US20130316606A1

US20130316606A1 - Composition and method for treating textiles

Info

Publication number: US20130316606A1
Application number: US13/901,983
Authority: US
Inventors: Wanchao Jiang; Shingo Tabei; Mark Leatherman; Renwei WANG; Yong Long
Original assignee: Momentive Performance Materials Inc
Current assignee: Momentive Performance Materials Inc
Priority date: 2012-05-24
Filing date: 2013-05-24
Publication date: 2013-11-28
Also published as: IN2014MN02260A; JP2015522670A; BR112014029306A2; WO2013177531A1; EP2855562A1; CN104350087A

Abstract

A curable composition useful for treating textiles to impart thereto upon the curing of one or more textile use-enhancing characteristics includes a first macromonomer (i) which is a polysiloxane possessing two or more terminal functional groups selected from the group consisting of hydroxyl, alkoxy and combinations thereof, a second macromonomer (ii) which is a polysiloxane containing two or more hydrosilyl (≡C—SiH) groups, catalyst (iii) and, optionally, one more additional component(s) (iv) such as surfactant(s), water, etc.

Description

FIELD OF THE INVENTION

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

BACKGROUND OF THE INVENTION

The frequent use and care of textile articles such as linens, garments and fabrics of all kinds, etc., can lead to their wrinkling. In particular, the wear and care (such as home laundering) of garments may result in their wrinkling. A variety of methods for imparting wrinkle resistance to textiles are known including physical and chemical approaches. A widely employed chemical-based procedure employs formaldehyde derivatives such as dimethyloldihydroxyethyleneurea (DMDHEU) as a textile-treating agent. Formaldehyde derivatives have long been used for this purpose due to their effectiveness and relatively low cost.
However, formaldehyde derivatives are subject to a number of drawbacks including reduction in fabric strength, formaldehyde release and harsh hand feel.
Approaches to avoiding or lessening the formaldehyde release problem have included reacting water-soluble alcohols with hydroxymethylated organic carbamates and using crosslinked polymaleates as formaldehyde-free durable press finishes. In order to reduce or inhibit reduction in textile strength and improve hand feel, polysiloxane has been employed together with known and conventional wrinkle reducing agents as cellulosic textile-treating agents.

SUMMARY OF THE INVENTION

The present invention fulfills the need for a composition and method for imparting at least one textile property-enhancing characteristic thereto, e.g., shrink resistance, wrinkle resistance, durable press, anti-pilling (in the case of woolen fabrics and wool blends), smoothness and/or elastic desirable hand feel, unaccompanied by the emission of harsh chemical odors and/or excessive or accelerated loss of strength of the treated textiles.
In accordance with the present invention, there is provided a cured resin composition for treating a textile to impart at least one textile property-enhancing characteristic thereto comprising:
at least one macromonomer (i) which is a polysiloxane of general formula (I):
M^A _aD^B _bD^C _cT^D _dT^E _eM^A _a (I)

- wherein
- M^Ais (OR¹)_y(R²)_3-ySiO_1/2;
- D^Bis R³ ₂SiO_2/2;
- D^Cis R⁴R⁵SiO_2/2;
- T^Dis R⁶SiO_3/2; and,
- T^Eis R⁷SiO_3/2;
- in which
- R¹, each instance, is independently hydrogen or a monovalent hydrocarbon group of from 1 to 22 carbon atoms;
- R², R³, R⁴and R⁶, each instance, is independently a monovalent hydrocarbon or alkoxy group of from 1 to 22 carbon atoms;
- R⁵and R⁷, each instance, is independently a monovalent hydrocarbon group of from 1 to 22 carbon atoms and substituted with at least one amino and/or oxirane 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 silylhydride (≡C—SiH) functional groups per molecule;
  - at least one catalyst (iii) for the curing reaction of macromonomers (i) and (ii); and,
  - optionally, at least one additional component (iv) selected from the group consisting of surfactant(s) and aqueous surfactant(s).

Further in accordance with the present invention, there is provided a method for treating a textile to impart at least one property-enhancing characteristic thereto comprising:
a) applying to a textile an amount of curable composition which after undergoing curing provides at least one cured resin composition which is effective to impart at least one textile property enhancing characteristic thereto, the curable composition comprising:
at least one macromonomer (i) which is a polysiloxane of general formula (I):
M^A _aD^B _bD^C _cT^D _dT^E _eM^A _a (I)

- wherein
- M^Ais (OR¹)_y(R²)_3-ySiO_1/2;
- D^Bis R³ ₂SiO_2/2;
- D^Cis R⁴R⁵SiO_2/2;
- T^Dis R⁶SiO_3/2; and,
- T^Eis R⁷SiO_3/2;
- in which
- R¹, each instance, is independently hydrogen or a monovalent hydrocarbon group of from 1 to 22 carbon atoms;
- R², R³, R⁴and R⁶, each instance, is independently a monovalent hydrocarbon or alkoxy group of from 1 to 22 carbon atoms;
- R⁵and R⁷, each instance, is independently a monovalent hydrocarbon group of from 1 to 22 carbon atoms and substituted with at least one amino and/or oxirane 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 silylhydride (≡C—SiH) functional groups per molecule;
  - at least one catalyst (iii) for the curing reaction of macromonomers (i) and (ii); and,
  - optionally, at least one additional component (iv) selected from the group consisting of surfactant(s) and aqueous surfactant(s); and,

b) subjecting the curable composition to curing conditions to produce a cured resin composition of macromonomer(s) (i) and (ii) and impart to the textile at least one property-enhancing characteristic.

