US3032442A - Process of finishing textiles with silicone-colloidal melamine resin mixtures, composition and resultant article - Google Patents

Description

United States Patent C) of Maine No Drawing. Filed Apr. 15, 1955, Ser. No. 501,741 19 Claims. (Cl. 117-139.4)

This invention relates to mixtures of organo polysiloxanes with positively charged colloidal solutions of partially polymerized aminotriazine-aldehyde condensation products, to the treatment of textile materials with these mixtures and to the resulting treated articles.

Textile fabrics have been impregnated with melamine resin acid colloids to provide resistance to shrinkage. However, a fairly stiff or crisp hand is produced, and this is undesirable on certain types of fabrics and for certain purposes where a soft hand is sought. The action of these colloidal resins difiers considerably from the noncolloidal melamine resins which are essentially of a monomeric nature. When a textile fabric is saturated with the noncolloidal resin, it appears that the resin particles penetrate into the interior of the individual fibers, whereas the colloidal resins seem to be deposited substantially entirely on the surface of the individual fibers. It is thought that the particle size of the partially polymerized colloidal resins is too large to permit any substantial penetration into the interior of textile'fibers. Neither type of melamine resin finish alone has any tendency to render textile fabrics water repellent. v

The use of various polysiloxanes as waterproofing agents for textiles has been proposed, but many practical diificulties have arisen, especially in connection with the curing of the silicone resin on the fabric. For example, United States Patent No. 2,612,482 describes the treatment of fabrics with a monomeric aminoplast and a mixture of organo polysiloxanes containing from 5 to 25% methyl hydrogen polysiloxane and curing these treated materials at an extremely high temperature or at a relatively high temperature in combination with aging for many hours to produce a water-repellent, crease-resistant finish. Curing such treated materials by aging for prolonged periods in the air is not commercially feasible because of the huge areas which would be required for this purpose in a modern high production textile finishing plant. On the other hand, curing at relatively high temperatures is beyond the capabilities of the drying equipment in many plants and is detrimental to certain of the more delicate fabrics.

An object of the invention is to provide improved resinous compositions.

A further object of the invention is to provide substantially permanent water repellency and improved dimensional stability in textile fabrics.

Another object of the invention is to provide a waterrepellent finish for textiles which may be converted to the water-insoluble state at moderate temperatures.

A still further object of the present invention is to provide a permanently softer hand on textile fabrics impregnated with a colloidal aminotriazine-aldehyde resin.

Still another object of this invention is to provide glazed or embossed fabrics having durable spot-resistant finishes.

Other objects and advantages of the invention will be apparent to those skilled in the art upon consideration of the detailed description hereinbelow.

The above objects and benefits are obtained with compositions which comprise an aqueous dispersion of methyl hydrogen polysiloxane, a partially polymerized colloidal cationic aminotriazine-aldehyde condensation product and between about 0.5 and about 7.0 mols of an acid per mol of the condensation product on a monomeric basis. The invention also includes the application and conversion of these compositions to the substantially water-insoluble state on fibrous materials and the resulting textile articles.

The compositions disclosed herein are suitable for the treatment of any fibrous textile material. However, the effects produced vary somewhat with the different types of textile fibers. A very high degree of substantially permanent water repellency is obtained with all textiles; that is, the water-repellent characteristics of the treated article are retained to an unusually high degree after prolonged and repeated washing and dry cleaning operations. In addition, the hand or feel of the treated fabric is markedly and unexpectedly softer in all instances than a similar specimen of the same textile material treated with methylated methylol melamine acid colloids alone since no additives are known which exert a durable softening effect on finishes produced with these colloidal resins. Improved dimensional stability is obtained with various fibrous textile materials upon following the treatment of the present invention. But again, the effect is not the same on all materials. A very considerable reduction in the shrinkage of cotton and viscose rayon is achieved, but this is somewhat less than the extremely high reduction in'shrinkage which is produced in wool. Suitable fabrics for application of the present treatment include cotton, linen, flax, ramie, viscose rayon, cuprammonium rayon, cellulose acetate, wool, silk, and the various synthetic materials containing linear superpolyamides such as nylon of both the adipamide and caprolactam types, acrylonitrile polymers and its copolymers with vinyl acetate, methyl acrylate, 2-methyl 5-vinyl pyridine, and other compatible ethylenic monomers, copolymers of vinyl chloride with vinylidene chloride, and polyesters such as polyethylene glycol terephthalate.

