JPH10140480A - Textile treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a textile treating agent capable of imparting water repellency, softness or smoothness rich in durability to a fiber by compounding a high- molecular weight polyorganosiloxane with a specific sulfonic acid-based anionic surfactant, a specifiedmiscible surfactant and a specific cationic surfactant. SOLUTION: This textile treating agent consisting essentially of a cationic silicone oil-in-water type emulsion is obtained by compounding a high-molecular weight polyorganosiloxane, prepared by carrying out the emulsion polymerization in the presence of an anionic surfactant selected from the group of a 1-20C aliphatic hydrocarbonsulfonic acid (salt), an aliphatic hydrocarbonsulfuric acid (salt), a 6-30C arylsulfonic acid (salt) and a 7-50C alkylarylsulfonic acid (salt) and having 10,000-10,000,000 cat vicosity at 25 deg.C with a miscible surfactant having 9-25 hydrophile-lipophile balance such as a polyglycerol fatty acid ester and a cationic surfactant comprising a bis(polyoxyethylene)hydrocarbylmethyl quaternary ammonium halide or sulfate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treating agent mainly comprising a stable cationic emulsion using a high molecular weight polyorganosiloxane, and more particularly, to a method for converting a low molecular weight organosiloxane to an anionic surfactant. After emulsion polymerization in the presence of an emulsion containing a high molecular weight polyorganosiloxane, a stable cationic polymer obtained by blending a miscible surfactant and further blending a cationic surfactant. The present invention relates to a fiber treating agent containing an organosiloxane emulsion as a main component.

[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, polyamide, polyacrylonitrile and poly Vinyl chloride, vinylon, polyethylene, polypropylene,
Synthetic fiber such as polyurethane elastic fiber; Water repellent, waterproof, flexible, smooth, anti-wrinkle, compression recovery, etc. for fiber materials such as glass fiber, carbon fiber and inorganic fiber such as silicon carbide fiber. Various silicone products, especially fiber treatment agents based on polyorganosiloxanes, have been used to impart odor.

[0003] When blending a polyorganosiloxane as a component of an aqueous emulsion used as a fiber treatment agent, an emulsification technique is an important factor. As a general emulsification method of polyorganosiloxane, there is a mechanical emulsification method.
The mechanical emulsification method is a method for uniformly emulsifying and dispersing these components by applying mechanical energy to a mixture of a polyorganosiloxane, a surfactant and water used as components in order to obtain a desired stable emulsion. . Emulsifiers such as colloid mills, homomixers, homogenizers, combimixes, and sand grinders are generally used to apply this mechanical energy. For example, in the method described in U.S. Pat. No. 2,755,194, a surfactant is added at 350.degree.
After mixing with polydimethylsiloxane having cSt and adding a small amount of water to the mixture and emulsifying and dispersing in a colloid mill, water is further continuously added to obtain a desired aqueous emulsion. .

[0004] In the mechanical emulsification method, only a polyorganosiloxane in a range that can be emulsified by the limited mechanical energy due to the structure of the equipment to be used can be used.
Only polyorganosiloxanes having a viscosity of up to about 000 cP could be emulsified (JP-A-63-125530).
No. 56-109227). For this reason, when this is used as a fiber treatment agent, sticky feeling remains, and it is not possible to sufficiently impart high water repellency, waterproofness, flexibility, smoothness, wrinkle resistance and compression recovery with high durability. However, it did not satisfy the sophisticated requirements for fiber treatment agents. In addition, the emulsion thus obtained generally has a large oil phase particle size, and stability (mechanical stability) in processes such as stirring, circulation, and squeezing of a treatment liquid, which are required for fiber treatment. 2. Insufficient stability to dilution with water (dilution stability) of 20 to 100 times and stability when various additives are used in combination (stability of blending). There is a problem that the emulsion is destroyed, and the polyorganosiloxane floats on the treatment bath, adheres to the fiber material as oil droplets (referred to as oil spots), and causes stains.
The solution was desired.

In the mechanical emulsification method, a method is known in which a high-viscosity fluid or resin which is difficult to mechanically emulsify is emulsified and dispersed by dissolving the same in an organic solvent such as toluene or xylene. (JP-B-63-45748, JP-A-60-1258, and JP-A-60-1259). However, this method uses an organic solvent,
There is a problem of danger due to solvent odor and combustibles, and there is a limitation in using it as a fiber treatment agent.

Further, by using a polyorganosiloxane containing a polyoxyalkylene group in combination with a normal polyorganosiloxane such as polydimethylsiloxane, the oil phase of the emulsion by mechanical emulsification is atomized,
Methods for improving the stability of emulsions are also known (JP-A-60-126209, JP-A-60-1976).
No. 10). However, the polyoxyalkylene group-containing polyorganosiloxane used in this method is expensive and is not suitable for imparting water repellency or waterproofness.
25 ° C of polyorganosiloxane to which this technology can be applied
, The upper limit was about 1,000 cP at most.

[0007] In particular, in the case of using a quaternary ammonium salt-based surfactant as a cationic surfactant itself having a softening effect on fibers, it is satisfactory in mechanical emulsification of polyorganosiloxane. In order to obtain a suitable emulsion, it has been necessary to use a large amount of a surfactant or to use a nonionic surfactant in combination.

On the other hand, the emulsion polymerization method emulsifies and disperses a mixture of low molecular weight organosiloxane and / or reactive siloxane oligomer as a siloxane monomer, a surfactant, a water-soluble polymerization catalyst and water, and polymerizes to a target molecular weight. This is a method of obtaining an emulsion by heating with stirring until an emulsion containing a polyorganosiloxane in a wide viscosity range from silicone oil to a high-molecular-weight raw rubber region can be obtained. In addition, the emulsion thus obtained is generally small in particle size of the oil phase of 0.1 to 0.5 μm and monodisperse, and has a mechanical stability required for fiber treatment. , Dilution stability, and blending stability with various additives.

The emulsion polymerization method includes, for example, a method of emulsifying and dispersing a low-molecular-weight organosiloxane, followed by addition of an acid or an alkali catalyst to carry out emulsion polymerization (Japanese Patent Publication No. 34-2041), a low-molecular-weight organosiloxane. Are simultaneously emulsified, dispersed and polymerized using a surfactant having catalytic activity (Japanese Patent Publication No. 43-18800).