DESCRIPTION OF THE INVENTION

As used herein, approximating language may be applied to modify a representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a description or value modified by a term or terms, such as “substantially” may not to be limited to the precise description or value specified, in some cases.
All ranges in the specifications and claims are inclusive of the endpoints and independently combinable. Numerical values in the specifications and claims are not limited to the specified values and may include values that differ from the specified value.
Numerical values are understood to be sufficiently imprecise to include values approximating the stated values, allowing for experimental errors due to the measurement techniques known in the art and/or the precision of an instrument used to determine the values.
It will be understood that any numerical range recited herein is intended to include all sub-ranges within that range and any combination of the various endpoints of such ranges or subranges.
The term “textile” as used herein shall be understood to include blended and non-blended textile fibers and strands, knitted, woven, non-woven or otherwise constructed fabrics, and finished and semi-finished textile articles and subunits thereof such as garments and garment sections, etc.
The curing of macromonomers (i) and (ii) involves the reaction of hydroxyl and/or alkoxyl groups present in each M^Amoiety of macromonomer(s) (i) with silyl hydride (≡C—SiH) groups present in macromonomer(s) (ii). When the reactive groups in moieties M^Aare hydroxyl (i.e., the case where each R¹group is hydrogen and each R²group, where present, is monovalent hydrocarbon), the curing reaction results in the condensation of macromonomers (i) and (ii) to form cured resin composition possessing —SiO— linkages accompanied by the release of hydrogen; when the reactive groups in moieties M^Aare alkoxy (i.e., the case where each R¹group is a monovalent hydrocarbon and each R²group, where present, is alkoxy), the curing reaction will also result in condensation of macromonomers (i) and (ii) to form cured resin composition possessing —SiO— linkages but with the splitting out of hydrocarbon R¹H wherein R¹is a monovalent hydrocarbon group as defined above. When macromonomer (i) possesses both hydroxyl and alkoxy functionality, in addition to the desired cured resin composition, hydrogen and hydrocarbon R¹H will both be formed as reaction by-products.
The present invention also includes the cured resin composition resulting from the curing reaction of macromonomers (i) and (ii) contained in the aforedescribed curable resin composition, textile treated with the curable resin composition and textile containing cured resin composition resulting from the curing reaction of macromonomers (i) and (ii).
Since cured resin composition derived from the curing reaction of macromonomers (i) and (ii) contains no formaldehyde-releasing component(s), a textile containing the cured resin composition is not subject to the release of disagreeable odors as are textiles treated with known and conventional formaldehyde derivative-based textile treating agents such as those referred to above. Use of the textile-treating composition of the invention permits one to dispense with the use of such formaldehyde derivatives entirely or to reduce their presence to such a level that formaldehyde release is no longer a significant problem. In general, it is preferred that the curable textile-treating composition of this invention and the resulting cured resin composition contain no, or at most 20 weight percent, formaldehyde derivative(s) as auxiliary anti-wrinkling additive(s).
The curable composition herein, the resulting cured resin composition and textile treating method of this invention are particularly advantageous for providing shrink resistant and wrinkle resistant textiles and textiles exhibiting favorable strength retention and hand characteristics. In the case of textiles based on wool and wool blends, the cured resin composition of the invention advantageously imparts an effective anti-pilling characteristic thereto.
(a) Hydroxyl and/or Alkoxy Group-Terminated Macromonomer (i)
