GB1578071A

GB1578071A - Process for treating textiles with polymers of acrylic acid and methacrylic acid esters

Info

Publication number: GB1578071A
Application number: GB5793/77A
Authority: GB
Original assignee: Chemische Fabrik Pfersee GmbH
Current assignee: Chemische Fabrik Pfersee GmbH
Priority date: 1976-02-21
Filing date: 1977-02-11
Publication date: 1980-10-29
Also published as: IT1081480B; NL7700131A; FR2343079A1; CH626219GA3; FR2343079B1

Abstract

Copolymers of alkyl acrylates and methacrylates containing 0.1 to 10% by weight of monomers having terminal free hydroxyl groups of the formula CH2=CR-COOR1 (I> and/or of the formula R2OOC-CH=CH-COOR1 (II> in copolymerised form are used in the form of solutions in organic, water-insoluble solvents in the presence of aminosilanes and/or aminosiloxanes for impregnating and coating textiles, preferably together with organometallic catalysts. In the formulae R is hydrogen or -CH3, R1 is -(CH2)n-OH, -CH2CH2-O-CH2CH2OH or -(CH2)3-O-(CH2)3-OH, n is from 2 to 4 and R2 is hydrogen or alkyl of 1 to 12 carbon atoms. The treated textiles are resistant to washing and dry cleaning, water-tight and water-repellent. These properties are further improved by using copolymers prepared in the presence of alkylhydrogenpolysiloxanes.

Description

(54) PROCESS FOR TREATING TEXTILES WITH POLYMERS OF ACRYLIC ACID AND METHACRYLIC ACID ESTERS (71) We, CHEMISCHE FABRIK PFERSEE GMBH, a joint stock company organised under the Laws of Germany of 8900 Augsburg, Faberstrasse 4, Germany, 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:- This invention relates to a process for treating textiles with polymers of acrylic and methacrylic acid esters.

Polymers which are produced by polymerization of organic monomers containing unsaturated C-C double bonds in the presence of free-radical initiators, have come into use on an exceedingly wide scale because their properties are suited to the particular purpose of application. For example, polymers of acrylic acid and methacrylic acid esters, which optionally contain incorporated therein by polymerization other monomers capable of polymerization are used inter alia for dressing leather, and for finishing or coating textiles and paper, as disclosed, for example, in "Ullmanns Encyclopadie der technischen Chemie", Verlag Urban & Schwarzenberg, Munich, 14th Volume (1963), page 273.

Preferably, when such materials are treated with these polymers, a water-tight but not a water-repelling impregnation is obtained, i.e. the water remains adhering to the impregnated fibre materials, and this, with relatively long wear and tear, leads to a gradual swelling and subsequently to destruction of the polymer and consequently to water penetrating into the interior of the fibre or to the water passing through the fibre material.

It has now surprisingly been found that a water-tight finish, which also provides water-repellant properties, may be obtained by using certain copolymers which contain hydroxyl groups and whch can be crosslinked in the presence of specific hardening agents.

According to the present invention there is provided a process for treating textile material with a copolymer containing hydroxyl groups, the copolymer being formed from 100 parts by weight of a monomer mixture comprising 0.1 to 10 parts by weight of an unsaturated hydroxy ester which has a free hydroxyl group in the end position of the alcohol moiety and a C-C double bond capable of polymerisation, an acrylic acid ester and/or a methacrylic acid ester, and optionally one or more other monomers capable of mixed copolymerization with the unsaturated monomers, the copolymer being applied to the textile in the presence of a hardening agent comprising a siloxane containing amino groups and/or a silane containing amino groups in an organic, water-insoluble solvent and the treated textile dried, and the copolymer cured.

The preferred copolymers containing hydroxyl groups for use in the invention are copolymers formed from 100 parts by weight of a monomer mixture comprising 0.1 to 10 preferably 2 to 8 parts by weight of compounds of the formula:

in which R represents a hydrogen atom or CH3 group, and R' represents -(CH2),,-OH, -CH2CH2-O-CH2CH2OH or CH2)3-OCH2b-Oll, in which n is 2 to 4 inclusive, and/or a compound of the formula: R2OOC-CH=CH-COOR1 (11) in which R2 represents a hydrogen atom or an alkyl radical containing 1 to 12 carbon atoms, and as the acrylic and/or methacrylic ester 99.9 to 80 parts by weight of compounds of the formula::

in which R3 represents an alkyl radical which is optionally branched and contains 1 to 18 carbon atoms provided that in at least 50% by weight, of the compounds of formula (III), R3 represents an alkyl radical which may be branched, containing 1 to 4 carbon atoms, and as the other monomer (IV) 0 to 10 parts by weight of monomer capable of mixed copolymerization with compounds of the formulae (I), (it), and (III).

The copolymers for use in the invention may be modified or unmodified. A certain disadvantage of the process, when using unmodified copolymers, is that the water repellency still does not satisfy all practical requirements and the resistance to dry cleaning sometimes leaves much to be desired. Also when using unmodified copolymers the "handle" of the textiles is deleteriously affected.

Consequently, modified copolymers are preferred as copolymers containing hydroxyl groups. The modified copolymers are obtained by the monomers (I) and/or (II), (III) and optionally (IV), the sum of these compounds amounting to 100 parts by weight, being copolymerized in the presence of 5 to 40 parts by weight of terminal-blocked alkyl-hydrogen polysiloxane, in which the alkyl radicals cuntain 1 to 4 carbon atoms and the ratio between the alkyl radicals bonded to silicon and the hydrogen atoms bonded to the silicon is in the range 13:1 to 1:1, and which has a viscosity of 20 to 1000 cP at 200 C.

To be understood by the expression "modified copolymers" within the terms of the specification, unless otherwise expressly indicated, are always the reaction products which are obtained, without further processing.

Examples of compounds of the formula (I) are acrylic and methacrylic acid esters which still contain free hydroxyl groups, e.g. 2-hydroxyethyl, 3hydroxypropyl and 4-hydroxybutyl acrylates or methacrylates. Methcrylic or acrylic acid esters of diethylene glycol and dipropylene glycol are also suitable.

The compounds of formula (I) are preferably polymerized into the copolymers which are employed in preference to the compounds of the formula (II), since these compounds are more easily available and therefore are less costly. Among the compounds of formula (I), the acrylic acid esters are preferred, since these latter provide a softer handle on the treated textiles.

Compounds of formula (II) include monohydroxyalkyl esters and alkylmonohydroxyalkyl esters of maleic acid and fumaric acid. Examples of maleic acid esters which can be used and whch may also be transformed into the corresponding fumaric acid esters include maleic acid monohydroxyethyl ester, maleic acid-2ethylhexyl hydroxypropyl ester, maleic acid ethyl hydroxyethyl ester and maleic acid butyl hydroxybutyl ester and also the unsymmetrical maleic acid butyl diethylene glycol ester.

