GB1589482A

GB1589482A - Fabric stiffening composition

Info

Publication number: GB1589482A
Application number: GB4729677A
Authority: GB
Original assignee: Kao Corp; Kao Soap Co Ltd
Current assignee: Kao Corp
Priority date: 1976-11-29
Filing date: 1977-11-14
Publication date: 1981-05-13
Also published as: BE861238A; JPS5370191A

Description

(54) FABRIC STIFFENING COMPOSITION (71) We, KAO SOAP CO. LTD., a Japanese Company, of l,l-chome, Nihonbashi-Kayabacho, Chuo-ku, Tokyo, JAPAN, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and, by the following statement::- The present invention relates to a household fabric stiffening composition (usually but loosely referred to as a "starch"). More particularly, the invention relates to a fabric stiffening composition comprising as an indispensable component and emulsion prepared by emulsion-polymerizing a vinyl or vinylidene monomer (exluding such monomers which can form salts by reaction with alkalis) in an aqueous solution of a polyvinyl alcohol, nonionic modified starch or nonionic cellulose derivative in the presence of a cationic vinyl polymer or a ring-closed polymer as herein defined of a cationic diallyl compound a cationic surface active agent and or a cationic monomer.

By a "ring-closed polymer" we mean a polymer formed by a reaction which involves the closing of a ring, and which therefore has rings in the polymer chain.

Natural starch has heretofore been used as a household fabric stiffening composition, and various modifications have been made to starch to facilitate treatment of fabric with it. At the present, a liquid fabric stiffening composition which can readily be diluted with cold water and be used very simply and conveniently and which is stable, is employed and such a composition generally comprises a 10 to 15% aqueous solution of for example carboxymethyl cellulose, starch, or polyvinyl alcohol and also additives such as a defoaming agent, a mildewproofing agent, a fluorescent whitening agent, and a perfume.

These polymeric substances, namely polyvinyl alcohol, starch and carboxymethyl cellulose, are hard polymers having a glass transition temperature higher than 80"C. Although they are cheap, clothes treated with them can become too stiff and adopt a paper-like appearance and impression. Further, such fabric stiffeners often damage the skin and cause roughening of the skin surface.

Moreover, the finish lacks a thick feel and is unpleasant to the touch. Accordingly, these stiffening materials are not suitable for treating high quality clothes. Further, the viscosities of aqueous solutions of these polymers are high even at low concentrations and they are thus difficult to handle.

When housewives treat clothes with a fabric stiffener, the stiffener is in general dissolved in a small quantity of water and the fabric is uniformly rubbed in the starch solution cause the stiffener to be absorbed by the cloth. If the quantity of water is too small, the treatment becomes uneven or the neck or sleeve edges of the garment are readily folded. In order to avoid occurrence of such inconvenience, it is preferred to carry out the treatment using a sufficient quantity of water.

However, since the majority of the stiffener dissolved in the water is discarded with the waste water, this method is wasteful.

As a fabric stiffener composition overcoming these defects and disadvantages, there has recently been developed and marketed a composition comprising as a main component a polyvinyl acetate emulsion.

In emulsion of this type, a surface active agent as an emulsifying dispersant for dispersing the polymer in water and a water-soluble polymer, such as polyvinyl alcohol, as a protective colloid for stabilizing the emulsified particles are included, and as is well-known in the art, these additives take important roles in preparation, storage and application of products. Protective colloids which have heretofore been mainly studied and used for industrial products are nonionic and anionic polymers, and most of the surface active agents used as emulsifying dispersant are nonionic or anionic. Accordingly, most of emulsion polymers now marketed are nonionic or anionic emulsion polymers.

In cationic polymer emulsions, since the polymer particles are cationically charged, electric attractive forces are generated between such polymer particles and fibers or synthetic resins that are generally negatively charged in water and therefore, such effects as prompt deposition and sticking, tight adhesion and quick attainment of water resistance are expected. However, the quantities and kinds of these cationic polymer emulsions which are manufactured on an industrial scale are very limited.

As a process for the production of cationic polymer emulsion, there is known, for example, a process in which emulsion polymerization is carried out in the presence of a nonionc surface active agent or anionic surface active agent and the ionic characteristic is reversed by addition of a cationic surface active agent while preventing coagulation of the dispersed polymer by addition of a nonionic surface active agent or amphoteric surface active agent, also a process in which emulsion polymerization is carried out in the presence of a cationic surface active agent (disclosed in, for example, Japanese Patent Publication No. 12125/64, Japanese Patent Application Laid-Open Specification No. 122584/74, Japanese Patent Publication No. 98990/75 and Japanese Patent Publication No. 26589/75), also a process in which a cationic vinyl monomer is emulsion-polymerized with other vinyl monomers to form a cationic emulsifiable polymer disclosed in, for example, Japanese Patent Publications No. 25707/70, 9410/72, 38108/74, and 60593/75), and also a process in which a water-soluble cationic polymer is used as a protective colloid (disclosed in, for example, U.S. Patent No. 3,001,957 and Japanese Patent Application Laid-Open Specification No. 9899/75.

In general, these cationic polymer emulsions are inferior in stability to ordinary anionic or nonionic emulsified polymers, and in practice a sufficient cationic characteristic is not imparted to them so that their selective adhesion to fibers or the like is insufficient.

In accordance with the present invention, there is provided a fabric stiffening composition comprising an emulsion prepared by emulsion-polymerizing a vinyl or vinylidene monomer (other than such a monomer that can form a salt by reaction with an alkali) in an aqueous solution containing 20 to 60% by weight of said monomer and 0.5 to 10% bv weight of polyvinyl alcohol, nonionic modified starch (as herein defined) or a nonionic cellulose derivative in the presence of 0.05 to 3% by weight of a cationic vinyl polymer or a ring-closed polymer of a cationic diallyl compound and up to 5% by weight of a cationic surface active agent and/or up to 2% by weight of a cationic monomer, and 0.01 to 5%, based on the weight of the vinyl or vinylidene monomer, of a polymerisation initiator, all other said percentages being based on the weight of the emulsion.

