JPH02210073A - Treating agent for fiber - Google Patents

Abstract

PURPOSE:To obtain the subject treating agent, containing a copolymer emulsion consisting of an organopolysiloxane and specific monomer and a water-soluble amino resin, etc., and capable of imparting crease resistance, shrinkproofness and wash and wear(W/W) properties and further soft hand, etc., to natural fiber, etc. CONSTITUTION:A treating agent for fiber obtained by blending (A) a copolymer emulsion prepared by carrying out emulsion polymerization of a mixture consisting of (A1) an O/W emulsion of 5-95 pts.wt. organopolysiloxane expressed by formula I (R<1> to R<3> are groups selected form 1-20C monofunctional hydrocarbons and monofunctional halogenated hydrocarbons; Y is group in which radically reactive group and SH group are selected from organic groups; X is H, etc.; m is >=10000; n is >=1) and (A2) 95-5 pts.wt. (mixed) monomers consisting of (i) 70-100wt.% polyfunctional monomer selected from acrylic and methacrylic monomers expressed by formula II (R<5> is H, etc.; R<6> is 1-18C alkyl, etc.), (ii) 0-20wt.% polyfunctional monomer, such as ethylenically unsaturated amide, and (iii) 0-20wt.% ethylenically unsaturated monomers other than those described above with (B) a water-soluble amino resin and (C) a curing catalyst.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a treatment agent for fibers, particularly for treatment of cellulose fibers such as cotton, hemp, regenerated cellulose (rayon, chiebra), or other natural fibers or Textile products made of synthetic fibers and blends have properties such as wrinkle resistance, shrink resistance, wash-and-wear suitability (hereinafter abbreviated as W/W properties), and permanent press suitability (hereinafter abbreviated as PP properties). The present invention relates to a treatment agent for fibers that imparts a texture rich in flexibility, rebound, and thickness.

(Prior art and problems to be solved) Textile products made of cellulose fibers or blends of these and other natural fibers or synthetic fibers are treated in a bath made of a water-soluble amino resin and an amino resin curing catalyst. Resin processing that imparts wrinkle resistance, shrink resistance, III/W properties, and PP properties is widely practiced.

However, while amino resin treatment imparts the above properties, it essentially reduces the tensile, tear, bending, and abrasion strengths of textile products, and also hardens the texture, resulting in many In some cases, so-called fabric softeners have been used in combination. As this softening agent, silicone-based ones, anionic, non-ionic, and cationic fatty acids or higher alcohol derivatives, polyethylene emulsions, etc. are well known, but among these, silicone-based ones have a slimy feeling. Polyethylene emulsion Since it has no adhesion to fibers or amino resins, this material also falls off with repeated washing, reducing its effectiveness.
Additionally, there is an undesirable slimy feeling.

As mentioned above, undesirable side effects of amino resin treatment include a decrease in strength and a tendency to develop a rough, hard, paper-like texture. It is necessary for a fabric softener to improve both of these aspects, but in particular, in terms of texture, it is most desirable to impart flexibility, rebound, and a thick feel. Furthermore, these properties must be able to withstand washing and dry cleaning. Regarding these points, existing amine resin fiber treatment agents do not have wrinkle resistance, wrinkle resistance,
A fiber that provides shrink-proofing properties, W/W properties, and PP properties, but does not cause a decrease in strength, and is also highly durable even after washing, is soft, has rebound resilience, and has a rich texture with a thick texture. It was hoped that a treatment agent would emerge.