Aminotriazine containing two or three reactive amino groups such as melamine, N-guanyl-melamine, ammeline, formoguanamine, acetoguanamine, propioguanamine, phenylguanamine, and N-alkyl-, aryl, and aralkylsubstitued derivatives thereof such as N-methylmelamine, N-phenylmelamine, N-benzylamine, etc., which contain a hydrogen atom attached to each nitrogen atom, as disclosed in United States Patent No. 2,197,357, may be reacted with aldehydes to form the condensation products which are used for preparing the cationic colloidal resin solutions used in the present process. Methylol melamines obtained by condensing melamine with varying amounts of formaldehyde, i.e., in molar ratios of about 1:1 to 1:20, but preferably and generally of about 1:2 to 1:6, and their water-dispersible alkylated derivatives obtained by reacting the methylol melamines with lower aliphatic alcohols such as methanol and ethanol are preferred.

Aldehydes other than the fomaldehyde of the examples, such as formaldehyde-yielding materials including paraformaldehyde and hexamethylene tetramine, benzaldehyde, furfural, acetaldehyde, paraldehyde, etc., may be used.

In general, the colloidal resin component of the present invention may be produced in the manner described in United States Patent No. 2,345,543, by aging a watersoluble noncolloidal unmethylated or methylated methylol aminotriazine in the presence of an acid until the molecules of the aminotriazine compound polymerize sufficiently to reach colloidal size and exhibit the characteristic Tyndall effect under the influence of a beam of light or a darkfield microscope. A bluish haze also develops in a solution of this nature. When these colloidal particles are subjected to electrophoresis, the existence of a definite positive charge is shown by the migration of the colloidal resin toward the cathode.

Although strong mineral acids may be employed in preparing resin colloids intended for the treatment of wool, as exemplified by hydrochloric acid, sulfuric acid, and phosphoric acid, nevertheless weak acids such as saturated aliphatic monocarboxylic acids with dissociation constants between 1.4 10- and about 2.5 which have water solubilities of at least about 10% are greatly preferred, especially for the treatment of cotton and other materials which are readily attacked by strong acids. Among the recommended hydrocarbon and hydroxy hydrocarbon acids are formic, acetic, propionic, gluconic, .glycolic and lactic acids. To obtain the desired results, the acidshould be employed in a molar ratio between about 0.5 and about 7.0 mols per mol of the aminotriazine compound on a monomeric basis. Acetic acid is preferred for the purpose since it provides excellent results at low cost, and the recommended quantity is between about 2 and about 5 mols per mol of aminotriazine charged.

The polysiloxane component of the compositions described herein may be either methyl hydrogen polysiloxane or mixtures thereof with other linear or cyclic siloxanes, including decamethyltetrasiloxane, octamethyl- Cyclotetrasiloxane, octamethyltrisiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octaphenyltfisiloxane, decaethyltetrasiloxane, octabenzyltrisiloxane, methyltri(trimethylsiloxy)silane, symmetrical 1,3-hexaphenyl-2 dimethyl trisiloxane, symmetrical 1,3-hexar'r'iethyl-Q-diphenyl trisiloxane, and 1,3-hexamethyl-2- rnetliyl-Z-phenyl trisiloxane. This material should contain at least one silicon-bonded hydrogen atom per 4 silicon atoms. Numerous suitable methyl polysiloxanes are diselosed in Patnode United States Patents 2,469,888 and 2,469,890. These materials have carbon-silicon'linkages with an average ratio of from about 1.75 to about 3.0 and preferably from about 1.9 to 2.1 organic groups per silicon atom. Methyl hydrogen polysiloxane for the present purpose is a fluid which contains between 1.0 and 1.5 methyl radicals and between 0.75 and 1.25 hydrogen atoms bonded to silicon per silicon atom in the compound and the sum of the methyl radicals and the hydrogen atoms ranges from 2.0 to 2.25 per silicon atom. Compounds of this type may be produced by the hydrolysis and condensation of methyl hydrogen dichlorosilane or by cohydrolyzing and condensing that material with another chlorosilane. Although methyl hydrogen polys'iloxan'e may be the sole silicone in the present compositions, the best results are obtained with a mixture comprising from 25 to 80% of methyl hydrogen polysiloxane and the balance a methyl polysiloxane fluid containing approximately two methyl radicals per siliconatom with a viscosity which may range as high as 100,000 centistokes. Silicon mixtures of this nature are set forth in the Dennett Patent No. 2,588,365.