By "modified starch" we mean starch that has been chemically modified to render it water soluble.

The drawing is a graph illustrating the relation between the total number of carbon atoms in the alkyl groups of the cationic surface active agent used in Example 7 and the relative amount of the cationic polymer emulsion adsorbed in the polymer sample (calculated on the assumption that the amount adsorbed of the polymer emulsion obtained in Comparative Example 1 is 1).

As the vinyl or vinylidene monomer that is used in the present invention, there can be mentioned, for example, vinyl esters or fatty acids such as vinyl acetate and vinyl propionate, esters of acrylic and methacrylic acids such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and acrylamide, styrene, butadiene and chloroprene. Among them, vinyl acetate is most preferred. Vinyl monomers capable of reacting with an alkali to form a salt, for example, acrylic acid, methacrylic acid and maleic anhydride, are not included in the scope of the present invention.

The vinyl monomer is used at a concentration of 20 to 60% by weight, preferably 25 to 50,0, by weight, based on the final emulsion.

In the present invention, it is preferred to use a cationic vinyl polymer having a viscosity of 3 to 500 centipoises as measured at 200C with respect to a 1% aqueous solution. Preferred structures for the cationic vinyl polymer that is used in the present invention are those comprising repeating units of the following general formulae (1) to (4)::

wherein R3 stands for a hydrogen atom or a methyl group, R4, R5 and R6, which may be the same or different, stand for an alkyl group or substituted alkyl group having 1 to 4 carbon atoms in the alkyl moiety, A stands for an oxygen atom or a nitrogen atom in the amide linkage, mis an integer of from 1 to 10, and X stands for,an anion,

wherein R7, R8 and Rg, which may be the same or different, stand for a hydrogen atom or an alkyl group or substituted alkyl group having 1 to 2 carbon atoms in the alkyl moiety, and X stands for an anion.

[poly (N-methylvinylpyridium chloride)]

[poly (N-vinyl-2,3-dimethylimidazolinium chloride)] Among polymers represented by the general formula (1), for example, poly(Nacrylamidopropyl-3-trimethyl-ammonium chloride) of the following formula (5) is most preferred.

A preferred structure of the ring-closed polymer of the cationic diallyl compound that is used in the present invention is one comprising repeating units of the following formula (6):

wherein R, and R2, which may be the same of different, stand for an alkyl group or substituted alkyl group having 1 to 2 carbon atoms in the alkyl moiety, X stands for an anion, In the above preferred structure, it is especially preferred that both of the groups R, and R2 stand for a methyl group.

The above-mentioned cationic vinyl polymer or ring-closed polymer of the cationic diallyl compound is used in an amount of 0.05 to 3% by weight, preferably 0. I to 1% by weight, based on the final emulsion.

In the present invention, it is preferred that the cationic monomer be one having in the molecule at least one nitrogen atom and at least one double bond.

Examples of the preferred cationic monomer are those having any of structures represented by the following formulae (7) to (10):

wherein R17 stands for a hydrogen atom or a methyl group, R,8, R,g and R20, which may be the same or different, stand for a hydrogen atom or an alkyl or substituted alkyl group having I to 22 carbon atoms in the alkyl moiety, X stands for an anion, k is an integer of from I to 10, A stands for an oxygen atom or a nitrogen atom of the amide linkage, and R18, R,g and R20 may form together a ring with N.

vvherein R2, stands for a hydrogen atom or a methyl group, R22, R23 and R24, which may be the same or different stand for a hydrogen atom or an alkyl group or substituted alkyl group having I to 2 carbon atoms in the alkyl moiety, and X stands for an anion.

Among the above exemplified compounds, vinylbenzyltrimethyl ammonium chloride and acrylic acid and methacrylic acid esters of hydroxyalkyltrialkyl ammonium salts are especially preferred.

The cationic monomer is added in an amount of 0 to 2% by weight, preferably 0.02 to 1% by weight, based on the final emulsion.

Any cationic surface active agents having such water-solubility that they can be completely dissolved when used in amounts specified in the present invention can be used as the cationic surface active agent in the present invention. Cationic surface active agents having a structure represented by any of the following general formula (11) to (18) are effectively used in the present invention:

wherein Ro, Rut1, R,2 and R13 each stand for a hydrogen atom, an alkyl group having at least one carbon atom or a hydroxyalkyl group having at least one carbon atom with the proviso that the sum of carbon atoms of these groups is 25 to 50, preferably at least 30, and X stands for an anion.

(12) [R,4-CONH(CH2),]2NR,5Rs8 X- wherein R,4 stands for an alkyl group or substituted alkyl group having at least 8 carbon atoms in the alkyl moiety, R15 and R1e, which may be the same or different, stand for an alkyl group or substituted alkyl group having at least one carbon atoms in the alkyl moiety with the proviso that the sum of carbon atoms of the groups R14, R,5 and R,6 is in the range of from 25 to 50, preferably 30 to 50, 1 is 2 or 3, X stands for an anion, and Ra5 and Rfi may form a ring with N.

wherein R25 stands for an alkyl group having at least 8 carbon atoms or a group RCOOCH2C H2 (in which R is an alkyl group), R25 stands for an alkyl group having at least one carbon atoms, and m and n stand for an integer with the proviso that the sum of m and n is at least 2.

wherein R2, stands for an alkyl group having at least 8 carbon atoms, and R25 to R,2 stand for an alkyl group having I to 3 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms with the proviso that the sum of carbon atoms in the molecule is in the range of from 25 to 50.

wherein R33 and R34 stand for an alkyl group having at least 8 carbon atoms, R33' and R34 stand for a hydrogen atom or an alkyl group having I to 3 carbon atoms, and X stands for an anion.

wherein R35 stands for an alkyl group having at least 8 carbon atoms, R35 stands for -H, -CH CH OH or -CH2CH2NHCOR39 (in which R39 is an alkyl group having at least 1 carbon atom), R37 stands for -H or an alkyl group having 1 to 5 carbon atoms, R38 stands for -H or -CH2OH, and the sum of carbon atoms of the groups R35, R38, R37 and R38 is at least 25, preferably 30 to 50.

wherein R40 stands for an alkyl group having at least 12 carbon atoms, preferably 20 to 50 carbon atoms, -RO, -RCOOCH2, -RCONHCH2 or -RCOOCH2CH2NHCOCH2 (in which R stands for an alkyl group having at least 12 carbon atoms, preferably 20 to 50 carbon atoms),

stands for a pyridinium, quinolinium or isoquinolinium group, and X stands for an anion.

