JPH09217282A - Fiber treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber treating agent, respectively excellent in mechanical, dilution and blending stabilities and stability with time without causing oil spots in a fiber material and capable of imparting water repellency, waterproofness, flexibility, smoothness, crease resistance and compression recovery properties having durability thereto. SOLUTION: This fiber treating agent consists essentially of a modified polyorganosiloxane-based emulsion prepared by copolymerizing (IV) 99-10 pts.wt. monomer component comprising (a) 19.5-99.5wt.% alkyl (meth)acrylate having a 1-10C alkyl group with (b) 0.5-50wt.% ethylenically unsaturated carboxylic acid and (c) 0-80wt.% copolymerizable other monomers in the presence of (III) 1-90 pts.wt. (solid content) aqueous dispersion of a polyorganosiloxane-based polymer prepared by polycondensing (I) an organosiloxane with (II) a graft crosslinking agent in an amount of 0.02-20wt.% based on the total amount of the components I and II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fiber treating agent containing a modified polyorganosiloxane emulsion as a main component, which is obtained by polymerizing a monomer component in the presence of an aqueous dispersion of a polyorganosiloxane polymer. More specifically, it has excellent mechanical stability, dilution stability, compounding stability, and temporal stability, does not generate oil spots on the fiber material, and has durable water repellency and waterproofness. The present invention relates to an aqueous fiber treatment agent capable of imparting flexibility, smoothness, wrinkle resistance, and compression recovery property.

[0002]

2. Description of the Related Art Conventionally, natural fibers such as cotton, hemp, silk, wool, angora, and mohair, regenerated fibers such as rayon and bemberg, semi-synthetic fibers such as acetate, polyester fibers, polyamide fibers, polyacrylonitrile fibers. , Polyvinyl chloride fiber, polyvinyl alcohol fiber,
Fiber materials such as polyethylene fiber, polypropylene fiber, synthetic fiber such as spandex, glass fiber, carbon fiber, inorganic fiber such as silicon carbide fiber, water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, compression Various fiber treatment agents have been proposed and used in order to impart recoverability and the like.

For example, in JP-A-55-152864, a carboxyl-modified polyorganosiloxane is emulsified with one or more of an anionic surfactant and a nonionic surfactant, and an average particle diameter is 300 nm. A fiber treatment agent containing the above emulsion as a main agent has been proposed. But,
This fiber treatment agent, stirring, which is required during fiber treatment,
Stability in processes such as circulation and squeezing (mechanical stability), stability against dilution with 20 to 100 times the amount of water (dilution stability), and stability when used in combination with various additives (blending stability) ) Is insufficient, the emulsion is broken and the modified polyorganosiloxane floats on the treatment bath, and this becomes an oil droplet called an oil spot on the fiber material, which is a serious defect that it becomes a stain. It was In addition, the carboxyl-modified polyorganosiloxane itself has poor adhesion to fibers, so it has low resistance to washing, and it also satisfies the durability of properties such as water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, and compression recovery. It wasn't possible.

On the other hand, Japanese Patent Laid-Open No. 7-97770 discloses a fiber repellent containing an acryl-silicone graft copolymer as a main component, which is obtained by radically copolymerizing a radical-polymerizable silicone macromonomer with an acrylate and / or a methacrylate. Water treatment agents have been proposed. However, in order to produce the acrylic-silicone-based graft copolymer, which is the main component of this treating agent, and the radical-polymerizable silicone macromonomer, which is its raw material, the solution polymerization method must be applied, and finally the aqueous-based method. Since it requires a solvent removal step and an emulsification step to be used as the treating agent of 1., the productivity was very poor. Moreover, the acrylic obtained in this way
The emulsion of the silicone-based graft copolymer is disclosed in
Similar to the carboxyl-modified polyorganosiloxane emulsion described in JP-A-55-152864, it has poor mechanical stability, dilution stability, and compounding stability, and thus has a problem of oil spot generation and has properties such as water repellency. However, there was a drawback that it could not be expressed sufficiently.

[0005]

The present invention has been made against the background of the problems of the prior art as described above, and is excellent in mechanical stability, dilution stability, compounding stability and temporal stability.
An object of the present invention is to provide a fiber treatment agent capable of imparting durable water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, and compression recovery without generating oil spots on the fiber material. And

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an aqueous dispersion of a polyorganosiloxane polymer containing a specific graft crossing group is present. In addition, a fiber treatment agent mainly composed of a modified polyorganosiloxane emulsion obtained by polymerizing a monomer component is excellent in mechanical stability, dilution stability, compounding stability and temporal stability, and As a result, they have found that they can impart durable water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, and compression recovery, and have completed the present invention.

That is, the fiber treating agent of the present invention comprises the organosiloxane (I) and the graft crossing agent (II) in an amount of 0.02 to 20% by weight based on the total amount of the components (I) and (II). In the presence of an aqueous dispersion of 1 to 90 parts by weight (solid content) of a polyorganosiloxane polymer (III) obtained by condensation, (a) an alkyl acrylate having an alkyl group having 1 to 10 carbon atoms and / Or 19.5 to 99.5% by weight of methacrylic acid alkyl ester, (b) 0.5 to 50% by weight of ethylenically unsaturated carboxylic acid, and (c) 0 to 80% by weight of other monomer copolymerizable therewith (however, a) + (b) +
(C) = 100% by weight] monomer component (IV) 99 to 10
It is characterized in that a modified polyorganosiloxane emulsion obtained by polymerizing parts by weight (however, (III) + (IV) = 100 parts by weight) is used as a main component.

The organosiloxane (I) used in the present invention has the general formula R ¹ _m SiO _{(4-m) / 2} (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, m is 0 ~
Indicates an integer of 3. ), The substituted or unsubstituted monovalent hydrocarbon group R ¹ is, for example, a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, or a halogen atom thereof. Alternatively, a substituted hydrocarbon group substituted with a cyano group and the like can be given. In addition, an organosiloxane having a linear, branched or cyclic structure can be used, but it is particularly preferable to use one having a cyclic structure.

