestuffs, especially dlirect dyestuffs. Also when the fibers are dyed with acid dyes any aftertreatment with alkali will bring about decolorization.

We have discovered that an animalized fiber can be produced which will not lose its affinity for dyestuffs on alkaline treatment, by introducing a quaternary ammonium group into the fiber, either by acetalizing the spun fiber with a compound containing an aldehyde group and also a quaternary ammonium group, or by a mixed spinning process using a spinning solution containing untreated polyvinyl alcohol, and polyvinyl alcohol which has been acetalized with a compound containing an aldehyde group and also a quaternary ammonium group.

A principal object of this invention is to provide a method of treating polyvinyl alcohol fibers which will produce improved dyeing characteristics.

Another object of the invention is to provide a polyvinyl alcohol fiber having improved dyeing characteristics and being suitable as a synthetic fiber for the manufacture of textiles.

Still another object of the invention is to provide an animalized polyvinyl alcohol fiber which will not lose its affinity for direct dyestulfs on treatment with alkali and which fiber, after being dyed with acid dyes, will not be decolorized by subsequent alkali treatment.

Other objects and advantages of the invention will be apparent from a consideration of the specification and claims.

It is known that quaternary ammonium salts differ very markedly from the salts of amines in their chemical behavior. The salts of the amines when treated with a strong base like sodium hydroxide are decomposed forming the free amine. The quaternary ammonium salts, however, do not react with strong alkalies, even potassium hydroxide, in aqueous solution. The reason for this is that the quaternary ammonium hydroxide dissociates completely into its ions, the quaternarygN and OH, in aqueous solution and hence it has the same basic strength in water as sodium or potassium hydroxide.

Thus when the fiber is acetalized with the weakly basic aminoaldehyde, the amine salt formed by this weak base with the acid dyestuii may be decomposed by alkali, whereas in case the fiber is acetalized with the quaternary ammonium compound, the strongly basic quaternary ammonium salt forms a union with the acid dyestuif which is unaffected by alkalies. Likewise, since the quaternary ammonium compound retains its basic nature in the presence of alkali, fibers containing the quaternary ammonium ion will not lose their ailinity for direct dyestuffs in the presence of alkali.

In order to introduce the quaternary ammonium group into the polyvinyl alcohol or a polyvinyl alcohol fiber quaternary ammonium compounds are used which have the following structural formulas:

and

R R and R stand for alkyl, aralkyl and cycloalkyl radicals, or alkylene groups which together with the nitrogen atom form part of a heterocyclic ring, such as pyridino or piperidino.

A and A are organic residues which contain an aldehyde group. Included also are compounds hydrolyzable into aldehydes in situ, i.e. aldehyde precursors, includ ing for example, the acetals and hemiacetals of aldehydes. It may be preferred touse the aldehyde in the form of its acetal since the acetal is more stable than the free aldehyde. It is also possible to use addition products of aldehydes with compounds such as sodium bisulfite, hydroxylamine, substituted hydrazines and semicarbazide, which are readily decomposed into the aldehyde.

X- represents an anion such as hydroxyl, bromine, chlorine, iodine, methyl sulfate, or sulfate.

Compounds containing the following cationic groups are illustrative of compounds which can be successfully used in this invention:

(Formylmethyl -trimethylammonium (Formylmethyl -cyclohexyl-dimethylammonium (Formylmethyl) -diethyl-methylammonium Formylmethyl) -dibutyl-methylammonium (Formylmethyl -dipropyl-methylammonium (Formylmethyl -ethyl-dimethyl ammonium (Formylmethyl -benZyl-dimethylammonium (Formylrnethyl -methyl-piperidinium (2-formylethyl -trimethylammonium (2-formylethy1 -cyclohexyl-dimethylammonium (2-formylethyl -diethyl-methylammonium (i-formylethyl -dibutyl-methylammonium (2-formylethyl -ethyl-dimethyl ammonium (Z-formylethyl) -b enzyl-dimethylammonium (Z-formylethyl -methyl-piperidinium (2-formylpropyl -trimethylammonium (Z-formylpropyl -cyclohexyl-dimethylammonium (2 formylpropyl) -benzyl-dimethylammonium 3 -formylpropyl -trimethyiammonium (Omega-forrnyloctyl -trimethylammonium Z-formyll-rnethylpyridinium 3-fo'rmyll-methylpyridinium 4-formyl- 1 methylpyridi'nium p-Fo'r'mylphenyl -t'rimethyl ammonium (o-Formylphenyl) -trimeth'ylammonium (Bis- (formylmethyl -dimethylammoniui'h (Bis- (formylmethyl -benzyl-methyl ammonium (Bis- (formylmethyl -ethyl-methylammonium (Bis- Z-formylethyl) -dimethylammonium (it (Bis- 2-formylethyl -b enzyl-methylammonium 1,3 -diformylpropyl) -trimethylammonium The acetalization of the polyvinyl alcohol or polyvinyl alcohol fiber with an aldehyde or aldehyde precursor containing the quaternary ammonium group is carried out with an acid catalyst, using a conventional acetalization procedure. Partial acetalization with an aldehyde con taining the quaternary ammonium group may be followed by acetalization with another aldehyde, such as formaldehyde, which is commonly used for acetalization in order to obtain a product which will have superior dyeing characteristics, and also good dry and wet heat resistance.