(18) R41-(NHCH2CH2)nNH2 wherein R4, stands for an acyl group or alkyl group having at least 12 carbon atoms, preferably 25 to 50 carbon atoms, and n is an integer of at least 1.

Among the above exemplified cationic surface active agents. those represented by the above formula (II) in which R10, $R11, R12 and $ > 013, which may be the same or different, stand for an alkyl group or substituted alkyl group and the sum of carbon atoms of these groups is in the range of from 25 to 50 are especially preferred.

The cationic surface active agent is added in an amount of 0 to 5% by weight, preferably 0.2 to 1.5% by weight, based on the final emulsion.

The modified starch that is used in the present invention includes watersoluble modified starches such as hydroxyethylated starch, hydroxypropylated starch and the like.

The polyvinyl alcohol that is used in the present invention includes partially and completely saponified products of vinyl acetate homopolymers and polyvinyl alcohol derivatives formed by modifying such saponified products with, for example, aldehyde. All of these polymers are included so far as the viscosity is 5 to 10000 centipoises as measured at 300C with respect to a 5% aqueous solution.

The nonionic cellulose derivative that is used in the present invention includes water-soluble hydroxyalkylated celluloses and alkyl celluloses having a viscosity of 5 to 10000 centipoises as measured at 300C with respect to a 5% aqueous solution.

For example, there can be mentioned hydroxyethyl cellulose, hydroxypropyl cellulose and methyl cellulose (degree of methylation of 10%).

The above-mentioned polyvinyl alcohol, modified starch or nonionic cellulose derivative is incorporated in an amount of 0.5 to 10% by weight, preferably 1.0 to 4.0% by weight, based on the final emulsion.

As the polymerization initiator that is used for practising the present invention, 2,2'-azobis(2-amidinopropane) is most preferred, but there may also be used hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide, methylethylketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid and the like. It is preferred that the polymerization initiator be used in an amount of 0.01 to 5.0 /O by weight based on the vinyl monomer.

The reaction temperature is preferably 40 to 1200C, more preferably 50 to 90"C. The polymerization is preferably carried out at a pH of 3 to 9, more preferably 4 to 8. It is preferred that an inorganic salt such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, sodium secondary phosphate, sodium primary phosphate, sodium chloride or sodium sulfate be added as a buffering agent in an amount of 0.05 to 2% by weight, especially 0.1 to 1% by weight.

Accordingly, an emulsion for production of a fabric stiffening according to the present invention may be prepared by emulsion polymerization of the following composition: Component Ordinary Amount Preferred Amount t% by weight) (% by weight) vinyl monomer 20 - 60 25 - 50 polyvinyl alcohol, modified 0.5-10 1.0-4.0 starch or cellulose- derivative water-soluble cationic polymer 0.05 - 3 0.1 - cationic monomer 0 - 2 0.02 - cationic surface active agent 0 - 5 0.2 - 1.5 polymerization initiator 0.01 - 5 0.02 - inorganic salt 0.052 0.1I All the components may be added simultaneously to effect reaction, but it is preferred to adopt a method in which the vinyl monomer is gradually added to a reaction vessel in which all the components other than the vinyl monomer have been charged.

When the cationic monomer is used for the emulsion polymerization, an effect of adjusting the size of polymer particles by adjusting the amount of the cationic monomer or adopting an appropriate structure thereof can be manifested simultaneously with the stabilizing effect and other effects. Moreover, the cationic vinyl polymer or the ring-closed polymer of the cationic diallyl compound exerts not only a stabilizing effect as a protective colloid for the polymer particles but also an effect promoting adhesion of the polymer particles of the polymer particles to a cloth which is readily charged negatively in water. In the emulsion polymerization, the cationic surface active agent forms a micell and solubilizes the vinyl polymer to impart polymerization sites thereto.Further, the cationic surface active agent imparts a dispersion stability to the resulting polymer and charges the polymer particles positively, whereby adhesion of the polymer particles to a cloth which is charged weakly negatively in water can be remarkably enhanced. This effect of charging the polymer particles positively and enhancing adhesion to clothes is synergistically improved by the combined use of the cationic monomer and cationic surface active agent. Accordingly, this effect is highest in an emulsion containing both the cationic monomer and cationic surface active agent.

The emulsion of the present invention to be used for a household fabric stiffening composition can be sufficiently used as a household fabric stiffener even if it does not include the above-mentioned cellulose derivative. However, if such polyvinyl alcohol, nonionic modified starch or nonionic cellulose derivative is used in combination with the cationic vinyl polymer or the ring-opened polymer of the cationic diallyl compound, the stability of the emulsion is further enhanced, and properties given to treated clothes, for example, good stiffness, can be remarkably improved. Namely, if good stiffness is given to, for example, a white shirt or blouse, on ironing a trim and neat feel or appearance is given to the cloth and this finish is durable for a long time.On the other hand, in the area making contact with the skin, the applied stiffening composition is softened by the body temperature and the skin is prevented from being irritated or stimulated, and it is free of such an undesirable property that the stiffening composition is readily dissolved out by sweat and adheres to the skin. Accordingly, the stiffening composition of the present invention is different from an ordinary adhesive or fiber sizing agent in which a polymer having a high adhesive force, namely a hard polymer, is desired or a polymer readily washed away by water is desired.

The composition of the present invention may further comprise additives customarily used foi polymer emulsions, for example, plasticizers such as dibutyl phthalate, dioctyl phthalate, dibutyl adipate, dioctyl adipate and triacetin, antifreezing agents such as ethylene glycol, propylene glycol and ethanol, and perfumes, fungicides, antiseptics, fluorescent dyes and pigments.