Specific examples of such an organosiloxane (I) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane and the like. In addition to the cyclic compound, a linear or branched organosiloxane can be mentioned. The organosiloxane (I) is condensed (polycondensed) in advance and has a polystyrene-equivalent weight average molecular weight of 500 to 1
It may be a polyorganosiloxane of about 0.000.
When the organosiloxane (I) is such a polyorganosiloxane, the molecular chain terminal is, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group or a methyldiphenylsilyl group. It may be blocked.

The graft crossing agent (II) used in the present invention includes the following.

(1) The following chemical formula

Embedded image (In the formula, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 12.) A compound having both an unsaturated group and an alkoxysilyl group.

(2) A compound represented by the general formula R ³ _p SiO _{(3-p) / 2} (wherein R ³ is a vinyl group or an allyl group, and p is an integer of 0 to 2). Specific examples include vinylmethyldimethoxysilane, tetravinyltetramethylcyclotetrasiloxane, and allylmethyldimethoxysilane.

(3) General formula HSR ⁴ SiR ⁵ _q O
_{(3-q) / 2} (In the formula, R ⁴ is a divalent or trivalent aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms, and R ⁵ is an aliphatic unsaturated group-containing 1 to 6 carbon atoms. It is a monovalent hydrocarbon group, and q is 0.
Indicates an integer of ~ 2. ). A specific example is 3-mercaptopropylmethyldimethoxysilane.

(4) The following chemical formula

Embedded image (In the formula, R ⁶ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group, r is an integer of 1 to 6, and s is
Indicates an integer from 0 to 2. ). As a specific example, 3-methacryloxypropylmethyldimethoxysilane can be mentioned.

Of these graft crossing agents (II), particularly preferable are the compounds having both the unsaturated group and the alkoxysilyl group of the above (1).

This (1) graft crossing agent will be described in more detail. As R ^{2 in the} above chemical formula, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms can be mentioned. A group is preferable, and a hydrogen atom or a methyl group is more preferable. Also, n
Is an integer from 0 to 12, more preferably 0.

Specific examples of such a (1) graft crossing agent include p-vinylphenylmethyldimethoxysilane, 2- (m-vinylphenyl) ethylmethyldimethoxysilane and 1- (m-vinylphenyl) methyldimethyl. Isopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy)
Propylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, 1-
(P-Vinylphenyl) -1,1-diphenyl-3-ethyl-3,3
-Diethoxydisiloxane, m-vinylphenyl- [3-
(Triethoxysilyl) propyl] diphenylsilane,
[3- (p-isopropenylbenzoylamino) propyl]
There may be mentioned compounds such as phenyldipropoxysilane, and these compounds may be used alone or in a mixture thereof. Among these, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane are preferably used, and p-vinylphenylmethyl is particularly preferable. The use of dimethoxysilane is preferred. By using these (1) graft crossing agents, a polymer having a high graft ratio can be obtained, and thus the fiber treating agent aimed at by the present invention having more excellent properties can be obtained.

The proportion of the above-mentioned graft crossing agent (II) (1) to (4) used is 0.02 to 20 relative to the total amount of the organosiloxane (I) component and (II) component.
% By weight, preferably 0.1-10% by weight, more preferably
0.5 to 5% by weight. The proportion of graft crossing agent (II)
If it is less than 0.02% by weight, a high graft ratio cannot be obtained in the graft polymerization of the resulting polyorganosiloxane polymer (III) and the monomer component (VI) described later, and as a result, it is imparted to the fiber material. Various properties such as water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, and compression recovery are insufficient, and sufficient durability cannot be obtained for those properties. 20% by weight of agent (II)
If it exceeds, the graft ratio will increase, but the polymer will have a low molecular weight as the proportion of the graft crossing agent (II) increases,
Also in this case, the above-mentioned various characteristics are insufficient, and sufficient durability cannot be obtained for those characteristics.

In order to produce the polyorganosiloxane polymer (III), for example, first, a surfactant such as an anionic surfactant or a cationic surfactant and, if necessary, a catalyst component such as potassium hydroxide. Dissolved in water,
Next, the organosiloxane (I) and the graft crossing agent (II) are added with stirring. An emulsion is obtained by roughly emulsifying this using an emulsifying machine such as a homomixer, a colloid mill or a line mixer, and further emulsifying through an emulsifying machine such as a pressure homogenizer or an ultrasonic homogenizer. Then, as a first reaction step, this emulsion is kept at 70 to 90 ° C for 1 to 15 hours, and then as a second reaction step, it is kept at 0 to 40 ° C for 1 to 500 hours to proceed with emulsion polymerization. The polymerization is stopped when the polyorganosiloxane polymer (III) reaches a desired degree of polymerization.

Upon termination of the polymerization, when an anionic surfactant is used as a surfactant, an alkaline substance is added to neutralize it, and when a cationic surfactant is used, an acidic substance is added. The polymerization is stopped by neutralizing the polymerization.

In the production of such a polyorganosiloxane polymer (III), as the anionic surfactant, an aliphatic substituted benzenesulfonic acid represented by the following general formulas (1) to (4), Aliphatic hydrogen sulfates,
Alternatively, a mixture of unsaturated aliphatic sulfonic acid and hydroxylated aliphatic sulfonic acid is preferably used.

R ⁷ C ₆ H ₄ SO ₃ H (1) R ⁷ OSO ₃ H (2) R ⁸ CH = CH (CH ₂ ) _n SO ₃ H (3) R ⁸ _{CH 2 CH (OH) (CH} 2) m SO 3 H ......... (4) ( wherein, R ⁷ is a monovalent aliphatic hydrocarbon group having 6 to 30 carbon atoms, R ⁸ is 1 to 30 carbon atoms Is a monovalent aliphatic hydrocarbon group, and n and m each have a total carbon number of 6 to 30 in the compound.
Indicates an integer such that ) Here, R ⁷ in the formulas (1) and (2) has 6 to 6 carbon atoms.
More preferably 30 is a monovalent aliphatic hydrocarbon group of 6 to 18, for example, hexyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, myricyl group, oleyl group, nonenyl group, octynyl group, Examples thereof include a phytyl group and a pentadecadienyl group. Further, R ⁸ in the formulas (3) and (4) is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and for example, R ⁷
The same aliphatic hydrocarbon group as can be mentioned.