The curable composition of the present invention includes at least one macromonomer (i) which is a polysiloxane of general formula (I):
M^A _aD^B _bD^C _cT^D _dT^E _eM^A _a (I)
wherein
M^Ais (OR¹)_y(R²)_3-ySiO_1/2;
D^Bis R³ ₂SiO_2/2;
D^Cis R⁴R⁵SiO_2/2;
T^Dis R⁶SiO_3/2; and,
T^Eis R⁷SiO_3/2;
in which
R¹, each instance, is independently hydrogen or a monovalent hydrocarbon group of from 1 to 22 carbon atoms;
R², R³, R⁴and R⁶, each instance, is independently a monovalent hydrocarbon or alkoxy group of from 1 to 22 carbon atoms;
R⁵and R⁷, each instance, is independently a monovalent hydrocarbon group of from 1 to 22 carbon atoms and substituted with at least one amino and/or oxirane group; and,
1≦a≦19, 1≦b≦9999, 1≦c≦19, 0≦d≦9, 0≦e≦9 and 0≦y≦3;
In monomer(s) (i), each R¹independently is hydrogen or a monovalent hydrocarbon group preferably having from 1 to 6 carbon atoms and more preferably from 1 to 4 carbon atoms.
Each R², R³, R⁴and R⁶independently is preferably a monovalent hydrocarbon or alkoxy group of from 1 to 6 carbon atoms, e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy and isomers thereof, and more preferably, from 1 to 4 carbon atoms, e.g., methoxy, ethoxy, propoxy, butoxy, and isomers thereof.
Each R⁵and R⁷group independently is preferably a monovalent linear or branched hydrocarbon group of from 2 to 20 carbon atoms, and more preferably, from 2 to 10 carbon atoms.
Values for a, b, c, d and are: 1≦a≦19, 1≦b≦9999, 1≦c≦19, 0≦d≦9, 0≦e≦9 and 0≦y≦3. Preferably the values are 2≦a≦9, 25≦b≦999, 1≦c≦9, 0≦d≦5, 0≦e≦5 and 0≦y≦2 and more preferably, 2≦a≦5, 100≦b≦999, 1≦c≦7, 0≦d≦3, 0≦e≦3 and 0≦y≦1.
Monomer(s) (i) preferably have a number average molecular weight ranging from 100 to 200,000 and preferably from 1000 to 100,000.
The macromonomer (i) component(s) of the curable composition can be obtained by combining at least one cyclic and/or linear siloxane, at least one alkoxy-terminated functional silane, optional catalyst, optional surfactant(s) and water to provide a reaction mixture and heating the mixture to a temperature and for a period of time sufficient to achieve substantially complete conversion of the siloxane and alkoxy silane reactants to monomer(s) (i). Thus, e.g., a reaction mixture can be prepared by combining at least one silanol group-containing cyclic siloxane such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane or decamethylcyctopentasiloxane (commonly referred to, respectively, as D₃, D₄and D₅, available from Momentive Performance Materials Inc.) and/or at least one silanol-containing linear siloxane with at least one aminoalkoxysilane, e.g., gamma-aminopropyl trimethoxy silane, aminopropyl triisopropoxy silane, and the like, optional catalyst(s), e.g., a strong base such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, and the like, optional surfactant(s), e.g., anionic surfactant(s) such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and the like, anionic surfactant(s) such as sodium lauryl sulfate, sodium dodecybenzene sulfonate, and the like, cationic surfactant(s) such as quarternary ammonium salts, and the like, combinations thereof, and water for emulsification of the macromonomer (i) reaction product(s) and heating the reaction mixture to a suitable reaction temperature, e.g., from 90 to 140° C., for a suitable period of time, e.g., from 5 to 10 hours, to achieve substantially complete conversation of the reactants to macromonomer(s) (i).
For further details of the foregoing method for making macromonomers (i), reference may be made to Published U.S. Patent Application No. 2012/0114928, the entire contents of which are incorporated by reference herein.
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) Silylhydride-Containing Macromonomers (II)
The curable resin-forming composition of the invention also includes at least one macromonomer (ii) which is an oligomer or polymer containing at least two silylhydride (≡C—SiH) functional groups per molecule.
In one embodiment of the invention, silylhydride (≡C—SiH)-containing macromonomers (ii) can be selected from among those of general formula (II):
M_fM^H _gD_hD^H _iT_jT^H _kQ_l (II)
wherein