When a fabric stiffening treatment is conducted by using the composition of the present invention, even if the composition is diluted with a sufficient quantity of water (for example, at a bath ratio higher than 1/4), a good composition strength can be attained and a cloth can be uniformly treated.

The present invention will now be described by reference to the following non limiting Examples in which all of "parts" are by weight.

Example 1.

In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 8 parts of polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) was dissolved in 130 parts of deionized water at 800C. After the solution was cooled to 400C, 0.5 part of poly(N-methylvinylpyridinium chloride) and an aqueous solution of 1 part of sodium carbonate in 10 parts of deionized water were added to the solution, and air in the flask was replaced by nitrogen.Then, 10 parts of monomeric vinyl acetate and a variable amount of methacryloxyethyltrimethyl ammonium chloride were added to the charge of the flask, and a polymerization initiator comprising 0.1 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 10 parts of deionized water was added and the temperature was elevated to 700C to initiate the polymerization. Over a period of 100 minutes from the point at which 10 minutes had passed from the initiation of polymerization, 90 parts of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for 1 hour at 800C to complete emulsion polymerization.

The relation between the amount added of methacryloxyethyltrimethyl ammonium chloride and the particle size is illustrated in Table 1.

The particle size was measured by an optical microscope, and it is expressed in terms of the average particle size.

Table 1.

Sample A* B C D E Amount Added (part) 0 0.05 0.1 0.2 0.3 Particle Size (/1) 4 2 1 0.5 0.2 *: comparison When each of the foregoing samples was stored at room temperature for I month in the state packed in a glass vessel, separation of a supernatant layer was observed in sample A, but all of the emulsions B, C, D and E according to the present invention were stable.

Example 2.

In the same reaction vessel as used in Example l, polymerization was carried out according to the method described in Example I in the following mariner.

In 130 parts of deionized water was dissolved at 800C 9 parts of polyvinyl alcohol (completely saponified product, degree of polymerization = 1600). After the solution was cooled to 400C, 1.0 part of a cationic polymer (Table 2) and an aqueous solution of 0.5 part of sodium carbonate in 5 parts of deionized water were added to the above solution. Then, air in the flask was replaced by nitrogen, and 10 parts of monomeric vinyl acetate and a cationic monomer (Table 2) were added to the charge of the flask. Then, a polymerization initiator comprising 0.1 part of 2,2'azobis(2-amidinopropane) hydroxide and 10 parts of deionized water was added and the temperature was elevated to 700C to initiate polymerization.Over a period of 100 minutes from the point at which 10 minutes had passed from the initiation of polymerization, 90 parts of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was carried out at 800C for 1 hour to complete emulsion polymerization.

The kinds of the cationic polymer and cationic monomer used and properties of the resulting emulsions are as shown in Table 2.

Table 2.

Particle Cationic Polymer Cationic Monomer Size Stability poly(vinylbenzyltrimethyl trimethylaminoethanol 1 1.5 M good ammonium chloride) acryloyl chloride having viscosity of 6.8 cps (0.1 part) as measured at 300C with respect to 10% solution (by B-type viscometer, rotor No. 1,60 rpm) poly (N,N-dimethyl-3,5- trimethylaminoethanol 1--15u good methylene piperidium methacryloyl chloride chloride) having viscosity (0.1 part) of 11.5 cps as measured at 30"C with respect to 10% solution (by B-type viscometer, rotor No. 1, 60 rpm) ditto vinylbenzyltrimethyl 0.5 - 1.5 good ammonium chloride (0.1 part) Example 3.

According to the method described in Example 1, an emulsion having the following composition was prepared: Water 140 parts Monomeric vinyl acetate 100 parts Methacryloxyethyltrimethyl ammonium chloride 0.1 part Poly(N,N-dimethyl-3,5-methylene piperidium chloride) 0 or 2.0 parts Polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) 8 parts Sodium carbonate I part Cationic surface active agent 0 - 5 parts The cationic surface active agent was added simultaneously with the cationic polymer.

The resulting emulsion was diluted with water so that the volume was increased to 50 times the original volume, and a desized 40-count cotton broadcloth was dipped in the resulting liquid. The weight of the cloth was 1/4 of the weight of the liquid. Then. the cloth was dehydrated and dried, and the amount of the stiffening composition adhereing to the cloth was measured to obtain results shown in Table 3.

TABLE 3 Amount (parts) of poly (N,N-dimethyl-3,5- Amount (parts) Amount (%) of methylene piperidium of cationic stiffening composition chloride) Cationic surface active agent surface agent stuck to cloth 0* - 0 18 0* distearyldimethyl ammonium chloride 1 32 2 - 0 48 2 distearyldimethyl ammonium chloride 0.05 60 2 ditto 0.1 75 2 ditto 0.5 85 2 ditto 1 92 2 ditto 3 95 2 ditto 5 95 2 [C18H37.CONH(CH2)3]2N+(CH3)2Cl- 1 86

2 C22H45 4N Ct 1 80 *: comparison Example 4.

In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 6.4 g of polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) was dissolved in 90 g of deionized water under heating. After the solution was cooled to 409C, 0.3 g .of poly(methyacryloxyethyltrimethyl ammonium chloride) (having a viscosity of 200 centipoises as measured at 200C with respect to a 1% aqueous solution) and 0.03 g of the monomer of the latter polymer were completely dissolved, and 0.4g of distearyldimethyl ammonium chloride and an aqueous solution of I g of sodium carbonate in lOg of deionized water were added to the solution.Then, air in the flask was replaced by nitrogen and 8 g of monomeric vinyl acetate was added to the charge of the flask, and a polymerization initiator comprising 0.08 g of 2,2'-azobis(2-amidinopropane) hydrochloride and lOg of deionized water was added and the temperature was elevated to 700C to initiate the polymerization. Over a period of 2 hours from the point at which 5 minutes had passed from the initiation of polymerization, 72 g of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for I hour at 800C to complete emulsion polymerization.

The solid content of the so obtained polyvinyl acetate emulsion was 44%, and the viscosity was 870 centipoises as measured at 30"C (by a B-type viscometer, rotor No. 2, 12 rpm).