Among them, a cationic emulsion polymerized silicone obtained by using a cationic surfactant in terms of imparting flexibility to fibers and stability of blending with cationic additives such as amides and amines. The use of the emulsion as a main component of the fiber treatment agent is considered to be a more effective method. However, in this emulsion polymerization method, for example, when a quaternary ammonium salt-based surfactant is used as the cationic surfactant, the polymerization rate is extremely low in a temperature range suitable for the emulsion polymerization, and therefore, industrial Even if the polymerization is carried out for a time that can actually be carried out, for example, for 48 hours, a linear product having a viscosity at 25 ° C. of at most about 10,000 cP can be obtained. Therefore, durable water repellency, waterproofness, flexibility,
There was a problem that it was difficult to provide a fiber treatment agent having a good balance of effects of imparting smoothness, wrinkle resistance, compression recovery, and the like.

On the other hand, when an anionic polymerization catalyst is used in the emulsion polymerization, a rapid reaction rate can be obtained, and an emulsion containing a high molecular weight polyorganosiloxane can be obtained by a short-time polymerization. However, emulsions produced in this manner generally result in destruction of the emulsion when the ion balance of the emulsion changes. Among fibers, wool, silk, polyamide and the like have a weak anionic property, so that the fiber treatment agent needs to have a cationic property.However, in the case of an emulsion polymerized silicone emulsion polymerized in the presence of an anionic polymerization catalyst, for example, cationic Emulsions become unstable when additives are added. This means that using a high molecular weight polyorganosiloxane emulsion obtained by emulsion anion polymerization as a fiber treatment agent,
Making it extremely difficult.

As described above, the means of simply adding a cationic surfactant to an emulsion containing a high molecular weight polyorganosiloxane prepared using an anionic surfactant destroys the emulsion. Adding surfactants of opposite conjugate properties is generally recognized as a technique for breaking emulsions. For example, U.S. Pat. No. 4,831,116 discloses that an emulsion containing a grafted rubber is prepared by a polymerization step in the presence of an anionic surfactant, and the emulsion is destroyed by the addition of a cationic surfactant. Thus, a technique for coagulating rubber is disclosed. Therefore, there is a need for a stable cationic fiber treating agent containing, as a main component, an emulsion containing a high molecular weight polyorganosiloxane obtained by emulsion polymerization having a high polymerization rate.

[0013]

SUMMARY OF THE INVENTION The present invention has been made to solve such problems of the prior art.
High durability, water repellency, waterproofness, flexibility, smoothness, anti-wrinkle and compression recovery properties for fiber materials, mechanical stability, dilution stability, stability over time and compounding A fiber treatment agent that is excellent in stability, especially in compounding stability with cationic additives, and does not generate oil spots,
The purpose is to provide it at low cost.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object. As a result, the low-molecular-weight organosiloxane was emulsion-polymerized in the presence of an anionic surfactant and then mixed. 1 prepared by blending a cationic surfactant and further blending a cationic surfactant.
The present invention has been found that a fiber treatment agent comprising a stable cationic polyorganosiloxane emulsion containing a polyorganosiloxane having a viscosity of from 0000 to 10,000,000 cSt can achieve the above object. Was completed.

That is, the present invention relates to (a) a high molecular weight polyorganosiloxane having a viscosity of 10,000 to 10,000,000 cSt at 25 ° C .; (b) a hydroxyl group having 1 to 20 carbon atoms which is substituted with a hydroxyl group. Or an anionic surfactant selected from the group consisting of aliphatic hydrocarbon sulfonic acid and aliphatic hydrocarbon sulfuric acid, aryl sulfonic acid having 6 to 30 carbon atoms, and alkylaryl sulfonic acid having 7 to 50 carbon atoms, or an anionic surfactant thereof. (C) a miscible surfactant having a hydrophilic-lipophilic ratio of 9 to 25; and (d) a halide or sulfate of bis (polyoxyethylene) hydrocarbylmethyl quaternary ammonium.
A cationic interface selected from the group consisting of alkyltrimethylammonium halides or sulfates having 8 to 30 carbon atoms in the alkyl group; and benzylalkyldimethylammonium halides or sulfates having 8 to 16 carbon atoms in the alkyl group. The present invention relates to a fiber treating agent mainly comprising a stable cationic silicone oil-in-water emulsion containing an activator.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION A stable cationic polyorganosiloxane emulsion used as a main component in the fiber treating agent of the present invention can be prepared by the following procedure.

(1) (a ′) General formula: R _n SiO _{(4-n) / 2} (I) (wherein R is a substituted or unsubstituted monovalent carbon atom which may be the same or different. Represents a hydrogen group, and 50
It may contain up to mol% of one or more groups selected from hydrogen atoms, hydroxyl groups and alkoxyl groups;
A low molecular weight organosiloxane comprising a structural unit represented by the formula: water, and (b) a carbon number of 1 to 2
0, an aliphatic hydrocarbon sulfonic acid and an aliphatic hydrocarbon sulfuric acid which may be substituted with a hydroxyl group, having 6 carbon atoms
To 30 arylsulfonic acids, and 7 to 50 carbon atoms
(2) emulsifying an anionic surfactant selected from the group consisting of alkylaryl sulfonic acids using an emulsifier;
Heat to a temperature of 98 ° C, cool to a temperature of 0 to 40 ° C,
(A ') is polymerized at 25 DEG C. from 10,000 to 1
Obtaining (a) an emulsion containing a high molecular weight polyorganosiloxane having a viscosity of 0,000,000 cSt; (3) a (c) miscible surfactant having a hydrophilic-lipophilic ratio (HLB) of 9 to 25; (4) bis (polyoxyethylene) hydrocarbylmethyl quaternary ammonium halides or sulfates;
And (d) adding a cationic surfactant selected from the group consisting of alkyltrimethylammonium and benzylalkyldimethylammonium halides and sulfates having 8 to 30 carbon atoms in the alkyl group.

It comprises a structural unit represented by the general formula: R _n SiO _{(4-n) / 2} (where R and n are as described above), which is used as (a ′) in the above procedure (1). As the low molecular weight organosiloxane, a cyclic organosiloxane and, if necessary, a linear or branched organosiloxane in which a molecular chain terminal is blocked with a triorganosilyl group, a hydroxyl group or an alkoxyl group can be suitably used, One type or a mixture of two or more types may be used, and the molecular weight is usually 160 to 5,000, preferably 290 to 1.0.
00 is used.

In order to synthesize the above-mentioned (a) high molecular weight polyorganosiloxane with good control by emulsion polymerization,
It is preferable that most or all of the (a ') low molecular weight organosiloxane is a cyclic organosiloxane. Further, in order to more precisely control the molecular weight of (a) to a specific range, a linear low molecular weight organosiloxane having a molecular chain terminal blocked with a toluorganosilyl group is used in combination.
On the other hand, when introducing a branched siloxane skeleton into the molecular structure of (a), a branched low molecular weight organosiloxane is used in combination.