In mixed spinning methods the polyvinyl alcohol may be dissolved in aqueous solution and heated with the aldehyde compound which contains the quaternary ammonium group to give a homogeneous reaction. The reaction mixture is then neutralized with alkali and dialyzed to remove the impurities. The acetalized polyvinyl alcohol and untreated polyvinyl alcohol are then dissolved in water to form a spinning solution from which the fiber may be spun by a conventional procedure.

Another procedure is to scatter the polyvinyl alcohol powder into an acidified aqueous salt solution and then heat with the aldehyde compound containing a quaternary ammonium group, while stirring, to give a heterogeneous reaction. The treated polyvinyl alcohol is then filtered. The partially acetalized polyvinyl alcohol may be blended with untreated polyvinyl alcohol before being spun into fiber by the customary procedure.

In mixed spinning methods one can use a polyvinyl alcohol which has been partially acetalized by means ofan aldehyde containing the quaternary ammonium group. Another satisfactory method is to treat a polyvinyl alcohol, which has been partially acetalized by means of an aldehyde containing a halogen group, with a tertiary amine. Still another method is to treat a polyvinyl alcohol, which has been partially acetalized by means of an aldehyde containing an amino group, with an alkylating agent, for example, an alkyl halide to con vert the amino derivative into a quaternary ammonium group. Then the acetalized polyvinyl alcohol containing the quaternary ammonium group may be mixed with untreated polyvinyl alcohol and an aqueous solution containing the mixture spun into fiber by conventional spinning methods.

The invention is illustrated in greater detail by the following examples, in which parts are by weight unless otherwise stated, and the degree of acetalization is shown as the percentage of acetalized hydroxyl groups calculated on the total amount of initial hydroxyl groups.

Example 1 \A polyvinyl alcohol fiber obtained by a conventional spinning process was subjected to heat treatment in air at 220 C. for 3 minutes under tension. The fiber was then treated with a bath consisting of an aqueous solution of 11.5% of (1-methyl-3,3-dimethoxypropyl)-trimethylammonium iodide, 17% of sulfuric acid, and 15% of sodium sulfate at C. for one hour. The resulting fiber contained 0.2% nitrogen. It showed superior dyeing properties for acidic direct dyestuffs. if this fiber is given a pretreatment with 2% caustic soda solution prior to dyeing, there will be no recognizable effect on its dyeing capacity. On the other hand, if a polyvinyl alcohol fiber which is acetalized with a weakly basic aminoaldehyde is given a pretreatment with 2% caustic soda solution prior to dyeing, there will be a considerable decrease in its dyeability for acidic direct dyestuffs due to the alkali treatment.

Example 2 A polyvinyl alcohol fiber obtained by a conventional spinning process was subjected to heat treatment in air at 220 C. for 3 minutes under tension as in Example 1.

The fiber was then treated with a bath consisting of an aqueous solution of 2.3 of (3,3-dimethoxypropyl) -cyclohexyl-dimethylammonium sulfate. The fiber thus obtained contained 0.21% nitrogen. It showed superior dyeing properties for acidic direct dyestuffs. For example, when the fiber was dyed with Acid Brilliant Scarlet 3R, the fiber completely absorbed the dyestutf in the dye bath. Even if the dyed material was dipped in an aqueous solution containing 2% of sodium carbonate, most of the dyestuif remained fast on the fiber. On the other hand, when the same polyvinyl alcohol fiber is acetalized with a weakly basic aminoaldehyde, dyed with the same dyestuff and then put into a solution of 2% sodium carbonate, almost all of the dyestutf will bleed off the fiber.

Example 3 A polyvinyl alcohol fiber obtained by a conventional wet spinning process was cut in 10 mm. lengths, and then subjected to heat treatment in air at 210 C. for 10 minutes. The fiber was then treated with a bath consisting of an aqueous solution of (2,2-diethoxyethy1)-trimethylammonium hydroxide, 20% of sulfuric acid and 15% of sodium sulfate at 7 C. for 2.5 hours. The fiber thus obtained contained 0.18% nitrogen.