Example 5.

In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 6.4 g of polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) was dissolved in 90g of deionized water under heating. After the solution was cooled to 400C, 0.2 g of a cationic amide compound of the following formula:

(in which Ra2 has an alkyl group distribution of the carbon number in the range of from 18 to 24; this compound was prepared by reacting I mole of diethylene triamine with 2 moles of a fatty acid having 18 to 24 carbon atoms to form an amide having an acid value lower than 10, adding about I to about 2 moles of epichlorohydrin to the resulting amide, subjecting the ring-closed adduct to ringopening polymerization so that 2.5 equivalents of the epoxy group was ring-opened and polymerized, and adding 2.5 moles of hydroxyacetic acid to the resulting polymer), 0.6 g of dimethyldistearyl ammonium chloride and 0.3 g of poly(vinylbenzyltrimethyl ammonium chloride) were dissolved. Then, an aqueous solution of I g of sodium carbonate in lOg of deionized water were added to the solution, and air in the flask was replaced by nitrogen.Then, 8 g of monomeric vinyl acetate was added to the charge of the flask, and a polymerization initiator comprising 0.08 g of 2,2'-azobis(2-amidinopropane) hyrochloride and 4 g of deionized water was added and the temperature was elevated to 700C to initiate the polymerization. Over a period of 2 hours from the point at which 5 minutes had passed from the initiation of polymerization, 72 g of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for 1 hour at 800C to complete emulsion polymerization.

The solid content of the so prepared polyvinyl acetate emulsion was 45% and the viscosity was 970 centipoises as measured at 300 C.

Comparative Example 1.

In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 50g of a 10% aqueous solution polyvinyl alcohol (completely saponified product, degee of polymerization = 1800) and an aqueous solution of 0.2 g of sodium lauryl sulfate and 1 g of sodium carbonate in 50 g of deionized water were charged. Then, air in the flask was replaced by nitrogen and 8 g of monomeric vinyl acetate was added and the temperature was elevated to 600C. A portion (12g) of a polymerization initiator comprising 0.15 g of ammonium persulfate and 16 g of deionized water was dropped to initiate the polymerization. Over a period of 200 minutes from the point at which 10 minutes had passed from the start of polymerization, the remainder of the initiator solution was added, and over a period of 3 hours from the point at which 10 minutes had passed from the initiation of polymerization, 72 g of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for 1 hour at 800C to complete emulsion polymerization. The solid content of the resulting emulsion was 43%, and the viscosity was 520 centipoises as measured at 300 C.

Comparative Example 2.

In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 8 g of polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) was dissolved in 130g of deionized water under heating. After the solution was cooled to 400C, 0.5g of an alkyltrimethyl ammonium chloride having 14 to 18 carbon atoms and an aqueous solution of 1 g of sodium carbonate in lOg of deionized water were added to the solution, and air in the flask was replaced by nitrogen. Then, 10g of monomeric vinyl acetate was added to the charge of the flask, and a polymerization initiator comprising 0.1 g of 2,2'-azobis(2amidinopropane) hydrochloride and 10g of deionized water was added and the temperature was elevated to 600C to initiate the polymerization.Over a period of 2 hours from the point at which 5 minutes had passed from the initiation of polymerization, 90 g of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for 1 hour at 800C to complete emulsion polymerization. The solid content of the resulting polyvinyl acetate emulsion was 42% and the viscosity was 1100 centipoises as measured at 30"C.

Test 1.

Each of the cationic and anionic polyvinyl acetate emulsions prepared in Examples 4 and 5, Comparative Example I and Referential Example 1 was charged in a 100ml-capacity polyethylene sample bottle and was stored at -150C for 8 hours. Then, the temperature was elevated to +50C over a period of 10 hours and this temperature was maintained for 20 hours. Then, the temperature was lowered to --150C over a period of 10 hours. This cycle of freezing and thawing was repeated. The sample stored for 8 hours at -l50C after the predetermined cycles of freezing and thawing was allowed to stand in a warm bath maintained at 300C for 1 hour and the viscosity of the sample was measured by a B-type viscometer (rotor No. 2, 12 rpm).Obtained results are shown in Table 4, from which it is apparent that the freeze stability of a cationic polymer emulsion including a cationic surface active agent as an emulsifier and a cationic water-soluble polymer is very good.

Separately, each of the cationic and anionic polyvinyl acetate emulsions prepared in Examples 4 and 5, Comparative Example 1 and Referential Example 1 was charged in a 100 ml-capacity sample bottle and stored at 500C for 30 days.

Then, the sample was allowed to stand in a warm water bath maintained at 300C for I hour and the viscosity of the sample was measured by a B-type viscometer (rotor No. 2, 12 rpm) to obtain results shown in Table 5, from which it is apparent that the cationic polyvinyl acetate emulsions prepared in Examples 4 and 5 are excellent in the high temperature stability.

Table 4.

Viscosities (centipoises, at 300C) of Polyvinyl Acetate Emulsions Sample Number of Cycles of Freezing-Thawing 0 1 3 7 Example 4 870 1060 1180 1290 Example 5 1060 1190 1210 1280 Comparative Example 1 520 1480 1520 1550 Comparative Example 2 1100 gelled, gelled, gelled, measurement measurement measurement impossible impossible impossible Table 5.

Viscosities (centipoises, at 300C) of Polyvinyl Acetate Emulsions After 30 Days at 50 C Initial Sample Viscosity Viscosity Appearance Example 4 870 720 white, opaque Example 5 1060 950 ditto Comparative Example 1 520 680 ditto Comparative Example 2 1100 gelled, phase measurement separation, impossible brown Example 6.

Cationic polyvinyl acetate emulsions shown in Table 6 were prepared according to the method described in Examples 4 and 5. Each of the so prepared compositions had a good storage stability.

