CN104350087A - Composition and method for treating textiles - Google Patents

Abstract

A curable composition useful for treating textiles to impart one or more textile use-enhancing properties to the textile when cured, said composition comprising a first macromer (i) having Two or more polysiloxanes with terminal functional groups selected from hydroxyl, alkoxy and combinations thereof; the second macromonomer (ii), which is a polysiloxane containing two or more hydrosilyl groups ( ≡C-SiH) group polysiloxane; catalyst (iii); and optionally one or more additional components (iv), such as surfactants, water, and the like.

Description

Compositions and methods for treating textiles

technical field

The present invention relates to a composition and method for treating textiles to impart one or more desired properties thereto, such as shrink resistance, wrinkle resistance, durable pressing, anti-pilling (in woolen fabrics) and wool blends), smoothness and elastic feel.

Background technique

Frequent use and care of textile items such as linens, clothing, and fabrics of all kinds, etc., can cause them to wrinkle. In particular, the wear and care of clothes, such as home laundry, can cause them to wrinkle. Various methods are known for imparting wrinkle resistance to textiles, including physical and chemical methods. A widely adopted chemical-based procedure employs formaldehyde derivatives such as dimethyloldihydroxyethyleneurea (DMDHEU) as textile-treatment agents. Formaldehyde derivatives have long been used for this purpose due to their availability and relatively low cost.

However, formaldehyde derivatives have several disadvantages including reduced fabric strength, formaldehyde release and harsh hand.

Methods for avoiding or mitigating the formaldehyde emission problem include reacting water-soluble alcohols with methylolated organic carbamates and using cross-linked polymaleates as formaldehyde-free durable press finishes. In order to reduce or suppress loss of textile strength and to improve hand, polysiloxanes have been used together with known and conventional wrinkle-reducing agents as cellulosic textile-treatment agents.

Contents of the invention

The present invention fulfills the need for compositions and methods for imparting at least one textile-property-enhancing characteristic to textiles, such as shrink resistance, wrinkle resistance, durable pressing, anti-pilling (in wool fabrics and wool blends) In the case of fabrics), smoothness and/or desirable elastic feel without concomitant emission of harsh chemical odors and/or excessive or accelerated loss of strength of the treated textile.

According to the present invention there is provided a cured resin composition for treating textiles to impart at least one textile-property enhancing property to textiles, said composition comprising:

at least one macromer (i), which is a polysiloxane of general formula (I):

M ^A _a D ^B _b D ^C _c T ^D _d T ^E _e M ^A _a (I)

in

M ^A is (OR ¹ ) _y (R ² ) _3-y SiO _1/2 ;

^DB is R ³ ₂ SiO _2/2 ;

^DC is R ⁴ R ⁵ SiO _2/2 ;

T ^D is R ⁶ SiO _3/2 ; and

^TE is R ⁷ SiO _3/2 ;

in

Each occurrence of ^R is independently hydrogen or a monovalent hydrocarbon group of 1-22 carbon atoms;

R ² , R ³ , R ⁴ and R ⁶ are each independently a monovalent hydrocarbon group or alkoxy group of 1 to 22 carbon atoms;

R and ^R are each independently a monovalent hydrocarbon group of 1-22 carbon atoms and are substituted by at least one amino and/ ^or oxiranyl group; and

1≤a≤19, 1≤b≤9999, 1≤c≤19, 0≤d≤9, 0≤e≤9 and 0≤y≤3;

at least one macromonomer (ii) which is an oligomer or polymer containing at least two hydrosilyl (≡C-SiH) functional groups per molecule;

at least one catalyst (iii) for the curing reaction of the macromers (i) and (ii); and

Optionally at least one additional component (iv) selected from surfactants and aqueous surfactants.

Furthermore, according to the present invention there is provided a method for treating textiles to impart thereto at least one - property enhancing properties, said method comprising:

a) applying to a textile an amount of a curable composition which, after undergoing curing, provides at least one cured resin effective to impart at least one textile property enhancing characteristic to said textile, said curable composition Include:

at least one macromer (i), which is a polysiloxane of general formula (I):

M ^A _a D ^B _b D ^C _c T ^D _d T ^E _e M ^A _a (I)

in

M ^A is (OR ¹ ) _y (R ² ) _3-y SiO _1/2 ;

^DB is R ³ ₂ SiO _2/2 ;

^DC is R ⁴ R ⁵ SiO _2/2 ;

T ^D is R ⁶ SiO _3/2 ; and

^TE is R ⁷ SiO _3/2 ;

in

Each occurrence of ^R is independently hydrogen or a monovalent hydrocarbon group of 1-22 carbon atoms;

R ² , R ³ , R ⁴ and R ⁶ are each independently a monovalent hydrocarbon group or alkoxy group of 1 to 22 carbon atoms;

R and ^R are each independently a monovalent hydrocarbon group of 1-22 carbon atoms and are substituted by at least one amino and/ ^or oxiranyl group; and

1≤a≤19, 1≤b≤9999, 1≤c≤19, 0≤d≤9, 0≤e≤9 and 0≤y≤3;

at least one macromonomer (ii) which is an oligomer or polymer containing at least two hydrosilyl (≡C-SiH) functional groups per molecule;

at least one catalyst (iii) for the curing reaction of the macromers (i) and (ii); and

Optionally at least one additional component (iv) selected from surfactants and aqueous surfactants; and

b) subjecting said curable composition to curing conditions to produce a cured resin composition of macromers (i) and (ii) and to impart at least one-property-enhancing properties to textiles.