- M is R⁸R⁹R¹⁰SiO_1/2;
- M^His R¹¹R¹²R¹³SiO_1/2;
- D is R¹⁴R¹⁵SiO_2/2;
- D^His R¹⁶R¹⁷SiO_2/2;
- T is R¹⁸SiO_3/2;
- T^H/is R¹⁹SiO_3/2;
- Q is SiO_4/2;
- in which
- R⁸, R⁹, R¹⁰, R¹⁴, R¹⁵and R¹⁸, each instance, independently is alkyl, aryl or aralkyl of up to 22 carbon atoms;
- R¹¹, R¹⁶and R¹⁹each is hydrogen;
- R¹², R¹³and R¹⁷, each instance, independently is hydrogen or alkyl, aryl or aralkyl of up to 22 carbon atoms; and,
- f, g, h, i, j, k and l are each integers wherein:
- 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, and provided that (f+g)≦(2+3i+3k+4l) and 1.5≦(g+i+k)≦200.

In a preferred embodiment, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵and R¹⁸, each instance, independently is alkyl of from 1 to 6 carbon atoms, and still more preferably methyl or ethyl, R¹³is hydrogen and 4≦i≦30; 1≦n≦15 and h, j, k, l and m are each 0. In an alternative preferred embodiment, R¹⁴, R¹⁵and R¹⁷, each instance, independently is alkyl of from 1 to 12 carbon atoms, R¹³and R¹⁶are each hydrogen and h+i=2, 0≦j≦100, 2≦k≦100 and l, m and n are each 0.
Some examples of silylhydride-containing macromonomer(s) (ii) include any of the linear, branched and/or crosslinked polymers having any two or more of a combination of M, D, T, and Q groups, as defined above, and having at least two silylhydride functional groups.
In a particular embodiment, macromonomer(s) (ii) of general formula (II) is an MD-type of polysiloxane having one or more M and/or M^Hgroups in combination with one or more D and/or D^Hgroups, wherein M represents Si(CH₃)₃O—, M^Hrepresents HSi(CH₃)₂O—, D represents Si(CH₃)₂O—, and D^H/represents Si(H)(CH₃)O—. Some examples of suitable MD-type polysiloxanes for monomer (ii) include the M^HD_nM^H, M^HD^H _nM, M^HD^H _nD_mM, M^HD_nM^H, M^HD^H _nD_mM^H, MD^H _nD_mM classes of MD-type polysiloxanes, and combinations thereof, wherein m and n each represent an integer at least 1 to 500. The D^Hgroups can also be randomly incorporated (i.e., not as a block) among the D groups. For example, M^HD^H _nD_mM can represent a polymer wherein n represents 5-20 and m represents 50-1500, and wherein the 5-20 D^Hgroups are randomly incorporated among the 50-1500 D groups.
In other embodiments, M^Hand D^Hgroups can independently have a higher number of silylhydride functional groups such as, for example, H₂Si(CH₃)O— and H₃SiO— groups for M^Hor —Si(H)₂O— for D^H.
Macromonomer(s) (ii) preferably have a number average molecular weight of from 200 to 30,000 and preferably from 500 to 20,000.
The macromonomer (ii) component(s) of the curable composition can be obtained by carrying out the cohydrolysis reaction of two or more different alkylhalosilanes, e.g., SiH(CH₃)Cl₂with one or more of Si(CH₃)₃Cl, SiH(CH₃)₂Cl, Si(CH₃)₂Cl₂and Si(CH₃)Cl₃, in the presence of water at, e.g., from 5 to 30° C. for from 5 to 30 hours.
Two commercially available macromonomers (ii) are TSF 484 and SS 4300C, both from Momentive Performance Materials Inc.
(c) Catalyst (iii)
The curable textile-treating composition of the invention includes at least one catalyst (iii) effective for catalyzing the curing reaction of macromonomers (i) and (ii) therein, to produce cured resin composition in which the macromonomer units are linked together through SiO— linkages.
Catalyst (iii) may be selected from the metallic fatty acid salts, amines, quaternary ammonium hydroxides, Lewis acids, and the like. Examples of useful metallic fatty acid salts include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin distearate, tributyltin acetate, tributyltin octoate, tributyltin laurate, dioctyltin diacetate, dioctyltin dilaurate, diethyltin dioleate and monomethyltin dioleate which have hydrocarbon groups directly bonded to metallic atoms, and zinc octenoate, iron octenoate and tin octenoate which do not have hydrocarbon groups directly bonded to metallic atoms. Examples of useful amines include organic amines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine and hexamethylenetetramine, amino group-containing silane compounds such as α-aminopropyltriethoxysilane and their salts. Examples of useful quaternary ammonium hydroxides include tetramethylammonium hydroxide, dimethylbenzyl ammonium hydroxide and their salts. Examples of useful Lewis acids include FeCl₃, AlCl₃, ZnCl₂, ZnBr₂, as well as those Lewis acids having greater solubility in siloxane media disclosed in U.S. Pat. No. 7,064,173, the entire contents of which are incorporated by reference herein.
(iv) Optional Components
Since mixtures of macromonomers (i) and (ii) even in the absence of catalyst (iii) can undergo a significant level of curing over relatively lengthy periods of time, say, over three months to two years and longer, it is desirable to keep them apart until just before they are needed for a textile coating operation. As a practical matter, then, it is preferred to provide the curable composition of this invention as two, or even three, isolated units, i.e., macromonomer(s) (i) as one unit, macromonomer(s) (ii) as the second unit with catalyst(s) (iii) and optional component(s) (iv) added to unit (i) and/or unit (ii) or, preferably, provided as its own separate third unit. Shortly prior to use in a textile-treating operation, predetermined amounts of each unit are combined employing known and conventional mixing equipment and procedures to provide the curable textile-treating composition of the invention.
In a preferred embodiment of the invention, the individual units of macromonomers (i) and (ii), and if maintained separately from the macromonomers, catalyst(s) (iii), are provided as aqueous emulsions employing suitable surfactant(s) as emulsifier(s). Following the curing reaction of macromonomers (i) and (ii) to yield cured resin composition, the cured resin will be dispersed within the surfactant(s) contained in the curable reaction medium. The use of surfactant(s) therefore allows both the curable composition and the subsequently cured resin to be applied to the textile as a water-based system, one containing no or at most only a minor amount by weight, e.g., not exceeding 20 weight percent of the total curable composition, of one or a mixture of organic solvents. In a more preferred embodiment, the curable textile-treating composition of the invention is substantially devoid of organic solvent(s) and thus can be regarded as an essentially organic solvent-free system.