The monoesters can be obtained in known manner by reaction of maleic acid anhydride with the glycol. The preparation of the diesters is also known, e.g. by reacting the maleic acid monoalkyl ester with alkylene oxides.

As well as the compounds of formulae (I) and/or (II), 80 to 99.9/o by weight of compounds of the formula (III) are polymerised into the copolymers used in the invention. These are acrylic or methacrylic acid alkyl esters, the alkyl radical containing 1 to 18 carbon atoms. Examples of such compounds included are the acrylic or methacrylic acid methyl esters, ethyl esters, butyl esters and n-octyl esters and the corresponding esters of 2-ethyl hexanol and also of l-dodecanol and octadecanol. At least 50% by weight and preferably at least 70% by weight of the monomers of formula (III), contain alkyl groups having I to 4 carbon atoms.

It is also possible for small amounts, namely up to 10% by weight and more particularly up to 5% by weight, based on the copolymer, of unsaturated compounds (IV) capable of mixed copolymerization with the compounds of formulae (I), (II) and (III) to be incorporated into the copolymers by polymerization. Examples of such compounds include styrene, vinyl toluene and acrylic acid.

The polymerization is effected in known manner in the presence of organic water-insoluble solvents and takes place in the same way as more fully explained in connection with the preparation of the modified copolymers.

The quantity of solvents is so chosen that the polymer solutions contain 30 to 60% by weight of unmodified copolymer. So that the solutions as thus prepared can also be used for the coating, the reaction is so controlled that, when polymerization has ended, the viscosity thereof is in the range from about 5000 to 35,000 cP (corresponding to 5 to 35 Pascal seconds) at 200C. In certain cases, it is preferable or necessary to remove unreacted monomers and solvent by distillation under reduced pressure or to add small quantities of solvent. Generally speaking, however, the so!utions as obtained can be used directly, both as coating medium and for impregnation of a wide range of textiles.

The monomers of formulae (I) to (IV) are used in preparing the modified copolymers. The preferred monomers and their content in the coplymers are as described above with reference to the unmodified copolymers.

All the polymerizable compounds are used in the usual industrial form.

In contrast with the unmodified copolymers, the polymerization of the modified polymers used in the invention is carried out in the presence of terminalblocked alkyl-hydrogen polysiloxanes, examples of which include ethyl-hydrogen, propyl-hydrogen and butyl-hydrogen polysiloxanes. Methyl-hydrogen polysiloxanes are the preferred compounds. Those alkyl-hydrogen polysiloxanes in which the ratio between the silicon-bonded alkyl radicals and silicon bonded hydrogen atoms is in the region of 1:1, without taking into account the terminal groups, such as the trimethylsilyl groups are preferred although alkyl-hydrogen polysiloxanes in which the ratio between the silicon-bonded alkyl radicals and the silicon bonded hydrogen atoms is larger than i:l. namely, up to 13:1, are also suitable.Products which have been prepared with the use of alkyl-hydrogen polysiloxanes in which the alkyl radical: hydrogen ratio is greater than 5:1 are less suitable for use in the invention, since the properties of the products which are advantageous for use in the invention are dependent on the hydrogen atoms bonded to the silicon present in the modified polymers. The alkyl-hydrogen polysiloxanes do not contain any hydroxyl groups or groups sensitive to hydrolysis, but they are blocked at the ends, for example by trimethylsilyl groups.

The alkyl-hydrogen polysiloxanes being used have a viscosity from 20 to 1000 cP at 20"C. Particularly preferred are methyl-hydrogen polysiloxanes which have a viscosity from 20 to 350 cP at 200 C.

The ratio between the polymerizable compounds (sum of the components (I) and/or (II), (III) and possibly (IV)) used for the reaction and the alkyl-hydrogen polysiloxanes amounts to 100 parts by weight to 5 to 40 parts by weight. Higher proportions of alkyl-hydrogen polysiloxanes do not provide any additional advantages. Since particularly good effects are obtained with a ratio of 100:5 to 20 parts by weight, it is this ratio which is especially preferred on economic grounds.

The polymerization is triggered by the usual initiators forming free radicals.

Examples of initiators include organic peroxides, e.g. dialkyl peroxides, such as diethyl peroxide, diisopropyl peroxide, di-(tert.-butyl)peroxide; dilauryl peroxide, alkyl-hydrogen peroxides, such as tert.-butyl hydro-peroxide; diacyl peroxides, such as diacetyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis-(2,4dichlorobenzoyl)peroxide; ketone peroxides, such as methyl ethyl ketone peroxide and cyclohexanone peroxide. Azo compounds, as for example azo (diisobutyronitrile), are also suitable.

Preferred initiators are those which are able to form sufficient radicals for initiating a polymerization at a temperature in the range from 50 to 1200C, optionally in the presence of a suitable solvent. Suitable examples include bis-(2,4dichlorobenzoyl)peroxide, dibenzoyl peroxide, tert-butyl peroctoate and dilauroyl peroxide. Azodiisobutyronitrile is also suitable.

The modified copolymers are preferably prepared in an organic solvent. The solvent serves three purposes: Firstly, it ensures that the reaction proceeds under controllable conditions, i.e.

avoiding any overheating with the initiation of the exothermic polymerization.

Secondly, it also influences the decomposition of the initiators into radicals and thirdly, it is ensured by the organic solvent that the reaction medium remains in a condition so that it can be satisfactorily stirred, since the viscosity of the reaction mixture increases during the reaction.

Suitable solvents include those which are water-soluble or have limited water solubility, such as dioxane, ethyl acetate and methyl ethyl ketone, and more preferably water-insoluble solvents including optionally substituted hydrocarbons, such as benzene, octane, cyclohexane, benzene, toluene, xylene and chlorobenzene. However, esters and ketones, as for example butyl acetate, methyl butyrate, methyl isobutyl ketone and many others are also suitable. Toluene has proved particularly suitable as solvent. The amount of the solvent is so chosen that the concentration of the modified copolymer (solid substance) amounts to about 30 to 60% by weight.

The reaction is carried out bv initially placing in a suitable reaction vessel a part of the compounds as listed above and capable of polymerization (components (I) and/or (II), (III) and (IV)), the alkyl-hydrogen polysiloxane and optionally the solvent, adding a part of the initiator and then heating.