[Means to solve the problem]

The invention of the present application relates to a treatment agent for fibers that solves the above-mentioned problems. The first invention of the present application is A, (1) general formula (I) (wherein R1, R2, and R3 are a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, respectively) 1f! or two or more groups selected from 1f!, Y is one or two or more groups selected from radically reactive groups and radical groups including SH groups, x is a hydrogen atom, a lower alkyl group and a group represented by the formula R'R''R'Si (R1,
R2 is the same as above, R4 is the same group as R1 or Y), m is a positive integer equal to or less than io or ooo, and n is 1 or more. organopolysiloxane, which is an integer of
5 to 95 parts by weight of an oil-in-water emulsion and (2) a) general formula (II) S CH2-C-(:OOR' (wherein, R5 is a hydrogen atom or a methyl group, and R6 has 1 carbon number)
-18 alkyl groups or alkoxy-substituted alkyl groups) One or more monomers selected from acrylic and methacrylic monomers
70-100% by weight) ethylenically unsaturated amide,
Alkylol or alkoxyalkyl substituted compounds of ethylenically unsaturated amides, oxirane groups, hydroxyl groups,
Ethylenically unsaturated monomers containing carboxyl groups, amino groups, sulfonic acid groups, phosphoric acid groups, polyalkylene oxide groups or quaternary ammonium groups, complete esters of polyhydric alcohols and acrylic acid or methacrylic acid, dibasic acids One or more polyfunctional monomers selected from the group of diallyl ester, allyl acrylate, allyl methacrylate, and divinylbenzene 0 to 2
0% by weight 8) One or more ethylenically unsaturated monomers other than (a) and 8) Total of single or mixed monomers (a) to 8) consisting of 0 to 20% by weight 1
00% by weight)) is emulsion polymerized in the presence of a radical polymerization initiator, and a water-soluble amino resin C4 is characterized by comprising a curing catalyst for water-soluble amino resin. The gist of this paper is a treatment agent for fibers.

A second invention of the present application is a liquid organopolysiloxane E containing at least three silicon-bonded hydrogen atoms per 0.1 molecule in addition to components A, B, and C according to claim 1; The object of the present invention is to provide a physical agent for fibers, characterized in that it contains a catalyst for a crosslinking reaction caused by a component.

In other words, the present inventors have provided textile products containing cellulose fibers with wrinkle resistance, shrink resistance, W/W properties, PP properties, and durable flexibility without causing a decrease in strength even after washing. As a result of intensive research in order to obtain a fiber treatment composition that can impart a texture rich in rebound and thickness, we have developed an emulsion of an organopolysiloxane having radically active groups and an acrylic and/or methacrylic composition. By using a composition consisting of a copolymerized emulsion obtained by emulsion polymerization of a mixture with a monomer mainly consisting of a water-soluble amino resin and its curing catalyst, it is possible to achieve the objective, and It was discovered that good results could be obtained by using the above composition in combination with an organopolysiloxane having a 51-H group, and further studies were conducted on the composition of the organopolysiloxane and monomer, the type and amount of the amino resin, etc. The present invention was completed.

The organopolysiloxane as component A (1) used in the fiber treatment agent of the present invention is represented by the general formula (I) as described above, and R
1, R2, and R3 have a carbon number of 1, exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl groups, and aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups.
~20 monovalent hydrocarbon groups and groups in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, and X is R'R"R'Si
Triorganosilyl group represented by (11, R2 is the same as above, R4 is the same group as R' or Y), hydrogen atom, methyl group, ethyl group, propyl group, butyl group, etc. having 1 to 5 carbon atoms
Y is a radical-reactive group exemplified by vinyl group, allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, and S) It is selected from group-containing organic groups. Also, m is 10. It is a positive integer less than or equal to Goo, and n is an integer greater than or equal to 1, preferably in the range of 500<1<a, ooo, and 1<n<500.

Organopolysiloxane represented by general formula (I) 4.5
．． Cyclic organopolysiloxane represented by 6), dimethylpolysiloxane represented by the formula n=o or a positive integer), etc., in which both ends of the molecule are blocked with trimethylsilyl groups, etc. As a raw material for introducing, liquid dimethylpolysiloxane in which both ends of the molecular chain are capped with hydroxyl groups, as exemplified by (Formula n is a positive integer), is liquid dimethyl polysiloxane in which both ends of the molecular chain are capped with alkoxy groups. Examples of polysiloxanes, silanes such as formulas, and their hydrolyzed products include (in the formulas, Rho 3.4, 5.6).