Useful surfactants for the emulsification of the textile-treating composition herein can be selected from known and conventional nonionic, cationic or anionic surfactants.
Useful nonionic surfactants include those having hydrophilic lipophilic balance (HLB) between 5 and 25. Some useful nonionic surfactants of this category are polyoxyalkylene alkyl ethers, polyoxyalkylene sorbitan esters, polyoxyalkylene esters and polyoxyalkylene alkylphenyl ethers. Some specific examples of primary surfactant are Brij 35, Brig 35L, Brij 58, Brij 78, Brij 98, Brij 700, and Brij 721, all products of Croda.
Cationic surfactants useful for emulsifying the components of the curable composition of this invention include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged such as quaternary ammonium salts or bases represented by R³R⁴R⁵R⁶N⁺X⁻ where R³to R⁶are alkyl groups containing from 10 to 30 carbon atoms, or alkyl groups derived from tallow, coconut oil or soy and X is hydroxide or halogen, e.g., chlorine or bromine. Dialkyl dimethyl ammonium salts which can be used are represented by R⁷R⁸N⁺(CH₃)₂X⁻ where R⁷and R⁸are alkyl groups containing from 10 to 30 carbon atoms or alkyl groups derived from tallow, coconut oil or soy and X is hydroxide or halogen. Monoalkyl trimethyl ammonium salts which can be used herein are represented by R⁹N⁺(CH₃)₃X⁻ where R₉is an alkyl group containing from 10 to 30 carbon atoms or an alkyl group derived from tallow, coconut oil or soy and X is halogen. Representative quaternary ammonium salts and hydroxides are dodecyltrimethyl ammonium chloride/lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammoniumchloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, didocosyldimethyl ammonium chloride, dicoconutdimethyl ammonium chloride, ditallowedimethyl ammonium chloride, ditallowedimethylammonium bromide and cetyltrimethyl ammonium hydroxide. These and other quaternary ammonium salts are commercially available under names such as Adogen, Arquad, Tomah and Variquat.
Anionic surfactants useful for emulsifying the components of the curable composition of this invention include sulfonic acids and their salt derivatives. Some representative examples of useful anionic surfactants are alkali metal sulfosuccinates; sulfonated glyceryl esters of fatty acids useful such as sulfonated monoglycerides of coconut oil acids; salts of sulfonated monovalent alcohol esters such as sodium oleyl isethionate; amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride; sulfonated products of fatty acidnitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate; condensation products of naphthalene sulfonic acids with formaldehyde; sodium octahydro anthracene sulfonate; alkali metal alkylsulfates; ether sulfates having alkyl groups of eight or more carbon atoms such as sodium lauryl ether sulfate; and alkylaryl sulfonates having one or more alkyl groups of eight or more carbon atoms such as hexadecylbenzene sulfonic acid and C₂₀alkylbenzene sulfonic acid.
Additional optional components of the curable composition of the invention include minor amounts of one or more organic solvents such as monohydric and polyhydric alcohols (when aqueous emulsions of curable and cured compositions are employed as described above), pH buffering agents such as strong or weak acids, e.g., HCl, H₂SO₄, phosphoric, benzoic or citric acid (the pH of the compositions are preferably less than 5.0), rewetting agents, viscosity modifiers such as electrolytes, for example, calcium chloride, anti-gelling agents, fragrances, fragrance carriers, fluorescers, colorants, hydrotropes, antifoaming agents, anti-redeposition agents, enzymes, optical brightening agents, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinking agents, fabric crisping agents, anti-spotting agents, soil-release agents, germicides, fungicides, biocides, anti-oxidants, anti-corrosion agents, preservatives, pigments, dyes, bleaches and bleach precursors, drape imparting agents, antistatic agents, fillers, thickeners, ironing aids, and the like.
These and other optional components, if utilized, can be incorporated in the copolymer-forming composition in known and conventional amounts. The optional components can be incorporated in one or more of the aforementioned individual reaction component units to be later combined to provide the copolymer-forming composition herein (with due attention to storage stability concerns) or they can be added individually, in various sub-combinations or all at once when several optional components are utilized during or after the combining and mixing operation resulting in the fully formulated copolymer-forming composition.
The amount of water used in the preparation of aqueous emulsions of macromonomers (i) and (ii) should be adequate to provide either an oil-in-water emulsion or a water-in-oil emulsion of good stability. In most cases, the amount of water can be in the range of 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).
Fully formulated curable compositions of this invention can be prepared by merely mixing and agitating macromonomers (i) and (ii), catalyst(s) (iii) and optional additional component(s) (iv) with a stirrer, e.g., a homogenizer. The components of the copolymer-forming composition can be introduced together into a vessel in a specific amount or as a pre-mixture of macromonomers (i) and (ii), catalyst(s) (iii) and optional component(s) (iv) followed by the addition of water. In this manner an aqueous emulsion of curable composition of the oil-in-water or water-in-oil type is readily and conveniently obtained to provide the cellulosic textile-treating composition herein. The length of time for agitation depends upon the balance of the interfacial properties between the components of the curable composition including any optional surfactant(s) (iv) and water.
(e) Procedures for Applying Curable Textile-Treating Composition to Textiles
Table 1 below sets forth suitable broad and preferred ranges for each of monomers (i) and (ii), catalyst(s) (iii) and optional components such as surfactants (iv), water, etc., for the copolymer-forming composition of the invention.