It is expedient for the reaction vessel to be flushed with nitrogen before supplying the components. After the commencement of the polymerization, which can be recognized by the increasing viscosity and the rise in temperature of the reaction mixture, the remaining quantity of monomers and optionally more solvent is allowed to run in slowly. Finally, it is preferable also to add more initiator and to permit a post-reaction at elevated temperature. In the presence of a solvent, the operating procedure is usually for the reaction mixture to boil under reflux during the reaction and post-reaction. The complete reaction is terminated after about 2 to 3 hours.

After cooling viscous, clear or cloudy solutions or stable dispersions are obtained, depending on the nature and quantity of the solvent being used and the nature and quantity of the introduced monomers. The splitting of hydrogen from the alkyl-hydrogen polysiloxane during the polymerization is exceptionally small. It has been found that the final product still contains about 85 to 95% of the siliconbonded hydrogen of the introduced alkyl-hydrogen polysiloxane.

For the use of the modified copolymers in accordance with the invention, especially for coating purposes, it is expedient so to control the polymerization that these copolymers, after polymerization has ended, exhibit a viscosity from 5000 to 35,000 cP (corresponding to 5 to 35 Pascal seconds) at 200C in the concentration range from 30 to 60% by weight. This control can for example be achieved by the solvent being added in parts during the polymerization. The nature of the solvent being used and the nature and quantity of the employed initiator is significant in such control. Furthermore, it is also possible for the viscosity to be regulated after polymerization has ended, by partially distilling off or by addition of more solvent.

It is strange that the type of introduced alkyl-hydrogen polysiloxane, i.e. whether alkyl-hydrogen polysiloxanes with an alkyl radical:hydrogen ratio of 1:1 or up to 13:1 are employed, has only a relatively small influence on the viscosity of the final products. If desired the small amounts of unreacted monomers and the solvent remaining can be removed by distillation under reduced pressure. Since the modified copolymers which are obtained are employed in the form of solutions in organic solvents, such a working-up procedure is usually unnecessary.

The yields from the reaction are very high, as is clear, from the fact that in an experiment in which the operation took place without solvent, the non-volatile reaction product was obtained in a yield of 98% of the theoretical after the volatile constituents had been distilled off.

The prepared unmodified and modified copolymers with the structure as described are crosslinked on the textile material by using specific hardening agents in accordance with the process of the invention. The hardeners comprise silanes and/or siloxanes containing amino groups and are preferably used together with organometallic catalysts. As a result of the concurrent use of the organometallic catalysts, the reliability in operation is increased and above all there is also obtained a substantially improved resistance to weather influences.

Particularly preferred silanes containing amino groups are those of the formula

in which Y represents an alkyl group having I to 3 carbon atoms A represents an alkylene group with more than 2 preferably 3 or 4 carbon atoms, M represents an amino group or diaminoalkyl group, which is bonded to A by a carbon-nitrogen bond and n is0 or 1.

Examples of aminosilanes of formula (V) are: H2N(CH2)3Si(OC2H5)3 (1) H2N(CH2)3Si(OC3H7)3 (2) H2N(CH2)2NH(CH2)Si(OC2H5)3 (3) H2N(CH2)2NH(CH2)3Si(OCH3)3 (4) H2N(CH2)NH(CH2)3Si(OC2H5)3 (5)

H2N(CH2)2NH(CH2)3Si(OC3H7)3 (7) H2N(CH2)4Si(OC2H5)3 (8) H2N(CH2)6Si(OCH3)3 (9) The aminosilanes of the formula (V) are preferred since they are readily available and cause particularly advantageous effects. Other amincsilanes, however, may also be used, for example (p-aminoethoxy) propyl trimethoxysilane, (p-aminopropoxy)-butyl tributoxysilane, methyl-(B-aminopropoxy)-propyl-di- (amino-ethoxy)silane and (-aminoethoxy)propylmethyl dimethoxysilane.

Examples of siloxanes containing amino groups are the hydrolysates of the compounds of formula (V) and the cohydrolysates of these compounds with silanes, which have no amino groups, in which case, however, as regards the cohydrolysates, the proportion of the aminosilanes of formula (V) is preferably predominant.

Examples of amino-functional siloxanes are:

The siloxanes and silanes containing amino groups are preferably used in admixture with organometallic catalysts. Suitable organometallic catalysts include zinc, tin and zirconium caprylate, tin and zinc octoate, alkyl aluminates, alkyl titanates, alkyl zirconates zinc naphthenate, tin naphthenate, zirconium naphthenate, ferric naphthenate, cobalt naphthenate, zinc formate and zirconium formate, tin, zinc and zirconium acetates and also dibutyl-tin dicaprylate, dilaurate, diacetate and maleinate, dioctyl-tin diformate, dibenzoate and dicrotonate.

Tin compounds are preferred and, of these compounds dialkyl-tin dicarboxylates have proved to be particularly suitable. The tin compounds do in fact cause a particularly rapid and complete crosslinking, so that a particularly reliable operation is guaranteed when these compounds are used. The simultaneous crosslinking and thus the improvement in the effects is shown particularly clearly with the concurrent use of the dialkyl-tin dicarboxylates.

With the process of the invention, the hardener is generally used in amounts from 0.5 to 10, preferably 1 to 10% by weight, more preferably in amounts of 2 to 6% by weight, calculated on 100% copolymer. Larger quantities can of course be used in principle, but these do not provide any appreciable improvement in the effect. The hardener is preferably a mixture of 0.5 to 5 and more particularly 1 to 3% by weight of siloxanes and/or silanes containing amino groups and 0.5 to 5 and more particularly 1 to 3% by weight of organometallic catalyst, preferably a tin compound and particularly dialkyl-tin dicarboxylates, each related to 100% copolymer, which are used as hardner.

The process of the invention is carried out with solutions in an organic, waterinsoluble solvent, since such solvents are inactive with respect to the textiles which are to be finished and the treatment agents. Conventional solvents which can be used are aromatic and aliphatic hydrocarbons, such as benzines, toluene, benzene and xylene, chlorinated aliphatic and aromatic hydrocarbon, such as trichloroethylene and chlorobenzene, and esters such as butyl acetate.

Trichloroethylene has proved to be particularly suitable.

The solvent is used in varying amounts, depending on whether the textile material is to be coated, or whether impregnation is to be carried out by padding, spraying or some similar procedure. When coating, highly concentrated solutions are applied, which contain on average 35 to 85% by weight of solvent, calculated on coating composition. The amount of solvent can fluctuate and is particularly dependent on the viscosity of the copolymer which is used. The coating composition, which optionally also contains pigments, fillers and finishing agents as well as the solvent, the unmodified or modified copolymer and the hardener is preferably formulated so that it has viscosity in the range 10,000 to 60,000 cP at 20"C.

On the other hand, if impregnation is carried out, i.e. the textile material is saturated, the bath solutions contain substantially larger amounts of solvents, generally 90 to 99% by weight, calculated on the finishing bath solution.