This fiber was then heated in a bath consisting of 3% formaldehyde, 1.2% sulfuric acid and 15% sodium sulfate at 60 C. for one hour. The resulting fiber was resistant to boiling water and also had the excellent dyeing properties and color fastness described for the fibers obtained in Examples 1 and 2.

Example 4 A polyvinyl alcohol fiber obtained by a conventional spinning process was subjected to heat treatment in air at 220 C. for 3 minutes under tension as in Example 1. The fiber was then treated with a bath consisting of an aqueous solution of 2% bis-(3,3-dimethyoxypropyl)-dimethylammonium chloride, 20% sulfuric acid, and 15 of sodium sulfate at 70 C. for 2 hours. The fiber thus obtained contained 0.85% nitrogen. It showed superior wet heat resistance, had excellent dyeing properties, as well as color fastness toward alkali as in the former examples.

Example 5 A polyvinyl alcohol fiber obtained by a conventional dry spinning process was stretched 3.5 times its original length in one second in Woods alloy at 210 C. and stretched again an additional original length in one second in Woods alloy at 220 C. The fiber was then heated with a bath consisting of an aqueous solution of 0.6% of (p-formylphenyl)-trimethylammonium iodide, of sulfuric acid, and 15 of sodium sulfate at 60 C. for one hour. The fiber thus obtained contained 0.45% nitrogen.

The fiber was then heated in a bath consisting of an aqueous solution of 2% sulfuric acid, 10% sodium sulfate and 2% terephthalaldehyde at 60 C. for minutes.

The fiber thus obtained was resistant to boiling water and had excellent dyeing properties. When dipped into a dye bath consisting of an aqueous solution of 4% Acid Brilliant Scarlet BR and 10% of an ammonia solution of concentration, the fiber absorbed most of the dyestuif. On the other hand, when a fiber acetalized with a weakly basic aminoaldehyde was given similar treatment, no absorption of the dyestulf could be observed at all.

Example 6 Thirty grams of polyvinyl alcohol having an average degree of polymerization of about 1600, 25 grams of sulfun'c acid, and 40 grams of (p-formylphenyl)-trimethylammonium iodide and 405 grams of water were mixed together to form a solution which was heated at 70 C. for 10 hours. After cooling, 180 grams of an aqueous solution of caustic soda was gradually added to the polyvinyl alcohol mixture. The resulting solution was di- 6 alyzed for 3 days iii running water using parchment paper, in order to remove the impurities. The acetalized polyvinyl alcohol was removed in the form of a condensed film which contained 3.13% nitrogen.

19 grams of the above film, and 131 grams of untreated polyvinyl alcohol were then dissolved in water to form a spinning solution from which the fiber was spun by a conventional procedure. After the usual heat treatment a fiber was obtained which contained 0.35% nitrogen. This fiber was then heated in an aqueous solution containing 5% formaldehyde, 12% sulfuric acid and 15% sodium sulfate at C. for 30 minutes. The resulting fiber had superior dyeing properties and was stable against alkaline solutions.

Example 7 One hundred and fifty grams of polyvinyl alcohol powder were scattered in 700 grams of an aqueous solution of 6% sulfuric acid, 25% sodium sulfate and 2% of (pformylphenyl)-trimethyla.mn1onium sulfate. This solution was stirred and heated at 60 C. for 30 minutes.

The partially acetalized polyvinyl alcohol granules thus obtained were filtered. A spinning solution was prepared by adding to the granules 850 grams of water and suflicient caustic soda to give a pH of 7. The polymer concentration was 15%. The spinning solution thus obtained was spun into fiber by a conventional wet spinning process. The fiber, which contained 0.26% nitrogen, was then heat treated.

This fiber was then treated with a bath consisting of an aqueous solution of 3% formaldehyde, 12% sulfuric acid and 15% sodium sulfate at 70 C. for 40 minutes. The fiber thus obtained was resistant to boiling water and showed excellent dyeing properties and resistance toward allcalies.

xample 8 Ten grams of polyvinyl alcohol were acetalized with dcyclohexylaminopropionaldehyde to a degree of acetalization of the fiber corresponding to about 28.3% of the hydroxyl groups in the polyvinyl alcohol. The acetalized polyvinyl alcohol was then treated with a bath consisting of a water-methanol mixture containing 3 parts by weight of water to 7 parts by Weight of methanol, to which methyl iodide was added in a little greater than the equivalent proportion. Sod-ium carbonate was then added, while stir ring, in a quantity slightly in excess of the equivalent proportion. Precipitation occurred, but on heating the mixture slightly, the precipitate gradually dissolved.