The cyclic organosiloxane is represented by the following general formula (II) (wherein R ¹ and R ² may be the same or different, and each represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon. And m is an average number of 3 to 8). In the case where a polymer polyorganosiloxane of a normal type is used as (a) obtained by emulsion polymerization, R ¹ , R ² A hydrogen atom; an alkyl group such as methyl, ethyl and propyl; an aryl group such as phenyl; and a fluoroalkyl group such as 3,3,3-trifluoropropyl. No carbon number 1
It is preferably selected from the group consisting of 8 unsubstituted or fluoro-substituted monovalent hydrocarbon groups.

[0021]

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Specific examples of such a cyclic organosiloxane include hexamethylcyclotrisiloxane,
Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1-diethyl-3,3,5,5,7,7-
Hexamethylcyclotetrasiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, phenylheptamethylcyclotetrasiloxane,
1,1-diphenyl-3,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1 , 3,5-Trimethyl-1,3,5-
Tris (3,3,3-trifluoropropyl) cyclotrisiloxane and the like are exemplified, and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,3
It is preferable to use one or more of 5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane.

The linear and branched low-molecular-weight organosiloxanes are represented by the following general formulas (III) and (IV) (where R ³ is a hydrogen atom which may be the same or different, R ⁴ represents a hydrogen atom, which may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group or an alkoxyl group; 50
Where, in formula (IV), the sum of n in the molecule is 0
And p is a number from 1 to 30). In the case of the above-mentioned ordinary type (a), R ³ is the aforementioned R ¹ , R ² The same range as above is preferable, and the same groups are exemplified. R ⁴ is the same as R ¹ and R ² described above.
And the same ranges as above, and a hydroxyl group, a methoxy group and an ethoxy group are preferred.

[0024]

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[0025]

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Specific examples of such linear and branched low molecular weight organosiloxanes include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, α, ω-bis (trimethylsilyl) polydimethyl Linear organosiloxanes having terminal triorganosilyl groups capped such as siloxanes; 1,1,3,
3-tetramethyl-1,3-dihydroxydisiloxane, 1,1,3,3,5,5,7,7-octamethyl-
1,7-dihydroxytetrasiloxane, 1,1,3,
Linear polyorganosiloxanes containing silicon functional groups such as 3,5,5-hexamethyl-1,5-diethoxytrisiloxane, α, ω-dihydroxypolydimethylsiloxane, α, ω-dimethoxypolydimethylsiloxane;
And 3- (trimethylsiloxy) -1,1,1,3,
5,5,5-heptamethyltrisiloxane, 1,7-dihydroxy-3- (trimethylsiloxy) -1,1,1
Examples include branched organosiloxanes such as 3,5,5,7,7-heptamethyltetrasiloxane, and hexamethyldisiloxane, decamethyltetrasiloxane, α, ω-dihydroxypolysiloxane are easy to synthesize and handle. Dimethylsiloxane, α, ω-dimethoxypolydimethylsiloxane and 1,7-dihydroxy-3-
(Trimethylsiloxy) -1,1,3,5,5,7,7
It is preferable to use one or more of heptamethyltetrasiloxane.

Further, as the low molecular weight organosiloxane represented by the general formula (II), (III) or (IV),
At least a part of the molecule in which at least a part or all of R ^{1 to} R ⁴ are organic functional groups such as a monovalent hydrocarbon group having an aliphatic unsaturated bond and / or a monovalent substituted hydrocarbon group; The organic functional group can be introduced into (a) the high molecular weight polyorganosiloxane obtained by emulsion polymerization. Thereby, the durability of the fiber treatment agent can be further improved.

Examples of such organic functional groups include alkenyl groups such as vinyl, allyl, 5-hexenyl and 7-octenyl; and monovalent vinyl group-containing aromatic hydrocarbon groups such as vinylphenyl and vinylphenylethyl. And 3-aminopropyl, N- (2-aminoethyl) -3
-Aminopropyl, N- (p-isopropenylbenzoyl) -3-aminopropyl, N-acryloyl-N-methyl-3-aminopropyl, N-methacryloyl-N-
Methyl-3-aminopropyl, 3-mercaptopropyl, 3-glycidoxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl, 3-carboxypropyl, 3-vinyloxypropyl, 3- (2-vinyloxy) ethoxy Propyl, 3- (vinylphenoxy)
Examples thereof include monovalent substituted hydrocarbon groups such as propyl and 3- (vinylbenzoyloxy) propyl.

As the low molecular weight organosiloxane having such an organic functional group, specifically, 1,3,5
Trivinyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetravinyl-1,3,5
7-tetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 1,3,5,7-tetraallyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (5- Hexenyl)-
1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (7-octenyl) -1,
Alkenyl-containing cyclic diorganosiloxanes such as 3,5,7-tetramethylcyclotetrasiloxane;
3,5,7-tetrakis (p-vinylphenyl) -1,
3,5,7-tetramethylcyclotetrasiloxane,
Cyclic diorgano having a vinyl group-containing aromatic hydrocarbon group such as 1,3,5,7-tetrakis [2- (p-vinylphenyl) ethyl] -1,3,5,7-tetramethylcyclotetrasiloxane Siloxane; and 1,3
5,7-tetrakis (3-aminopropyl) -1,3,3
5,7-tetramethylcyclotetrasiloxane, 1,
3,5,7-tetrakis [N- (2-aminoethyl)-
3-aminopropyl] -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (3-mercaptopropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (3-glycidoxypropyl) -1,3,5,7
-Tetramethylcyclotetrasiloxane, 1,3,5
7-tetrakis (3-acryloxypropyl) -1,
3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetrakis (3-methacryloxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (3-carboxypropyl) -1,3 1,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (vinyloxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis ( 3
-Vinyloxyethoxypropyl) -1,3,5,7-
Tetramethylcyclotetrasiloxane, 1,3,5,7
-Tetrakis [3- (p-vinylphenoxy) propyl] -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis [3- (p-vinylbenzoyloxy) propyl]- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-
Tetrakis [3- (p-isopropenylbenzoylamino) propyl] -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (N-
Acryloyl-N-methyl-3-aminopropyl)-
1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (N-methacryloyl-N-methyl-3-aminopropyl) -1,3,5,7
-Tetramethylcyclotetrasiloxane, 1,3,5
7-tetrakis [N, N-bis (acryloyl) -3-
Aminopropyl] -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis [N, N-bis (methacryloyl) -3-aminopropyl] -1,3,5,7 And cyclic diorganosiloxanes having a substituted hydrocarbon group such as tetramethylcyclotetrasiloxane. Examples of the alkenyl group-containing cyclic diorganosiloxane include 1,3,5,7-tetravinyl-1,3,5. Preferred is 7-tetramethylcyclotetrasiloxane; examples of the substituted hydrocarbon group-containing cyclic diorganosiloxane include 1,3,5,7-tetrakis (3-aminopropyl) -1,3,5,7-tetramethylcyclotetrasiloxane Siloxane, 1,3,5,7-tetrakis [N-
(2-aminoethyl) -3-aminopropyl] -1,
3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetrakis (3-mercaptopropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (3-glycidoxypropyl) -1, 3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis (3-acryloxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7 -Tetrakis (3-methacryloxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane is preferred. Further, linear and branched low molecular weight organosiloxanes having similar organic functional groups are exemplified.