Specific examples of the anionic surfactant represented by the formula (1) or (2) include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid and octylsulfate. , Lauryl sulfate, oleyl sulfate, cetyl sulfate, and the like. Examples of the anionic surfactant represented by the formula (3) include tetradecene sulfonic acid, and examples of the anionic surfactant represented by the formula (4) include hydroxytetradecane sulfonic acid. .

Further, an anionic surfactant having a weak catalytic action can also be used in combination with the polymerization catalyst. Examples of such anionic surfactants include
Aliphatic substituted benzenesulfonic acid represented by the formula (1), (2)
Aliphatic hydrogen sulfates represented by the formula, or sodium salt, potassium salt, and ammonium salt of a mixture of unsaturated aliphatic sulfonic acid and hydroxylated aliphatic sulfonic acid represented by formulas (3) and (4) Specific examples include sodium octylbenzenesulfonate, sodium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium tetradecenesulfonate, hydroxytetradecane sulfone. Mention may be made of sodium acidate.

In addition to the anionic surfactant represented by the above formula (1) or (2), for example, polyoxyethylene (4) lauryl ether sulfuric acid, polyoxyethylene (13) cetyl ether sulfuric acid, Polyoxyethylene (6)
Stearyl ether sulfate, polyoxyethylene (4) Sodium lauryl ether sulfate, polyoxyethylene (4)
Polyoxyethylene alkyl ether sulfate ester or salt such as octyl phenyl ether ammonium sulfate, polyoxyethylene (3) lauryl ether carboxylic acid, polyoxyethylene (3) stearyl ether carboxylic acid, polyoxyethylene (6) sodium lauryl ether carboxylate, One or more polyoxyethylene alkyl ether carboxylic acid esters such as sodium polyoxyethylene (6) octyl ether carboxylate or salts thereof can be used, but the present invention is not limited thereto.

As the polymerization catalyst used in combination with the anionic surfactant, an aliphatic-substituted benzenesulfonic acid, an aliphatic hydrogen sulphate, an unsaturated aliphatic sulfonic acid, which is usually used as a polymerization catalyst for low molecular weight organosiloxanes, is used. A mixture of carboxylic acid and hydroxylated aliphatic sulfonic acid, and acidic catalysts such as chlorine, sulfuric acid and phosphoric acid are preferably used, but not limited to these, and a low molecular weight organosiloxane is polymerized in the presence of water. Any catalyst can be used as long as it is capable of

The amount of such anionic surfactant used is 0.5 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (I) and (II). It is preferable. If the amount used is less than 0.5 parts by weight, the stability of the obtained emulsion may be poor and separation may occur.
On the other hand, if it exceeds 20 parts by weight, the emulsion may thicken and the fluidity may deteriorate, which is not preferable. When the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of the components (I) and (II). Further, at this time, the amount of water used is usually 50 to 500 parts by weight, and more preferably 100 to 300 parts by weight, based on 100 parts by weight of the total amount of the components (I) and (II).

In the production of the polyorganosiloxane polymer (III), the cationic surfactant has the following chemical formula:

Embedded image (In the formula, R ⁹ represents a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, R ¹⁰ , R ¹¹ and R ¹² each represent a monovalent organic group, and X represents a hydroxyl group, a chlorine atom or a bromine atom.) A quaternary ammonium salt-based surfactant represented by is preferable.

Here, R ⁹ is a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, preferably 8 to 18, such as hexyl group, octyl group, decyl group, dodecyl group, cetyl group and stearyl group. , Myricyl group, oleyl group, hexadecyl group, nonenyl group, octynyl group, phytyl group, pentadecadienyl group and the like. Also, R ¹⁰ ,
R ¹¹ and R ¹² are the same or different monovalent organic groups, for example, alkyl groups such as methyl group, ethyl group and propyl group, alkenyl groups such as vinyl group and allyl group, phenyl group, xenyl group and naphthyl. Aryl groups such as groups,
Examples thereof include cycloalkyl groups such as cyclohexyl group.

Specific examples of such a quaternary ammonium salt surfactant include lauryl trimethyl ammonium hydroxide, stearyl trimethyl ammonium hydroxide, dioctyl dimethyl ammonium hydroxide, distearyl dimethyl ammonium hydroxide and lauryl trimethyl chloride. Ammonium, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, benzalkonium chloride, stearyldimethylbenzylammonium chloride and the like can be used, and one or more of these can be used. You can

Since such a cationic surfactant has a weak catalytic action, it is preferably used in combination with a polymerization catalyst. As the polymerization catalyst used in combination with the cationic surfactant, an alkali metal such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide which is usually used as a polymerization catalyst for low molecular weight organosiloxanes. Mention may be made of hydroxides.

The amount of the cationic surfactant used is (I)
0.5 to 100 parts by weight of the total amount of the component and (II) component
It is preferably 50 parts by weight, and particularly preferably 1 to 20 parts by weight. If the amount used is less than 0.5 part by weight, the cationicity of the resulting emulsion is insufficient, and the stability of the emulsion may be poor, and separation may occur, while if it exceeds 50 parts by weight, the emulsion may thicken. The fluidity may deteriorate, which is not preferable. When the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but is 0.05 to 10 per 100 parts by weight of the total amount of the components (I) and (II).
It is preferable to use parts by weight.

Further, in order to improve the stability of the aqueous dispersion of the polyorganosiloxane polymer (III) obtained by emulsion polymerization, and the finally obtained modified polyorganosiloxane emulsion, a nonionic surfactant is used. May be used in combination with the above surfactant within a range not impairing the object of the present invention, and may be used before or after emulsion polymerization.