The process according to the invention serves for the treatment of textiles, and is suitable both for coating and for impregnating textiles of all types.

When a coating technique is used the copolymers are thoroughly mixed in usual amounts from about 13.6 to 59.1% by weight, calculated on the total coating composition, in the form of their solutions with the hardening agent. White and/or coloured pigments, such as titanium dioxide, red lead, permanent white, carbon black or conventional organic and/or inorganic pigment dyestuffs and/or fillers, such as kaolin, colloidal silicon dioxide, talcum or alumina may be added and then composition applied in known manner by doctoring (e.g. with rollers or preferably pneumatic and rubber cloth doctors), brushing, printing or similar methods to the textile material which is to be treated. In practice, it is usual to operate continuously, whereas in the laboratory, the coating composition may be brushed on intermittently.With the continuous working procedure, the textile fabric, depending on material, runs at a speed of 5 to 25 m/min and, immediately after the application, is passed through a heating duct and is dried at temperatures from 100 to 1900C and optionally condensed, the residence time varying, on average between 30 seconds and 6 minutes. The application of the composition is between 5 and 100 g/m2. Lighter materials, which are processed to provide leisure clothing and rainwear or umbrellas, are given a coating of 5 to 20 g/m2. Medium weight materials, such as used for tarpaulins, sailcloth, tents and awnings, are provided with 20 to 70 g/m2, and heavier materials, such as industrial fabrics, are given a coating of up to 100 g/m2 (figures related to solid substance).It is desirable or even necessary to produce a uniform and coherent film, especially when relatively large quantities are applied and therefore it may be necessary to apply the coating in two or more operations. Most articles are only coated on one side, but articles can also be treated to provide a coating on the other side.

The materials which are coated on both sides and more particularly the materials coated on one side are frequently post-impregnated. An optimisation of the effects is achieved by this post-impregnation and, in addition, when the coating is only on one side, the other side is also provided with a finish which may preferably be water-repellent. The post-impregnation is carried out in known manner with the use of the known finishing or dressing agents, such as paraffin emulsions which contain metal salt and silicon emulsions and can also be combined with an oil-resistant, rot-proof and/or crease-resistant finish, the known finishing agents being used. The technical procedure as regards the post-impregnation is generally known. As a general rule, the material is padded and then finished by drying and condensation. The supplementary impregnation can also be carried out before the coating.

When impregnation techniques are used to treat the textiles 4 to 100 g/l (higher quantities not advisable on economic grounds), more especially 5 to 40 g/l of the 100% unmodified or modified copolymer are dissolved, the amount usually depending on the liquor absorption and the required effect, together with the hardener, in the organic-water insoluble solvent. Treatment of the textile is carried out in the usual manner by immersion and wringing-out (slop-padding), padding or spraying. Drying then takes place and, depending on the treated material, condensation is carried out for a few seconds up to minutes at 120 to 1900C.

The coating compositions and the finishing solutions can also contain other substances suitable for the treatment of textiles and consisting of organic, waterinsoluble solvents, such as dressing agents e.g. polyurethanes and silicone elastomers, optionally in the form of their solutions in organic, water-insoluble solvents.

The process of the invention is suitable for the treatment of textiles of all types, in the form of woven or knitted fabrics or fleeces. These textiles can be manufactured both from cellulose fibres and from man-made fibres, such as polyacrylonitrile, polyamide, polyvinyl alcohol or polyester. Textile materials which consist of mixtures of cellulose fibres with man-made fibres may also be treated. Easily made-up woven fabrics, such as taffeta, or easily made-up poplin materials, can be given a weather-resistant, water-tight and water-repellant finish by the process of the invention. This is important for rainwear, such as anoraks and the like. Because of the weather resistance of the finish, the present process is also particularly suitable for the treatment of materials for awnings and camping articles.

Using the process of the invention, textiles may be obtained which show simultaneously water-repellent and, particularly as a result of coating, water-tight properties. When using the modified copolymers, the water-repelling action is particularly pronounced. These properties are surprisingly resistant to weather influence, dry cleaning and washing. The permanence of the effects against dry cleaning is noticeably improved when the modified copolymers are used. In addition, with process of the invention, a finish or dressing with a filling action is imparted to the treated textiles. This dressing provides for improved crease resistance, and improvement in the handle and a reduced pilling formation. A particular advantage with the use of the modified copolymers is in the handle of the treated textile, because the finished textiles have a very pleasing "feel", which which is very similar to that of the typical "silicone feel". It must be surprising that these effects are obtained by the process of the invention, since in the process finishing is carried out using polymers and such polymers are generally unsuitable for producing water-tight and water-repelling properties.

The preparation of the unmodified or modified copolymers used in the invention will be illustrated by the following preparations.

Preparation A.

A 2-litre, four-necked spherical flask, fitted with an efficient anchor-type stirrer device, a reflux condenser, thermometer and two supply vessels was powerfully flushed with nitrogen and 100 ml of a mixture of 240 g of methyl acrylate, 120 g of ethyl acrylate, 32 g of 2-ethylhexyl acrylate, 8 g of 2-hydroxyethyl acrylate and 45 g of toluene, in which are dissolved 0.19 g of benzoyl peroxide were introduced and the flask heated to 80 to 820 C. The residual monomers were initially placed in the supply vessel I. Supply vessel II was charged with 455 g of toluene.

After the commencement of the polymerization, which was recognized from the initiation of reflux and increasing viscosity of the flask contents, the temperature rose to 90 to 929C. At this temperature and with constant reflux, the residual monomer mixture was added over a period of 20 to 30 minutes. The viscosity was prevented from rising above the range at which stirring could take place by addition of toluene. After completing the supply of monomers, 0.56 g of benxylol peroxide, dissolved in 100 g of toluene, were added slowly and the remaining quantity of toluene added dropwise at relux temperature.Further stirring of the batch was carried out for about 1+ hours under weak relux, until the temperature reached about 108"C. After cooling, about 1 kg of a clear solution with about 40% by weight of solid substance and a viscosity of about 25,000 cP (measured with the Brookfield viscosimeter, type RVF, Spindle C, 10 r.p.m.) was obtained.

Preparation B.

Using the method described in Preparation A, 80 g of methyl acrylate, 240 g of butyl acrylate, 72 g of 2-ethylhexyl acrylate, 6 g of 2-hydroxyethyl acrylate and 2 g of methacrylic acid ester of diethylene glycol were reacted, using a total of 600 g of toluene 1.0 g of bis-(2,4-dichlorobenzylol)peroxide was used as an initiator, of which 0.25 g was used for initiation and 0.75 g for the post reaction.