In the case of such a linear or branched low molecular weight organosiloxane having an organic functional group, the terminal of the molecular chain is not particularly limited. From the viewpoint of introducing a functional group, the molecular chain terminal is an organic group other than a hydroxyl group, for example, an alkoxy group such as methoxy and ethoxy; or trimethylsilyl, dimethylvinylsilyl, methylphenylvinylsilyl, methyldiphenylsilyl, 3,3,3
Those which are blocked with a triorganosilyl group such as trifluoropropyldimethylsilyl are preferred.

When a low molecular weight organosiloxane having an organic functional group is used as the above (a ') low molecular weight organosiloxane, the amount thereof is determined by the amount of the organic functional group in all the organic groups bonded to the silicon atom. It is preferably at most 5 mol%, more preferably at 0.05-2.5 mol%. Further, the amount of (a ') in the reaction system depends on the emulsification efficiency by giving a sufficient shear force to each component at the time of emulsification,
And from the stability, apparent viscosity and workability of the emulsion containing (a) obtained by emulsion polymerization,
It is preferably 0% by weight, more preferably 10 to 50% by weight.

Further, in the present invention, the objective (a) is to easily introduce a branched siloxane skeleton into the desired high molecular weight polyorganosiloxane or introduce a special organic group such as an organic functional group. Further, a hydrolyzable silane compound and / or a partially hydrolyzed condensate thereof may be used in combination with the above (a ′) low molecular weight organosiloxane.

Specific examples of the hydrolyzable silane compound or the partially hydrolyzed condensate thereof include trimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3,3,3-trifluoropropyl Those having a branched siloxane skeleton introduced into the component (a), such as trimethoxysilane and partially hydrolyzed condensates thereof; vinylmethyldimethoxysilane, vinylethyldiisopropoxysilane, allylmethyldimethoxysilane, 5-hexenyl Alkenyl-containing alkoxysilanes such as methyldiethoxysilane and 7-octenylethyldiethoxysilane; vinyls such as p-vinylphenyl (methyl) dimethoxysilane and 2- (p-vinylphenyl) ethyl (methyl) dimethoxysilane Group-containing aromatic carbonized Alkoxysilane having originally; 3-aminopropyl (methyl) dimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl)
-3-aminopropyl (methyl) dimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane,
3-acryloxypropyl (methyl) diethoxysilane, 3-methacryloxypropyltrimethoxysilane,
3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3
-Mercaptopropyltrimethoxysilane, 3-carboxypropyl (methyl) dimethoxysilane, 3-vinyloxypropyl (methyl) dimethoxysilane, 3- (vinyloxyethoxy) propyl (methyl) dimethoxysilane, 3- (p-vinylphenoxy) Propyltriethoxysilane, 3- (p-vinylbenzoyloxy) propyl (methyl) dimethoxysilane, 3- (p-isopropenylbenzoylamino) propyl (phenyl) dipropoxysilane, N-acryloyl-N-methyl-3-amino Propyl (methyl) dimethoxysilane, N-methacryloyl-N-methyl-3-aminopropyl (methyl)
Dimethoxysilane, N-methacryloyl-N-methyl-
3-aminopropyl (phenyl) diethoxysilane,
N, N-bis (acryloyl) -3-aminopropyltrimethoxysilane, N, N-bis (methacryloyl)-
A substituted hydrocarbon group-containing alkoxysilane such as 3-aminopropyl (methyl) dimethoxysilane is exemplified.
Species or two or more species may be used in combination.

The amount of the hydrolyzable silane compound and / or its partially hydrolyzed condensate is preferably (a ') a low molecular weight organosiloxane in order to avoid instability of the emulsion due to alcohol by-produced by hydrolysis. Is preferably 20% by weight or less with respect to

From the (a ') low-molecular-weight organosiloxane and optionally a hydrolyzable silane compound and / or a partially hydrolyzed condensate thereof, a high-molecular-weight poly (component (a)) synthesized by anionic emulsion polymerization. In the fiber treating agent of the present invention, the organosiloxane forms a film on the surface of the fiber, and depending on the type of (a), the fiber has high durability such as water repellency, waterproofness, flexibility, smoothness, and wrinkles. It imparts some or all of properties such as properties and compression recovery properties, and its molecular structure, type of organic group and reactivity can be arbitrarily selected according to the purpose.

The viscosity of the component (a) at 25 ° C. is 1
In the range of 0000-10,000,000 cSt,
100,000 to 1,000,000 cSt is preferred.
If it is less than 10,000 cSt, the treated fiber cannot have sufficient water repellency, waterproofness, smoothness and durability. If it exceeds 10,000 cSt, the flexibility, wrinkle resistance and This is because the compression recovery is inferior. The siloxane skeleton structure may be linear or branched,
It is determined by the type of the (a ') low molecular weight organosiloxane used as a raw material, the hydrolyzable silane compound used in some cases, and / or the partial hydrolysis condensate thereof.

The organic group bonded to the silicon atom includes (a ′) a low molecular weight organosiloxane used as a raw material,
It is derived from an organic group present in a hydrolyzable silane compound and / or a partial hydrolyzed condensate thereof used in some cases. Accordingly, those in the range exemplified as R ^{1 to} R ⁴ described above are exemplified, and water repellency as a fiber treatment agent,
In order to exhibit properties such as flexibility and smoothness, it is preferable that 50 mol% or more is a methyl group. Examples of the organic group other than the methyl group include an alkenyl group such as vinyl and allyl; a vinyl group-containing aromatic hydrocarbon group such as vinylphenyl and vinylphenylethyl; and 3-aminopropyl and N- (2-aminoethyl) Substituted hydrocarbon groups such as -3-aminopropyl, 3-mercaptopropyl, 3-glycidoxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl are preferred, and such organic functions account for all organic groups. The amount of the functional group is 0.01 to 5
Mol% is preferable, and 0.05 to 2.5 mol% is more preferable.