In addition, if it is a small amount that does not impede the purpose of the present invention, 3.
Functional trialkoxysilanes and their hydrolysis products can also be used.

The emulsion of the organopolysiloxane represented by the general formula CI) may be produced by any known method, and one method is to use a cyclic low-molecular-weight siloxane such as the above-mentioned octamethylcyclotetrasiloxane as a raw material and a radical-reactive group. Alternatively, a dialkoxysilane compound containing an SH group and/or a hydrolyzate thereof is polymerized in the presence of a strong alkaline catalyst or a strong acidic catalyst to obtain a high molecular weight organopolysiloxane, and then a suitable emulsifier is added. This is done by emulsifying and dispersing it in water. Another method uses, for example, the above-mentioned low-molecular-weight organopolysiloxane and a radical-reactive group or SH group-containing dialkoxysilane and/or its hydrolyzate as raw materials, and a sulfonic acid surfactant and a hydrolyzate thereof. /or by emulsion polymerization in water in the presence of a sulfate ester surfactant. In addition, in the case of this emulsion polymerization,
Using similar raw materials, they are emulsified and dispersed in water using a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, and then polymerized by adding an appropriate amount of a strong alkaline substance such as potassium hydroxide or sodium hydroxide. You can also do it.

Among the methods for producing an emulsion of organopolysiloxane described above, the strong alkaline polymerization catalyst used to obtain a high molecular weight organopolysiloxane in advance is potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, and tetrabutyl. Phosphonium hydroxide, etc., and strong acidic polymerization catalysts include sulfuric acid, trifluoromethanesulfonic acid, etc., and any of them can be used for subsequent use if they are neutralized to eliminate the catalytic activity after completion of polymerization. Examples of surfactants for emulsifying the obtained high molecular weight organopolysiloxane include various nonionic polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan fatty acid esters, and polyoxyethylene. Examples include sorbitan fatty acid ester, sucrose fatty acid ester, anionic sodium lauryl sulfate, sodium polyoxyethylene dodecyl sulfate, etc., and cationic alkyltrimethylammonium chloride, alkylbenzylammonium chloride, dialkyldimethylammonium chloride, etc.

In addition, when producing an emulsion of organopolysiloxane by emulsion polymerization, the above-mentioned sulfonic acid surfactant and sulfuric acid ester surfactant serve as both an emulsifier and a polymerization catalyst, and CxaH2*<Saka5Q3H,
CaHry(OCzH4)zO5OsH.

Examples include CroHzx (OC2HJ 20SO3H, sodium lauryl sulfate, sodium polyoxyethylene dodecylphenyl sulfate, etc.) Among these, sulfuric acid ester salts are converted into the corresponding acids by contacting with a cation exchange resin after emulsification, and become polymerization catalysts. After the emulsion polymerization is completed, the acid type surfactant can be neutralized to eliminate the catalytic activity.Also, as a cationic emulsifier, quaternary ammonium salts such as those mentioned above can be used as cationic emulsifiers. system, and after emulsion polymerization, the surfactant, which is in the basic form, may be neutralized to eliminate the catalytic activity.

If the molecular weight of the organopolysiloxane represented by general formula (I) is small, the effect of imparting the intended elasticity and flexibility to the fibers will be poor, so it is desirable that the molecular weight is as large as possible. When emulsifying and dispersing organopolysiloxane obtained by polymerization, the organopolysiloxane must have a high molecular weight.If emulsion polymerization is used, lowering the temperature during aging after polymerization will lower the molecular weight of the organopolysiloxane. Therefore, the ripening temperature is desirably 30°C or lower, more preferably 15°C or lower.

Next, component A(2) will be explained. This is a polymerizable monomer or a mixture thereof for graft copolymerization with the organopolysiloxane of component A(1) above, and is described in the following a) to 8). A (meth)acrylic monomer [where (meth) The expression acrylic refers to both acrylic and methacrylic, and the same applies hereinafter. ), methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate
Acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate
Acrylates, alkyl (meth)acrylates such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; and alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate and butoxyethyl (meth)acrylate.
Acrylate is exemplified, and these 11! Or 2f1 or more are used in combination. If the amount of this component is less than 70% by weight in component A (2), the properties of (meth)acrylic, especially mechanical strength, ozone resistance, adhesion to fibers, etc., will be insufficient. It is necessary to do so.

