JP2648515B2 - Method for treating cellulosic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for treating a cellulosic fiber product, in particular, a method of blending cellulose fibers or a mixture of cellulose fibers and other fibers.
It improves the strength of mixed fiber products while maintaining their original properties, prevents a drop in tear strength after washing, and at the same time is durable, soft, rebound resilient, thick and smooth. The present invention relates to a processing method capable of providing a texture with rich properties.

[Conventional technology and problems to be solved]

It is well known that cellulosic textiles, especially cotton-based products, are the best clothing materials since ancient times, because they have a good balance of hygienic functions, comfort, feeling, appearance, physical and chemical functions. In recent years, various synthetic fibers have been invented, but none of them has surpassed cotton in terms of hygienic functions, comfort, and feeling.

In recent years, cotton products have become increasingly popular as high-grade materials due to the sophistication of clothing life, and unprecedented ultrafine yarns, thin fabrics and knitted fabrics have emerged. These thin cotton products are softer and more drapable than thicker ones, and are more excellent in comfort, feel and appearance, but on the other hand, they have low strength (tear, tension, abrasion, etc.) due to the thinness of the yarn. The disadvantage that the strength is further reduced by washing has become more serious. Among them, the tear strength is particularly important in practical use.

It is well known that the strength of cotton products is reduced by washing.However, it is not problematic for thick woven or knitted fabrics that use thick yarns. Was enough. However, such a thick product has a rough hand feeling and lacks drapability, so that an elegant clothing-like appearance cannot be obtained.

As one method for improving the drawbacks of such thin cotton products, blending and blending of synthetic fibers is carried out, whereby the strength is improved, but the moisture absorption, sweat absorption, feel, feeling, etc. The inherent advantages of cotton products are diminished.

If a thin cotton product is treated with a so-called softening agent, which is a higher fatty acid or higher alcohol derivative, there is some effect in improving the strength, but it falls off by washing and loses its effect. As a drawback, this method gives a feeling of slimming opposite to the feeling of cotton, and the obtained effect is low in washing resistance. Therefore, with respect to the cellulosic fiber products mainly made of cotton thin fiber products, the strength is improved while maintaining the original sanitary function, comfort, feeling and appearance, and the strength after washing is prevented from lowering. It has been desired to develop a processing method capable of performing such processing. Further, it is preferable to impart a durable, soft, resilient and rich feeling to the cellulosic fiber product, and a treatment method that enables this is desired.

[Means for solving the problem]

The method for treating cellulosic fibers of the present application has solved the above-mentioned problems.

The first invention of the present application is: (1) General formula (I) [Wherein, R ¹ , R ² , and R ³ are each one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or two or more groups selected from a radical reactive group and an organic group including an SH group, and X is a hydrogen atom, a monovalent lower alkyl group and represented by the formula R ¹ R ² R ⁴ Si Groups (R ¹ and R ² are the same as described above;
R ⁴ is the same or different atom or group selected from R ^{1 and} 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 an oil-in-water emulsion of polysiloxane and (2) a) general formula (II) (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a C 1-18
One or more monomers selected from acrylic and methacrylic monomers represented by the following formulas: 70 to 100% by weight b) ethylenically unsaturated amide, ethylenic Alkylol or alkoxyalkyl substituted compounds of unsaturated amides, oxirane groups, hydroxyl groups, carboxyl groups, amino groups, sulfonic acid groups, phosphoric acid groups, polyalkylene oxide groups or quaternary ammonium base-containing ethylenically unsaturated monomers, One or more polyfunctional monomers selected from the group consisting of a complete ester of a polyhydric alcohol and acrylic acid or methacrylic acid, diallyl ester of dibasic acid, allyl acrylate, allyl methacrylate and divinylbenzene 20% by weight c) One or more ethylenically unsaturated compounds other than the above a) and b) Total mer consisting 0-20% by weight monomer or monomer mixture (a) to c) 100
% By weight of a mixture comprising 95 to 5 parts by weight of a mixture comprising: a fiber treatment agent mainly comprising a copolymerized emulsion obtained by emulsion polymerization in the presence of a radical polymerization initiator. It is an abstract.