The acetalized polyvinyl alcohol was then dialyzed to remove the impurities. The acetalized polyvinyl alcohol was then mixed with untreated polyvinyl alcohol, and water was added to adjust the polymer concentration of the resulting solution to 15 After a conventional spinning process, and heat treatment, the finished fiber showed excellent dyeing properties and resistance toward alkalies.

We claim:

1. A method of preparing fibers having improved dyeing properties which comprises acetalizing fibers of a vinyl alcohol homopolymer with a quaternary ammonium compound selected from the group consisting of quaternary ammonium compounds having the formula and quaternary ammonium compounds having the formula wherein R R and R are selected from the group consisting of a lower alkyl radical containing up to 4 carbon atoms, va benzyl radical, a cyclohexyl radical, and alkylene groups which together with the nitrogen atom form part of a heterocyclic ring selected from the group consisting of pyridinium and piperidiniurn, and A and A are or- :ganic radicals selected from the group consisting of a hydrocarbon radical containing a member of the class consisting of an aldehyde group, an acetal of the aldehyde group, and an addition product of the aldehyde group with a compound selected from the group consisting of sodium bisulfite, hydroxylamine, substituted hydrazines and semicarbazide, and X is an anion selected from the group consisting of hydroxyl, bromine, chlorine, iodine, sulfate and methyl sulfate, whereby to form polyvinyl alcohol fibers containing a quaternary ammonium group, said acetalizing of said vinyl alcohol homopolymer fibers being effected at a temperature of about 60-70" C. with an acid catalyst in an aqueous bath containing up to about 20% of said catalyst, whereby said acetalizing is effected without decomposition of said quaternary ammonium group.

2. A method of preparing fibers having improved dyeing properties which comprises acetalizing fibers of a vinyl alcohol homopolymer with a quaternary ammonium compound selected from the group consisting of quaternary ammonium compounds having the formula and quaternary ammonium compounds having the formula wherein R R and R are selected from the group consisting of a lower alkyl radical containing up to 4 carbon atoms, a benzyl radical, a cyclohexyl radical, and alkylene groups which together with the nitrogen atom form part of a heterocyclic ring selected from the group consisting of pyridinium and piperidinium, and A and A are organic radicals selected from the group consisting of a hydrocarbon radical containing a member of the class consisting of an aldehyde group, an acetal of the aldehyde group, and an addition product of the aldehyde group with a compound selected from the group consisting of sodium bisulfite, hydroxylamine, substituted hydrazines and semicanbazide, and X is an anion selected from the group consisting of hydroxyl, bromine, chlorine, iodine, sulfate and methyl sulfate, whereby to form polyvinyl alcohol fibers containing a quaternary ammonium group, and further acetalizing said fibers with an aldehyde selected from the group consisting of formaldehyde and terephthaldehyde, said acetalizing of said vinyl alcohol homopolymer fibers being effected at a temperature of about '6070 C. with an acid catalyst in an aqueous bath containing up to about 20% of said catalyst, whereby said acetalizing is effected without decomposition of said quaternary ammonium group.

3. A method of preparing fibers having improved dyeing properites which comprises acetalizing a vinyl alcohol homopolymer with a quaternary ammonium compound selected from the group consisting of quaternary ammonium compounds having the formula N+X Ra u and quaternary ammonium compounds having the formula wherein R R and R are selected from the group consisting of'a lower alkyl radical containing up to 4 carbon atoms, a benzyl radical, a cyclohexyl radical, and alkylene groups which together with the nitrogen atom form part of a heterocyclic ring selected from the group consisting of pyridinium and piperidinium, and A and A are organic radicals selected from the group consisting of a a hydrocarbon radical containing a member of the class consisting of an aldehyde group, an acetal of the aldehyde group, and an addition product of the aldehyde group with a compound selected from the group consisting of sodium bisulfite, hydroxylamine, substituted hydrazines and semicarbazide, and X* is an anion selected from the group consisting of hydroxyl, bromine, chlorine, iodine, sulfate and methyl sulfate, whereby to form polyvinyl alcohol containing a quaternary ammonium group, said acetalizing of said vinyl alcohol homopolymer being effected at a temperature of about 60-70 C. with an acid catalyst in an aqueous bath containing up to about 20% of said catalyst, whereby said acetalizing is effected without decomposition of said quaternary ammonium group, and spinning an aqueous solution of said last-named polyvinyl alcohol to form fibers therefrom.