Detailed ways

Approximate language used herein may be used to modify representatives that may vary without resulting in a change in the essential function to which it is related. Accordingly, a description or value modified by one or more terms (eg, "substantially") may not be limited to the precise description or value specified, in some cases.

All ranges in the specification and claims are inclusive of endpoints and independently combinable. Numerical values in the specification and claims are not limited to the specified values, and may include values other than the specified values.

Numerical values are understood to be sufficiently imprecise to include values approximating the stated values, allowing for experimental error due to measurement techniques known in the art and/or the precision of the instruments used to determine the values.

It will be understood that any numerical range recited herein is intended to include all subranges within that range and any combination of such ranges or subranges.

As used herein, the term "textile" is understood to include blended and non-blended textile fibers and yarns, woven, woven, nonwoven or otherwise constructed fabrics and finished and semi-finished textile articles and their subunits ), such as clothes and parts of clothes, etc.

Curing of macromonomers (i) and (ii) involves combining the hydroxyl and/or alkoxy groups present in each ^MA portion of macromonomer (i) with the Hydrosilyl (≡C-SiH) groups react. When the reactive group in part ^MA is a hydroxyl group (i.e., the case where each ^R group is hydrogen and each ^R group (when present) is a monovalent hydrocarbon), the curing reaction results in Macromonomers (i) and (ii) condense to form a cured resin composition with -SiO- bonds, with release of hydrogen; when the reactive group in part ^MA is an alkoxy group (i.e., where each In the case where one ^R group is a ^monovalent hydrocarbon and each R group (when present) is an alkoxy group), the curing reaction also results in condensation of macromonomers (i) and (ii) to form A cured resin composition of SiO-bonds, but cleavage of the hydrocarbon R ¹ H, wherein R ¹ is a monovalent hydrocarbon radical as defined above. When the macromonomer (i) has both hydroxyl and alkoxy functional groups, both hydrogen and the hydrocarbon R ¹ H will be formed as by-products in addition to the desired cured resin composition.

The present invention also includes a cured resin composition obtained from the curing reaction of the macromonomers (i) and (ii) contained in the aforementioned curable resin composition, a textile treated with the curable resin composition , and textiles comprising a cured resin composition resulting from the curing reaction of macromers (i) and (ii).

Since the cured resin composition derived from the curing reaction of the macromonomers (i) and (ii) does not contain formaldehyde-releasing components, textiles containing the cured resin composition do not emit unpleasant odors, while using Textiles treated with known and conventional formaldehyde derivative-based textile treatments, such as those mentioned above, release unpleasant odours. Use of the inventive textile-treating composition allows one to either completely dispense with the use of such formaldehyde derivatives or reduce their presence to a level at which formaldehyde emission is no longer a significant problem. In general, it is preferred that the curable textile-treating compositions of the present invention and the resulting cured resin compositions contain no or up to 20% by weight of formaldehyde derivatives as auxiliary anti-wrinkle additives.

The curable compositions of the present application, the resulting cured resin compositions and the textile treatment methods of the present invention are particularly advantageous for providing shrink and wrinkle resistant textiles and textiles exhibiting advantageous strength retention and hand properties. In the case of textiles based on wool and wool blends, the cured resin composition of the invention advantageously imparts effective anti-pilling properties thereto.

(a) Hydroxy- and/or alkoxy-terminated macromers (i)

The curable composition of the present invention comprises at least one macromer (i), which is a polysiloxane of general formula (I):

M ^A _a D ^B _b D ^C _c T ^D _d T ^E _e M ^A _a (I)

in

M ^A is (OR ¹ ) _y (R ² ) _3-y SiO _1/2 ;

^DB is R ³ ₂ SiO _2/2 ;

^DC is R ⁴ R ⁵ SiO _2/2 ;

T ^D is R ⁶ SiO _3/2 ; and

^TE is R ⁷ SiO _3/2 ;

in

Each occurrence of ^R is independently hydrogen or a monovalent hydrocarbon group of 1-22 carbon atoms;

R ² , R ³ , R ⁴ and R ⁶ are each independently a monovalent hydrocarbon group or alkoxy group of 1 to 22 carbon atoms;

R and ^R are each independently a monovalent hydrocarbon group of 1-22 carbon atoms and are substituted by at least one amino and/ ^or oxiranyl group; and

1≤a≤19, 1≤b≤9999, 1≤c≤19, 0≤d≤9, 0≤e≤9, and 0≤y≤3.

In monomer (i), each R ¹ is independently hydrogen or a monovalent hydrocarbon group preferably having 1-6 carbon atoms, more preferably 1-4 carbon atoms.

Each of R ² , R ³ , R ⁴ and R ⁶ is independently preferably a monovalent hydrocarbon group or alkoxy group of 1-6 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, Pentyloxy groups and their isomers, more preferably monovalent hydrocarbon groups or alkoxy groups of 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy and their isomers .

Each R ⁵ and R ⁷ group is independently preferably a monovalent linear or branched chain hydrocarbon group of 2-20 carbon atoms, more preferably 2-10 carbon atoms.

The values of a, b, c, d, e and y are: 1≤a≤19, 1≤b≤9999, 1≤c≤19, 0≤d≤9, 0≤e≤9 and 0≤y≤3 . Preferably each value is 2≤a≤9, 25≤b≤999, 1≤c≤9, 0≤d≤5, 0≤e≤5 and 0<y≤2, more preferably 2≤a≤5, 100≤ b≤999, 1≤c≤7, 0≤d≤3, 0≤e≤3 and 0<y≤1.