While no accelerator is required for the acidified colloidal aminotriazine resin component of the present agents, a conventional catalyst is necessary or at least desirable for the polysiloxane component. A wide variety of such catalysts is known, including metallic salts such as sodium aluminate, iron, cobalt, manganese, lead and zinc salts of carboxylic acids such as acetates, stearates, palmitates, arachidates, octoates, and naphthenates. In treating a textile fabric, the catalyst for the silicone may be mixed therewith in the same bath or may be applied either before or after the pad bath treatment by spraying or immersing the fabric in a solution or emulsion of the catalyst for the o rgano polysiloxane. The usual amount of such catalyst is employed; that is, from about 0.5 to

5.0% of the metal component of the salt based on the weight of the organo polysiloxane.

Thev silicone component and its catalyst are emulsified i'n'the usual'manner in water with known'a'cid-stable dispersing agents, including polyvinyl alcohol, condensates:- of nonyl phenol with ethylene oxide, polyethylene glycol tertdodecyl thioether, Pluramine 8-100 (a nonionic condensation product of fatty acids with mono-, di-, or tri-- ethanolamine and many mols of ethylene oxide) and condensation products of dimerized soya bean fatty acids;

with 273 mols of ethylene oxide to name only a few.

present treatment.

azine resin in order to avoid any tendency toward gelling the colloid when the aminotriazine resin concentration of The resulting mixture the mixture exceeds about 8%. has ample stability for commercial purposes.

While primarily intended for the treatment of textile materials, the compositions of the present invention are appropriate for other purposes, including the manufacture of strong waterproof papers suitable for large shipping: bags, etc., and the treatment of ropes and fish nets. Such: treatment increases the .life of manila hemp and other vegetable fibers for marine use by rendering them water resistant.

The present treatment is particularly effective in pro ducing water-repellentsoft finishes on fabrics composed.

of substantial proportions of cotton, viscose rayon, cu-- prammonium rayon, and cellulose acetate fibers, especially where a subsequent mechanical-finishing operation is employed to glaze or emboss the impregnated fabric in a: However, the present process may also be 'used with all types of fabrics including woven, knitted, felted and nonwoven oriented constructions of any textile.-

durable manner.

Although the aqueous dispersions described herein may be applied to the fabric undergoing treatment by any known method including spraying, a conventional pad bath is usually preferred. The concentration of silicone and colloidal melamine resin in the treating solution is desirably between 1 and 15%, and customarily between about 4 and 10% for maximum stability. The deposit of the impregnant onthe fabric is regulated in customary manner by selection of the bath concentration and the pressure on the squeeze rolls which remove excess solution from the fabric undergoing treatment. The deposit of silicone and.

resin on the textile material may range from 1 to 15% based on the weight of the untreated fabric, and between '4 and about 10% is recommended for most purposes in-- cluding treating materials subsequently subjected to mechanical finishing.

The impregnated material is dried in a single operation, except where a glazed or embossed finish is desired. An outstanding advantage of the present invention is the fact that the aqueous solution of the novel compositions may be converted to the water-insoluble state by merely drying the treated material at the relatively low temperatures which are obainable in any textile finishing plant with conventional drying equipment. Actually, temperatures as low as 65 F. are operative; but they are too slow for most commercial usage. This conversion is preferably accomplished at temperatures extending from to 250 F. in from 30 seconds to 30 minutes, and the range between 200- and 225 F. is especially recommended. Higher temperatures may also be employed in the drying apparatus ranging up to about 350 F. for conventional equipment or up to about 900 F. for radiant-heating apq paratus. However, no benefits appear to be gained by this more severe and costly operation which may result in the tendering of the fabrics, especially those of a more delicate nature.

An excellent glazed or embossed finish is readily procurable on the treated cloth by the use of the customary embossing calender or a glazing or friction calender. Such operations are carried out with a partially dried textile material having a moisture content between 1 and 30%, and the optimum range is between 4 and 12%. One or more of the rolls of such calenders may be heated preferably to temperatures between about 300 and about 600 F. After passage through the calender, the fabric is substantially completely dried in the manner described hereinabove, except that less time is required in view of the low moisture content of the material. Other compatible textile-treating compositions may be employed with the mixtures described herein either in the same treating bath or as separate baths or sprays; for example, aluminum phosphate, titanium dioxide, silicon dioxide, and aluminum oxide.