As such a nonionic surfactant, it is preferable to use one having an HLB (hydrophilic / lipophilic balance) of 6 to 20. Examples of such nonionic surfactants include polyoxyethylene (6) lauryl ether, polyoxyethylene (7) cetyl ether, polyoxyethylene (20) stearyl ether, polyoxyethylene (3) octylphenyl ether, and polyoxyethylene (3) octylphenyl ether. Oxyethylene
(18) Nonyl phenyl ether, polyethylene glycol monostearate (EO14), polyethylene glycol distearate (EO80), polyoxyethylene (20) hydrogenated castor oil, polyoxyethylene monolaurate (20) sorbitan, polyoxyethylene monopalmitate (20) sorbitan, polyoxyethylene monostearate (6) sorbitan, polyoxyethylene trioleate (20) sorbitan, polyoxyethylene tetraoleate (40) sorbit, polyoxyethylene monooleate (15) glyceryl, mono Polyoxyethylene (15) glyceryl stearate, sorbitan monopalmitate, polyoxyethylene
(10) Behenyl ether, polyoxyethylene (10) phytosterol, polyoxyethylene (10) polyoxypropylene (4) cetyl ether, polyoxyethylene (5) stearylamine, polyoxyethylene (8) stearylpropylenediamine, polyoxy Examples include ethylene (5) cetyl ether sodium phosphate, but are not limited thereto.

When the nonionic surfactant is used in combination before emulsion polymerization, the amount of the nonionic surfactant used is 100 parts by weight of the above-mentioned anionic or cationic surfactant.
It is preferably from 0 to 500 parts by weight. When the amount used exceeds 500 parts by weight, the activity as a polymerization catalyst is impaired, which is not preferable.

The polystyrene-reduced weight average molecular weight of the polyorganosiloxane polymer (III) thus obtained is preferably 30,000 to 1,000,000, more preferably 50,000 to 300,000. If the average molecular weight is less than 30,000, sufficient smoothness, wrinkle resistance and compression recovery cannot be imparted to the fiber material, while if it exceeds 1,000,000, the flexibility imparted to the fiber material will be insufficient.

The modified polyorganosiloxane-based emulsion used as the main component in the fiber treatment agent of the present invention comprises (a) in the presence of an aqueous dispersion of the polyorganosiloxane-based polymer (III) thus obtained. Acrylic acid and / or methacrylic acid whose alkyl group has 1 to 10 carbon atoms (hereinafter referred to as (meth) acrylic acid) alkyl ester, (b) ethylenically unsaturated carboxylic acid, and (c)
It is obtained by polymerizing a monomer component (IV) composed of another monomer copolymerizable with these.

Examples of the (meth) acrylic acid alkyl ester having 1 to 10 carbon atoms in the alkyl group (a) constituting the monomer component (IV) include, for example, methyl (meth) acrylate and (meth) acrylate. Ethyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate,
N-Butyl (meth) acrylate, (meth) acrylic acid i
-Butyl, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate,
Examples include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, i-nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, and hydroxyethyl (meth) acrylate. it can. These (a) (meth) acrylic acid alkyl esters can be used alone or in combination of two or more. The (meth) acrylic acid alkyl ester (a) is an essential component for imparting durable smoothness, wrinkle resistance, and compression recovery to the fiber material, and the mixing ratio of the (meth) acrylic acid alkyl ester is a monomer component. (IV)
It is 19.5 to 99.5% by weight, preferably 30 to 99% by weight, more preferably 40 to 98% by weight, based on the whole. Mixing ratio
If it is less than 19.5% by weight, smoothness, wrinkle resistance, and compression recovery are insufficiently imparted, and these properties are inferior.
If it exceeds 5% by weight, the stability of the polymerization system becomes poor and the durability of smoothness, wrinkle resistance and compression recovery becomes low, which is not preferable.

Further, it constitutes the monomer component (IV) (b)
Examples of the ethylenically unsaturated carboxylic acid include itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, crotonic acid and the like, and (meth) acrylic acid is particularly preferably used. These (b) ethylenically unsaturated carboxylic acids may be used either individually or in combination of two or more. This (b) ethylenically unsaturated carboxylic acid is an essential component for maintaining a high balance of stability of the obtained emulsion and water repellency and waterproofness, and the mixing ratio of the ethylenically unsaturated carboxylic acid is a monomer component (IV ) For the whole
It is 0.5 to 50% by weight, preferably 0.5 to 30% by weight. If the blending ratio is less than 0.5% by weight, the stability of the obtained emulsion is lowered, while if it exceeds 50% by weight, the water repellency and waterproofness are deteriorated, which is not preferable.

Further, (c) other monomers copolymerizable with them include, for example, 1,3-butadiene, isoprene,
Aliphatic conjugated dienes such as 2-chloro-1,3-butadiene; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylolacrylamide Alkyl amides; vinyl carboxylates such as vinyl acetate and vinyl propionate; acid anhydrides of ethylenically unsaturated dicarboxylic acids, monoalkyl esters, monoamides; ethylene such as aminoethyl acrylate, dimethylaminoethyl acrylate and butylaminoethyl acrylate Aminoalkyl amides of unsaturated unsaturated carboxylic acids; Aminoalkylamides of unsaturated ethylenic carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide, methylaminopropylmethacrylamide; (meth) Vinyl cyanide compounds such as acrylonitrile and α-chloroacrylonitrile; unsaturated aliphatic glycidyl esters such as glycidyl (meth) acrylate, and the like, 1,3-butadiene, styrene, acrylonitrile, α-methylstyrene It is preferable to use glycidyl (meth) acrylate or the like. These (c) other copolymerizable monomers may be used alone or in combination of two or more. (C) The mixing ratio of the other copolymerizable monomer is
It is 0 to 80% by weight, preferably 20 to 60% by weight, based on the total amount of the monomer component (IV). If the blending ratio exceeds 80% by weight, problems such as discoloration and shrinkage of fibers after fiber treatment may occur. It is not preferred.

The charge composition for polymerizing the monomer component (IV) in the presence of an aqueous dispersion of the polyorganosiloxane polymer (III) is 1 to 90 in terms of solid content of the component (III).
Parts by weight, preferably 5 to 80 parts by weight, and the component (IV) is
The amount is 99 to 10 parts by weight, preferably 95 to 20 parts by weight. However, the total of component (III) and component (IV) should be 100 parts by weight. Polyorganosiloxane polymer (III)
Is less than 1 part by weight, it is impossible to impart sufficient water repellency, waterproofness and flexibility to the fiber material. On the other hand, if it exceeds 90 parts by weight, not only sufficient smoothness, anti-wrinkle property and compression recovery property cannot be imparted, but also the adhesiveness between the polymer constituting the emulsion and the fiber material is deteriorated, which results in impartation. Durability of various properties to be reduced also decreases.