Monomer (i) preferably has a number average molecular weight of 100-200,000, preferably 1000-100,000.

The macromonomer (i) component of the curable composition can be obtained by adding at least one cyclic and/or linear siloxane, at least one alkoxy-terminated functional silane, optionally The catalyst, optional surfactant and water are combined to provide a reaction mixture which is heated to a temperature and for a period of time sufficient to achieve substantially complete conversion of the siloxane and alkoxysilane reactants to monomer (i). Thus, for example, a reaction mixture can be prepared by adding at least one cyclic siloxane containing silanol groups (for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane or decamethylcyclosiloxane Pentasiloxane (commonly referred to as _D3 , _D4 , and _D5 , respectively, available from Momentive Performance Materials Inc.)) and/or at least one linear silanol-containing siloxane with at least one aminoalkoxy base silane (for example, γ-aminopropyltrimethoxysilane, aminopropyltriisopropoxysilane, etc.), optional catalyst (for example, strong base, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc. ), optional surfactants (for example, anionic surfactants (such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, etc.), anionic surfactants (such as sodium lauryl sulfate, lauryl sodium alkylbenzenesulfonate, etc.), cationic surfactants (such as quaternary ammonium salts, etc.), their combination) and the water used to emulsify the macromer (i) reaction product are combined, and the reaction mixture is heated to a suitable reaction temperature, eg, 90-140°C, for a suitable period of time, eg, 5-10 hours, to achieve substantially complete conversion of the reactants to macromonomer (i).

For additional details on the aforementioned methods for preparing macromonomer (i), reference may be made to published US patent application 2012/0114928, the entire contents of which are incorporated herein by reference.

Several macromonomers (i) are commercially available, in particular, YMR7212, LE-467, Magmasoft SL-501, SM 2725 and SM2068A, all from Momentive Performance Materials Inc.

(b) Macromonomer (ii) containing a hydrosilyl group

The curable resin-forming composition of the present invention further comprises at least one macromonomer (ii), which is an oligomer or polymeric compound containing at least two hydrosilyl (≡C-SiH) functional groups per molecule things.

In one embodiment of the invention, the macromer (ii) containing a hydrosilyl group (≡C-SiH) may be selected from those of the general formula (II):

M _f M ^H _g D _h D ^H _i T _j T ^H _k Q _l (II)

in

M is R ⁸ R ⁹ R ¹⁰ SiO _1/2 ;

M ^H is R ¹¹ R ¹² R ¹³ SiO _1/2 ;

D is R ¹⁴ R ¹⁵ SiO _2/2 ;

D ^H is R ¹⁶ R ¹⁷ SiO _2/2 ;

T is R ¹⁸ SiO _3/2 ;

^TH is R ¹⁹ SiO _3/2 ; Q is SiO _4/2 ;

in

R ⁸ , R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ and R ¹⁸ are each independently an alkyl, aryl or aralkyl group of up to 22 carbon atoms;

R ¹¹ , R ¹⁶ and R ¹⁹ are each hydrogen;

R ¹² , R ¹³ and R ¹⁷ are each independently hydrogen or alkyl, aryl or aralkyl of up to 22 carbon atoms; and

f, g, h, i, j, k and l are each integers where:

f, g, j, k and l are each greater than or equal to 0 and less than or equal to 50,

0≦h≦2000, 0≦i≦200, the condition is (f+g)≦(2+3i+3k+4l) and 1.5≦(g+i+k)≦200.

In a preferred embodiment, R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁸ are each independently an alkyl group of 1-6 carbon atoms, and more Preferably methyl or ethyl, R ¹³ is hydrogen, 4≦i≦30; 1≦n≦15, h, j, k, l and m are each 0. In an alternative preferred embodiment, R ¹⁴ , R ¹⁵ and R ¹⁷ are each independently an alkyl group of 1-12 carbon atoms, R ¹³ and R ¹⁶ are each hydrogen, h+ i=2, 0≦j≦100, 2≦k≦100, l, m and n are each 0.

Some examples of hydrosilyl group-containing macromers (ii) include combinations of any two or more of M, D, T and Q groups as defined above and having at least two hydrosilyl groups Any linear, branched and/or crosslinked polymer.

In a specific embodiment, the macromer (ii) of general formula (II) is a compound having one or more M and/or M ^H groups and one or more D and/or D ^H groups Combined MD-type polysiloxane, where M represents Si(CH ₃ ) ₃ O-, M ^H represents HSi(CH ₃ ) ₂ O-, D represents -Si(CH ₃ ) ₂ O-, D ^H represents -Si(H)( _CH3 )O-. Some examples of suitable MD-type polysiloxanes for monomer (ii) include M ^H D _n M ^H , M ^H D ^H _n M, M ^H D ^H _n D _m M, M ^H D ^H _n M MD _- type polysiloxanes of _the classes ^H , _MHDHnDmMH ^{, MDHnM} _, and ^MDHnDmM , and combinations _thereof , wherein m ^and n each represent an integer of at ^least 1-500 . The ^DH group can also be incorporated randomly (ie, not as a block) into the D group. For example, M ^H D ^H _n D _m M can represent a polymer where n represents 5-20 and m represents 50-1500, wherein 5-20 D ^H groups are randomly incorporated into 50-1500 D groups .

In other embodiments, the M ^H and D ^H groups may independently have a higher number of hydrosilyl groups, for example, H ₂ Si(CH ₃ )O— and H ₃ SiO— groups (for M ^H ) or -Si(H) ₂ O- (for D ^H ).