The component is a polyfunctional monomer, including (meth)acrylamide, ethylenically unsaturated amide, alkylol or alkoxyalkyl compound of ethylenically unsaturated amide,
Glycidyl (meth)acrylate, glycidyl as an oxirane group-containing unsaturated monomer, such as Dia7ton (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, etc. Allyl ether, etc., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. as hydroxyl group-containing unsaturated monomers, (meth)acrylic acid, anhydride as ethylenically unsaturated monomers containing carboxyl group. Maleic acid, crotonic acid, itaconic acid, etc., as unsaturated monomers containing amino groups, as well as unsaturated monomers containing sulfonic acid groups, such as N-dimethylaminoethyl (meth)acrylate, N-diethylaminoethyl (meth)acrylate, etc. Ch'C
Alkyl group X of H30sX: H, NaJ or NH4) X: H, Ha, or NH4) (X: )l, Na, K or NH4) 12COOR(R:
5OsX having 1 to 18 carbon atoms Alkyl group X: )l, Na, K or NNa) Ch-〇-COOCHzCHzSOsX (R:H or methyl group As a polyalkylene oxide group-containing unsaturated monomer, n: 2
or higher integer) ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate as a complete ester of a quaternary ammonium base-containing unsaturated monomer, a polyhydric alcohol such as CH5, and (meth)acrylic acid, Examples include trimethylolpropane tri(meth)acrylate, -t, etc., allyl(meth)acrylate, and divinylbenzene, and these may be used alone or in combination of two or more.

These polyfunctional monomers increase the adhesion of the polymer component in the IA treatment agent to the fibers and participate in crosslinking between the polymers in the treatment agent, thereby improving durability, especially washing resistance and dry cleaning resistance. Furthermore, the hydrophilic functional group prevents the polymer in the treatment agent from making the fiber surface hydrophobic, reducing water absorption and sweat absorption, and preventing triboelectric charging.

If the amount of this component (B) is increased, the desired properties will be improved, but if it is too much, the texture of the processed product will be damaged and the water resistance will decrease, so 20 of
It is necessary to keep it below % by weight.

Component 8) is another ethylenically unsaturated monomer that imparts texture, durability, or adhesion to fibers that cannot be achieved by component A) alone, but component A(2) If it exceeds 20% by weight, the properties of (meth)acrylic will be impaired, so it is necessary to keep it below this range. Examples of these monomers include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl versatate, and the like.

In order to impart a soft texture to the fibers, it is sufficient to soften the polymerized product of component A (2), and this can be done by adjusting the glass transition point of the polymerized product of component A (2) to 0°C or lower, preferably -10°C. It is desirable to keep the temperature below ℃. Therefore, it is desirable to take this glass transition point into consideration when selecting the monomers that are components (a) to (eight) above. In addition, the glass transition point of the polymerized mixture of monomers of component ^(2) in the examples described below is based on Ann, Rev., published in 1980.
Phys, Chem, described in N31@491 page, F
It shows numerical values calculated by the method of Renkel et al.

Regarding the ratio of A(1) component and A(2) component, ^(2
) 95 parts by weight of component ^ (1) When the component is 5 parts by weight, a sticky feeling, which is a drawback of (meth)acrylic polymers, occurs, resulting in poor flexibility; On the other hand, if the amount of component (1) exceeds 95 parts by weight, the toughness of the film, adhesion to fibers, durability, etc. will be impaired, making it impractical.

The emulsion copolymerization of component A(1) and component A(2) may be carried out by a known emulsion polymerization method using an ordinary radical initiator.