After cooling, 1 kg of a clear solution with about 40% by weight of solid substance and a viscosity of about 14,800 cP (measured as indicated under A) was obtained.

Preparation C.

72 g of methyl acrylate, 36 g of ethyl acrylate, 9.6 g of 2-ethylhexyl acrylate, 1.0 g of maleic acid monohydroxyethyl ester, 2.4 g of 2-hydroxyethyl acrylate and 178 g of trimethyl benzene were introduced into a l-litre, three-necked spherical flask with a stirrer mechanism, reflux condenser and thermometer and carefully heated to 90 to 1000C after adding 2 g cf benzoyl peroxide. After the reaction had started, the temperature rose quickly with violent reflux and to about 140 to 1500C, a clear, viscous product being formed.

After cooling, about 300 g of a clear product with a viscosity of about 12,000 cP were obtained.

Preparation D.

100 g of a mixture of 123.5 g of methyl acrylate, 24.3 of ethyl methacrylate, 136.3 g of 2- ethyl-hexyl acrylate, 9 g of styrene and 26.9 g of 3-hydroxy-propyl acrylate were introduced into a 2-litre, four-necked spherical flask, having the equipment as used in Preparation A, after initial flushing with nitrogen. After adding 0.22 g of benzoyl peroxide, dissolved in 60 ml of n-butyl acetate, the mixture was heated to about 75 to 800C under stirring conditions. After the reaction had started the further procedure in accordance with Preparation A was adopted, 0.64 g of benzoyl peroxide being added for the post-reaction. Altogether 320 g of n-butyl acetate were used. so that the product is an approximately 50% by weight solution.

Preparation E.

Using the techniques of Preparation D the following components were reacted: 112.0 g of methyl acrylate, 78.4 g of ethyl acrylate, 110.4 g of 2-ethylhexyl acrylate, 10.2 g of lauryl acrylate and 9.0 g of maleic acid butylhydroxyethy! ester.

A total of 480 g of toluene was used as solvent and altogether 1.2 g of tert. butyl peroctoate were used as catalyst, of which 0.3 g was added at the start and the remainder for the post-reaction, in each case dissolved in toluene.

Preparation F.

100 ml of a mixture of 218.3 g of methyl acrylate, 109.1 g of ethyl acrylate, 29.1 g of 2-ethylhexyl acrylate, 7.3 g of 2-hydroxyethyl acrylate, 36.4 g of methylhydrogen polysiloxane blocked at the ends with trimethylsilyl (ratio between the methyl groups and the hydrogen capable of being split off = 1:1, viscosity 30 cP at 20"C) and 45 g of toluene, in which are dissolved 0.19 g of benzyol peroxide were introduced into a 2-litre, four-necked spherical flask, fitted with an efficient anchor-type stirrer device, a reflux condenser, thermometer and two supply vessels after strong initial flushing with nitrogen and heated to 80 to 820 C.

The residual monomers were placed in the supply vessel 1 and supply vessel Il charged with 455 g of toluene.

After the initiation of the polymerization, which was recognized from the commencement of reflux and increasing viscosity of the flask contents, the temperature rose to 90 to 920C. At this temperature and under constant reflux, the residual monomer mixture was added over a period of 20 to 30 minutes. The viscosity was prevented from rising above the level at which it could be stirred by addition of toluene. After completing the supply of monomers, 0.56 g of benzyol peroxide, dissolved in 100 g of toluene, were slowly added and the remaining quantity of toluene added dropwise at the reflux temperature. The batch was stirred about 1 to 1+ hours under gent!e reflux, until the temperature reached about 108"C.

After cooling, about 1 kg of a cloudy solution with about 40 Ó by weight of solid substance, a viscosity of about 25,000 cP (measured with the Brookfield Viscosimeter, type RVF, Spindle C, 10 r.p.m.) was obtained The crosslinking capacity of the resulting modified copolymer was almost completely retained, because the resultant product still contained about 90% of the silicon-bonded hydrogen of the introduced methyl-hydrogen polysiloxane, which hydrogen can be split off.

Preparation G.

Using the technique of Preparation F, 36.4 g of methyl-hydrogen polysiloxane (for particulars see F), 72.8 g of methyl acrylate, 218.3 g of butyl acrylate, 67.3 g of 2-ethylhexyl acrylate and 7.3 g of 2-hydroxyethyl acrylate are reacted, using altogether 600 g of toluene. 1.0 g of bis-(2,4-dichlorobenzoyl)peroxide was used as initiator, 0.25 g of the initiator being used at the start and 0.75 g for the post reaction.

After cooling, about 1 kg of a cloudy solution with approximately 40% by weight of solid substance, and a viscosity of about 14,800 cP (measured as under F) was obtained. The resulting final product contained about 91% of the siliconbonded hydrogen of the employed methyl-hydrogen polysiloxane, which hydrogen can be split off.

Preparation H.

The procedure of preparation F is repeated, using, as methyl-hydrogen polysiloxane, 36.4 g of methyl-hydrogen polysiloxane in which the ratio between the methyl groups and the silicon-bonded hydrogen atoms was 5:1 (viscosity 200 cP at 20"C).

0.8 g of azodiisobutyrodinitrile was used as initiator.

About 1 kg of a cloudy solution (solid content about 40% by weight) with a viscosity of 19,600 cP was obtained.

Preparation J.

The procedure of preparation H is repeated, using a methyl-hydrogen polysiloxane in which the ratio between the methyl radicals and the hydrogen which can be split off was about 13:1 (viscosity 230 cP at 20"C). 36.4 g of this siloxane were used.

The resulting product (solid content 40 Ó by weight) had a viscosity of 18,300 cP.

Preparation K.

48 g of methyl-hydrogen polysiloxane as used in Preparation F 72 g of methyl acrylate, 36 g of ethyl acrylate, 9.6 g of 2-ethylhexyl acrylate and 2.4 g of 2 hydroxyethyl acrylate were introduced into a I-litre, three-necked spherical flask with a stirrer device, reflux condenser and thermometer, and heated carefully to 90 to 1000C after adding 2 g of benzoyl peroxide. After the initiation of the reaction, the temperature quickly rose to 180 to 2000C, a milky, viscous product being formed. After stirring for 2 hours at 1600C residual monomers were drawn off under reduced pressure.

After cooling, 165 g of a white cloudy product with a viscosity of about 18,000 cP were obtained. The viscosity of the product (solid substance 40% by weight) dissolved in toluene was 8500 cP.

The hydrogen which can be split off from the final product amounts to about 95% of the introduced methyl-hydrogen polysiloxane.

Preparation L.