For a better understanding of the nature and objects 6 in. The controls are untreated fabrics which are identical of those employed in the various examples. The results of these tests are set forth in Tables 1 and 2 below.

EXAMPLE II Using a piece of 80 x 80 cotton print cloth, Example I is duplicated in all respects except for the type of laundering operation.

EXAMPLE A The treatment of Example I is repeated using a pad bath which consists only of aqueous colloidal resin C diluted with an equal weight of water to produce a bath containing 5% resin solids. Another sample of the same rayon fabric is padded through this bath with an 80% expression and dried in the same fashion.

EXAMPLE B Example A is repeated with the substitution of a sample of the 80 x 80 cotton print cloth of Example II.

Table 1 Fabric AATCC Spray Ratings After 3 Dry Cleanings After 21 Dr: Cleanings Hand After 12 rayon Washes After one Sanforized Wash (cotton) After Int 3 tial rayon Washes Rayon Cotton. Rayon Cotton" Soft... .do Stiff.-. do...

therein.

EXAMPLE I Silicone emulsion A is prepared by adding parts by weight of 95% polyethylene glycol tertdodecyl thioether (reaction product of 9.1l0.3 mols of ethylene oxide per mol of tertdodecyl mercaptan) to parts of water; then 70 parts of methyl hydrogen polysiloxane are emulsified therein by slow addition with vigorous stirring. Sulficient sodium bisulfate is introduced to lower the pH to 3.5.

Silicone catalyst solution B is made up by adding with moderate stirring a solution of 12.8 parts of zinc 2-ethyl hexoate (zinc octoate) in 67.2 parts of mineral spirits into a solution of 5 parts by weight of 95% polyethylene glycol tertdodecyl thioether and 15 parts of water.

Colloidal melamine resin C is prepared by dissolving 100 parts of 80% aqueous methylated trimethylol melamine prepared in accordance with Example 2 of British Patent No. 566,347 in 642.4 parts of water at about 85 F. with thorough stirring; then 57.6 parts of glacial acetic acid is slowly introduced with constant stirring, and the mixture is allowed to age from 12 to 16 hours at 70 to 90 F. The resulting solution contains 10% resin solids by weight and may be diluted with cold water as desired.

The pad bath is made up by adding 5.4 parts of Ernulsion A and 1.2 parts of solution B to 50 parts of solution C in 43.4 parts of water with suitable mixing. A viscose rayon is passed through this bath with sufiicient pressure on the pad roll to give an expression (wet pickup) of 80% based on the fabric weight. The impregnated fabric is then dried for 4% minutes in a ventilated oven maintained at 225 F. The cloth is found to have an add-on of 3% polysiloxane and 4% of melamine resin based on the untreated fabric weight. Shrinkage and AATCC spray rating (water-repellency) tests are made before and after washing and dry cleaning the treated material.

The laundering of rayon is carried out according to test method 40-52 in the 1952 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, while the washing of cotton employed in succeeding examples follows test method 14-52 there- The shrinkage tests are made after the rayon is subected to three rayon washes, andcotton is subjected to one sanforized wash.

Table 2 Percent Percent Example Fabric arp Filling Shrinkage Shrinkage Control Untreated Rayon. 13 1 Do Untreated Cotton. 5. 5 2. 5 I Rayon 6. 5 1. 5 II. Cotton 2. 5 0.5

Silicone emulsion D is prepared by stirring 2.0 parts of polyvinyl alcohol as an emulsifier and 8.0 parts of xylol into 50.0 parts of water and then adding 40.0 parts of a mixture of 40 to 50% methyl hydrogen polysiloxane and 50 to 260% dimethyl polysiloxane.

A silicone catalyst solution E is made up of 2.0 parts of Pluronic L-64 (a condensate of polypropylene glycol and polyethylene glycol), 1.0 part of polyethylene glycol 600 monooleate, 22.0 parts of water and 75.0 parts of a solution of zinc octoate in mineral spirits having an 8% zinc content by weight.

Colloidal methylated trimethylol melamine resin solution F containing 10% solids is prepared similarly to resin solution C, except that 24 parts lactic acid are substituted for the acetic acid therein, and 676 parts water are used.