The radical initiators used here include persulfates such as potassium persulfate and ammonium persulfate, water-soluble types such as hydrogen peroxide, t-butyl hydroperoxide, HCl salt of azobisamidinopropane, and benzoyl persulfate. Examples include oil-soluble types such as oxide, kyene hydroperoxide, dibutyl peroxide, diisopropyl peroxy carbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, and azobisisobutyronitrile. If necessary, a redox system using a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, sugars, amines, etc. can also be used.

As an emulsifier, since the emulsifier is contained in the emulsion of component (1), it is not necessarily necessary to use it again.
A necessary amount of emulsifier may be added to prevent coagulation during polymerization and improve emulsion stability. Examples of emulsifiers used here include 7-ionic emulsifiers such as alkyl or alkylaryl sulfates or sulfonates, alkylaryl succinates, cationic emulsifiers such as alkyltrimethylammonium chloride, alkylbenzylammonium chloride, polyoxy Nonionic emulsifiers such as ethylene alkylphenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene carboxylic acid ester are suitable.

Next, the water-soluble amino resin of component B will be explained.
Component B of the fiber treatment agent of the present invention is used to provide wrinkle-proofing, shrink-proofing, W/W,
Known water-soluble amino resins used for the purpose of imparting PP properties can be used.

Such amino resins include urea/formaldehyde initial condensate and its lower alkyl ether, ethylene urea/formaldehyde initial condensate and its lower alkyl ether, propylene urea/formaldehyde initial condensate, 1゜3-bis(hydroxy methyl)tetrahydro-5-alkyl-s-triazon-2-one (
(commonly known as triazone), N, N', commonly known as uron resin
-bis(methoxymethyl)uron and N,N'-bis(
methylol) uron, glyoxal monourein, 1,3-dialkyl-4,5-dihydroxyethyleneurea, 1,3-dimethylol-4,5-dihydroxyethyleneurea, 1-methylol-3-methoxymethyl-4
, 5-dihydroxyethylene urea, glyoxal resins such as glyoxal diurein and tetramethylol glycoluril, melamine formaldehyde initial condensates, and dimethylol alkyl carbamates and dimethylol hydroxyalkyl carbamates of carbamate resins.

Component C is a curing catalyst for the amino resin that is component B, and includes inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as acetic acid, lactic acid, and citric acid, ammonium salts such as diammonium phosphate, ammonium chloride, etc. Organic amine salts such as tanolamine hydrochloride, 2-methyl-2-aminopropatur hydrochloride, 1,3-diamino-2-propatur hydrochloride, zinc nitrate, zinc chloride, magnesium chloride, aluminum chloride, borofluoride Examples include metal salts such as zinc and magnesium borofluoride.

The weight ratio of component C to component B is preferably C/B.1/100 to 40/100 in terms of their respective anhydrous states.

Furthermore, the polymer content contained in the organopolysiloxane-(meth)acrylic monomer copolymer emulsion, which is the A component of the fiber treatment agent of the present invention, and the resin content of the water-soluble amino resin, which is the B component, are the same. The weight ratio is preferably from 5795 to 9515, more preferably from 20/80 to 80/20 (polymer content of component ^/resin content of component B). If the A component is less than this, wrinkle resistance, shrink resistance, lol
Although 1w properties and P/P properties are imparted, the tensile, tear, bending, and abrasion strengths are reduced, and it is also imparted with a durable, flexible, rebound, and thick texture. becomes difficult to do. Conversely, when the B component is less than this,
Satisfactory results can be obtained in that a good texture is imparted and no decrease in fiber strength is observed, but sufficient wrinkle resistance, shrink resistance, W/W properties, and P/P properties must be imparted. becomes difficult.

Next, the D component and E component of the fiber treatment agent of the present invention will be explained. Component D is a crosslinking agent for the organopolysiloxane-(meth)acrylic thread polymer copolymer in component ^ described above, and component E is a catalyst for the crosslinking reaction by component D.

As this component D, an organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule can be used, such as X≧3), and a copolymer of Siloxane can also be used and may be included, and the molar ratio of triorganosiloxy units to 5tO2 units may be set within the range of 0.5 to 2.0.