When (a ') a cyclic organosiloxane alone is used as the low-molecular-weight organosiloxane, when a linear or branched organosiloxane having a silicon functional group is used, or when (a') is hydrolyzed. When the decomposable silane compound was used in combination, the obtained (a)
At the molecular end of the component there is a hydroxyl group attached to the silicon atom as a silicon functional group. Due to the presence of such a hydroxyl group, the fiber treating agent can form a crosslinked and network structure on the fiber surface.

The concentration of the component (a) obtained by emulsion polymerization in the emulsion is such that a sufficient shearing force is applied to the (a ') low molecular weight organosiloxane, which is a raw material thereof, and the surfactant during emulsification. , Effectively emulsified,
Further, since there is no decrease in workability due to an increase in apparent viscosity of the emulsion after emulsion polymerization, the range is preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

In the present invention, the anionic surfactant used as the component (b) is an acid which is a polymerization catalyst for emulsifying the component (a ') to carry out anionic emulsion polymerization, or a salt formed by neutralization after polymerization. It is. Such a component (b)
At the stage where it is blended as a polymerization catalyst, an aliphatic hydrocarbon sulfonic acid having 1 to 20 carbon atoms, an aliphatic hydrocarbon sulfuric acid, an aryl sulfonic acid having 6 to 30 carbon atoms which may be substituted with a hydroxyl group, and a carbon number Selected from the group consisting of 7 to 50 alkylarylsulfonic acids;
More than one species may be used in combination. In the above aliphatic hydrocarbon sulfonic acid and aliphatic hydrocarbon sulfuric acid which may be substituted with a hydroxyl group, the aliphatic hydrocarbon group may be a saturated hydrocarbon group such as an alkyl group or an unsaturated hydrocarbon group such as an alkenyl group. Saturated hydrocarbon groups can be used. The anionic surfactant is selected from benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, alkyl and alkenylsulfonic acids having 12 to 18 carbon atoms, hydroxytetradecanesulfonic acid, octyl sulfate, lauryl sulfate, cetyl sulfate and oleyl sulfate. It is preferable to be selected from the group consisting of

Further, as another component (b), an anionic surfactant having a weak catalytic action can be used in combination with the polymerization catalyst. Examples of such an anionic surfactant include the above-mentioned aliphatic hydrocarbon sulfonic acid which may be substituted with a hydroxyl group having 1 to 20 carbon atoms, aliphatic hydrocarbon sulfuric acid, and arylsulfonic acid having 6 to 30 carbon atoms. And sodium salts, potassium salts, and ammonium salts of alkylarylsulfonic acids having 7 to 50 carbon atoms. Specific examples thereof include sodium benzenesulfonate, sodium xylenesulfonate, sodium dodecylbenzenesulfonate, and 12 to 12 carbon atoms. 18 sodium and alkyl alkenyl sulfonates, sodium hydroxytetradecane sulfonate, sodium octyl sulfate, sodium lauryl sulfate, sodium cetyl sulfate and sodium oleyl sulfate.

As the surfactant, other surfactants may be used in addition to the above-mentioned component (b). Examples of such a surfactant include polyoxyethylene (4) lauryl ether sulfate, polyoxyethylene (1
3) Polyoxyethylene alkyl ether sulfates such as cetyl ether sulfate, polyoxyethylene (6) stearyl ether sulfate, polyoxyethylene (4) sodium lauryl sulfate, polyoxyethylene (4) ammonium octyl phenyl ether sulfate, and salts thereof. One or two or more can be used, but the present invention is not limited thereto.

Further, another polymerization catalyst may be used in combination with the component (b). As such a polymerization catalyst, an acidic catalyst such as hydrochloric acid, sulfuric acid, or phosphoric acid, which is generally used as a polymerization catalyst for (a ') a low molecular weight organosiloxane, is preferably used, but is not limited thereto. And low molecular weight organosiloxane (a ') in the presence of water
Any catalyst can be used as long as it can polymerize the compound.

Component (b) is used in an amount of 0.5 to 100 parts by weight of the low molecular weight organosiloxane (a ').
It is preferably 20 parts by weight, more preferably 0.5 to 10 parts by weight. If the amount is less than 0.5 part by weight, the stability of the emulsion is poor and the emulsion may be separated. If the amount exceeds 20 parts by weight, the emulsion may be thickened and the fluidity may be deteriorated. When another polymerization catalyst is used in combination, the amount of the polymerization catalyst is not particularly limited, but is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the (a ') low molecular weight organosiloxane.

Of the above-mentioned anionic surfactants, those used in the form of an acid are neutralized after the completion of the polymerization reaction,
The fiber treatment agent exists in the form of a salt. Examples of such salts include alkali metal salts such as lithium salts, sodium salts, and potassium salts; and ammonium salts.

In the present invention, the miscible surfactant used as component (c) is added to the silicone emulsion obtained as a result of the anionic emulsion polymerization, and the emulsion is mixed with the cationic surfactant. Is to give. Such a (c) miscible surfactant has a hydrophilic-lipophilic ratio (HLB) of 9 to 25, preferably 10 to 25, more preferably 11 to 20, and most preferably 12 to 18. . Miscible surfactants which give particularly good results are nonionic surfactants. Preferred nonionic surfactants are polyglycerin fatty acid ester, polyoxyethylene fatty acid ester,
Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkyl whose alkyl group is a primary or secondary alkyl group having 6 to 40 carbon atoms Ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylamine having 6 to 40 carbon atoms in the alkyl group, polyoxyethylene alkylamide having 6 to 40 carbon atoms in the alkyl group and polyoxy It is selected from the group consisting of ethylene lanolin. Particularly preferred groups of nonionic surfactants are POE (4) lauryl ether, POE (9) lauryl ether, POE (2
1) Lauryl ether, POE (15) cetyl ether, POE (23) cetyl ether, POE (20) stearyl ether, POE (20) oleyl ether,
POE (18) nonylphenyl ether and POE
(20) A group consisting of sorbitan monopalmitate. Other preferred groups of miscible surfactants that can be used to render the anionic emulsion miscible with the cationic surfactant are lauryl dimethylamino acetate betaine, coconut oil fatty acid amidopropyl dimethyl dimethyl amino acetate betaine, -Alkyl-N-carboxymethyl-N
Amphoteric betaine surfactants such as -hydroxyethyl imidazolinium betaine; N-lauroyl sarcosine sodium; and lanolin derivatives of quaternary ammonium salts.