The macromonomer (ii) preferably has a number average molecular weight of 200-30,000, preferably 500-20,000.

The macromonomer (ii) component of the curable composition can be obtained by combining two or more different alkylhalosilanes (eg, SiH(CH ₃ )Cl ₂ ) with Si(CH ₃ ) ₃ Cl, One or more of SiH(CH ₃ ) ₂ Cl, Si(CH ₃ ) ₂ Cl ₂ and Si(CH ₃ )Cl ₃ are co-hydrolyzed for 5-30 hours in the presence of water at, for example, 5-30° C. get.

Two commercially available macromers (ii) are TSF 484 and SS 4300C, both from Momentive Performance Materials Inc.

(c) Catalyst (iii)

The curable-textile-treating composition of the present invention comprises at least one catalyst (iii) effective for catalyzing the curing reaction of the macromers (i) and (ii) therein to produce the macromer units therein A cured resin composition linked together by -SiO- bonds.

Catalyst (iii) may be selected from metal fatty acid salts, amines, quaternary ammonium hydroxides, Lewis acids and the like. Examples of usable metal fatty acid salts include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin distearate, Butyl tin, tributyl tin acetate, tributyl tin octoate, tributyl tin laurate, dioctyl tin diacetate, dioctyl tin dilaurate, diethyl tin dioleate and monomethyl tin dioleate, and Zinc octenate, iron octenate, and tin octenate of hydrocarbon groups to which metal atoms are directly bonded. Examples of usable amines include organic amines (such as monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine, and hexamethylenetetramine), amino-containing silane compounds (such as α -aminopropyltriethoxysilane) and their salts. Examples of usable quaternary ammonium hydroxides include tetramethylammonium hydroxide, dimethylbenzylammonium hydroxide, and salts thereof. Examples of useful Lewis acids include _FeCl3 , _AlCl3 , _ZnCl2 , _ZnBr2 , and those Lewis acids with greater solubility in silicone media described in U.S. Patent 7,064,173, the entire contents of which are incorporated herein by reference .

(iv) optional components

Since even in the absence of catalyst (iii), over relatively long periods of time (i.e., over three months to two years and longer), mixtures of macromers (i) and (ii) can experience significant levels of , so it is desirable to keep them separate until just before a textile coating operation is required. In fact, it is then preferred to provide the curable composition of the invention as two or even three separate units, i.e. macromonomer (i) as one unit, macromonomer (ii) as a second unit, Where catalyst (iii) and optional component (iv) are added to unit (i) and/or unit (ii), or, preferably themselves, are provided as a separate third unit. Predetermined amounts of each unit are combined using known and conventional mixing equipment and procedures immediately prior to use in textile-treating operations to provide the curable textile-treating compositions of the present invention.

In a preferred embodiment of the invention, using suitable surfactants as emulsifiers, the macromonomers (i) and (ii) and (when kept separate from the macromonomer) the catalyst (iii) Individual units are supplied as aqueous emulsions. After the curing reaction of macromers (i) and (ii) to obtain a cured resin composition, the cured resin will be dispersed in the surfactant contained in the curable reaction medium. Thus, the use of surfactants allows the curable composition and subsequently cured resin to be applied to textiles as a water-based system that contains no or at most only a small amount (by weight, e.g., no more than the curable composition 20% by weight of the total weight) of an organic solvent or a mixture of multiple organic solvents. In a more preferred embodiment, the present invention-curable composition for treating textiles is substantially free of organic solvents and thus can be regarded as an essentially organic solvent-free system.

Useful surfactants for emulsification of the textile-treating composition of the present application may be selected from known and conventional nonionic, cationic or anionic surfactants.

Useful nonionic surfactants include those having a Hydrophile-Lipophile Balance (HLB) of 5-25. Some useful nonionic surfactants of this type are polyoxyalkylene alkyl ethers, polyoxyalkylene sorbitan esters, polyoxyalkylene esters and polyoxyalkylene alkylphenyl ethers. Some specific examples of primary surfactants are Brij35, Brig35L, Brij58, Brij78, Brij98, Brij700 and Brij721, all products of Croda.

Cationic surfactants useful for emulsifying the components of the curable compositions of the present invention include positively charged compounds containing a quaternary ammonium hydrophilic moiety in the molecule, for example R ³ R ⁴ R ⁵ R ⁶ N ⁺ X ^- represents quaternary ammonium salt or base, wherein ^R3 - ^R6 is an alkyl group containing 10-30 carbon atoms or an alkyl group derived from tallow, coconut oil or soybean, and X is a hydroxide or a halogen, for example, chlorine or bromine. Dialkyl dimethyl ammonium salts that can be used are represented by R ⁷ R ⁸ N ⁺ (CH ₃ ) ₂ X ^- , wherein R ⁷ and R ⁸ are alkyl groups containing 10-30 carbon atoms or derived from tallow, Alkyl group of coconut oil or soybean, X is hydroxide or halogen. The monoalkyltrimethylammonium salt that can be used in this application is represented by R ⁹ N ⁺ (CH ₃ ) ₃ X ^- , wherein R ⁹ is an alkyl group containing 10-30 carbon atoms or derived from tallow, coconut oil or The alkyl group of soybean, X is halogen. Representative quaternary ammonium salts and hydroxides are lauryltrimethylammonium chloride/lauryltrimethylammonium chloride (LTAC), cetyltrimethylammonium chloride (CTAC), di(decyltrimethylammonium Dialkyl)dimethylammonium bromide, Di(hexadecyl)dimethylammonium chloride, Di(hexadecyl)dimethylammonium bromide, Dioctadecyldimethylammonium chloride ammonium chloride, bis (eicosyl) dimethyl ammonium chloride, bis (eicosyl) dimethyl ammonium chloride, dicoco dimethyl ammonium chloride, di tallow dimethyl ammonium chloride Ammonium, Ditallow Dimethyl Ammonium Bromide and Cetyl Trimethyl Ammonium Hydroxide. These and other quaternary ammonium salts are commercially available under tradenames such as Adogen, Arquad, Tomah and Variquat.