The second invention of the present application relates to a copolymer emulsion obtained by emulsion-polymerizing the above-mentioned main components (1) and (2), as a cross-linking agent to at least three silicon atoms in one molecule. It is another object of the present invention to provide a method for treating a cellulosic fiber, characterized by using a fiber treating agent comprising a liquid organopolysiloxane having a bonded hydrogen atom and a catalyst for a crosslinking reaction.

That is, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an organopolysiloxane having an organic group having radical reactivity and an acrylic and / or methacrylic monomer or a mixed monomer mainly composed of the same. When a cellulose fiber product is treated with a treating agent having an emulsion composed of a copolymer with a monomer as a main component, it has been found that it is possible to impart desired properties. The present invention was completed by repeatedly studying the composition of the mixed monomer, the crosslinking agent, and the like.

 Hereinafter, the present invention will be described in detail.

The organopolysiloxane as the component (1) of the treating agent used in the method of the present invention has the general formula (1) R ¹ , R ² , R ³ is a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a phenyl group, a tolyl group,
A monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified by an aryl group such as a xylyl group or a naphthyl group, or a group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms. X is a triorganosilyl group represented by R ¹ R ² R ⁴ Si (R ¹ and R ² are the same as above, R ⁴ is
R ¹ or Y), a hydrogen atom, a methyl group, an ethyl group,
Propyl group, butyl group and the like are selected from lower alkyl groups having 1 to 5 carbon atoms, Y is a vinyl group, an allyl group,
It is selected from a radical reactive group exemplified by a γ-acryloxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, and an SH group-containing organic group. In addition, m is a positive integer of 10,000 or less, and n is an integer of 1 or more, preferably 500 <m <8,000, 1 <n
It should be in the range of <500.

As a raw material of the organopolysiloxane represented by the general formula (I), (Wherein p = 3,4,5,6) a cyclic organopolysiloxane represented by the formula: (Where n is a positive integer) a liquid dimethylpolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups, (Where n is a positive integer) and a liquid dimethylpolysiloxane in which both terminals of the molecular chain are blocked with an alkoxy group; (Where n = 0 or a positive integer) dimethylpolysiloxane or the like having both ends of the molecular chain blocked with a trimethylsilyl group, or as a raw material for introducing a radical reactive group and an SH group, Silanes and their hydrolysis products (Where n = 3, 4, 5, 6).

In addition, if it is a small amount that does not disturb the object of the present invention,
Trifunctional trialkoxysilanes and their hydrolysis products can also be used.

The production of the emulsion of the organopolysiloxane represented by the general formula (I) may be performed according to a known method.
One method is to use a low-molecular-weight cyclic siloxane such as octamethylcyclotetrasiloxane described above and a dialkoxysilane compound containing a radical reactive group or SH group and / or a hydrolyzate thereof as a raw material, and use a strong alkaline catalyst as a raw material. Alternatively, the polymerization is carried out in the presence of a strongly acidic catalyst to obtain a high molecular weight organopolysiloxane, and then emulsified and dispersed in water in the presence of a suitable emulsifier. Another method is to use a low-molecular-weight organopolysiloxane as a raw material and a radical-reactive group or
This is based on emulsion polymerization in water in the presence of a sulfonic acid-based surfactant and / or a sulfate ester-based surfactant using a dialkoxysilane containing an SH group and / or a hydrolyzate thereof. In addition, in the case of this emulsion polymerization, after using the same raw materials and emulsifying and dispersing in water with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, an appropriate amount of potassium hydroxide, sodium hydroxide or the like is used. Polymerization can also be carried out by adding a strongly alkaline substance.

Among the above-mentioned methods for producing an organopolysiloxane emulsion, potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetrabutyl Phosphonium hydroxide and the like, and strong acid polymerization catalysts such as sulfuric acid and trifluoromethanesulfonic acid are exemplified. Any of these can be used after neutralization after completion of the polymerization to eliminate the catalytic activity. As a surfactant for emulsifying the obtained high molecular weight organopolysiloxane, various nonionic polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ether,
Polyoxyethylene alkyl ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, etc .; anionic sodium lauryl sulfate, polyoxyethylene dodecyl sulfate, etc .; cationic alkyl trimethylammonium chloride, alkyl benzyl Ammonium chloride,
Examples thereof include dialkyldimethylammonium chloride.