TABLE 1

Weight Ranges of Components of the Curable Textile-Treating
Composition As a Percent of the Total Composition

	Broad Range	Preferred Range

Required Components
macromonomer(s) (i)	60-97	75-90.0
macromonomer(s) (ii)	3-35	5-20
catalyst(s) (iii)	0.1-5	0.5-1
Optional Components (iv)
(when utilized)
surfactant(s)	1-80	2-10
Water	35-90	45-70
Other(s)	0.25-5	0.5-2

Examples of textiles for treatment herein include nylon (polyamides), polyester, wool, cotton, flax, hemp, jute and ramie, and the like, including blends of any of the foregoing with one or more other natural or synthetic fibers. Thus, e.g., cotton and wool can be blended with fibers derived from polyesters, polyamides (e.g., nylons), acrylics (e.g., polyacrylonitrile), polyolefins, polyvinyl chloride, and polyvinylidene chloride. Preferably, the textiles based on blends of fibers include at least 35 to 40 percent by weight, and most preferably at least 50 to 60 percent by weight, of cotton or other cellulosic fiber.
The curable cellulosic textile treating composition of the present invention, advantageously containing one or more surfactants (iv) as described above, can be diluted with water to a desired active level and applied to a fiber or textile by any suitable means such as spraying, dipping, padding, kiss roll, and the like. Removal of any treating composition can be achieved by using a mangle, centrifugal separator, or the like, to control the amount of liquid absorbed by the textile. Drying can be effected with or without heat. Depending upon the particular textile being treated, when drying is performed by application of heat, the drying temperature can generally range from 70° to 130° C. and its duration from 1 to 30 minutes. After removal of any excess emulsion, subsequent heating to complete curing is usually required. Effective curing temperatures generally range from 130° C. to 200° C. for periods of from 1 to 30 minutes. Following curing, the cured resin(s) impart one or more advantageous properties to the treated textile, e.g., shrink resistance, wrinkle resistance and/or desirable hand feel characteristics.
The amount of aqueous emulsion of curable composition that a treated textile absorbs will generally range from 0.1 to about 5 weight percent based on the total weight of macromonomers (i) and (ii). It may be desirable to prepare emulsified reaction component units having higher macromonomer contents in order to reduce shipping and/or handling costs and then to dilute the emulsions with water immediately prior to use. The macromonomer contents of the curable composition herein can range from 10 to 80 weight percent, preferably from 20 to 40 weight percent, based on the total weight of the composition.
The following examples illustrate the preparation of several curable textile-treating compositions and their use in treating textiles, specifically, cotton woven (Table 2) and wool knits (Table 3), to impart, respectively, a wrinkling resistance property and an anti-pilling property thereto in accordance with the invention.
Examples 1 to 3 illustrate the preparation of three different macromonomers (i), Examples 4 to 6 illustrate the preparation of three different macromonomers (ii) and Examples 7-9 illustrate the preparation of three different catalysts (iii). In these examples, all indicated percents and parts are by weight.

Example 1

0.4% of a C-15 secondary alcohol with 15 moles ethylene oxide (tergitol 15-s-15, Dow Chemical), 4% hexadecyl trimethyl ammonium chloride (cationic surfactant), 4% polyoxyethylene alkyl ether (nonionic surfactant; Emulsogen 1135S-70, Kao Chem.) and 59.6% water were charged to a 4-neck 250 ml reactor and mixed for 10 min under low agitation (200 rpm) with a radical flow sweep blade. Thereafter, 30% of octamethylcyclotetrasiloxane (D₄) was charged to the vessel and mixed for 50 min under high agitation (600 rpm). The pre-emulsion was homogenized with the first pressure 50 kg and the second pressure 500 kg to provide an emulsion. Thereafter catalyst (2.0% of an aqueous solution of 10% KOH in water) was charged into the vessel. The vessel was then slowly heated to 80° C. for 5 hours, and then the temperature was decreased to 45° C. and maintained for 12 hours. Thereafter, 0.2% of acetic acid was charged to neutralize the solution.

Example 2

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

Example 3

2.4% of a C-15 secondary alcohol with 15 moles ethylene oxide (tergitol 15-s-15, Dow Chemical), 4% hexadecyl trimethyl ammonium chloride (cationic surfactant) and 56.4% water were charged to a 4-neck 250 ml reactor and mixed for 10 min. under low agitation (200 rpm) with a radical flow sweep blade. Thereafter, 35% of octamethylcyclotetrasiloxane (D₄) was charged to the vessel and mixed for 50 min under high agitation (600 rpm). The pre-emulsion was homogenized with the first pressure 50 kg and the second pressure 500 kg to give an emulsion. Thereafter catalyst (2.0% of an aqueous solution of 10% KOH in water) was charged into the vessel. The vessel was then slowly heated to 80° C. for 5 hours, and then the temperature was decreased to 45° C. and maintained for 12 hours. Thereafter, 0.2% of acetic acid was charged to neutralize the solution.

Example 4

2% of a C-13 isotridecanol with 5 moles ethylene oxide, 2% of a C-13 isotridecanol with 7 moles ethylene oxide, 30% of hydrogen polysiloxane (TSF 484, 1.6% hydrogen content, Momentive Performance Materials), 0.5% of acetic acid and 65.5% of water were charged to a 4-neck 1 liter reactor and mixed for 10 min. And then the pre-emulsion was homogenized with the first pressure 50 kg and the second pressure 500 kg to provide a stable emulsion.

Example 5

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

Example 6

1% of a C-13 isotridecanol with 6 moles ethylene oxide, 3% of a C-13 isotridecanol with 12 moles ethylene oxide, 35% of hydrogen polysiloxane (TSF 484, 1.6% hydrogen content, Momentive Performance Materials), 0.5% of acetic acid and 60.5% of water were charged to a 4-neck 1 liter reactor and mixed for 10 min. And then the pre-emulsion was homogenized with the first pressure 50 kg and the second pressure 500 kg to provide a stable emulsion.