Anionic surfactants useful for emulsifying the components of the curable compositions of the present invention include sulfonic acids and their salt derivatives. Some representative examples of useful anionic surfactants are alkali metal sulfosuccinates; sulfonated glycerides of useful fatty acids, such as sulfonated monoglycerides of cocoic acid; sulfonated monovalent alcohol esters; Salts, such as oleyl isethionate sodium; Amides of sulfamic acids, such as oleyl methyl taurine sodium salt; Products of sulfonation of fatty acid nitriles, such as palmitonitrile sulfonate; Sulfonated Aromatic hydrocarbons, such as sodium α-naphthalene monosulfonate; condensation products of naphthalenesulfonic acid and formaldehyde; sodium octahydroanthracene sulfonate; alkali metal alkyl sulfates; alkyl ethers having 8 or more carbon atoms Sulfates, such as sodium lauryl ether sulfate; and alkylaryl sulfonates having one or more alkyl groups having 8 or more carbon atoms, such as cetylbenzenesulfonic acid and _C20 alkane phenylsulfonic acid.

Additional optional components of the curable compositions of the present invention include small amounts of one or more organic solvents such as monohydric and polyhydric alcohols (when using curable and cured composition aqueous emulsions as described above) , pH buffering agents such as strong or weak acids (e.g. HCl, _H2SO4 , phosphoric acid, benzoic acid or citric acid (the pH of _the composition is preferably less than 5.0)), rewetting agents, viscosity modifiers (e.g. electrolytes such as chlorine calcium chloride), anti-gelling agents, fragrances, fragrance carriers, optical brighteners, colorants, hydrotropes, defoamers, anti-redeposition agents, enzymes, optical brighteners, opacifiers, stabilizers (such as melon ear gel and polyethylene glycol), anti-shrink agent, fabric drying agent, anti-spot agent, stain remover, bactericide, fungicide, biocide, antioxidant, anti-corrosion agent, preservative, pigment, dye, bleach Agents and bleach precursors, drape imparting agents, antistatic agents, fillers, thickeners, ironing aids, etc.

These and other optional components, if utilized, can be incorporated into the copolymer-forming composition in known and conventional amounts. The optional components may be incorporated into one or more of the aforementioned individual reactive component units and then combined to provide the copolymer-forming compositions of the present application (storage stability should be of concern), or they may vary Subcombinations are added individually, or when several optional components are utilized during or after combining and mixing operations, all at once, resulting in a fully formulated copolymer-forming composition.

The amount of water used to prepare the aqueous emulsion of macromers (i) and (ii) should be sufficient to provide an oil-in-water emulsion or a water-in-oil emulsion with good stability. In most cases, the amount of water may range from about 20 parts by weight (pbw) to about 2000 pbw, preferably from about 100 pbw to about 500 pbw, per 100 pbw of the total amount of monomers (i) and (ii).

A fully formulated curable composition of the present invention may be prepared by merely mixing and agitating the macromers (i) and (ii), the catalyst (iii) and the optional additional components using a mixer (eg, a homogenizer). and prepared according to (iv). The components of the copolymer-forming composition may be introduced into the vessel together in specified amounts or as a premix of macromonomers (i) and (ii), catalyst (iii) and optionally component (iv), Then add water. In this way, aqueous emulsions of oil-in-water or water-in-oil curable compositions are readily and conveniently obtained to provide compositions for treating cellulosic-textiles of the present application. The length of time for agitation depends on the balance of interfacial properties between the various components of the curable composition comprising any optional surfactant (iv) and water.

(e) Procedure for Applying Curable-Textile-Treatment Compositions to Textiles

Table 1 below describes the suitable widths for each of monomers (i) and (ii), catalyst (iii) and optional components such as surfactant (iv), water, etc. range and preferred range.

Examples of textiles for the treatment of the present application include nylon (polyamide), polyester, wool, cotton, linen, hemp, jute, and ramie, etc., including combinations of any of the foregoing with one or more other natural or synthetic fibers. Blends. Thus, for example, cotton and wool can be blended with fibers derived from polyesters, polyamides (eg, nylon), acrylics (eg, polyacrylonitrile), polyolefins, polyvinyl chloride, and polyvinylidene chloride. Preferably, the textile based on the blend of fibers comprises at least 35-40% by weight, most preferably at least 50-60% by weight of cotton or other cellulosic fibers.

The curable cellulosic textile treatment composition of the invention, advantageously containing one or more surfactants (iv) as described above, may be diluted with water to the desired activity level and applied to the fibers or Textiles, such as spraying, dipping, filling, kiss roll, etc. Removal of any treatment composition can be accomplished through the use of plate mills, centrifuges, etc. to control the amount of liquid absorbed by the textile. Drying can be performed with or without heat. When drying is effected by application of heat, the drying temperature may typically range from 70°C to 130°C and for a duration of 1-30 minutes, depending on the particular textile being treated. After removal of any excess emulsion, subsequent heating is generally required to complete curing. Effective curing temperatures typically range from 130°C to 200°C for a period of 1-30 minutes. After curing, the cured resin imparts one or more beneficial properties to the treated textile, for example, shrink resistance, wrinkle resistance, and/or desirable hand characteristics.