The graft ratio of the polymer (including the graft copolymer and the non-grafted (co) polymer) constituting the modified polyorganosiloxane emulsion thus obtained is usually 5% or more, preferably. Is 10%
Or more, more preferably 30% or more. As described above, when the graft ratio of the polymer constituting the modified polyorganosiloxane emulsion is high, the interfacial adhesive force between the graft copolymer and the non-grafted (co) polymer increases, and the durability is improved. A fiber treatment having an excellent balance of properties can be achieved.

In producing the modified polyorganosiloxane-based emulsion used as the main component in the fiber treating agent of the present invention, the polyorganosiloxane-based polymer (III) is used.
A method in which the monomer component (IV) is graft-polymerized to the aqueous dispersion by the ordinary radical polymerization method is adopted. Examples of the radical polymerization initiator include, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, oxidizers composed of organic hydroperoxides such as paramenthane hydroperoxide, sugar-containing iron pyrophosphate prescription, sulfoxylate prescription, and the like. Redox initiators in combination with reducing agents such as mixed preparations of iron sugar pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl-2, Azo compounds such as 2'-azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoylperoxide and lauroylperoxide can be mentioned, and in particular, the use of redox type initiators. Is preferred. The amount of these radical polymerization initiators used depends on the monomer component (IV)
Generally, 0.05 to 5 parts by weight, preferably 100 parts by weight,
0.1 to 2 parts by weight. The radical polymerization method at this time is preferably carried out by emulsion polymerization. In emulsion polymerization, the radical polymerization initiator, a surfactant,
A chain transfer agent or the like is used. Here, examples of the surfactant include the anionic, cationic, and nonionic surfactants. One or two of these can be used.
More than one species can be used in combination. The amount of the surfactant used is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the monomer component (IV). Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan, and n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide. It can be used in a proportion of 0.02 to 1% by weight based on the component (IV).

In the emulsion polymerization, in addition to the above radical polymerization initiator, surfactant, chain transfer agent, etc.,
If necessary, various electrolytes, pH adjusters and the like are used in combination. Then, 100 to 500 parts by weight of water is used with respect to 100 parts by weight of the monomer component (IV), and the radical polymerization initiator, the surfactant, the chain transfer agent, and the like are used in an amount within the above range to perform polymerization. Temperature 5 ~ 100 ℃, more preferably 50 ~ 90 ℃, polymerization time
Emulsion polymerization is performed for 0.1 to 10 hours. In this emulsion polymerization, each monomer component (IV) was added to an aqueous dispersion containing a polyorganosiloxane polymer (III) obtained by polycondensation of an organosiloxane (I) and a graft crossing agent (II). ) And radical polymerization initiator are preferably added directly.

Further, each of the above-mentioned monomer components (a) to
The addition method of (c) is not particularly limited, and any method such as a batch addition method, a continuous addition method or a divided addition method can be adopted. Further, the polymerization conversion rate (reaction rate) of the obtained emulsion is preferably 99.5% or more. Further, in obtaining a modified polyorganosiloxane-based emulsion used as the main ingredient in the present invention, when seed polymerization is adopted, the polyorganosiloxane-based polymer (III) is used as seed particles, and a monomer component is added to the seed particles. Emulsion polymerization may be performed by adding (IV). The polystyrene-equivalent weight average molecular weight of the modified polyorganosiloxane emulsion thus obtained is not particularly limited, but is preferably 50,000 to 2,000,000, more preferably 100,000 to 800,000. Average molecular weight 50,0
When it is less than 00, smoothness, wrinkle resistance, and
The compression recovery becomes insufficient. On the other hand, when it exceeds 2,000,000, the adhesiveness between the polymer constituting the emulsion and the fiber material is deteriorated, and the durability of various imparted properties is deteriorated, which is not preferable.

Further, in the modified polyorganosiloxane emulsion used as the main component in the fiber treatment agent of the present invention, in order to impart excellent flexibility, smoothness, wrinkle resistance, compression recovery property and the like to the fiber material. , The highest glass transition temperature measured by a differential thermal analyzer of a polymer (including a graft copolymer and a non-grafted (co) polymer) constituting an emulsion may be 80 ° C or lower. The temperature is preferably -60 ° C to + 60 ° C, more preferably. The glass transition temperature of this polymer can be appropriately determined by adjusting the composition of the monomer in the monomer component (IV).

The particle size of the modified polyorganosiloxane emulsion is preferably 30 to 800 nm, more preferably 50.
It is desirable that particles having a particle size of up to 600 nm have a particle size distribution such that they account for 80% by weight or more of all particles. When the particle size distribution is in such a range, the system stability is maintained and the physical properties are balanced. The particle size of the modified polyorganosiloxane emulsion can be easily adjusted by adjusting the amount of the surfactant, the polymerization temperature and the like. Further, the solid content concentration of the modified polyorganosiloxane emulsion is usually 20 to 70% by weight, preferably 30 to 60% by weight.

The fiber-treating agent of the present invention may contain the above-mentioned modified polyorganosiloxane emulsion as a main agent for fiber treatment, and does not impair the object of the present invention as it is or if necessary. It is obtained by adding any material to any extent in any ratio. Such optional ingredients include the following, one of which
One kind or two or more kinds can be added in a proportion of 0 to 99.9% by weight.