Further, when an emulsion of an organopolysiloxane is produced by an emulsion polymerization method, the above-mentioned sulfonic acid-based surfactant and sulfate ester-based surfactant also serve as an emulsifier and a polymerization catalyst. Examples thereof include sodium lauryl sulfate and polyoxyethylene dodecylphenyl sodium sulfate. Of these, the sulfates are converted into the corresponding acids by contacting with a cation exchange resin after the emulsification, and function as a polymerization catalyst. After the completion of the emulsion polymerization, the surfactant in the acid form may be neutralized to eliminate the catalytic activity. Also,
As the cationic emulsifier, a quaternary ammonium salt as described above is mainly used, and after the emulsion polymerization, a basic surfactant may be neutralized to eliminate the catalytic activity.

The organopolysiloxane represented by the general formula (I)
If the molecular weight is small, the effect of imparting the desired feeling of elasticity and flexibility of the target fiber is poor, so that the molecular weight is desirably as large as possible. For this reason, when emulsifying and dispersing an organopolysiloxane obtained in advance by polymerization, it is necessary to keep this organopolysiloxane of high molecular weight.In the case of emulsion polymerization, it is necessary to lower the temperature during ripening performed after polymerization. For example, since the molecular weight of the organopolysiloxane becomes large, the aging temperature is preferably set to 30 ° C. or lower, more preferably 15 ° C. or lower.

Next, the component (2) will be described. The component (2) is a polymerizable monomer or a mixture thereof for graft copolymerization with the organopolysiloxane of the component (1). It consists of components.

A) The component is represented by the general formula (II) (Wherein, R ⁵ is hydrogen or a methyl group, and R ⁶ is an alkyl group or an alkoxy-substituted alkyl group having 1 to 18 carbon atoms) (meth) acrylic monomer [herein, the expression (meth) acryl is acrylic And methacryl are collectively represented in the same manner. And methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylates such as isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate And alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate.
Used in combination of more than one species. If the component (a) is less than 70% by weight of the component (2), the properties of methacryl, particularly the properties such as mechanical strength, ozone resistance, and adhesion to fibers, become insufficient. It is necessary.

B) The component is a polyfunctional monomer, and (meth) acrylamide as an ethylenically unsaturated amide, an alkylol of an ethylenically unsaturated amide or an alkoxyalkyl compound,
Diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N-methoxymethyl (meth) acrylamide and the like, oxirane group-containing unsaturated monomers such as glycidyl (meth) acrylate and glycidyl allyl ether; and hydroxyl group-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; N-dimethyl as an amino group-containing unsaturated monomer such as (meth) acrylic acid, maleic anhydride, crotonic acid and itaconic acid as a carboxyl group-containing ethylenically unsaturated monomer such as 2-hydroxypropyl (meth) acrylate; As sulfonic acid group-containing unsaturated monomers such as aminoethyl (meth) acrylate and N-diethylaminoethyl (meth) acrylate CH ₂ CHCHSO ₃ X (X: H, Na, K or NH ₄ ) As a phosphate group-containing unsaturated monomer As an unsaturated monomer containing a polyalkylene oxide group Etc. as quaternary ammonium base-containing unsaturated monomers Ethyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc., allyl (meth) acrylate, divinyl benzene, etc. as the complete ester of polyhydric alcohol and (meth) acrylic acid These are exemplified and used alone or in combination of two or more. These polyfunctional monomers increase the adhesiveness of the polymer in the treating agent to the fiber, and contribute to durability, especially washing resistance and dry cleaning resistance, by participating in crosslinking between the polymers in the treating agent. The hydrophilic functional group is provided to prevent hydrophobicity of the fiber surface by the polymer in the treating agent, decrease in water absorption and sweat absorption, and prevent triboelectric charging.

If the amount of component (b) is increased, the desired properties can be improved. However, if the amount is too large, the texture of the processed product is impaired or the water resistance is reduced. % Or less.

The component (c) is another ethylenically unsaturated monomer, and the feeling, durability,
Alternatively, the adhesiveness to the fiber or the like is imparted.
If it exceeds 20% by weight, the properties of the (meth) acryl are impaired. Examples of these monomers include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and vinyl versatate.