TABLE 6 Cationic Polyvinyl Acetate Emulsions Sample No. cationic Surface Active Agent Cationic Water-Soluble Polymer

ao CH3 o 7 - 1 (C1sHs7)2Nle2 1, 0.4 g CH2C)n I U e D U m + t C00CH2CH2NMe3Cl 0.32 g o' 0 " u 2 z 7 Z C~) = U r r r r 5:: oU 5 (C18H37)2N Cl , 0.4 g ditto CH2CH2OH 7 - 6 same as in Example 5 &num;c112-CH+jr Cl S CH2N Me3 Cil1 7-7 same as in ExampleS CH2Cn 0 C on t &commat; on t t oo oo = m} v) o o o o o o - o &commat; N a E; U x x rn nn ' > E E U C) s ~ cs t m T rv F rs F F F F F TABLE 6 (continued) Sample No.Cationic Surface Active Agent Cationic Water-Soluble Polymer

CH3 7 o 8 same as in Example 5 CH2-C I C' C on t o u 7-9 ditto t or or CH2 CH2 1.0 g Me Me C) O N if sZE Me Me Me 7 - 11 ditto N\(cH2 CH2O)2CH2C112 - I N - CH2COOCH2 Me Me 1.0 g "a o C X ca E Ct CO TABLE 6 (continued) Sample No. Cationic Surface Active Agent Cationic Water-Soluble Polymer

Ins m C? o Me (CH2CH20)nH (m + n = 50), NMe C0, OI z < ) 'Z CONHCH2CH2 HN1&commat; - o 7 - '4 Cl7H35CONHCCH2CNlO CH2CH2OH 2CH3COO, ditto eo Q o Q &commat; N U o P N 0N O n X X ,0 + (3 Zb O = 8 Z e E T T F K t1 tt l l I ts TABLE 6 (continued) Sample No. Cationic Surface Active Agent Cationic Water-Soluble Polymer

co m K o' Cli 0.8 g 3 C O.3S g cill37 vo, 9 Z- ,5.

9 + N (t h 08 6 5 8 > > S so I > r Test 2.

Fabric stiffening treatment was carried out by using the cationic polyvinyl acetate emulsions prepared in Examples 4 and 5, and the amount of the stiffening compositiona dhering to the fabric and its hardness were determined. A desized sample cloth (60-count cotton broadcloth) was wetted with water and dehydrated for 1 minute by a dehydrating machine, and it was dipped in a diluted stiffening composition in a washbowl and lightly rubbed for 30 seconds. Then, the cloth was dehydrated for 1 minute by a dehydrqting machine, air-diredand stored for 1 day in a chamber maintained at a temperature of 20 C and a relative humidity of 65%.

Then, the weight of the sample cloth was measured, and the amount of the stiffening composition adhereing was calculated by subtracting the weight of the sample cloth before the treatment from the thus measured weight. Separately, the aair-dried sample cloth was sprinkled by spraying and pressed ant 130 C for 1 minute, and the hardness was measured according to the cantilever method according to JIS 1005-1959. Obtained results are shown in Tables 7 and 8.

Table 7.

Amount Stuck of Polyvinyl Acetate Emulsion (% of the polymer stuck on cloth based on the used polymer) Sample Concentration 0.8% 0.4% 0.2% 0.1% (bath ratio (bath ratio (bath ratio (bath ratio of 1/1) of 1/2) of 1/4) of 1/8) Example 4 95% 88 84 78 Example 5 93 92 90 81 Comparative 73 54 30 19 Example 1 Table 8.

Stiffening Composition Hardness (cm of Polyvinyl Acetate Emulsion-Treated Cloth (according to cantilever method) Sample Concentration 0.8% 0.4% 0.2% 0.1% (bath ratio (bath ratio (bath ratio (bath ratio of 1/1) of 1/2) of 1/4) of 1/8) Example 4 6.9 6.9 6.8 6.4 Example 5 7.3 7.2 7.1 6.9 Comparative 6.7 6.3 6.0 5.7 Example 1 From the foregoing results, it will readily be understood that the cationic polyvinyl acetate emulsions prepared in the foregoing Examples of the present invention are selectively adsorbed and stuck onto fibers which are negatively charged in water during the fabric stiffening treatment.Although conventional nonionic or anionic polyvinyl acetate emulsions should be used in large quantities because of such selective adsorbing property to fibers, when the cationic polyvinyl acetate emulsions according to the present invention are used, the amounts of the starches can be reduced to 1.2 to 1/8.

When the treatment was similarly carried out by using the cationic polyvinyl acetate emulsions prepared in Example 6, it was found that they were superior to the conventional products with respect to both the amount of the adsorbed and stuck.polymer and the hardness of the treated cloth.

Test 3.

A fabric stiffening treatment was carried out by using the cationic polyvinyl acetate emulsions prepared in Examples 4 and 5, and the starch hardness of the treated clothes were determined.

A desized sample cloth (60-count cotton broadcloth) was wetted with about 17 g of water and dehydrated for 1 minute by a dehydration machine. About 500 g of a dilution of the cationic polyvinyl acetate emulsion composition was charged in a Terg-O-Meter and agitated. Then, the sample cloth was put into the dilution, stirred at 60 rpm for 3 minutes and dehydrated for 1 minute by a dehydrating machine. Then, the sample cloth was air-dried, pressed at 1300C for 1 minute and sprinkled by spraying. The hardness was measured according to the cantilever method ofJIS-1005-1959 to obtain results shown in Table 9.

Table 9.

Hardness (cm) of Polyvinyl Acetate Emulsion-Treated Cloth (According to cantilever method*) Starch Concentration 0.02% 0.03% 0.05% 0.1% (bath ratio (bath ratio (bath ratio (bath ratio of 1/30) of 1/30) of 1/30) of 1/30) Example 4 5.8 6.2 6.9 8.4 Example 5 6.0 6.5 7.4 8.8 Comparative Example 1 5.3 5.4 5.5 5.9 Comparative Example 2 5.6 5.8 6.2 7.0 Cantilever Method*.

According to JIS 1005-1959, a specimen, each having a length of 15 cm and a width of 2.5 cm, were collected from one sample cloth, and each specimen was in agreement with the base line of a scale. According to an appropriate method, the specimen was slid toward the inclined face and when one end of the specimen fell into contact with the inclined face, the position of the other end was read from the scale. The hardness of the fabric was expressed in terms of an average value of the values thus detern.ined with respect to the 5 specimens.