As component E, dibutyltin and dioctyltin acetate,
Examples include organic acid salts such as octylate and laurate, organic acid salts such as zinc octylate and laurate, and titanate esters.

Component D is 0 to 50 parts by weight based on 100 parts by weight of the above copolymer of components A (1) and A (2), and component E is also 0.
~50 parts by weight may be used, but for both component D and component E,
It can be formulated as an emulsion by emulsifying and dispersing it in water using an emulsifier as described above.

This crosslinking agent component 0 forms a crosslinked film on the textile product by reacting with the hydroxyl group or alkoxy group bonded to the silicon atom of the organopolysiloxane, which is the A(1) component, and improves the rebound effect of the treatment agent. This further increases the durability against washing.

The textile products to which the textile treatment agent of the present invention is applied include:
cotton, mercerized or mercerized cotton,
Threads and yarns made of cellulose fibers such as hemp, ramie, jute, regenerated cellulose (viscose rayon, cupra), or blends of these cellulose fibers and other natural fibers or synthetic LA#11. , string, woven fabric, knitted fabric, non-woven fabric, etc.

The method of treating the above-mentioned textile products with the fiber treatment agent of the present invention includes a mixed bath method consisting of ^, B and C components or ^, B, C, D and E components; Two-step method (hereinafter abbreviated as silicone/(meth)acrylic pretreatment method) in which treatment is performed with a bath consisting of components A, D, and E, followed by treatment with a bath consisting of components 6 and C (hereinafter abbreviated as silicone/(meth)acrylic pretreatment method), and after treatment with a bath consisting of components B and C. There is a two-step method (hereinafter abbreviated as amino resin pretreatment method) in which the resin is treated with a bath consisting of component A or components A, D, and E, and effects can be obtained using either method.

In the same bath method, an appropriate amount of water and components A, B, and C or ^, B,
Either immerse the textile product in a treatment bath consisting of a mixture of components C, D, and E, and then squeeze the solution, or apply the above mixed solution to the textile product by spraying, coating, etc., and then apply as necessary. Squeeze the liquid. Next, this is dried and further heated and cured. Drying conditions are not particularly limited, but drying can usually be carried out at 40 to 140°C. The heat curing may be carried out at a temperature of 110 to 200°C, but the preferred temperature is 140 to 180°C. The textile product treated in this way is used as is, but may be soaped if necessary.

In the silicone/(meth)acrylic pretreatment method, a mm product is treated by dipping, spraying, coating, etc. using a treatment solution containing an appropriate amount of water and component A or ^, D, and E. After drying and heat curing, a treatment solution containing an appropriate amount of water and components B and C is applied to the pretreated fibers in the same manner as described above, and the fibers are squeezed, dried, and heat cured. The silicone/(meth)acrylic pretreatment method requires a longer process and is less economical than the same bath method, but the pretreated fibers are used as intermediate materials and after processing such as weaving, knitting, sewing, etc. By post-treating with a treatment solution containing ingredients, a different texture can be obtained compared to the same bath method.

The amino resin pretreatment method may be operated by reversing the pretreatment and posttreatment of the silicone/(meth)acrylic pretreatment method.

The amount of the treatment agent of the present invention applied to the treated textile product is not particularly limited, but is 0.1 per 100 parts by weight of fiber on an anhydrous basis.
The effect is obtained at ~30 parts by weight, preferably 0.5~1O
Parts by weight. If the amount of this adhesion is too small, the effect will be insufficient, and if it is too large, the texture and characteristics of the mu wood will change too much.
It is also undesirable because it becomes heavy.

〔Effect of the invention〕

When textile products are treated with the fiber treatment agent of the present invention, the excellent film-forming properties of the treatment agent give the mm product a soft texture that is highly durable against washing, has high rebound resilience, and a thick texture. Wrinkle resistance, shrink resistance, WZW property, P/
It can give P properties. In addition, windproof processing is also possible by controlling air permeability based on the excellent film-forming properties.