4. A method of preparing fibers having improved dyeing properties which comprise-s forming an aqueous solution of a mixture of polyvinyl alcohol and of a vinyl alcohol ihomopolymer acetalized with a quaternary ammonium compound selected from the group consisting of quaternary ammonium compounds having the formula and quaternary ammonium compounds having the formula N+X- A i wherein R R and R are selected from the group consisting of a lower alkyl radical containing up to 4 carbon atoms, a benzyl radical, a cyclohexyl radical, and alkylene groups which together with the nitrogen atom form part of a heterocyclic ring selected from the grou consisting of pyridinium and piperidinium, and A and A are organic radicals selected from the group consisting of a hydrocarbon radical containing a member of the class consisting of an aldehydegroup, an acetal of the aldehyde group, and an addition product of the aldehyde group with a compound selected from the group consisting of sodium bisulfite, hydroxylamine, substituted hydrazines and semicarbazide, and X is an anion selected from the group consisting of hydroxyl, bromine, chlorine, iodine, sulfate and methyl sulfate, whereby to provide said homopolymer with a quaternary ammonium group, said vinyl alcohol homopolymer being acetalized at a temperature of about 6070 C. with an acid catalyst in an aqueous bath containing up to about 20% of said catalyst, whereby said acetalizing is effected without decomposition of said quaternary ammonium group, and spinning fibers from said solution.

5. The method of preparing fibers having improved dyeing properties as defined in claim 3, wherein the vinyl alcohol homopolymer is acetalized in aqueous solution.

6. The method of preparing fibers having improved dyeing; properties as defined in claim 4, wherein the vinyl alcohol homopolymer is acetalized in aqueous solution.

71 A method according to claim 1 in which the quaternary ammonium compound is (1-methyl-3,3-dimethoxypropyl -trimethylammonium iodide.

8. A method according to claim 1 in which the quaternary ammonium compound is (3,3-dimethoXypropyD- cyclohexyl-dimethylammonium sulfate.

9. A method according to claim 1 in which the quaternary ammonium compound is (2,2-diethoXyethy-D-trimethylammonium hydroxide.

10. A method according to claim 1 in which the quaternary ammonium compound is bis-(3,3-dimethoXypropyD- dimethyl ammonium chloride.

11. A method according to claim 1 in which the quaternary ammonium compound is (p formylphenyl)-trimethylammoni-um iodide.

References Cited in the file of this patent UNITED STATES PATENTS Rein Apr. 6, 1937 Bock June 18, 1940 Bock Aug. 11, 1942 Book June 20, 1944 Smith July 9, 1946 Unr-uh May 19, 1958 Suyama June 16, 1959 Osugi Sept. 29, 1959 Osugi July 11, 1961 Matsubayashi Nov. 7, 1961 OTHER REFERENCES Nomura: I.S.D.C., May 1958, pp. 3S9371.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3316089 *Jul 3, 1963Apr 25, 1967Polaroid CorpPhotographic products and processes utilizing cross-linking agents containing intralinear quaternary nitrogen atoms
US3322855 *May 24, 1961May 30, 1967Kurashiki Rayon CoShaped articles from blends of a polyvinyl acetal and a polymer of an alpha-methyl styrene
US4689217 *Jun 21, 1985Aug 25, 1987Ici Americas Inc.Amine and ammonium nitrogen containing polyvinyl alcohol polymers having improved lipophilic properties for use in skin conditioning, cosmetic and pharmaceutical formulations
US4690817 *Jun 21, 1985Sep 1, 1987Ici Americas Inc.Quaternary nitrogen containing polyvinyl alcohol polymers for use in skin conditioning, cosmetic and pharmaceutical formulations
US4775715 *Jul 23, 1987Oct 4, 1988E. I. Du Pont De Nemours And CompanyDry blending process for the quaternization of polyvinyl alcohol
US4822851 *Dec 29, 1986Apr 18, 1989Degussa AktiengesellschaftProcess for the preparation of cationized polyvinyl alcohol
US5001191 *Nov 20, 1989Mar 19, 1991Degussa AktiengesellschaftProcess for dry cationization of polyvinyl alcohol
Classifications
U.S. Classification8/115.55, 8/115.65, 525/61, 8/115.57, 260/DIG.230, 8/DIG.100, 525/56
International ClassificationD01F6/14, D06P3/58, D06P5/22
Cooperative ClassificationD01F6/14, Y10S260/23, Y10S8/10, D06P5/22, D06P3/58
European ClassificationD01F6/14, D06P3/58, D06P5/22