Test 4.

In the same manner as described in Test 2, the fabric stiffening treatment was carried out by using the cationic vinyl acetate emulsion composition sample No. 76 prepared in Example 6, and the hardness of the treated cloth was determined according to the method of JIS 1005-1959. For comparison, the polyvinyl acetate emulsion prepared in Comparative Example 1 was similarly tested. Obtained results are shown in Table 10.

TABLE 10 Hardness (cm) of Polyvinyl Acetate Emulsion-Treated Cloth (according to cantilever method) Concentration 0.1 % 0.2% 0.4 % 0.6 % 0.8 % (bath (bath (bath (bath (bath ratio ratio ratio ratio ratio Sample Cloth Starch of 1/4 of 1/4 of 1/4 of 1/4 of 1/4 60-Count Sample 6.4 7.2 8.6 9.3 9.6 Cotton No. 7 - 6 Broadcloth ditto Comparative 5.6 6.2 6.8 7.5 7.8 Example 1 80-Count Sample 6.4 6.8 7.3 7.7 8.0 Broadcloth of No. 7 - 6 65% Polyester and 35% Cotton ditto Comparative 5.9 6.1 6.6 7.0 7.1 Example t Example 7.

According to the method described in Example 4, cationic polymer emulsions were prepared by using 0.4 g of a cationic surface active agent and 0.3 g of poly(methacryloxyethyltrimethyl ammonium chloride) (having a viscosity of 200 centipoises as measured at- 200C with respect to a 1% aqueous solution). As the cationic surface active agent, various cationic surface active agents differing in the total number of carbon atoms of the alkyl groups were employed separately. By using the so prepared cationic polymer emulsions, the treatment of sample clothes (60-count cotton broadclothes) was carried out in the same manner as described in Test 2, and the amounts of the adsorbed and stuck stiffening compositions were measured.The relation between the sum of carbon atoms in the alkyl groups and the relative adsorbed amount (calculated ba.sed on the assumption that the adsorbed amount of the composition of Comparative Example I is 1.0) is shown in Fig. l, in which 1 to 6 show data when the following cationic surface active agents were used: 1 : lauryltrimethyl ammonium chloride 2 : stearyltrimethyl ammonium chloride 3 : trioctylmethyl ammonium chloride 4 : dilauryldimethyl ammonium chloride 5 : dimyristyldimethyl ammonium chloride 6: distearyldimethyl ammonium chloride From the results shown in the drawing, it is seen that as the total number of carbon atoms in the alkyl groups of the cationic surface active agent, the adsorbing property is higher. When the sum of carbon atoms in the alkyl groups is smaller than 25, the adsorbent property of the cationic polymer emulsion is inferior to that of the anionic polymer emulsion, but when the sum of carbon atoms in the alkyl groups is 25 or larger, the adsorbing property of the cationic polymer emulsion is much superior to that of the anionic polymer emulsion.

Comparative Example 3.

Vinyl acetate was emulsion-polymerized in the same manner as described in Example 4 except that cationic starch (degree of substitution = 0.3, viscosity of 2% aqueous solution = 450 centipoises) was used instead of the polyvinyl alcohol used in Example 4. The particle size of the resulting emulsion was about I u, and the viscosity was 3110 centipoises as measured at 300C. When this polymer emulsion was stored at 500C for 30 minutes, the polymer emulsion was gelled and the phase separation was caused. The polymer was solidified and could not be dispersed again, and the polymer was yellowed.

Example 8.

In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 8 parts of polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) was dissolved in 130 parts of deionized water at 800C. After the solution was cooled to 40"C, 0.5 part of poly(N,N-dimethyl-3,5-methylenepiperidium chloride) (viscosity = 30 centipoises (as measured with respect to 1% aqueous solution), 0.5 part of distearyldimethyl ammonium chloride and an aqueous solution of I part of sodium carbonate in 10 parts of deionized water were added to the solution, and air in the flask was replaced by nitrogen.Then, 10 parts of monomeric vinyl acetate and 0.1 part of methacryloxyethyltrimethyl ammonium chloride were added to the charge of the flask, and a polymerization initiator comprising 0.1 part of 2,2'azobis(2-amidinopropane) hydrochloride and 10 parts of deionized water was added and the temperature was elevated to 700C to initiate the polymerization.

Over a period of 100 minutes from the point at which 10 minutes had passed from the initiation of polymerization, 90 parts of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for I hour at 80"C to complete emulsion polymerization. When the particle size of the resulting emulsion was measured by an optional microscope, it was found that the average particle size was about 1 ,u. The solid content was 45.7%.

A fabric stiffening composition was prepared by adding 2 parts of dibutyl adipate, 4 parts of ethanol, 0.5 parts of a silicone emulsion (30% emulsion of 10000 centistoke silicone oil) and 3.5 parts of deionized water to 90 parts of the so prepared emulsion. This composition is designated as "composition S".

Example 9.

A 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen-introducing device was charged with 80 parts of a 10% aqueous solution of hydroxypropyl cellulose, and 58 parts of deionized water, 0.5 part of a cationic surface active agent of the following formula:

1 part of a quaternary cationic polymer (JR-l25) and an aqueous solution of 1 part of disodium phosphate in 10 parts of deionized water were added to the charge of the flask. Then, a portion (10 parts) of a mixture of 55 parts of ethyl acrylate and 45 parts of methyl methacrylate and 0.1 part of cumene hydroperoxide were added to the charge of the flask, and air in the flask was replaced by nitrogen gas. Then, the temperature was elevated to 600C to initiate polymerization.Over a period of 100 minutes from the point at which 5 minutes had passed from the start of polymerization, the remainder (90 parts) of the above monomer mixture was continuously added. After completion of the continuous addition, aging was conducted at 80"C for 1 hour to complete emulsion polymerization. The resulting polymer emulsion was used as a starting material of a household fabric stiffening composition.