EXAMPLE III A pad bath is made by stirring 5.8 parts of the silicone emulsion D and 08 part of catalyst solution E into 53.3 parts of the colloidal melamine resin solution F mixed with 41.1 parts of water. A fabric woven from polyethylene glycol terephthalate fibers is padded therethrough with the squeeze rolls adjusted to provide for an expression of about 60% for an add-on of 3.2% of the colloidal resin and 1.4% of the polysiloxane based on the dry weight of untreated fabric. The treated material is subjected to five minutes of drying in an apparatus operating at 225 F. The initial water repellency of this cloth is found to be by the AATCC spray rating method; whereas an untreated swatch of the same fabric is found to have a rating of 0. i

p of colloidal resin solution F in 50.0 parts of water.

EXAMPLE C The procedure of Example III is duplicated exactly, with the substitution of the same quantity on a dry basis of a non-colloidal methylated trimethylol melamine resin in place .of the colloidal resin. Again the drypickup is 3.2% melamine resin solids and 1.4% of the organo polysiloxane. After the same heat treatment, .the treated fabric is found to have an initial spray rating of 0.

EXAMPLE IV A treating bath is prepared from 8.8 parts of silicone emulsion D, 1.2 parts of catalyst solution B, and 80.0 parts of the colloidal resin solution F in 10.0 parts of water. The method of Example III is followed in general, but the pad rolls are set for a dry pickup of 4.8% colloidal resin and 2.1% of the mixed polysiloxanes on a different fabric woven from staple fibers of a copolymer of acrylonitrile with about 6.0% methyl acrylate. After drying, the treated material is found to have an initial AATCC spray rating of 90 in contrast to a rating of for an untreated swatch of the same fabric.

EXAMPLE V A textile treating dispersion is prepared by introducing 3 parts of silicone emulsion D and 0.4 part of accelerator solution E with stirring into 100 parts of colloidal resin solution F. A woolen suiting fabric is padded through this bath with the squeeze rolls adjusted for 90% expression. The impregnated fabric is dried in an oven maintained at 225 F. for 9 minutes to width andpartly released in the warp. The resulting fabric bears 9% of the colloidal aminoplast and 1.1% of the organo polysiloxane based on the untreated fabric weight. It is dollywashed in an aqueous solution containing 0.012% sodium dodecyl toluene sulfonate and 0.024% of the reaction product of tertbutyl mercaptan with about 12 mols of ethylene oxide for five minutes and then rinsed for five minutes before drying. No softener is employed. The treated material is subjected to AATCC spray rating tests and also to shrinkage tests both initially and after AATCC Wool washes, as described in AATCC tentative test method No. 41-52. The results appear in Table 3 below.

EXAMPLE v1 The procedure of Example V is in all respects duplicated, except for omitting the step of dollywashing. It is found that the hand of the fabric is sufficiently soft and pleasing to obviate any need for a processor rope washing step. Table 3 contains the test results.

EXAMPLE VII The same cloth is treated according to Example VI using a different pad bath containing 3 parts of silicone emulsion D, 0.4 part of catalyst solution E, and 50 parts The wet pickup amounts to 98% here, and the treated fabric carries 4.9% of the melamine resin and 1.2% of mixed polysiloxanes based on the dry weight of untreated cloth. This material is also found to have a pleasant soft hand, and the shrinkage characteristics are set forth in Table 3 below.

EXAMPLE VIII The procedure of Example VI is repeated with another agent prepared by mixing 2.0 parts of silicone emulsion D and 0.26 part of catalyst solution E into 30.0 parts of colloidal resin solution F and 70.0 parts of water. The resin deposited on the suiting amounts to 2.7% of the melamine acid colloid and 0.7% of the organo polysiloxanes. The finished material has a soft and pleasant hand. The shrinkage test data tabulated indicate that even this light treatment reduces shrinkage to a considerable extent.

From the results set forth in Examples VI to VIII and Table 3, it is apparent that treating textiles with compositions containing both colloidal aminotriazine resins and organo polysiloxanes produce not only a high degree of water repellency and spot resistance but also excellent shrinkage control and a hand sufficiently soft to permit omitting both the softening additive and the process wash customarily employed with melamine acid colloid treatments.