100 g of a mixture of 123.5 g of methyl acrylate, 33.3 g of ethyl methacrylate, 136.3 g of 2-ethylhexyl acrylate and 26.9 g of 3-hydroxypropyl acrylate were introduced into a 2-litre, four-necked spherical flask, equipped as in Preparation F, after it was flushed with nitrogen. After adding 77.4 g of methyl-hydrogen polysiloxane (as used in Preparation F), and 0.22 g of benzoyl peroxide, dissolved in 60 ml of n-butyl acetate, the mixture was heated under stirring to 75 to 800 C. After the reaction was initiated, the further procedure in accordance with Preparation F was adopted, 0.64 g of benzoyl peroxide being added for the post-reaction.

Altogether, 600 g of n-butyl acetate were used, so that an approximately 40% by weight solution was obtained.

The cloudy product does not separate, even after standing for a relatively long time.

Preparation M.

80.0 g of methyl-hydrogen polysiloxane (as used in Preparation F), 100 ml of a monomer mixture consisting of 112.0 g of methyl acrylate, 78.4 g of ethyl acrylate, 110.4 g of 2-ethylhexyl acrylate, 10.2 g of lauryl acrylate and 9.0 g maleic acid butylhydroxyethyl ester were introduced into a 2-litre, four-necked spherical flask, equipped as in Preparation F, together with 50 g of trimethyl benzene. 0.8 g of benxoyl peroxide was added and the mixture was carefully heated to 90 to 1000C.

After initiation of the reaction, the temperature rose to 140 to 1500C. The remaining monomer mixture was run in, together with 420 g of trimethyl benzene over a period of 30 minutes. For the post-reaction, 1.2 g of benzoyl peroxide, dissolved in 30 g of trimethyl benzene, were added and the reaction mixture was maintained for 2 more hours under gentle reflux.

After cooling 800 g of a cloudy solution which did not settle even after standing for 3 months were obtained.

Preparation N.

In a manner analogous to the procedure of preparation F, 72.0 g of methyl acrylate, 36.0 g of ethyl acrylate, 9.6 g of 2-ethylhexyl acrylate, 1.0 g of maleic acid monohydroxyethyl ester and 2.4 g of 2-hydroxyethyl acrylate were reacted in the presence of 48.0 g of methyl-hydrogen polysiloxane (as used in Preparation F), using a total of 0.3 g of dibenzoyl peroxide. A total of 120 g of toluene was used as solvent.

After cooling, a viscous, slightly cloudy solution with a solids content of 58.5% by weight was obtained.

This invention will now be illustrated by the following Examples: Example 1.

The following coating compositions were prepared:

I 1000 g of modified copolymer (40% by weight (according solids) as prepared in Preparation F to the and invention) 20 g of aminosilane of formula (3), Il 1000 g of modified copolymer (4070 by weight (according solids) as prepared in Preparation F to the invention) 15 g of aminosilane of formula (3) and 15 g of dibutyl-tin dilaurate, III 1000 g or copolymer so@@mon as prepare@ in (according to the Preparation A and invention) 20 g of aminosilane of formula (3), IV 1000 g of copolymer solution as prepared in (according Preparation A, to the invention) 15 g of aminosilan@ of formula (3) and 15 g of dibutyl-iin dilaurate V 1000 g of copolymer solution as prepared in (control) Preparation A.

The compositions were coated onto polyamide taffeta (about 70 g/m2) and polyester taffeta (about 80 g/m2). The coating was carried out by means of an air doctor at a speed of 10 metres per minute and the coated fabric was continuously conducted into a heating duct (residence time 80 seconds and dried

Sprinkling test according to Water tightness according to Dressings DIN 53888 DIN 53886 (Water column in mm) Handle Original 5 Machine 3 x DC Original 5 Machine 3 x DC washings washings at 40 C at 40 C Polyamide taffeta I 8.7% 12.8% 12.2% above 300 280 Full, resilient, 3/3/2 2/2/1/ 2/2/2 1000 non-tacky handle II 6.7% 10.4% 9.2% above 360 450 as I 3/3/3 2/2/2 3/2/2 1000 III 13.2% 19.1% 19.6% above 260 130 Full, slightly tacky 2/2/2 2/1 2/1 1000 handle IV 10.4% 15.6% 16.9% above 240 170 Full, dry somewhat 3/2/2 2/2/2 2/2/2 1000 stiff handle V (without catalyst) 15.0% 22.7% (film 390 150 0 Full, extremely tacky 1 1 partially (film handle dissolved) partially dissolved) untreated 45.0% - - 0 - - 1 TABLE Continued

Sprinkling test according to Water tightness according to Dressings DIN 53888 DIN 53886 (Water column in mm) Handle Original 5 Machine 3 x DC Original 5 Machine 3 x DC washings washings at 40 C at 40 C Polyester taffeta I 5.2% 8.0% 9.7% above 320 460 Full, resilient, 3/3/3/ 2/2/2 2/2/2 1000 non-tacky handle II 2.8% 6.5% 6.7% above 370 560 as I 4/4/4/ 3/3/3/ 3/3/3 1000 III 8.0% 10.5% 13.3% above 190 140 Full, slightly tacky 3/3/2 2/1 2/1 1000 handle IV 7.9% 10.1% 11.8% above 230 180 Full, dry, somewhat 3/3/2 2/1 2/2/2 1000 stiff handle V (without catalyst) 12.3% 18.7% (film 420 170 0 Full, extremely 1 1 partially (film tacky handle dissolved) partially dissolved) Untreated 43.0% - - 0 - - 1 at 145"C and condensed. With the polyamide taffeta, the coating was about 22 g/m2 and, with the polyester taffeta about 24 g/m2. A portion of the finished textiles was washed in the usual manner 5 times at 400C in the machine, another portion was subjected 3 times to dry cleaning (DC) in the presence of 2 g/l of a conventional cleaning intensifier and 2 gil of water.

The results, after conditioning, under normal climatic conditions, are set out in the following Tables. In each case, it was the coated side which was tested.

Example 2.

A tent cloth consisting of polyacrylonitrile fibres (200 g/m2) was preimpregnated with the following aqueous solutions: 15 gl hexamethylol melamine tetramethyl ether 7 g/l 35% aqueous zinc nitrate solution (pH value about 1, adjusted with hydrochloric acid) 2 m/l 60% acetic acid 45 g/l of the paraffin emulsion prepared according to Example 1 of U.S. Patent No. 3,887,390 9 gil of a known approximately 25% emulsion of oil-resisting agent (as in U.S.

Patent No. 2,803,615) and 40 g/l of the emulsion prepared according to Example 8 of U.S. Patent No.

3,320,197).

The woven fabric was slop-padded (liquor absorption about 55",/,), dried at 130"C and then condensed at 1500C. Thereafter, the impregnated fabric was coated on one side, using an air doctor, with the following coating compositions, the coating taking place with two strokes of the doctor (total solid layer 50 g/m2) and thereafter was continuously conducted through a heating duct (10 m per minute) and dried at 1500C for 2 minutes.