Example 7

80% of Dibutyltin Dilaurate was blended with 20% C-13 isotridecanol with 5 moles ethylene oxide (Multiso 13-50, available from Sasol Chemical).

Example 8

50% of diethyltin dioleate was blended with 50% C-13 isotridecanol with 6 moles ethylene oxide (Multiso 13-60, available from Sasol Chemical).

Example 9

50% of tributyltin laurate was blended with 50% C-13 isotridecanol with 9 moles ethylene oxide (Multiso 13-90, available from Sasol Chemical),
The following treatment conditions were employed: drying at 130° C. for 2 minutes and curing at 160° C. for 1 minute. The treated textiles were specimens of 100% cotton woven (40*40, 186 g/m²) (Table 2) and 100% wool knits (Table 3).
In the experimental data reported in Table 2 below, hand feel was evaluated by a panel of five experienced individuals, hand feel being rated on a scale of 1 to 5 with 5=very soft and slick and 1=harsh. Recovery Angle, a measure of wrinkle resistance for woven fabrics, was measured substantially in accordance with AATCC Test Method 66-2003 and Tear Strength was measured by Falling-Pendulum (Elmendorf-type) Apparatus in accordance with ASTMD 1429-09.
In the experimental data reported in Table 3, hand feel was evaluated by a panel of five as in the case of Table 2 and the anti-pilling rating was measured substantially in accordance with ASTMD Test Method 3512.
The results of the aforedescribed tests were as follows:

TABLE 2

Test Results for Treated Cotton Woven

		Curing		Recovery
Macromonomer	Macromonomer	Catalyst		Angle (°,	Tear Strength
(i)	(ii)	(iii)	Hand Feel	weft + warp)	(N, weft + warp)

Control	—	—	—	Harsh	90	35
Dosage	100 of	10 of	1 of	Smooth	200	56
(g/l)	Example 1	Example 4	Example 7	and bouncy
	200 of	20 of	2 of	Smooth	220	67
	Example 2	Example 5	Example 8	and bouncy
	100 of	30 of	2 of	Smooth	230	62
	Example 3	Example 6	Example 9	and bouncy

As the test data in Table 2 show, compared with the control specimens of cotton woven to which no wrinkle resistant additive was applied, the specimens of cotton woven dosed with curable compositions formulated with macromonomers (i) and (ii) and catalyst (iii) in accordance with the invention (Examples 1-9) and, following curing, containing the resulting cured resin composition, exhibited significantly improved hand feel, Recovery Angle and Tear Strength.

TABLE 3

Test Results for Treated Wool Knits

Macromonomer	Macromonomer	Curing		Anti-pilling
(i)	(ii)	Catalyst (iii)	Hand Feel	rating

Control	—	—	—	Harsh	2
Dosage	100 of	10 of Example 4	1 of Example 7	Smooth and	3
(g/l)	Example 1			bouncy
	200 of	20 of Example 5	2 of Example 8	Smooth and	3
	Example 2			bouncy
	100 of	30 of Example 6	2 of Example 9	Smooth and	3
	Example 3			bouncy

As shown in the experimental data set forth in Table 3, the control specimens of wool knits to which no anti-pilling additive was applied exhibited harsh hand feel and a relatively low anti-pilling rating compared with the specimens of wool knits treated in accordance with the invention which exhibited both significantly improved hand feel and anti-pilling rating.
While the invention has been described with reference to a preferable embodiment, those skilled in the art will understand 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 for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. All citations referred herein are expressly incorporated herein by reference.

Claims

1. A curable composition comprising:

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

M^A _aD^B _bD^C _cT^D _dT^E _eM^A _a (I)

wherein

M^Ais (OR¹)_y(R²)_3-ySiO_1/2;

D^Bis R³ ₂SiO_2/2;

D^Cis R⁴R⁵SiO_2/2;

T^Dis R⁶SiO_3/2; and,

T^Eis R⁷SiO_3/2;

in which

R¹, each instance, is independently hydrogen or a monovalent hydrocarbon group of from 1 to 22 carbon atoms;

R², R³, R⁴and R⁶, each instance, is independently a monovalent hydrocarbon or alkoxy group of from 1 to 22 carbon atoms;

R⁵and R⁷, each instance, is independently a monovalent hydrocarbon group of from 1 to 22 carbon atoms and substituted with at least one amino and/or oxirane 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 silylhydride functional groups per molecule;

at least one catalyst (iii) for the copolymerization reaction of macromonomer(s) (i) and (ii); and,

optionally, at least one additional component (iv) selected from the group consisting of surfactant(s) and aqueous surfactant(s).

2. The curable composition of claim 1 wherein each R¹is hydrogen.

3. The curable composition of claim 1 wherein in general formula (I) each R¹independently is a monovalent hydrocarbon group of from 1 to 6 carbon atoms.