EXAMPLE IX 'Into 40.6 parts of water and 2.5 parts of a 50% polyvinyl acetate dispersion are stirred 3.6 parts of silicone emulsion A and 0.8 part of catalyst solution B and 62.5 parts of colloidal melamine resin solution C to form a pad bath. An x 80 cotton print cloth is padded through the mixed resin solution with the squeeze rolls set for an 80% wet pickup. The treated cotton fabric is partially dried in equipment maintained at 225 F. until the moisture content is reduced to 8 to 10%. Then it is fn'ction-calendered by one pass between calender rolls with the nip pressure maintained at. 20 tons and thetop roll heated to 350 F. One sample of the treated fabric is then dried for five minutes in equipment operating at 225 F., and another sample is subjected to a 6-minute cure in an apparatus maintained at 300 F. The add-on amounts to 1.6% of the polysiloxane and 4.6% melamine resin on a dry basis. The material dried at 225 F. is found to have AATCC spray rating of initially, 70 after a Sanforized wash at F., and 80 after three dry-cleaning operations. It has an excellent durable gloss which produces readings of 22 initially on a 45 Hunter glossmeter and 17 after a Sanforized wash in contrast with a reading of 3 for the untreated fabric. Substantially identical results are obtained with the treated cloth cured at 300 F.; hence, no advantages appear to be gained by the more severe heat treatment.

EXAMPLE X Example IX is repeated with an all viscose gabardine suiting fabric. Similar results are obtained.

EXAMPLE XI Exampe I is repeated using an aqueous colloidal dimethylol melamine resin of equivalent resin: acid molar ratio and resin solids content prepared in the same manner with 60 parts of spray-dried dimethylol melamine, 43.2 parts of glacial acetic acid, and 496.8 parts of water. The results obtained in treating the same viscose rayon fabric are similar to those obtained in Example I.

While there are above disclosed only a limited-number of embodiments of the compositions, process, and prodnet of the invention herein presented, it is possible to produce still other embodiments without departing from the inventive concept herein disclosed; and it is desired, therefore, that only such limitations be imposed on the appended claims as are stated therein or required by the prior art.

What I claim is:

1. A composition of matter which comprises an aqueous dispersion of 1 part by weight of a polysiloxane including a fluid methyl hydrogen polysiloxane having between 1.0 and 1.5 silicon-bonded methyl radicals and between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total of between 2 and 2.25 of said silicon-bonded radicals and atoms per silicon atom; between 0.5 and 14 parts of a partially polymerized colloidal cationic aminotriazinealdehyde condensation product and between about 0.5 and about 7.0 mols of an acid per mol of the condensation product on a monomeric basis.

2. A composition according to claim 1 in which a hydrogen atom is linked to at least about 25 percent of the silicon atoms.

3. A composition according to claim 1 in which the acid has a dissociation constant between about 1.4 10" and about 2.5 X and is selected from the group consisting of water-soluble hydrocarbon and hydroxy hydrocarbon acids.

4. A process -for finishing textile materials which comprises applying a composition according to claim 1 to a textile material and drying the treated material to convert the finish to the substantially water-insoluble state.

5. A process for finishing textile materials which comprises applying a composition according to claim 1 in which a hydrogen atom is linked to at least about 25 percent of the silicon atoms to a textile material and drying the treated material to convert the finish to the substantially water-insoluble state.

6. A process for finishing textile materials which comprises applying to a textile material composition according to claim 1 containing an acid of the group consisting of water-soluble hydrocarbon and hydroxy hydrocarbon acids with dissociation constants between about 1.4x 10-- and about 2.5x 10" and drying the treated material to convert the finish to the substantially water-insoluble state.

7. An article which comprises a textile material bearing the substantially water-insoluble reaction product of the composition of claim 1.

8. An article which comprises a textile material bearing the substantially water-insoluble reaction product of a composition according to claim 1 in which a hydrogen atom is linked to at least about 25 percent of the silicon atoms.

9. A composition of matter which comprises an aqueous dispersion of 1 part by weight of a polysiloxane including a fluid methyl hydrogen polysiloxane having between l.0 and 1.5 silicon-bonded methyl radicals and between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total of between 2 and 2.25 of said silicon-bonded radicals and atoms per silicon atom; between 0.5 and 14 parts of a partially polymerized colloidal cationic methylated methylol melamine and between about 0.5 and about 7.0 mols of a water-soluble acid per mol of methylated methylol melamine on a monomeric basis, said acid having a dissociation constant between about 1.4 10"' and about 2.5 1O" and being selected from the group consisting of hydrocarbon and hydroxy hydrocarbon acids.