The amount of aqueous emulsion of the curable composition absorbed by the treated textile is generally from 0.1 to about 5% by weight, based on the total weight of macromers (i) and (ii). It may be desirable to prepare emulsified reactive component units with higher macromer content to reduce shipping and/or handling costs, and then dilute the emulsion with water just before use. The curable composition of the present application may have a macromer content of 10-80% by weight, preferably 20-40% by weight, based on the total weight of the composition.

The following examples illustrate the preparation of several curable-textile-treating compositions and their use for treating textiles, in particular, according to the invention, cotton woven fabrics (Table 2) and woolen woven fabrics (Table 3) respectively impart wrinkle resistance properties and anti-pilling properties.

Examples 1-3 illustrate the preparation of three different macromers (i), Examples 4-6 illustrate the preparation of three different macromers (ii), and Examples 7-9 illustrate the preparation of three different Preparation of Catalyst (iii). In these examples, all indicated percentages and parts are by weight.

Example 1

0.4% of C-15 secondary alcohol with 15 moles of ethylene oxide (tergitol 15-s-15, Dow Chemical), 4% cetyltrimethylammonium chloride (cationic surfactant), 4% poly Oxyethylene alkyl ether (nonionic surfactant; Emulsogen 1135S-70, Kao Chem.) and 59.6% water were charged into a 4-port 250ml reactor, using a radial flow sweep blade, at Mix for 10 minutes with low speed agitation (200 rpm). Subsequently, 30% octamethylcyclotetrasiloxane (D ₄ ) was charged into the container and mixed under high-speed agitation (600 rpm) for 50 minutes. The pre-emulsion was homogenized using a first pressure of 50 kg and a second pressure of 500 kg to provide an emulsion. The catalyst (2.0% aqueous solution of 10% KOH in water) was then charged into the vessel. The vessel was then heated slowly to 80°C for 5 hours, then the temperature was lowered to 45°C for 12 hours. Subsequently, 0.2% acetic acid neutralizing solution was charged.

Example 2

16 parts of silanol-terminated polysiloxane (viscosity: 40,000 cps) were mixed with 8 parts of TERGITOL™ N-6, and then 76 parts of water were slowly added at 800-1000 rpm to form a homogeneous mixture.

Example 3

2.4% of a C-15 secondary alcohol with 15 moles of ethylene oxide (tergitol 15-s-15, Dow Chemical), 4% cetyltrimethylammonium chloride (cationic surfactant) and 56.4% water Load into a 4-port 250ml reactor and mix under low speed agitation (200rpm) for 10 minutes using radial flow sweep blades. Subsequently, 35% octamethylcyclotetrasiloxane (D ₄ ) was charged into the container and mixed under high-speed agitation (600 rpm) for 50 minutes. Using a first pressure of 50 kg and a second pressure of 500 kg, the pre-emulsion was homogenized to obtain an emulsion. The catalyst (2.0% aqueous solution of 10% KOH in water) was then charged into the vessel. The vessel was then slowly heated to 80°C for 5 hours, then the temperature was lowered to 45°C for 12 hours. Subsequently, 0.2% acetic acid neutralizing solution was charged.

Example 4

2% of C-13 isotridecyl alcohol with 5 moles of ethylene oxide, 2% of C-13 isotridecyl alcohol with 7 moles of ethylene oxide, 30% of hydrogen polysiloxane ( Hydrogen polysiloxane) (TSF484, 1.6% hydrogen content, Momentive Performance Materials), 0.5% acetic acid and 65.5% water were charged into a 4-port 1-liter reactor and mixed for 10 minutes. The pre-emulsion was then homogenized using a first pressure of 50 kg and a second pressure of 500 kg to provide a stable emulsion.

Example 5

3% of C-13 isotridecyl alcohol with 6 moles of ethylene oxide, 3% of C-13 isotridecyl alcohol with 9 moles of ethylene oxide, 35% of hydrogen polysiloxane ( TSF 484, 1.6% hydrogen content, Momentive Performance Materials), 0.5% acetic acid and 58.5% water were charged into a 4-port 1 liter reactor and mixed for 10 minutes. The pre-emulsion was then homogenized using a first pressure of 50 kg and a second pressure of 500 kg to provide a stable emulsion.

Example 6

1% of C-13 isotridecyl alcohol with 6 moles of ethylene oxide, 3% of C-13 isotridecyl alcohol with 12 moles of ethylene oxide, 35% of hydrogen polysiloxane ( TSF 484, 1.6% hydrogen content, Momentive Performance Materials), 0.5% acetic acid and 60.5% water were charged into a 4-port 1 liter reactor, mixed for 10 minutes, then using a first pressure of 50 kg and a second pressure of 500 kg to make The pre-emulsion is homogenized to provide a stable emulsion.

Example 7

80% dibutyltin dilaurate was blended with 20% C-13 isotridecyl alcohol (Multiso 13-50, available from Sasol Chemical) with 5 moles of ethylene oxide.

Example 8

50% diethyltin dioleate was blended with 50% C-13 isotridecyl alcohol (Multiso 13-50, available from Sasol Chemical) with 6 moles of ethylene oxide.