That is, as additive components, silane compounds such as trimethoxysilane, vinyltrimethoxysilane, triethoxysilane, vinyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, and the like. Partial hydrolyzate of 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 4-ethenylphenyltrimethoxysilane Organic functional group-containing silane compounds such as silane, and partial hydrolysis products or reaction mixtures thereof; 3-aminopropyl group, N- (2-
Aminoethyl) -3-aminopropyl group, 3-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, 3-
Organic functional group-containing polydimethylsiloxane containing mercaptopropyl group, vinyl group, 3-methacryloxypropyl group, 4-ethenylphenyl group and the like; and a reaction mixture thereof; the aforementioned organic functional group-containing silane compound and organic functional group-containing poly Reaction mixture with dimethyl siloxane; linear or branched polyorganosiloxane which does not contain the above-mentioned specific organic functional group and whose molecular end is blocked with an alkyl group or a hydroxyl group; dibutyltin laurate, dioctyltin laurate, Organic acid metal salts such as dibutyltin diacetate, tin octylate, iron octylate, zinc octylate; kaolin, talc, silica, diatomaceous earth, perlite, calcium carbonate, zeolite, alumina, hydrous silicic acid, chromium oxide, oxidation Titanium, zinc oxide, iron oxide, zirconium oxide, silicon oxide , Cerium oxide, magnesium oxide, calcium fluoride, bentonite, montmorillonite, silaspaloon, mica, calcium silicate,
Zirconium silicate, diamond powder, glass powder, ceramic powder, polyolefin powder, nylon powder, polystyrene powder, cellulose powder, Teflon powder, higher fatty acid bisamide, higher fatty acid metal soap, amino acid powder, silicone powder, other synthetic resin powder Hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane, olefin oligomers; acid esters such as isopropyl palmitate, stearyl stearate, octyldodecyl myristate, and triglyceride 2-ethylhexanoate; lauryl alcohol, cetyl alcohol, stearyl alcohol Higher alcohols such as; palmitic acid, higher fatty acids such as stearic acid; morpholine, monoethanol Emissions, ethylenediamine, diethylaminoethanol, complete alkyl type methylated melamine resins such as hexamethoxymethylmelamine melamine resin, partially alkylated melamine resins, base Nzoguanamin resin, an amine compound such as an alkyl-etherified urea resins;
Ethylene glycol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, sorbitol
Polyglycidyl ethers of polyhydric alcohols such as polyglycidyl ether, hydrogenated bisphenol A / diglycidyl ether or bisphenol A / diglycidyl ether, or p-oxybenzoic acid glycidyl ether, phthalic acid diglycidyl ether or hexahydrophthalic acid diglycidyl ether. Glycidyl ether, further hydantoin ring-containing epoxy resins, epoxy compounds such as vinyl polymers having an epoxy group in the side chain; tolylene diisocyanate and its hydrogenated products and adducts, diphenylmethane diisocyanate and its hydrogenated products, triphenylmethane Triisocyanate and its hydrogenated product, hexamethylene diisocyanate, xylylene diisocyanate and its hydrogenated product, isophorone diisocyanate, dianishi Isocyanate compounds such as diisocyanates, tolidine diisocyanates, blocked polyisocyanates with blocked isocyanate groups; tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2- Methyl) aziridinyl] phosphine oxide, hexa [1- (2-methyl) aziridinyl]
Aziridine compounds such as triphosphatriazine; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, hydrazide and hydrazide. Compounds; resin-based processing agents such as glyoxal resin, melamine resin, urea resin, polyester resin, epoxy resin and acrylic resin; organic solvents such as ethanol; water; various surfactants exemplified above. . In addition, other additives such as a viscosity adjusting agent, a pH adjusting agent, an antioxidant, an ultraviolet absorber, an antiseptic, a rust preventive, a fragrance, and a coloring agent may be added as necessary.

In order to add these components to the fiber treatment agent of the present invention, the modified polyorganosiloxane emulsion and other optional components are simply mixed uniformly, or other than the modified polyorganosiloxane emulsion. The components may be previously emulsified by an emulsifier such as a homogenizer, a colloid mill, a line mixer, or uniformly mixed by a stirrer, and the modified polyorganosiloxane emulsion may be added thereto.

To treat the fiber material with the fiber treatment agent of the present invention, the treatment agent is attached to the fiber by a method such as spray attachment, roll attachment, brush coating, or dipping, and then left at room temperature and blown with hot air. , Dry by a method such as heat treatment. The amount of adhesion varies depending on the type of fiber material and is not particularly limited, but usually 0.01 to 10 in terms of solid content with respect to the fiber material.
% By weight. If the amount of adhesion is less than 0.01% by weight, various properties such as water repellency, waterproofness and flexibility will be insufficiently provided, while if it exceeds 10% by weight, the texture of the fiber will be unfavorable.

The fibrous material to be treated includes, as materials, natural fibers such as cotton, hemp, silk, wool, angora and mohair, regenerated fibers such as rayon and bemberg, and semi-synthetic fibers such as acetate. Polyester fiber, polyamide fiber, polyacrylonitrile fiber, polyvinyl chloride fiber, polyvinyl alcohol fiber, polyethylene fiber,
Examples include polypropylene fibers, synthetic fibers such as spandex, glass fibers, carbon fibers, and inorganic fibers such as silicon carbide fibers. Further, in terms of shape, staple-like, filament-like, tow-like, top-like, and thread-like ones are mentioned, and materials such as knitted fabrics, woven fabrics, non-woven fabrics, and papers made of these fibers can be processed it can.

[0053]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to examples. The parts and percentages in the examples are:
Unless otherwise specified, parts by weight and% by weight are shown.

First, polyorganosiloxane polymer aqueous dispersions A, B and C were prepared.

(Production of Polyorganosiloxane Polymer Aqueous Dispersion A) 1.5 parts of p-vinylphenylmethyldimethoxysilane and octamethylcyclotetrasiloxane 9
Dodecylbenzene sulfonic acid mixed with 8.5 parts
Add 2.0 parts to 150 parts of ion-exchanged water, and stir with a homomixer, then use a pressure homogenizer to
The mixture was emulsified and dispersed by passing it twice at a pressure of 00 kgf / cm ² . This dispersion was transferred to a separable flask equipped with a condenser, nitrogen inlet and stirrer, heated at 85 ° C for 5 hours with stirring and mixing, and then slowly cooled to 5 ° C over 3 hours, and then at 5 ° C. Cooled for 24 hours. And
The obtained dispersion was treated with 10% aqueous sodium carbonate solution
A polyorganosiloxane-based polymer aqueous dispersion A was obtained by neutralizing with H 7 to stop the polymerization reaction.