10. A process for finishing textile materials which comprises applying a composition according to claim 9 to a textile material and drying the treated material to convert the finish to the substantially water-insoluble state.

11. An article which comprises a textile material bearing the substantially water-insoluble reaction product of a composition according to claim 9.

12. A composition of matter which comprises an aqueous dispersion of 1 part by weight of a polysiloxane including a fluid methyl hydrogen polysiloxane having between 1.0 and 1.5 silicon-bonded methyl radicals and between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total of between 2 and 2.25 of said silicon-bonded radicals and atoms per silicon atom; between 0.5 and 14 parts of a partially polymerized colloidal cationic methylol melamine and between about 0.5 and about 7.0 mols of a water-soluble acid per mol of methylol melamine on a monomeric basis, said acid having a dissociation constant between about 1.4x l0- and about 2.5 10 and being selected from the group consisting of hydrocarbon and hydroxy hydrocarbon acids.

13. A process for finishing textile materials which comprises applying a composition according to claim 12 to a textile material and drying the treated material to convert the finish to the substantially water-insoluble state.

14. An article which comprises a textile material bearing the substantially water-insoluble reaction product of a composition according to claim 12.

15. A composition of matter which comprises an acidic aqueous dispersion of 1 part by Weight of a methyl polysilo-xane mixture containing between about 25 and about percent of a fluid methyl hydrogen polysiloxane having between 1.0 and 1.5 silicon-bonded methyl radicals and between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total of between 2 and 2.25 of said siliconbonded radicals and atoms per silicon atom; between 0.5 and 14 parts of a partially polymerized colloidal cationic methylated trimet-hylol melamine and between about 0.5 and about 7 mols of acetic acid per mol of the melamine ether on a monomeric basis.

16. A textile finishing process which comprises treating a textile material with a sufficient quantity of a composition according to claim 15 to deposit a total of at least about 1 percent of the polysiloxane and the melamine resin thereon based on the dry weight of the material and drying the treated textile material at a temperature between about and about 250 degrees Fahrenheit to convert the finish to the substantially waterinsoluble state.

17. A textile finishing process which comprises treating a textile material with a sufiicient quantity of the composition of claim 15 to deposit thereon a total of between about 4 and about 10 percent based on the weight of the dry untreated textile material, partially drying the treated material to a moisture content between about 4 and about 12 percent by weight, mechanically finishing the partially dry textile material under heat and pressure, and substantially completely drying the mechanically finished textile material to convert the finish to the substantially water-insoluble state.

18. An article which comprises a mechanically finished textile material prepared according to the process of claim 17.

19. An article which comprises a textile material bearing at least about 2 percent based on the weight of the dry untreated textile material of the substantially waterinsoluble reaction product of the composition of claim 15.

References Cited in the file of this patent UNITED STATES PATENTS 2,121,005 Bener June 21, 1938 2,588,365 Dennett Mar. 11, 1952 2,612,482 Rasmussen Sept. 30, 1952 2,661,262 Folkers Dec. 1, 1953 2,757,152 Solomon July 31, 1956 2,758,946 Spalding et a1. Aug. 14, 1956

Claims (2)

1. A COMPOSITIOIN OF MATTER WHICH COMPRISES AN AQUEOUS DISPERSION OF 1 PART BY WEIGHT OF A POLYSILOXANE INCLUDING A FLUID METHYL HYDROGEN POLYSILOXANE HAVING BETWEEN 1.0 AND 1.5 SILICON-BONDED METHYL RADICALS AND BETWEEN 0.75 AND 1.25 SILICON-BONDED HYDROGEN ATOMS FOR A TOTAL OF BETWEEN 2 AND 2.25 OF SAID SILICON-BONDED RADICALS AND ATOMS PER SILICON ATOM; BETWEEN 0.5 AND 14 PARTS OF A PARTIALLY POLYMERIZED COLLOIDAL CATIONIC AMINOTRIAZINEALDEHYDE CONDENSATION PRODUCT AND BETWEEN ABOUT 0.5 AND ABOUT 7.0 MOLS OF AN ACID PER MOL OF THE CONDENSATION PRODUCT ON A MONOMERIC BASIS.

7. AN ARTICLE WHICH COMPRISES A TEXTILE MATERIAL BEARING THE SUBSTANTIALLY WATER-INSOLUBLE REACTION PRODUCT OF THE COMPOSITION OF CLAIM 1.