In order to impart a soft feeling to the fiber, the polymerized product of the component (2) may be softened. For this purpose, the glass transition point of the polymerized product should be 0 ° C or lower, preferably -10 ° C or lower. desirable. Therefore, it is desirable to consider this glass transition point when selecting the monomers which are the components (a) to (c). In addition, the glass transition point of the polymerized product of the mixed monomer of the component (2) in Examples described later was calculated by the TGFox method described in Bull. Am. Phys. Soc. It shows the numerical value obtained by.

About the ratio of the component (1) and the component (2), the component (2)
If (1) component is less than 5 parts by weight to 95 parts by weight (meth)
Adhesiveness, which is a drawback of the acrylic polymer, occurs, resulting in poor flexibility. Also, when component (1) exceeds 95 parts by weight with respect to component (2) 5 parts by weight, the toughness of the film and the adhesion to fibers are increased. In addition, the durability is impaired, which is not practical.

Emulsion copolymerization of the components (1) and (2) may be carried out by a known emulsion polymerization method using a usual radical initiator.

Examples of the radical initiator used herein include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen peroxide, t-butyl hydroperoxide, water-soluble types such as the HCl salt of azobisamidinopropane, and benzoyl peroxide. Oil-soluble types such as oxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxycarbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, azobisisobutyronitrile and the like can be mentioned. If necessary, a redox system using a reducing agent such as sodium acid sulfite, Rongalit, L-ascorbic acid, saccharide, amine or the like can also be used.

As the emulsifier, since the emulsifier is contained in the emulsion of the component (1), it is not always necessary to newly use the emulsifier,
A necessary amount of an emulsifier may be added in order to prevent agglomeration during polymerization and to improve emulsion stability. Examples of the emulsifier used herein include alkyl or alkyl allyl sulfate or sulfonate, anionic emulsifier such as alkyl allyl succinate, cationic emulsifier such as alkyl trimethyl ammonium chloride, alkyl benzyl ammonium chloride, and polyoxyethylene. Nonionic emulsifiers such as alkyl phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene carboxylate are preferred.

Next, the cross-linking agent and the catalyst for the cross-linking reaction to be mixed with the main component will be described.

An organopolysiloxane having at least three hydrogen atoms bonded to at least three silicon atoms in one molecule can be used as a crosslinking agent component. (Where x and y are positive integers, where x ≧ 3), and the like. And copolymerized siloxanes of (SiO ₂ ) units can also be used, A triorganosiloxy unit and SiO ₂
The molar ratio of the units may be set in the range of 0.5 to 2.0.

As a catalyst for the crosslinking reaction, dibutyltin and dioctyltin acetates, octylates, organic acid salts such as laurate,
Organic acid salts such as octylate and laurate of zinc, and titanates are exemplified.

The crosslinking agent may be used in an amount of 0 to 50 parts by weight based on 100 parts by weight of the total of the copolymers of the above components (1) and (2), and the crosslinking reaction catalyst may be used in an amount of 0 to 50 parts by weight. Both the components and the catalyst for the crosslinking reaction can be blended as an emulsion by emulsifying and dispersing in water using the above-described emulsifier.

This cross-linking agent component forms a cross-linked film on textiles by reacting with a hydroxyl group or an alkoxy group bonded to a silicon atom of the organopolysiloxane which is the component (1). The durability is further improved.

Further, as a crosslinking agent other than the above, an aqueous block isocyanate crosslinking agent such as sodium bisulfite having an isocyanate group, phenol, and cresol adduct can be effectively used as a material for further improving the washing durability.

The cellulosic fibers to which the method for treating cellulosic fibers of the present invention is applied include cotton, regenerated cellulose such as rayon and cupra, natural or regenerated cellulose fibers such as hemp, or a blend thereof with other natural fibers and synthetic fibers.・
It refers to a mixture, and examples of the form include a thread, a yarn, a string, a woven fabric, a knitted fabric, and a nonwoven fabric, but are not limited to a particular form.