WHAT WE CLAIM IS: 1. A fabric stiffening composition comprising an emulsion prepared by emulsion-polymerizing a vinyl or vinylidene monomer (other than such a monomer that can form a salt by reaction with an alkali) in an aqueous solution containing 20 to 60% by weight of said monomer and 0.5 to 10% by weight of polyvinyl alcohol, nonionic modified starch (as herein defined) or a nonionic cellulose derivative in the presence of 0.05 to 3% by weight of a cationic vinyl polymer or a ring-closed polymer (as herein defined) of a cationic diallyl compound and up to 5% by weight

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. was stored at 500C for 30 minutes, the polymer emulsion was gelled and the phase separation was caused. The polymer was solidified and could not be dispersed again, and the polymer was yellowed. Example 8. In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen-introducing device and a metering dropping device, 8 parts of polyvinyl alcohol (completely saponified product, degree of polymerization = 1800) was dissolved in 130 parts of deionized water at 800C. After the solution was cooled to 40"C, 0.5 part of poly(N,N-dimethyl-3,5-methylenepiperidium chloride) (viscosity = 30 centipoises (as measured with respect to 1% aqueous solution), 0.5 part of distearyldimethyl ammonium chloride and an aqueous solution of I part of sodium carbonate in 10 parts of deionized water were added to the solution, and air in the flask was replaced by nitrogen.Then, 10 parts of monomeric vinyl acetate and 0.1 part of methacryloxyethyltrimethyl ammonium chloride were added to the charge of the flask, and a polymerization initiator comprising 0.1 part of 2,2'azobis(2-amidinopropane) hydrochloride and 10 parts of deionized water was added and the temperature was elevated to 700C to initiate the polymerization. Over a period of 100 minutes from the point at which 10 minutes had passed from the initiation of polymerization, 90 parts of monomeric vinyl acetate was continuously added. After completion of the continuous addition, aging was conducted for I hour at 80"C to complete emulsion polymerization. When the particle size of the resulting emulsion was measured by an optional microscope, it was found that the average particle size was about 1 ,u. The solid content was 45.7%. A fabric stiffening composition was prepared by adding 2 parts of dibutyl adipate, 4 parts of ethanol, 0.5 parts of a silicone emulsion (30% emulsion of 10000 centistoke silicone oil) and 3.5 parts of deionized water to 90 parts of the so prepared emulsion. This composition is designated as "composition S". Example 9. A 5-neck separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen-introducing device was charged with 80 parts of a 10% aqueous solution of hydroxypropyl cellulose, and 58 parts of deionized water, 0.5 part of a cationic surface active agent of the following formula:

of a cationic surface active agent and/or up to 2% by weight of a cationic monomer, and 0.01 to 5%, based on the weight of the vinyl or vinylidene monomer, of a polymerisation initiator, all other said percentages being based on the weight of the emulsion.

2. A fabric stiffening composition as set forth in Claim 1, wherein the viscosity of the cationic vinyl polymer or the ring-closed polymer of the cationic diallyl compound is 3 to 500 centipoises as measured at 200C with respect to a 1% by weight aqueous solution.

3. A fabric stiffener composition as set forth in Claim 2, wherein the ringclosed polymer of the cationic diallyl compound comprising repeating units of the general formula:

wherein R, and R2, which may be the same or different, stand for alkyl or substituted groups having 1 to 2 carbon atoms in the alkyl moiety, X stand for an anion.

4. A fabric stiffening composition as set forth ih Claim 2, wherein the cationic vinyl polymer comprises repeating units of the formula:

wherein R3 stands for hydrogen atom or a methyl group, R4, R5 and R8, which may be the same or different, stand for hydrogen atoms or alkyl or substituted alkyl groups having I to 4 carbon atoms in the alkyl moiety, A stands for an oxygen atom or a nitrogen in an amide linkage, m is an integer of from I to 10, X stands for an anion.

or by repeating units of the general formula:

wherein R7 R5 and R9, which may be the same or different, stand for hydrogen atoms, or alkyl groups or substituted alkyl groups having i to 2 carbons atoms in the alkyl moiety, X stands for anion.

5. A fabric stiffening composition as set forth in any preceding Claim, wherein the cationic surface active agent is represented by the general formula:

wherein R,,, RX1, R,2 and R13, which may be the same or different stand for hydrogen atoms, alkyl groups having at least one carbon atoms or hydroxyalkyl groups having at least I carbon atom with the proviso that the sum of carbon atoms in these groups is from 25 to 50, and X stands for an anion.

6. A fabric stiffening composition as set forth in any of Claims I to 4, wherein the cationic surface active agent is represented by the general formula:

wherein R,4 stands for an alkyl group or substituted alkyl group having at least

8 carbon atoms in the alkyl moiety, R,s and Rte, which may be the same or different, stand for alkyl groups or substituted alkyl groups having at least one carbon atoms in the alkyl moiety with the proviso that the sum of carbon atoms of the groups Ria, R1s and R,5 is from 25 to 50, 1 is 2 or 3, X stands for an anion, and R,s and R16 may form a ring with the N atom, or docosyl pyridinium.

7. A fabric stiffener compositon as set forth in any preceding Claim, wherein the cationic monomer has at least one nitrogen atom and at least one double bond.

8. A fabric stiffener composition as set forth in Claim 7, wherein the cationic monomer is represented by the general formula:

wherein R,7 stands for a hydrogen atom or a methyl group, R15, R,g and R20, which may be the same or different, stand for hydrogen atoms or alkyl or substituted alkyl groups having 1 to 22 carbon atoms in the alkyl moiety, X stands for an anion, k is an integer of from 1 to 10, A stands for an oxygen atom or a nitrogen atom of an amide linkage, and R,8, R,g and R20 may together form a ring with the N atom, or by the general formula: :

wherein R2, stands for a hydrogen atom or a methyl group, R22, R23 and R24, which may be the same or different stand for hydrogen atoms or alkyl groups or substituted alkyl groups having 1 to 2 carbon atoms in the alkyl moiety, and X stands for an anion.

9. A fabric stiffener composition in accordance with Claim I and substantially as herein described with reference to the accompanying drawing.