Furthermore, a liquid organopolysiloxane (component D) having at least three Sins in one molecule, which serves as a crosslinking agent for the organopolysiloxane/(meth)acrylic monomer copolymer in the component ^, is subjected to a crosslinking reaction. It has been found that by blending with a catalyst for use (component E), it is possible to further improve rebound and wash resistance.

(Examples) Next, the present invention will be specifically explained based on Examples. In addition, all parts in the examples represent parts by weight.

Reference Example 1 (Preparation of organopolysiloxane emulsion) Octamethylcyclotetrasiloxane 1500K, methacryloxypropylmethylsiloxane 3.8 parts and pure water 150
0 parts of sodium lauryl sulfate, and 15 parts of sodium lauryl sulfate.
After adding 10 parts of dodecylbenzenesulfonic acid and emulsifying it by stirring with a homomixer, the pressure was 3.0 DOps.
A stable emulsion was made by passing it through the Hosogenizer (No. 1) twice. Next, put this in a flask and heat it at 70℃ for 12
After heating for an hour, cooling to 25℃ and aging for 24 hours,
The pH of this emulsion was adjusted to 7 using sodium carbonate, bubbled with N2 for 4 hours, then steam distilled to remove volatile siloxanes, and then pure water was added to adjust the non-volatile content to 45%. As a result, an emulsion of polysiloxane containing 0.1 mole of methacrylic group was obtained (hereinafter abbreviated as E-1), and as shown in Table 1, the type, amount, and aging conditions of silochitin were determined. Other changes are E
-1 Polysiloxane emulsion E-2
~E-5 was obtained.

E-1333 parts (siloxane content 150 parts) and pure water 5
After adjusting the temperature inside the vessel to 30°C under a N2 gas stream, 1.0 part of t-butyl hydroperoxide, 0.5 part of bu-ascorbic acid, and 0.5 parts of ferrous sulfate heptahydrate were charged. 0
Then, while keeping the salt in the vessel at 30°C, a mixture of 328.6 parts of butyl acrylate, 10.5 parts of acrylic acid, and 5.3 parts of methacrylic acid and N-methylolacrylamide were added. 56 parts of the aqueous solution was added dropwise over 3 hours, and after the addition was completed, stirring was continued for an additional hour to complete the reaction. The obtained copolymer emulsion (hereinafter referred to as p-
1) has a solid content concentration of 39.8k, and a calculated glass transition point of a polymerized material such as a (meth)acrylic monomer, which is 14.
The temperature was 6°C. Similarly, copolymerization was carried out using the types and amounts of polysiloxane emulsions and (meth)acrylic monomers shown in Table 2 to obtain copolymerized emulsions G1-2 to G1-a with solid content concentrations of 39 to 4. Obtained.

Table (Blending unit: parts) Reference Example 2 (Copolymer emulsion) Emulsion Examples 1 to 8 obtained in Reference Example 1 was placed in a reaction vessel equipped with a stirrer, condenser, thermometer, and N2 gas inlet.
, Comparative Examples 1 to 5 ^ Copolymer emulsion P-1 obtained in Reference Example 2 as a component
~6, Glyoxal resins MS-11 and N5-19 (both manufactured by Sumitomo Chemical Co., Ltd., active ingredient 40) as component B, Accelerator x-80 and X-110 (both manufactured by Sumitomo Chemical Co., Ltd.) as component C Using the SiH-containing organopolysiloxane (described below) as component D and dibutyltin dilaurate as component C, fabric treatment agent 1 was prepared using the formulation shown in Table 3, and this treatment bath was used to prepare cotton broad #40. (mercerization) and padding processing,
I narrowed it down to plckuploO zero with a roll (1dIp
-1 nip), then dried at 130°C for 5 minutes,
Cure for 1 minute at 0°C, and test the treated fabric before and after washing (
2 times and 5 times), the tear strength in the warp direction and the tear strength in the two directions were measured, and the texture was also examined, and the results shown in Table 3 were obtained.