The amount of the component (c) is from 0.5 to 100 parts by weight of the low molecular weight organosiloxane (a ').
It is preferably 50 parts by weight, more preferably 1 to 20 parts by weight. If the amount is less than 0.5 part by weight, the effect of mixing with the cationic surfactant is insufficient, and the stability of the emulsion is poor, and the emulsion may be separated. If the amount exceeds 50 parts by weight, the emulsion thickens and flows. May be lost.

In the present invention, the cationic surfactant used as the component (d) imparts excellent stability to the fiber treating agent of the present invention. Examples of the cationic surfactant (d) include halides and sulfates of bis (polyoxyethylene) hydrocarbylmethyl quaternary ammonium, such as chloride; and the alkyl group having 8 to 30 carbon atoms, preferably Is a halide or sulfate of alkyltrimethylammonium having 9 to 30 carbon atoms, such as chloride; and 8 to 16, preferably 9 to 9 carbon atoms.
14 benzylalkyldimethylammonium, selected from the group consisting of halides such as chlorides or sulfates, by adding one or more kinds thereof,
Convert to cationic emulsion. (D) Particularly preferred groups as cationic surfactants are lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, benzylalkyl chloride ( _C10-14 ). Dimethyl ammonium and polyoxyethylene (15) cocoalkyl methyl ammonium chloride (methylpolyox
yethylene (15) cocammonium chloride, for example Ethoqu
adC / 25, registered trademark).

The amount of the component (d) is from 0.5 to 100 parts by weight of the low molecular weight organosiloxane (a ').
It is preferably 50 parts by weight, more preferably 1 to 20 parts by weight. If the amount is less than 0.5 part by weight, the cationicity of the emulsion itself is insufficient, and the stability of the emulsion is poor, and the emulsion may be separated. If the amount exceeds 50 parts by weight, the emulsion thickens and loses fluidity. is there.

The cationic polyorganosiloxane used as a main component in the fiber treatment agent of the present invention is typically
It can be prepared through the following steps (1) to (4).

Step (1) is a step of mixing and emulsifying the above-mentioned components (a '), water and (b). For example, using a mixer such as a high shear mixer, usually after mixing at 20 to 40 ° C. for 10 to 30 minutes,
Continuous emulsification is performed using an emulsifier such as a homogenizer, a colloid mill, and a line mixer.

In the step (2), the emulsion obtained in the step (1) is heated and cooled to polymerize the (a ') contained in the emulsion and optionally a hydrolyzable silane compound used in combination. This is a step of obtaining an aqueous emulsion containing the component (a) and the component (b). The polymerization is carried out by heating the emulsion with stirring.
~ 98 ° C, preferably kept at 80-90 ° C for 1-5 hours, then slowly cooled to 0-40 ° C, preferably 5-25 ° C
For 1 to 48 hours, preferably 1 to 24 hours. If the heating temperature in the first stage is lower than 75 ° C., a sufficient polymerization rate cannot be obtained. If the temperature exceeds 98 ° C., the water will evaporate and the emulsion will be destroyed unless closed and pressurized. If the temperature of the second step is lower than 0 ° C., the emulsion is destroyed by icing, and if the temperature exceeds 40 ° C., the polycondensation reaction at the molecular terminals does not proceed sufficiently. Polyorganosiloxane cannot be obtained. After the polymerization is completed, an alkaline substance such as an aqueous solution of sodium carbonate is added to neutralize (b) the anionic surfactant and optionally other polymerization catalysts used in the system, thereby obtaining the desired molecular weight and the desired molecular weight. An anionic polyorganosiloxane emulsion containing the component (a) having a molecular structure is obtained.

Step (3) is a step of adding the component (c) to the aqueous emulsion containing the components (a) and (b) obtained in the step (2);
Is a step of further adding the component (d). These steps are usually performed by adding each component or an aqueous solution thereof at 15 to 35 ° C. and stirring for an arbitrary time.

The fiber treating agent of the present invention contains 2
The viscosity at 5 ° C. is 10,000 to 10,000,000
A stable cationic polyorganosiloxane emulsion containing (a) a high-molecular-weight polyorganosiloxane having a viscosity of 0 cSt is used as a main component, and any amount of an arbitrary component may be used as it is or as necessary so as not to impair the object of the present invention. Obtained by addition. Such optional components include hydrocarbons such as liquid paraffin, vaseline, solid paraffin, squalane, and olefin oligomers; esters such as isopropyl palmitate, stearyl stearate, octyl myristate, and 2-ethylhexanoic acid triglyceride; lauryl alcohol; Higher alcohols such as cetyl alcohol and stearyl alcohol; higher fatty acids such as palmitic acid and stearic acid; resin processing agents such as glyoxal resin, melamine resin, urea resin, polyester resin and acrylic resin; organic solvents such as ethanol; water; Perfume; coloring agents and the like. Further, when the terminal group of the polyorganosiloxane of the main ingredient is blocked with a hydroxyl group, in order to cure this into an elastomeric form, a polymethyl hydrogen siloxane or a hydrolyzable silane compound as described above, especially an alkoxy group, is used as a crosslinking agent. Silanes may be used, or a tin compound or a titanium compound may be used as a condensation catalyst.

These optional components, depending on their type,
It may be added at any stage where a cationic polyorganosiloxane emulsion is formed, or may be added and mixed immediately before use as a fiber treatment agent. Examples of the latter include the above-mentioned crosslinking agents and condensation catalysts. In that case,
For the optional component that is not water-soluble, it is preferable from the viewpoint of operation that a separate cationic emulsion containing the optional component is prepared and added.

To treat a fiber material with the fiber treating agent of the present invention, it can be applied by spraying, by roll,
By brushing or dipping. The amount of adhesion varies depending on the fiber material and is not particularly limited.
A range of weight percent is common. Next, the fiber material is treated by leaving it at room temperature, blowing with hot air, heating, or the like, and a film containing the component (a) of the fiber treatment agent or a cured product thereof is formed on the surface of the fiber material.