The treatment of the fibers can be performed as follows. First, a fiber is added to a treatment bath comprising an appropriate amount of water and the above-mentioned copolymerized emulsion of the components (1) and (2) or a treatment bath in which the above-mentioned emulsion of the crosslinking agent and the emulsion of the catalyst for crosslinking reaction are blended. The product is dipped and then squeezed, or the treatment bath is applied to the textile by spraying or coating, and then squeezed if necessary.
Then, it is dried and further heated to cure. The drying conditions are not particularly limited, but the drying can be usually performed at 40 to 140 ° C. Heat curing can be performed at 110-200 ° C, but the preferred temperature is 140-180 ° C. Although the fiber product thus treated can be used as it is, soaping may be performed if necessary.

The amount of the treatment agent attached to the fiber product to be treated is not particularly limited, but the effect can be obtained at 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the fiber on an anhydrous basis. If the amount is too small, the effect is insufficient. If the amount is too large, the original feeling and characteristics of the fiber are changed too much and the fiber becomes undesirably heavy.

(Effect of the Invention) When the cellulosic fiber is treated by the method of the present invention, the tear strength, abrasion resistance and the like of the fiber product are improved due to the excellent physical properties and film forming property of the treating agent, and this is repeatedly washed. Even hardly decreases. Further, while maintaining the hygienic function and the crisp feel, which are the characteristics of the cellulosic fiber, a texture rich in flexibility, drapability, rebound resilience, thickness and smoothness is provided. For this reason, if a product using cellulosic fiber, particularly a thin cotton product, is treated by the method of the present invention, a product extremely suitable as a material for high-grade underwear, shirts, outer garments and the like can be obtained. It was also found that the combined use of a crosslinking agent and a crosslinking reaction catalyst can further improve the washing resistance and the rebound resilience. Thus, the method of the present invention is extremely advantageous in practical use.

〔Example〕

Next, the present invention will be specifically described based on examples. All parts in the examples are parts by weight.

Reference Example 1 (Preparation of organopolysiloxane emulsion) 1500 parts of octamethylcyclotetrasiloxane, 3.8 parts of methacryloxypropylmethylsiloxane, and 150 parts of pure water
After mixing 0 parts, add 15 parts of sodium lauryl sulfate and 10 parts of dodecylbenzenesulfonic acid, stir with a homomixer and emulsify, then pass twice through a homogenizer at 3,000 psi to make a stable emulsion. Was. Then, this was charged into a flask, heated at 70 ° C for 12 hours, and then heated to 25 ° C.
After cooling and aging for 24 hours, the pH of this emulsion was adjusted to 7 using sodium carbonate, N ₂ was blown in for 4 hours, and then steam distillation was performed to remove volatile siloxanes. Was added to adjust the nonvolatile content to 45%. As a result, an emulsion of polysiloxane containing 0.1 mol% of methacryl groups was obtained (hereinafter, abbreviated as E-1). Also, as shown in Table 1, polysiloxane emulsions E-2 to E-4 were obtained in the same manner as in E-1, except that the type, amount and aging conditions of siloxane were changed.

Reference Example 2 (Copolymer emulsion) Emulsion E-1 333 obtained in Reference Example 1 was placed in a reactor equipped with a stirrer, a condenser, a thermometer and an N ₂ gas inlet.
Parts (siloxane content: 150 parts) and 517 parts of pure water, and the inside of the vessel was adjusted to 30 ° C. under a stream of N ₂ gas. Then, 1.0 part of t-butyl hydroperoxide, 0.5 part of 1-ascorbic acid, and sulfuric acid 0.002 parts of iron heptahydrate were added, and then 328.6 parts of butyl acrylate and 10.5 parts of acrylic acid were
And a mixture of 5.3 parts of methacrylic acid and 56 parts of a 10% aqueous solution of N-methylolacrylamide were added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour to complete the reaction. The resulting copolymer emulsion (hereinafter referred to as p-1
Abbreviation) was 39.8%, and the calculated glass transition point of a polymerized product such as an acrylic monomer was -46 ° C. In the same manner, copolymerization was carried out with the kinds and amounts of the polysiloxane emulsion and the (meth) acrylic monomer shown in Table 2 to obtain a copolymer emulsion p-2 having a solid content of 39 to 40%.
p-5 was obtained.