Of course, for the SiH-containing organopolysiloxane, which is component D, 30 parts of methylhydrodiene polysiloxane with a viscosity of 150 cs as shown by the formula is emulsified and dispersed in 65 parts of water using 5 parts of polyoxyethylene alkylphenyl ether. Component C, dibutyltin dilaurate, was used as an emulsion in which 30 parts of dibutyltin dilaurate was emulsified and dispersed in 67 parts of water using 3 parts of polyoxyethylene alkylphenyl ether.

In addition, as a comparative example, a treatment agent ((11 The same cloth used in the example was treated in the same manner as in the example, and the tear strength and texture of the treated cloth were measured in the same manner as in the example, and the results are listed in Table 4. was obtained.In addition, the fourth
The table also shows the results for untreated fabric (the same fabric simply passed through water).

In the above Examples and Comparative Examples, washing and measurement were performed by the following methods.

Laundry treatment Using a household washing machine, detergent (Top: Lion Co., Ltd. product name) concentration 2g/i, bath ratio 1:30.5 at 40°C.
Stir for 1 minute, wash with water, dehydrate and dry at room temperature.
It was times.

Tear strength JIS L 1096^-1 method (single tongue method),
The evaluation was made by the tactile sensation with the hand at a tensile speed of 200 mm/min, and the results were expressed as (good) O-Q-Δ-x (poor).

0owf).

The tear strength of this treated fabric is 1.26 kg in width after treatment.
, 1.01kg vertically, 1.22kg horizontally after 2 washes,
The weight was 0.95 kg in the vertical direction, 1.15 kg in the horizontal direction after washing 5 times, and 0.90 kg in the vertical direction, and as in Examples 1 to 8, the strength was higher than that of the comparative example. Moreover, the feel was also good as in Examples 1-8.

As shown in the test results in Tables 3 and 4, the after-treatment tear strength of the treated fabric in the example is greater than that of the comparative example using amino resin alone, and the rate of decrease due to washing is smaller than that of the comparative example. Furthermore, there was a significant difference in feel between the treated fabrics of the Examples and the treated fabrics of the Comparative Examples.

Example 9

Claims (1)

[Claims] 1.A (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, and R^3 each have a carbon number of 1 to
Y is one or more groups selected from 20 monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and Y is 1 selected from radical reactive groups and organic groups containing SH groups. X is a hydrogen atom, a monovalent lower alkyl group, and a group represented by the formula R^1R^2R^4Si (R^1 and R^2 are the same as above, and R ^4 is R^
1 or the same group as Y), m is a positive integer of 10,000 or less, and n is an integer of 1 or more. 5 to 95 parts by weight of oil-in-water emulsion and (2) A) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R^5 is a hydrogen atom or a methyl group, R^5 is a carbon One or more monomers selected from acrylic and methacrylic monomers represented by (number 1 to 18 alkyl group or alkoxy-substituted alkyl group) 70 to 100
Weight% b) Ethylenically unsaturated amide, alkylol or alkoxyalkyl substituted compound of ethylenically unsaturated amide, oxirane group, hydroxyl group, carboxyl group, amino group, sulfonic acid group, phosphoric acid group, polyalkylene oxide group or quaternary one selected from the group consisting of ethylenically unsaturated monomers containing a class ammonium base, complete esters of polyhydric alcohols and acrylic acid or methacrylic acid, diallyl esters of dibasic acids, allyl acrylate, allyl methacrylate, and divinylbenzene; or 2 or more types of polyfunctional monomers 0 to 20% by weight c) One or more types of ethylenically unsaturated monomers other than the above a) and b) 0 to 20% by weight Single or mixed Total of monomers (a) to c) 10
0% by weight) in the presence of a radical polymerization initiator, a water-soluble amino resin C, and a curing catalyst for the water-soluble amino resin. A treatment agent for fibers. 2. Liquid organopolysiloxane E containing at least three hydrogen atoms bonded to silicon atoms in 0.1 molecule in addition to components A, B, and C according to claim 1, and a crosslinking reaction using component D. A fiber processing agent characterized by containing a catalyst. 3. The treatment agent for fibers according to claim 1 or 2, wherein the polymerized monomer or mixed monomer as component (2) in component A has a glass transition point of 0° C. or lower.