I 1000 g of modified copolymer (40% by weight solids) prepared as in preparation G 18 g of red pigment dyestuff (consisting of pigment and hydrated colophony ester as support) made soluble in the solvent 15 g of aminosilane of formula (7) and 15 g of dioctyl-tin benzoate, II as I, but 1000 g of copolymer solution prepared as in Preparation B, instead of the indicated modified copolymer, III as II,but without dicotyl-tin benzoate IV as II, without aminosilane and without (control) dioctyl-tin benzoate.

The finished or dressed specimens were exposed to the weathering test with the coated side on top (supported in the open, facing south, at an angle of 45"C), the following results being obtained:

Water tightness according to DIN 53886 (water column in mm) Dressing original after 4 months after 6 months 1 950 910 900 II 800 750 720 III 360 250 210 IV 320 140 30 (without catalyst) If the post-impregnation is carried out in similar manner instead of preimpregnation, similarly good results are produced.

Example 3.

A polyacrylonitrile jersey (yarn dyed with basic dyestuffs, 250 g/m2, precleaned in pure trichloroethylene for removing the preparations) is slop-padded with the following finishing or dressing solution: 20 g of the modified copolymer prepared as in Preparation J.

0.2 g of aminosiloxane of formula (10), 0.2 g of zinc octoate and 979.5 g of trichlorethylene The solution absorption was 175%. The fabric was dried at 1200C until residual vaporisation of the solvent was obtained and was then levelled with slight steaming.

In this way, there was obtained a fabric with a water-repellent finish and having a soft, smooth handle, improved dimensional stability and good stretch properties and also a substantially improved anti-pilling effect. The crease resistance of the fabric as thus treated was also considerably improved by comparison with the untreated fabric.

The same fabric can also be dressed with a bath solution containing only 10 g instead of 20 g of the indicated copolymer and containing in addition 10 g of an a,-dihydroxydimethyl polysiloxane (Viscosity 4,000 cP at 200 C.

When the finishing was carried out with a copolymer solution prepared as in Preparation D, a fuller, wool-like handle was obtained with in other respects similarly good effects. In this case also, it is readily possible for a part of the copolymer D to be replaced by sr,-dihydroxydimethyl polysiloxane (viscosity 4,000 cP at 20"C.

Example 4.

A polyacrylonitrile-cotton mixed woven 60/40 (280 g/m2, yarn-dyed, precleaned in trichloroethylene) was treated in the manner indicated in Example 3, but replacing the modified copolymer of Preparation J by the modified copolymer of Preparation K and replacing the aminosiloxane by the aminosiloxane of formula (2).

Advantageous results similar to those in Example 3 were obtained.

Example 5.

The polyacryionitrile-cotton mixed fabric referred to in Example 4 was treated in the manner indicated, using the copolymer of Preparation E instead of the modified copolymer of Preparation K. Similar advantageous results were obtained.

Example 6.

A polyester cord-ribbed jersey (300 g/m2) was dyed with dispersion dyestuff in aqueous solution in the usual manner and after being dried a tenter was padded with the following solution on the rear side (solution absorption 130%): 40 g of copolymer solution preparation in Preparation C 0.4 g of aminosilane of formula (5) 0.4 g of zirconium caprylate 0.5 g of antistatic agent (1:1 mixture of monophosphoric and diphosphoric acid esters of the 2-ethylhexanol ethoxylated with 5 mols of ethylene oxide for each mol of alcohol, neutralised with KOH) and 958.7 g of 1,1,1-trichloroethane.

The jersey was dried at 1200C and heat fixed for 30 seconds at 1800C.

The resulting fabric exhibited a full, voluminous handle, good anti-pilling and good water repelling properties. The finish was resistant to washing and dry cleaning. Instead of trichlorethane, it is possible to use methylene chloride as solvent.

Example 7.

A polyamide knitwear with interlock weave (180 g/m2) was dyed in the usual manner with acid dyestuff in aqueous solution and, after drying a tenter frame, was padded with the following solution (solution absorption 140%): composition as Example 6, but with 40 g of modified copolymer according to Preparation H, instead of the copolymer of Preparation C.

The material was dried as described in Example 6 and is heat-fixed.

The resulting fabric exhibited a full, siliconc-like handle, good anti-pilling and good water repelling properties. The finish was resistant to washing and dry cleansing.

In addition, there was observed a substantial improvement in the mesh and in the stretch properties.

Instead of trichloroethane, trichloroethylene can also be used as solvent, and likewise a comparable amount of the modified copolymer of Preparation N can be used in place of the copolymer of Preparation H.

Example 8.

The following coating composition was applied with the aid of a roller-type doctor on both sides of a cotton sail cloth (about 400 g/m2): 1000 g of modified copolymer according to Preparation L (1) 20 g of aminosilane of the formula (3) (2) 20 g of dibuty!-tin diacetate (3) 50 g of toluene (4) and 50 g of titanium dioxide (5).

(Preparation: (5) was formed into a paste with (4) and introduced into (1) stirring strongly. Thereafter, (2) and (3) were added).

The material was provided with a coating of about 28 g/m2 (solid substance) on each side. The coated material was dried at 1200C and condensed for 30 seconds at 1800C.

The treated sail cloth was weather-resistant and also exhibited a sufficient water-repelling capacity. The permanent nature of the effects was found to be high.

When the modified copolymer of Preparation L was replaced by the same amount of copolymer solution according of Preparation B, the permanence was only given to a weakened degree, but with otherwise similarly good effects.

Example 9.

Example 8 was repeated using the same quantity of the amino-functional siloxane of formula (12) in place of the formula (3) and of the modified copolymer according to Preparation M in place of that of Preparation L. Comparable results obtained, but the resistance to dry cleaning was somewhat less pronounced.