Examples 1 to 9 and Comparative Examples Using the copolymer emulsions p-1 to p-5 obtained in Reference Example 2, treatment baths were prepared at the compounding ratios shown in Table 3, and the cotton bath # 40 ( (Mercerizing treatment) was padded and reduced to 100% with a roll (1dip-1nip). After drying at 120 ° C for 5 minutes,
Cured for minutes. When the tear strength of the obtained treated cloth was measured and the feeling was examined, the results shown in Table 3 were obtained.

Here, the crosslinking agent in Table 3 is represented by the formula Is an emulsion obtained by emulsifying and dispersing 30 parts of methyl hydrogen polysiloxane having a viscosity of 150 cs in 65 parts of water using 5 parts of polyoxyethylene alkyl phenyl ether. The catalyst is 30 parts of dibutyltin dilaurate in polyoxyethylene. This emulsion is emulsified and dispersed in 67 parts of water using 3 parts of alkylphenyl ether.

 The test of the treated cloth was performed by the following method.

Laundry Detergent using a home washing machine (top: Lion Corporation)
The mixture was stirred at 40 ° C. for 5 minutes at a concentration of 2 g / l and a bath ratio of 1:30, washed with water and dehydrated, and dried at room temperature.

Tear strength Measured at a tensile speed of 200 mm / min by the JIS L 1096 A-1 method (single tongue method).

The feeling was evaluated by the feel of the hand and indicated by the following.

Good ◎ ~ ○ ~ △ ~ × Poor Furthermore, for comparison, the same cotton broad as that used in the examples was simply passed through with water, and the tear strength was measured in the same manner as in the examples. Upon examination, the results shown in Table 3 were obtained.

As shown in Table 3, the treated cloth of the example had a higher tear strength than that of the comparative example, and the difference was particularly remarkable after washing. Furthermore, the treated cloth of the example was superior to the comparative example in the feeling.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Ohashi 2-13-1 Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Inventor Hiroshi Saga Kitafu, Takefu-shi, Fukui 2-17-1733 Nissin Chemical Industry Co., Ltd. (72) Inventor Satoshi Terasaki 2-17-1733 Kitafu, Takefu City, Fukui Prefecture Nissin Chemical Industry Co., Ltd.

Claims (3)

(57) [Claims] (1) General formula (I) [Wherein, R ¹ , R ² , and R ³ are each one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or two or more groups selected from a radical reactive group and an organic group including an SH group, and X is a hydrogen atom, a monovalent lower alkyl group and represented by the formula R ¹ R ² R ⁴ Si Groups (R ¹ and R ² are the same as described above;
R ⁴ is the same or different atom or group selected from R ^{1 and} 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 an oil-in-water emulsion of polysiloxane and (2) a) general formula (II) (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a C 1-18
One or more monomers selected from acrylic and methacrylic monomers represented by the following formulas: 70 to 100% by weight b) ethylenically unsaturated amide, ethylenic Alkylol or alkoxyalkyl substituted compounds of unsaturated amides, oxirane groups, hydroxyl groups, carboxyl groups, amino groups, sulfonic acid groups, phosphoric acid groups, polyalkylene oxide groups or quaternary ammonium base-containing ethylenically unsaturated monomers, One or more polyfunctional monomers selected from the group consisting of a complete ester of a polyhydric alcohol and acrylic acid or methacrylic acid, diallyl ester of dibasic acid, allyl acrylate, allyl methacrylate and divinylbenzene 20% by weight c) One or more ethylenically unsaturated compounds other than the above a) and b) Of a monomer or mixed monomer (a) to (c) of 100 to 100% by weight) in the presence of a radical polymerization initiator in the presence of a radical polymerization initiator. A method for treating a cellulosic fiber, comprising using a fiber treatment agent comprising a copolymer emulsion as a main component. 2. The crosslinking agent according to claim 1, wherein the crosslinking agent is
A method for treating a cellulosic fiber, comprising using a fiber treating agent comprising a liquid organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms in a molecule and a catalyst for a crosslinking reaction. 3. The method for treating a cellulosic fiber according to claim 1, wherein the glass transition point of the polymerized product of the monomer or the mixed monomer as the component (2) is 0 ° C. or lower.