Example 9

50% tributyltin laurate was blended with 50% C-13 isotridecyl alcohol (Multiso 13-50, available from Sasol Chemical) with 9 moles of ethylene oxide.

The following processing conditions were used: drying at 130°C for 2 minutes and curing at 160°C for 1 minute. The treated textiles were samples of 100% cotton woven fabric (40*40, 186 g/m ² ) (Table 2) and 100% wool knits (Table 3).

In the experimental data reported in Table 2 below, the hand was evaluated by a panel of five experienced individuals, rating the hand on a scale of 1-5, where 5=very soft and smooth and 1=rough. The recovery angle (which is a measure of wrinkle resistance of woven fabrics) is measured basically according to AATCC test method 66-2003, and the tear strength is measured according to ASTM D1429-09 by Falling-Pendulum (Elmendorf-type) equipment.

In the experimental data reported in Table 3, as in the case of Table 2, the touch was evaluated by a panel of five persons, and the anti-pilling grade was basically measured according to ASTM D test method 3512.

The results of the preceding tests are as follows:

As shown by the test data in Table 2, the samples of cotton woven fabric dosed with the curable composition exhibited significantly improved hand, recovery angle and tear compared to the control sample of cotton woven fabric to which no anti-wrinkle additive was applied Strength, the curable composition is formulated according to the invention (Examples 1-9) using macromers (i) and (ii) and catalyst (iii), and after curing, contains the resulting cured resin combination things.

The experimental data, as described in Table 3, shows that the wool knit in which no anti-pilling additives were applied has a higher percentage of the wool knit in which no anti-pilling additive is applied compared to samples of the wool knit treated according to the invention exhibiting significantly improved both hand and anti-pilling ratings. The control sample exhibited a rough hand and a relatively low anti-pilling rating.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. It is intended that the invention not be limited to the particular embodiment disclosed as the best mode disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. All references cited in this application are incorporated herein by reference.

Claims (29)