WHAT WE CLAIM IS: 1. A process for treating textile materials with a copolymer cnPtninine hydroxyl groups, the copolymer being formed from 100 parts by weight of a monomer mixture comprising 0.1 to 10 parts by weight of an unsaturated hydroxy ester which has a free

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

Claims

**WARNING** start of CLMS field may overlap end of DESC **. 0.4 g of aminosilane of formula (5) 0.4 g of zirconium caprylate 0.5 g of antistatic agent (1:1 mixture of monophosphoric and diphosphoric acid esters of the 2-ethylhexanol ethoxylated with 5 mols of ethylene oxide for each mol of alcohol, neutralised with KOH) and 958.7 g of 1,1,1-trichloroethane. The jersey was dried at 1200C and heat fixed for 30 seconds at 1800C. The resulting fabric exhibited a full, voluminous handle, good anti-pilling and good water repelling properties. The finish was resistant to washing and dry cleaning. Instead of trichlorethane, it is possible to use methylene chloride as solvent. Example 7. A polyamide knitwear with interlock weave (180 g/m2) was dyed in the usual manner with acid dyestuff in aqueous solution and, after drying a tenter frame, was padded with the following solution (solution absorption 140%): composition as Example 6, but with 40 g of modified copolymer according to Preparation H, instead of the copolymer of Preparation C. The material was dried as described in Example 6 and is heat-fixed. The resulting fabric exhibited a full, siliconc-like handle, good anti-pilling and good water repelling properties. The finish was resistant to washing and dry cleansing. In addition, there was observed a substantial improvement in the mesh and in the stretch properties. Instead of trichloroethane, trichloroethylene can also be used as solvent, and likewise a comparable amount of the modified copolymer of Preparation N can be used in place of the copolymer of Preparation H. Example 8. The following coating composition was applied with the aid of a roller-type doctor on both sides of a cotton sail cloth (about 400 g/m2): 1000 g of modified copolymer according to Preparation L (1) 20 g of aminosilane of the formula (3) (2) 20 g of dibuty!-tin diacetate (3) 50 g of toluene (4) and 50 g of titanium dioxide (5). (Preparation: (5) was formed into a paste with (4) and introduced into (1) stirring strongly. Thereafter, (2) and (3) were added). The material was provided with a coating of about 28 g/m2 (solid substance) on each side. The coated material was dried at 1200C and condensed for 30 seconds at 1800C. The treated sail cloth was weather-resistant and also exhibited a sufficient water-repelling capacity. The permanent nature of the effects was found to be high. When the modified copolymer of Preparation L was replaced by the same amount of copolymer solution according of Preparation B, the permanence was only given to a weakened degree, but with otherwise similarly good effects. Example 9. Example 8 was repeated using the same quantity of the amino-functional siloxane of formula (12) in place of the formula (3) and of the modified copolymer according to Preparation M in place of that of Preparation L. Comparable results obtained, but the resistance to dry cleaning was somewhat less pronounced. WHAT WE CLAIM IS:

1. A process for treating textile materials with a copolymer cnPtninine hydroxyl groups, the copolymer being formed from 100 parts by weight of a monomer mixture comprising 0.1 to 10 parts by weight of an unsaturated hydroxy ester which has a free

hydroxyl group in the end position of the alcohol moiety and a C-C double bond capable of polymerisation, an acrylic acid ester and/or a methacrylic acid ester, and optionally one or more other monomers capable of mixed copolymerization with the unsaturated monomers, the copolymer being applied to the textile in the presence of a hardening agent comprising a siloxane containing amino groups and/or silane containing amino groups in an organic, water-insoluble solvent and the treated textile dried, and the copolymer cured.

2. A process as claimed in Claim 1, in which the monomer mixture comprises 0.1 to 10 parts by weight of a compound of the formula:

in which R represents a hydrogen atom or CH3 group, and R1 represents (CH2)nOH, -CH2CH2-O-CH2CH2OH or -(CH2)3-O-(CH2)3-OH in which n is 2 to 4 inclusive, and/or a compound of the formula: R2OOC-CH--CH-COOR1 (11) in which R2 represents a hydrogen atom or an alkyl radical containing 1 to 12 carbon atoms, and as the acrylic and/or methacrylic ester 99.9 to 80 parts by weight of a compound of the formula::

in which R3 represents an alkyl radical which is optionally branched and contains I to 18 carbon atoms, provided that in at least 50% by weight, of the compound of formula (111), R3 represents an alkyl radical which may be branched, containing I to 4 carbon atoms, and as the other monomer (IV) 0 to 10 parts by weight of monomer capable of mixed polymerization with compounds of the formulae (I), (if), and (III).

3. A process as claimed in Claim 1 or Claim 2 in which the copolymer containing hydroxyl groups is an unmodified copolymer.

4. A process as claimed in Claim 2, in which the copolymer containing hydroxyl groups, is a modified copolymer which has been obtained by the monomers (I) and/cr (II), (III) and optionally (IV), the sum of these compounds amounting to 100 parts by weight, being copolymerized in the presence of 5 to 40 parts by weight of terminal-blocked alkyl-hydrogen polysiloxane, in which the alkyl radicals contain 1 to 4 carbon atoms in which the ratio between the silicon-bonded alkyl radicals and the hydrogen atoms bonded to silicon is in the range 13:1 to 1:1 and which has a viscosity from 20 to 1000 cP at 200 C.

5. A process as claimed in Claim 4, in which in the terminal-blocked alkylhydrogen polysiloxane, the ratio between the silicon-bonded alkyl radicals and the silicon-bonded hydrogen atoms is in the range 5:1 to 1:1.

6. A process as claimed in Claim 4 or Claim 5 in which the terminal-blocked alkyl-hydrogen polysiloxane is methyl-hydrogen polysiloxane.

7. A process as claimed in any of Claims 4 to 6 in which the modified copolymer is obtained by copolymerization of 5 to 20 parts by weight of alkylhydrogen polysiloxane with 100 parts by weight of compounds of the formulae (I) and/or (II), (III) and optionally (IV).

8. A process as claimed in any preceding claim in which the silane containing amino groups, has the formula

in which Y represents an alkyl group having 1 to 3 carbon atoms.

A represents an alkylene group having more than 2 carbon atoms M represents an amino group or diaminoalkyl group, which is linked to A through a carbon-nitrogen bond and n is 0 or 1.

9. A process as claimed in Claim 8 in which A represents an alkylene group containing 3 or 4 carbon atoms.

10. A process as claimed in any preceding claim in which the hardening agent additionally includes organo-metallic catalyst.

11. A process as claimed in Claim 10 in which the organometallic catalyst contains aluminium, zinc, zirconium, titanium, cobalt, iron or tin.

12. A process as claimed in Claim 11, in which the organometallic catalyst is a dialkyl-tin dicarboxylate.

13. A process as claimed in any preceding claim in which the copolymer is applied in the presence of 0.5 to 5% by weight based on the weight of copolymer of siloxane containing amino groups and/or silane containing at least one amino group.

14. A process as claimed in any preceding claim in which the copolymer is applied in the presence of 0.5 to 5% by weight based on the weight of copolymer of an organometallic catalyst.

15. A process as claimed in any preceding claim in which the treated textiles are heated to cure the copolymer.

16. A process for treating textile materials with polymers of acrylic acid esters and/or methacrylic acid esters subtantially as herein described with reference to any of the Examples.

17. A textile when treated by a process as claimed in any preceding claim.