The nonvolatile content of this aqueous dispersion A at 105 ° C. for 3 hours was 36.5%, and the average particle size was 260 nm.
Further, this aqueous dispersion A was destroyed with isopropyl alcohol, the polyorganosiloxane polymer was taken out, and G
When measured by PC, the weight average molecular weight was 520,000.
Met.

(Production of Polyorganosiloxane Polymer Aqueous Dispersion B) In the production of the aqueous dispersion A described above,
without using p-vinylphenylmethyldimethoxysilane,
A polyorganosiloxane polymer aqueous dispersion B was obtained in the same manner except that 100 parts of octamethylcyclotetrasiloxane was used.

The nonvolatile content of this aqueous dispersion B at 105 ° C. for 3 hours was 36.7%, and the average particle size was 262 nm.
Further, this aqueous dispersion B was destroyed with isopropyl alcohol, the polyorganosiloxane polymer was taken out, and G
When measured by PC, the weight average molecular weight was 515,000.
Met.

(Production of Polyorganosiloxane Polymer Aqueous Dispersion C) In the production of the above aqueous dispersion A, instead of 2.0 parts of dodecylbenzenesulfonic acid, sodium tetradecenesulfonate / sodium hydroxytetradecanesulfonate = 75 / A polyorganosiloxane polymer aqueous dispersion C was obtained in the same manner except that 2 parts by weight of 25 (weight ratio) Lipolan PJ-400 manufactured by Lion Corporation and 0.4 parts by weight of sulfuric acid were used.

The nonvolatile content of this aqueous dispersion C at 105 ° C. for 3 hours was 36.5%, and the average particle size was 260 nm.
Further, this aqueous dispersion C is destroyed with isopropyl alcohol, the polyorganosiloxane polymer is taken out, and G
When measured by PC, the weight average molecular weight was 520,000.
Met.

Examples 1 to 5, Comparative Examples 1 to 5 In a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, a predetermined amount of the polyorganosiloxane polymer aqueous dispersion A, B or C, and ions were added. 70 parts of exchanged water and 0.3 part of potassium persulfate were charged, the gas phase part was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. On the other hand, in another container,
30 parts of ion-exchanged water, 1.0 part of polyoxyethylene alkylphenyl ether sulfate ammonium salt, 0.5 part of sodium alkylbenzene sulfonate, and vinyl monomers shown in Table 1 and Table 2 are mixed with stirring to prepare a pre-emulsion. It dripped into the said flask over 4 hours.
During the dropping, the reaction was carried out at 80 ° C. while introducing nitrogen gas. After the dropping was completed, the reaction was further terminated by stirring at 85 ° C. for 2 hours. Then cool to 25 ° C and pH with ammonia water.
Adjusting to 7, a modified polyorganosiloxane emulsion was obtained. The amounts of the polyorganosiloxane polymer aqueous dispersion A, B or C and each vinyl monomer charged are as shown in Tables 1 and 2, respectively. Also,
* 1) to * 4) in Table 1 and Table 2 show the following compounds, respectively.

* 1) nBA = n-butyl acrylate * 2) MMA = methyl methacrylate * 3) ST = styrene * 4) ΑΑ = acrylic acid Comparative Example 6 The same separable flask as in Example 1 was ion-exchanged. water
Charge 70 parts and 0.3 parts of potassium persulfate, and add 15 parts to the gas phase.
The atmosphere was replaced with nitrogen gas, and the temperature was raised to 80 ° C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of polyoxyethylene alkylphenyl ether sulfate ammonium salt, 0.5 part of sodium alkylbenzene sulfonate, and vinyl monomers shown in Table 2 are mixed with stirring to prepare a pre-emulsion. ,
It dripped into the said flask over 4 hours. During the dropping, the reaction was carried out at 80 ° C. while introducing nitrogen gas. After the dropping was completed, the reaction was further terminated by stirring at 85 ° C. for 2 hours. After that, it was cooled to 25 ° C. and adjusted to pH 7 with aqueous ammonia. The obtained copolymer emulsion was mixed with the above-mentioned polyorganosiloxane polymer aqueous dispersion A. The amount of each vinyl monomer charged and the amount of the polyorganosiloxane polymer aqueous dispersion mixed are as shown in Table 2.

Then, Examples 1 to 5 and Comparative Examples 1 to 6
The modified polyorganosiloxane-based emulsion obtained in 1. was evaluated according to the following. The evaluation results are shown in Table 1 and Table 2, respectively.

[Evaluation Method of Modified Polyorganosiloxane Emulsion] (1) Glass Transition Temperature About 5 g of a sample was thinly drawn on a glass plate and dried at 25 ° C. for 7 days to obtain a polymer film. Then, the glass transition temperature (Tg) of the obtained dried film was measured under the following conditions using a differential scanning calorimeter (DSC) manufactured by Rigaku Denki Co., Ltd.

Conditions: Temperature rising rate 20 ° C./min Atmosphere: Nitrogen gas Sample amount: 20 mg (2) Graft ratio A certain amount (X) of the graft polymerization product is put into acetone and shaken for 2 hours on a shaker. After that, the ungrafted (ungrafted) polymer is dissolved. Then, it is centrifuged for 30 minutes at a rotation speed of 23,000 rpm using a centrifuge to obtain an insoluble matter (graft polymer). Then, this is dried at 120 ° C. for 1 hour using a vacuum dryer, the insoluble matter weight (Y) is measured, and the graft ratio is calculated by the following formula.

Graft ratio [%] = {(Y)-[(X) ×
(Fraction of (III) component in graft polymerization product]} × 100 /
{(X) x (fraction of (III) component in graft polymerization product)} (3) Particle size Laser particle size analysis system LPA-3000s / manufactured by Otsuka Electronics Co., Ltd.
The particle size of the sample was measured using a 3100.

Next, the modified polyorganosiloxane emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were diluted with water so that the concentration of the active ingredient was 5% to prepare fiber treatment agents. . Then, the mechanical stability of the obtained fiber treatment agent and various characteristics of the fiber treated with this fiber treatment agent were evaluated according to the following. The evaluation results are also shown in Tables 1 and 2.