The fiber material to be treated by the fiber treatment agent of the present invention includes natural fibers such as wool, silk, hemp, cotton, Angola, mohair, and asbestos;
Regenerated fiber such as rayon and Bemberg; Semi-synthetic fiber such as acetate; Synthetic fiber such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, polyurethane elastic fiber; Glass fiber, carbon fiber, Inorganic fibers such as silicon carbide fibers are exemplified, and staples, filaments, tows, tops, and yarns are exemplified in form, and knits, woven fabrics, nonwoven fabrics, and papers are exemplified in form.

[0058]

According to the fiber treating agent of the present invention, a high molecular weight polyorganosiloxane is obtained in the form of an anionic emulsion with high production efficiency by emulsion polymerization at a high polymerization rate.
A stable cationic polyorganosiloxane emulsion containing the above polyorganosiloxane is obtained by blending a miscible surfactant and further blending a cationic surfactant, and using it as a main component. .
Therefore, very high water repellency, waterproofness, flexibility, smoothness, wrinkle resistance and compression recovery can be imparted to the fiber material. Moreover, these effects are not easily reduced by washing or the like. Furthermore, when preparing the treatment bath and treating the fiber, the fiber material has excellent mechanical stability against stirring and circulation, dilution stability against dilution with water, and excellent compounding stability against various additives, especially cationic additives, Also, it has the feature that no oil spot is generated, which is extremely useful in industry.

[0059]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. In these examples,
Parts and percentages are by weight unless otherwise indicated.
It is. The present invention is not limited by these examples. Evaluation of the obtained emulsion, analysis of the polyorganosiloxane contained therein, and evaluation of the fiber treatment agent containing the emulsion as a main component were performed as follows.

(1) Evaluation of Emulsion and Analysis of Polymer The average particle size of the emulsion particles was determined by a dynamic light scattering method, a laser particle size analysis system LPA-30 manufactured by Otsuka Electronics Co., Ltd.
It was measured using 00S / 3100. In addition, to measure the degree of swelling and gel content of the polyorganosiloxane into which the crosslinking point was introduced, the emulsion was dropped into isopropyl alcohol, and the polyorganosiloxane in the emulsion obtained by coagulation and drying was used. The procedure was as follows. That is, the degree of swelling was determined by immersing the polyorganosiloxane in toluene at 23 ° C. for 48 hours, and dividing the weight of the toluene absorbed by the polyorganosiloxane by the weight of the polyorganosiloxane before immersion. The gel content was determined by extracting the polyorganosiloxane in toluene at 23 ° C. for 48 hours. Further, the content of the organic functional group of the polyorganosiloxane into which the organic functional group was introduced was measured by coagulating and drying the polyorganosiloxane in the same manner as in the measurement of the degree of swelling. Magnetic resonance spectrometer A
The analysis was performed by ¹ H-NMR analysis using M-300.

(2) Evaluation of Fiber Treatment Agent Water was added to the obtained emulsion to prepare a fiber treatment agent having a predetermined silicone concentration, and was subjected to a test.

A) Adhesion to rubber roll A fiber treatment agent having a silicone concentration of 2% was prepared in a stainless steel square bat measuring 20 cm × 35 cm × 3 cm, and 400 ml of the fiber treatment agent was collected. Two rubber rollers (nip pressure 0.5 kg / cm ² ) were set such 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 treating agent due to the roller treatment was evaluated based on the following evaluation criteria by observing the state where the separated polyorganosiloxane adhered to the rubber roller. ：: There is no attached matter at all. Δ: Polyorganosiloxane is partially adhered to the rubber roll surface and repelled. ×: The polyorganosiloxane adheres to the entire surface of the rubber roll.

B) Mechanical Stability After measuring the adhesion to the roller, 25 ml of the fiber treating agent was sampled and centrifuged at a rotation speed of 2,500 rp for 30 minutes. Were evaluated according to the following evaluation criteria. ：: A completely uniform emulsion, with no suspended matter. Δ: The surface is glaring, and slight floating of the polyorganosiloxane is observed. ×: A large amount of floating polyorganosiloxane was observed on the surface.

C) Formulation stability After measuring the adhesion to the roller, 100 parts of the fiber treating agent was added to a cationic strip inhibitor (manufactured by Kyoeisha Chemical Co., Ltd.).
CLA-530) was added, 0.5 part was added, sealed in a glass bottle, and allowed to stand at 40 ° C. for 3 days, and the state was evaluated according to the following evaluation criteria. ：: A completely uniform emulsion, with no suspended matter. Δ: The surface is glaring, and slight floating of the polyorganosiloxane is observed. ×: A large amount of floating polyorganosiloxane was observed on the surface.

D) Stability by Mixer Treatment A fiber treatment agent having a silicone concentration of 5% was prepared.
0 ml was placed in a household mixer, stirred at a speed of 4,000 rpm for 60 minutes, and the stability of the fiber treating agent by the mixer treatment was evaluated according to the following evaluation criteria. ：: No deposits were observed on both the blades of the mixer and the glass wall. Δ: Slight adhesion of polyorganosiloxane to the blades and glass wall of the mixer was observed. X: Polyorganosiloxane adheres to the blades and glass wall of the mixer, and the polyorganosiloxane floats on the surface.

E) Oil spot and hand The fiber treatment agent after the mixer treatment was sprayed on beige dyed nylon naphtha using a simple hair spray. After drying at room temperature, a heat treatment was performed at 150 ° C. for 3 minutes to obtain a treated cloth. Next, the presence or absence and the feeling of the oil spot on the treated cloth were evaluated by the naked eye and touch according to the following evaluation criteria. Presence or absence of oil spot ○: No oil spot at all. Δ: There are slight oil spots. X: There are many oil spots. Feeling ：: No slimy feeling, good flexibility, rebound resilience and good smoothness. Δ: Slight slimy feeling, good flexibility, rebound resilience, and smoothness. ×: Strong slimy feeling, poor flexibility, rebound resilience, and smoothness.

F) Water repellency and waterproofness The surface of the treated cloth was sprayed with water, and the surface condition of the treated cloth was observed. The water repellency and waterproofness were evaluated according to the following evaluation criteria. did. A: There is no wetting or water droplets on the surface. ：: The surface is wetted by small individual water droplets. Δ: Half of the surface was wet and small individual water droplets penetrated the cloth. X: Only the surface is entirely wet. XX: The front and back surfaces are entirely wet.

G) Durability The treated cloth obtained by the above-mentioned spray treatment is put in a washing bath in which 5 parts of sodium alkylbenzenesulfonate and 2 parts of sodium carbonate are added to 1,000 parts of water. After washing with an electric washing machine at a washing bath: treatment cloth ratio of 100: 1 at a water temperature of 50 ° C. for 15 minutes,
The above-described feeling, water repellency, and waterproofness tests were performed, and a durability test was performed. The evaluation of hand, water repellency and waterproofness is as described above.