4. The curable composition of claim 1 wherein silylhydride-containing macromonomer(s) (ii) are of the general formula (II):

M_fM^H _gD_hD^H _iT_jT^H _kQ_l (II)

wherein

M is R⁸R⁹R¹⁰SiO_1/2;

M^His R¹¹R¹²R¹³SiO_1/2;

D is R¹⁴R¹⁵SiO_2/2;

D^His R¹⁶R¹⁷SiO_2/2;

T is R¹⁸SiO_3/2;

T^H/is R¹⁹SiO_3/2;

Q is SiO_4/2;

in which

R⁸, R⁹, R¹⁰, R¹⁴, R¹⁵and R¹⁸, each instance, independently is alkyl, aryl or aralkyl of up to 22 carbon atoms;

R¹¹, R¹⁶and R¹⁹each is hydrogen;

R¹², R¹³and R¹⁷, each instance, independently is hydrogen or alkyl, aryl or aralkyl of up to 22 carbon atoms; and,

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

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, and provided that (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 an MD-type of polysiloxane having one or more M and/or M^Hgroups in combination with one or more D and/or D^Hgroups, wherein M represents Si(CH₃)₃O—, M^Hrepresents HSi(CH₃)₂O—, D represents —Si(CH₃)₂O—, and D^Hrepresents —Si(H)(CH₃)O—.

6. The curable composition of claim 1 wherein catalyst (iii) is at least one member of the group consisting of metallic fatty acid salt, amine, quaternary ammonium hydroxide and Lewis acid.

7. The curable composition of claim 1 substantially devoid of organic solvent(s).

8. A method for treating a textile to impart at least one property-enhancing characteristic thereto comprising:

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

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

M^A _aD^B _bD^C _cT^D _dT^E _eM^A _a (I)

wherein

M^Ais (OR¹)_y(R²)_3-ySiO_1/2;

D^Bis R³ ₂SiO_2/2;

D^Cis R⁴R⁵SiO_2/2;

T^Dis R⁶SiO_3/2; and,

T^Eis R⁷SiO_3/2;

in which

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

optionally, at least one additional component (iv) selected from the group consisting of surfactant(s) and aqueous surfactant(s); and,

9. The method of claim 8 wherein the textile is in whole or in part a cellulosic textile to which the cured resin composition imparts a wrinkling resistant characteristic or the textile is in whole or in part a woolen textile to which the cured resin composition imparts an anti-pilling characteristic.

10. The method of claim 8 wherein in general formula (I), each R¹is hydrogen.

11. The method of claim 8 wherein in general formula (I), each R¹is a monovalent hydrocarbon group of from 1 to 6 carbon atoms.

12. The method of claim 8 wherein silylhydride-containing macromonomer(s) (ii) are of the general formula (II):

M_fM^H _gD_hD^H _iT_jT^H _kQ_l (II)

wherein

M is R⁸R⁹R¹⁰SiO_1/2;

M^His R¹¹R¹²R¹³SiO_1/2;

D is R¹⁴R¹⁵SiO_2/2;

D^His R¹⁶R¹⁷SiO_2/2;

T is R¹⁸SiO_3/2;

T^H/is R¹⁹SiO_3/2;

Q is SiO_4/2;

in which

R¹¹, R¹⁶and R¹⁹each is hydrogen;

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

13. The method of claim 12 wherein at least one monomer is an MD-type of polysiloxane having one or more M and/or M^Hgroups in combination with one or more D and/or D^Hgroups, wherein M represents Si(CH₃)₃O—, M^Hrepresents HSi(CH₃)₂O—, D represents Si(CH₃)₂O—, and D^Hrepresents —Si(H)(CH₃)O—.

14. The method of claim 8 wherein catalyst (iii) is at least one member of the group consisting of metallic fatty acid salt, amine, quaternary ammonium hydroxide and Lewis acid.

15. The method of claim 8 wherein the curable composition is substantially devoid of organic solvent(s).

16. The cured resin composition obtained from the curing of the curable composition of claim 1.

17. The cured resin composition obtained from the curing of the curable composition of claim 4.

18. A textile having applied thereto the curable composition of claim 1.

19. A textile having applied thereto the curable composition of claim 4.

20. A textile having applied thereto the curable composition of claim 7.

21. The textile of claim 18 which in whole or in part is a cellulosic textile or a woolen textile.

22. The textile of claim 19 which in whole or in part is a cellulosic textile or a woolen textile.

23. The textile of claim 20 which in whole or in part is a cellulosic textile or a woolen textile.

24. A textile having applied thereto the cured resin composition resulting from the curing of the curable composition of claim 1.

25. A textile having applied thereto the cured resin composition resulting from the curing of the curable composition of claim 4.

26. The textile of claim 24 which in whole or in part is a cellulosic textile or a woolen textile.

27. The textile of claim 25 which in whole or in part is a cellulosic textile or a woolen textile.

28. The textile of claim 26 wherein the textile is in whole or in part a cellulosic textile to which the cured resin composition imparts a wrinkling resistant characteristic or the textile is in whole or in part a woolen textile to which the cured resin composition imparts an anti-pilling characteristic.

29. The textile of claim 27 wherein the textile is in whole or in part a cellulosic textile to which the cured resin composition imparts a wrinkling resistant characteristic thereto or the textile is in whole or in part a woolen textile to which the cured resin composition imparts an anti-pilling characteristic.