[Test Method for Fiber Treatment Agent] (1) Mechanical Stability i) Roller Treatment 400 ml of the fiber treatment agent was sampled and placed in a square bat made of stainless steel of 20 cm × 35 cm × 3 cm. 2 rubber rollers with a diameter of 6 cm (nip pressure 0.5 kg / cm ² )
Was set so that the lower roller was immersed in the fiber treatment agent at a depth of 0.5 cm. Then, the roller was rotated at a speed of 20 rpm for 8 hours, and the stability of the fiber treatment agent by the roller treatment was evaluated according to the following evaluation criteria.

◯: No polymer was precipitated.

Δ: Polymer was slightly precipitated.

X: A large amount of polymer was precipitated.

Ii) Mixer-treated fiber treatment agent 500 ml to 1000 m
It is collected in a l-death cup and stirred for 60 minutes at a speed of 4000 rpm using a homomixer (made by Tokushu Kika Co., Ltd.), and the stability of the fiber treatment agent by the mixer treatment is evaluated according to the following evaluation criteria. Therefore evaluated.

○: No polymer was precipitated.

Δ: Polymer was slightly precipitated.

X: A large amount of polymer was precipitated.

(2) Evaluation of Treated Fibers Polyester fiber taffeta (fiber A), nylon taffeta (fiber B) and cotton broad (fiber C) were each dipped in a fiber treatment agent, and then the fibers were taken out to remove excess. The treating agent was removed and the product was dried at 80 ° C for 2 minutes. The fibers thus treated were allowed to stand at room temperature for one day, and then the following test items were evaluated.

I) Water repellency and waterproofness The surface condition of the treated fiber after spraying water thereon was observed and evaluated according to the following evaluation criteria.

∘ ... No wetness or water drops on the surface.

O ... Wetting by small water droplets on the surface.

Δ ... Half of the surface is wet and small individual water droplets penetrate the cloth.

X: Only the surface is totally wet.

XX ... The entire front and back surfaces are wet.

Ii) Softness The fibers before treatment and the treated fibers were compared in softness by feeling, and evaluated according to the following evaluation criteria.

⊚ The treated fiber has very good flexibility.

O: Good.

Δ: Insufficient improvement in flexibility.

No effect of processing.

Iii) Smoothness The smoothness of the untreated fiber and that of the treated fiber were compared by touch and evaluated according to the following evaluation criteria.

⊚ The treated fibers have very good smoothness.

O: Good.

Δ: Improvement in smoothness is insufficient.

X: No effect

Iv) Impact resilience (wrinkle resistance, compression recovery) The impact resilience of the untreated fiber and that of the treated fiber were compared by touch and evaluated according to the following evaluation criteria.

⊚ The treated fiber has very good impact resilience.

O: Good.

Δ: Insufficient improvement in impact resilience.

X: No effect

V) Durability The treated fiber was placed in a washing bath added with 5 g of sodium alkylbenzenesulfonate and 2 g of sodium carbonate in 1000 ml of water, and a household electric washing machine was used at a bath ratio of 100: 1. After washing for 15 minutes at a water temperature of 50 ° C, the above i) ~ i
The test evaluation of v) was carried out.

[0099]

[Table 1]

[Table 2] As is clear from Table 1, Examples 1 to 5 are examples using the modified polyorganosiloxane emulsion within the scope of the present invention, and the fiber treating agent intended by the present invention was obtained.

On the other hand, as is clear from Table 2,
In Comparative Example 1, the amount of the (meth) acrylic acid alkyl ester constituting the monomer component (IV) was less than the range of the present invention, and the treated fiber had smoothness and impact resilience (wrinkle resistance,
Compression recovery). In Comparative Example 2, the amount of the ethylenically unsaturated carboxylic acid constituting the monomer component (IV) exceeds the range of the present invention, and the treated fiber is inferior in water repellency and waterproofness. In Comparative Example 3, the amount of each monomer component (IV) used exceeds the range of the present invention, and the treated fiber is inferior in water repellency, waterproofness and flexibility. In Comparative Example 4, the amount of each monomer component (IV) used was less than the range of the present invention, so that the smoothness and impact resilience (wrinkle resistance, compression recovery) were poor, and these characteristics The durability is insufficient. In Comparative Example 5, the blending composition did not include the graft crossing agent (II), and in Comparative Example 6, the copolymer emulsion of the vinyl monomer and the aqueous dispersion of the polyorganosiloxane polymer (III) were used. In each of the examples, the graft ratio is low, and the durability of each property imparted to the fiber is inferior.

[0101]

As is apparent from the above description, the fiber treating agent of the present invention is characterized by the presence of an aqueous dispersion of a polyorganosiloxane polymer containing a specific graft crossing group,
The main component is a modified polyorganosiloxane emulsion obtained by polymerizing the monomer components, so it is extremely good for fiber materials as water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, and compression recovery. Properties can be imparted, and the imparted effects are not deteriorated by washing or the like. In addition, it has excellent mechanical stability against stirring, circulation, etc., dilution stability against dilution with water, and compounding stability with various additives. It does not generate oil spots on the fiber material and is extremely useful industrially. Is.

[0102]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minor Kato 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (72) Kouji Tamori 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A polyorgano obtained by polycondensing an organosiloxane (I) with a graft crossing agent (II) in a proportion of 0.02 to 20% by weight based on the total amount of the components (I) and (II). Siloxane polymer (III) 1 to 90 parts by weight (solid content)
In the presence of the aqueous dispersion of (a), the carbon number of the alkyl group (a)
1-10 acrylic acid alkyl ester and / or methacrylic acid alkyl ester 19.5-99.5% by weight, (b)
0.5 to 50% by weight of ethylenically unsaturated carboxylic acid, and (c) 0 to 80% by weight of other monomer copolymerizable therewith
99 to 10 parts by weight of a monomer component (IV) consisting of (a) + (b) + (c) = 100% by weight [where (III) +
(IV) = 100 parts by weight] is used as a main component, and a modified polyorganosiloxane emulsion obtained by polymerizing the fiber treatment agent. 2. The graft crossing agent (II) has the following chemical formula: (Wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 12) and a compound having an alkoxysilyl group in combination. Item 1. The fiber treatment agent according to item 1.