1. A curable composition comprising: at least one macromer (i), which is a polysiloxane of general formula (I): M ^A _a D ^B _b D ^C _c T ^D _d T ^E _e M ^A _a (I) in M ^A is (OR ¹ ) _y (R ² ) _3-y SiO _1/2 ; ^DB is R ³ ₂ SiO _2/2 ; ^DC is R ⁴ R ⁵ SiO _2/2 ; T ^D is R ⁶ SiO _3/2 ; and ^TE is R ⁷ SiO _3/2 ; in Each occurrence of ^R is independently hydrogen or a monovalent hydrocarbon group of 1-22 carbon atoms; R ² , R ³ , R ⁴ and R ⁶ are each independently a monovalent hydrocarbon group or alkoxy group of 1 to 22 carbon atoms; R and ^R are each independently a monovalent hydrocarbon group of 1-22 carbon atoms and are substituted by at least one amino and/ ^or oxiranyl group; and 1≤a≤19, 1≤b≤9999, 1≤c≤19, 0≤d≤9, 0≤e≤9 and 0≤y≤3; at least one macromer (ii) which is an oligomer or polymer containing at least two hydrosilyl groups per molecule; at least one catalyst (iii) for the copolymerization of macromonomers (i) and (ii); and Optionally at least one additional component (iv) selected from surfactants and aqueous surfactants. 2. The curable composition of claim 1, wherein each ^R1 is hydrogen. 3. The curable composition of claim 1, wherein in general formula (I), each R ¹ is independently a monovalent hydrocarbon group of 1 to 6 carbon atoms. 4. The curable composition of claim 1, wherein the hydrosilyl-containing macromer (ii) has the general formula (II): M _f M ^H _g D _h D ^H _i T _j T ^H _k Q _l (II) in M is R ⁸ R ⁹ R ¹⁰ SiO _1/2 ; M ^H is R ¹¹ R ¹² R ¹³ SiO _1/2 ; D is R ¹⁴ R ¹⁵ SiO _2/2 ; D ^H is R ¹⁶ R ¹⁷ SiO _2/2 ; T is R ¹⁸ SiO _3/2 ; ^TH is R ¹⁹ SiO _3/2 ; Q is SiO _4/2 ; in R ⁸ , R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ and R ¹⁸ are each independently an alkyl, aryl or aralkyl group of up to 22 carbon atoms; R ¹¹ , R ¹⁶ and R ¹⁹ are each hydrogen; R ¹² , R ¹³ and R ¹⁷ are each independently hydrogen or alkyl, aryl or aralkyl of up to 22 carbon atoms; and f, g, h, i, j, k and l are each integers where: f, g, j, k and l are each greater than or equal to 0 and less than or equal to 50, 0≦h≦2000, 0≦i≦200, the condition is (f+g)≦(2+3i+3k+4l) and 1.5≦(g+i+k)≦200. 5. The curable composition of claim 4, wherein at least one monomer is MD- with a combination of one or more M and/or M ^H groups and one or more D and/or D ^H groups Type of polysiloxane, where M represents Si(CH ₃ ) ₃ O-, M ^H represents HSi(CH ₃ ) ₂ O-, D represents -Si(CH ₃ ) ₂ O-, D ^H represents -Si(H )(CH ₃ )O-. 6. The curable composition of claim 1, wherein the catalyst (iii) is at least one selected from the group consisting of metal fatty acid salts, amines, quaternary ammonium hydroxides, and Lewis acids. 7. The curable composition of claim 1, said composition being substantially free of organic solvents. 8. A method for treating textiles to impart at least one - property enhancing properties thereto, said method comprising: a) applying to a textile an amount of a curable composition which, after undergoing curing, provides at least one cured resin effective to impart at least one textile property enhancing characteristic to said textile, said curable composition Include: At least one monomer (i) which is a polysiloxane of general formula (I): M ^A _a D ^B _b D ^C _c T ^D _d T ^E _e M ^A _a (I) in M ^A is (OR ¹ ) _y (R ² ) _3-y SiO _1/2 ; ^DB is R ³ ₂ SiO _2/2 ; ^DC is R ⁴ R ⁵ SiO _2/2 ; T ^D is R ⁶ SiO _3/2 ; and ^TE is R ⁷ SiO _3/2 ; in Each occurrence of ^R is independently hydrogen or a monovalent hydrocarbon group of 1-22 carbon atoms; R ² , R ³ , R ⁴ and R ⁶ are each independently a monovalent hydrocarbon group or alkoxy group of 1 to 22 carbon atoms; R and ^R are each independently a monovalent hydrocarbon group of 1-22 carbon atoms and are substituted by at least one amino and/ ^or oxiranyl group; and 1≤a≤19, 1≤b≤9999, 1≤c≤19, 0≤d≤9, 0≤e≤9 and 0≤y≤3; at least one macromer (ii) which is an oligomer or polymer containing at least two hydrosilyl groups per molecule; at least one catalyst (iii) for the copolymerization of macromonomers (i) and (ii); and Optionally at least one additional component (iv) selected from surfactants and aqueous surfactants; and b) subjecting said curable composition to curing conditions to produce a cured resin composition of macromers (i) and (ii) and to impart at least one-property-enhancing properties to textiles. 9. The method of claim 8, wherein said textile is all or part of a cellulosic textile, said cured resin composition imparts wrinkle-resistant properties to said textile, or said textile is all or part of wool textile, said cured The resin composition imparts anti-pilling properties to the textile. 10. The method of claim 8, wherein in general formula (I), each R ¹ is hydrogen. 11. The method of claim 8, wherein in general formula (I), each R ¹ is a monovalent hydrocarbon group of 1-6 carbon atoms. 12. The method of claim 8, wherein the hydrosilyl-containing macromer (ii) has the general formula (II): M _f M ^H _g D _h D ^H _i T _j T ^H _k Q _l (II) in M is R ⁸ R ⁹ R ¹⁰ SiO _1/2 ; M ^H is R ¹¹ R ¹² R ¹³ SiO _1/2 ; D is R ¹⁴ R ¹⁵ SiO _2/2 ; D ^H is R ¹⁶ R ¹⁷ SiO _2/2 ; T is R ¹⁸ SiO _3/2 ; ^TH is R ¹⁹ SiO _3/2 ; Q is SiO _4/2 ; in R ⁸ , R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ and R ¹⁸ are each independently an alkyl, aryl or aralkyl group of up to 22 carbon atoms; R ¹¹ , R ¹⁶ and R ¹⁹ are each hydrogen; R ¹² , R ¹³ and R ¹⁷ are each independently hydrogen or alkyl, aryl or aralkyl; and f, g, h, i, j, k and l are each integers where: f, g, j, k and l are each greater than or equal to 0 and less than or equal to 50, 0≦h≦2000, 0≦i≦200, the condition is (f+g)≦(2+3i+3k+4l) and 1.5≦(g+i+k)≦200. 13. The method of claim 12, wherein at least one monomer is a polysiloxane of the MD-type having one or more M and/or M ^H groups in combination with one or more D and/or D ^H groups Alkane, where M represents Si(CH ₃ ) ₃ O-, M ^H represents HSi(CH ₃ ) ₂ O-, D represents -Si(CH ₃ ) ₂ O-, D ^H represents -Si(H)(CH ₃ ) O-. 14. The method of claim 8, wherein the catalyst (iii) is at least one selected from the group consisting of metal fatty acid salts, amines, quaternary ammonium hydroxides, and Lewis acids. 15. The method of claim 8, wherein the curable composition is substantially free of organic solvents. 16. A cured resin composition obtained by curing the curable composition of claim 1. 17. Cured resin composition obtained by curing the curable composition of claim 4. 18. A textile to which the curable composition of claim 1 has been applied. 19. A textile to which the curable composition of claim 4 has been applied. 20. A textile to which the curable composition of claim 7 has been applied. 21. The textile of claim 18 which is wholly or partly a cellulosic textile or a woolen textile. 22. The textile of claim 19 which is wholly or partly a cellulosic textile or a woolen textile. 23. The textile according to claim 20, which is wholly or partly a cellulosic textile or a woolen textile. 24. A textile to which has been applied a cured resin composition resulting from curing of the curable composition of claim 1. 25. A textile to which has been applied a cured resin composition resulting from curing of the curable composition of claim 4. 26. The textile according to claim 24, which is wholly or partly a cellulosic textile or a woolen textile. 27. The textile according to claim 25, which is wholly or partly a cellulosic textile or a woolen textile. 28. The textile of claim 26, wherein said textile is all or part of a cellulosic textile, and said cured resin composition imparts wrinkle-resistant properties to said textile; or said textile is all or part of wool textile, said cured The resin composition imparts anti-pilling properties to the textile. 29. The textile of claim 27, wherein said textile is all or part of a cellulosic textile, and said cured resin composition imparts wrinkle-resistant properties to said textile; or said textile is all or part of wool textile, said cured The resin composition imparts anti-pilling properties to the textile.