Example 1, Comparative Example 1 Octamethylcyclotetrasiloxane 1 was added to a mixture of 1 part of n-dodecylbenzenesulfonic acid and 150 parts of distilled water.
After adding 00 parts and preliminarily mixing with a homomixer, the mixture was passed twice through a pressure homogenizer at a pressure of 300 kgf / cm ² to emulsify and disperse. This emulsion was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, then cooled to 15 ° C. over 3 hours, and further cooled at 15 ° C. for 6 hours. The polymerization reaction was advanced by holding for a time. A 10% aqueous solution of sodium carbonate was added dropwise to the emulsion to neutralize it to pH 7, thereby terminating the polymerization reaction. Thus, an anionic polyorganosiloxane emulsion of Comparative Example 1 was obtained.

The nonvolatile content of the obtained anionic emulsion of Comparative Example 1 was 35.9%, and the average particle size of the oil phase was 3%.
18 nm. Further, the emulsion was broken with isopropyl alcohol, and the polyorganosiloxane in the emulsion was taken out. By IR analysis, it was confirmed that both ends were hydroxyl-blocked polydimethylsiloxane,
The viscosity at 25 ° C. was measured to be 854,000.
cSt.

After adding 4.0 parts of polyoxyethylene (18) nonylphenyl ether to the anionic polydimethylsiloxane emulsion of Comparative Example 1 at 15 ° C. and stirring for 1 hour, 30% of cetyltrimethylammonium chloride was further added. 6.7 parts of an aqueous solution was added and stirred for 1 hour to obtain a cationic polyorganosiloxane emulsion of Example 1.

The cationic emulsion of Example 1 obtained had a non-volatile content of 37.1% and an average particle size of the oil phase of 2%.
It was 74 nm. Further, the emulsion was broken with isopropyl alcohol, and the polyorganosiloxane in the emulsion was taken out. By IR analysis, it was confirmed that both ends were hydroxyl-blocked polydimethylsiloxane,
The viscosity at 25 ° C. was measured to be 854,000.
cSt.

Comparative Example 1 obtained by the same emulsion polymerization
Using the anionic emulsion of Example 1 and the cationic emulsion of Example 1, the stability of the treating agent and the properties of the treated cloth were evaluated by the above-described method for evaluating the fiber treating agent. The results were as shown in Table 1.

Comparative Example 2 30% aqueous solution of cetyltrimethylammonium chloride
7 parts, polyoxyethylene (18) nonylphenyl ether 4.0 parts, potassium hydroxide 0.5 part and distilled water 1
50 parts of a mixed solution was prepared, 100 parts of octamethylcyclotetrasiloxane was added, and the mixture was preliminarily stirred by a homomixer, and then passed twice through a pressure homogenizer at a pressure of 300 kgf / cm ² to emulsify and disperse. The emulsion was transferred to a separable flask equipped with a condenser, a nitrogen inlet, and a stirrer, and mixed while stirring.
After heating at 5 ° C. for 5 hours and then cooling to 15 ° C. over 3 hours, the temperature was further maintained at 15 ° C. for 6 hours to advance the polymerization reaction. Acetic acid was added dropwise to this emulsion to neutralize it to pH 7 to terminate the polymerization reaction, thereby obtaining a cationic polydimethylsiloxane emulsion.

Evaluation of the emulsion and analysis of the contained polyorganosiloxane were carried out in the same manner as in Example 1. The nonvolatile content of the emulsion was 36.2%, the average particle size of the oil phase was 203 nm, and the polyorganosiloxane was contained in both. It was a polydimethylsiloxane endblocked with hydroxyl groups, and its viscosity at 25 ° C. was 5,500 cP. The evaluation results of the fiber treatment agent using this emulsion were as shown in Table 1.

COMPARATIVE EXAMPLE 3 100 parts of a polydimethylsiloxane having hydroxyl groups at both ends and having a viscosity of 997,000 cSt at 25 ° C., 8.0 parts of polyoxyethylene (21) lauryl ether, 13.4 parts of a 30% aqueous solution of cetyltrimethylammonium chloride After uniformly mixing 30 parts of water and water, the mixture was emulsified using a colloid mill, and this was uniformly dispersed in 150 parts of water to obtain a mechanically emulsified emulsion. The nonvolatile content of the obtained emulsion is 37.2%, and the average particle size of the oil phase is 85%.
It was 0 nm. The evaluation results of the fiber treatment agent using this emulsion were as shown in Table 1.

[0077]

[Table 1]

According to the present invention, the fiber treating agent of Example 1
Table 1 shows an example using a cationic polyorganosiloxane emulsion containing a polyorganosiloxane having a viscosity of 10,000 to 10,000,000 cSt.
As is clear from the above, the stability of the treating agent and the properties of the treated cloth are both excellent, and the object of the present invention has been sufficiently achieved.

On the other hand, the fiber treating agent of Comparative Example 1
This is an example in which an anionic emulsion prepared by an emulsion polymerization method was used as a main ingredient as it was, and the compounding stability with a cationic stripping inhibitor was poor, and the object of the present invention could not be achieved. Further, the fiber treating agent of Comparative Example 2 is an example in which a general cationic emulsion polymerization emulsion was prepared under the same emulsion polymerization conditions as the anionic emulsion as an intermediate of Example 1, and used as the main agent. Since the viscosity of the polyorganosiloxane contained in the emulsion was low, it was not possible to impart excellent properties to the treated cloth, and the object of the present invention could not be achieved. Furthermore, the fiber treating agent of Comparative Example 3 is an example in which a cationic emulsion prepared by a mechanical emulsification method is used as a main component, and achieves the objects of the present invention, such as inferior stability and imparting properties to fibers. Could not.

Examples 2 to 4 and Comparative Examples 4 and 5 The same procedure as in Example 1 was carried out except that the raw materials used and / or the production conditions of the intermediate anionic polyorganosiloxane emulsion were changed. A siloxane emulsion was prepared. Table 2 shows the raw material composition of each emulsion and the production conditions. Table 3 shows the properties of the obtained cationic polyorganosiloxane emulsion, the terminal groups of the polymer, and the evaluation results of the fiber treating agent containing the emulsion as a main component.

[0081]

[Table 2]

[0082]

[Table 3]

As is clear from Tables 2 and 3, the fiber treating agents of Examples 2 to 4 were all 10,000 to 1
This is an example in which a cationic polyorganosiloxane emulsion containing a polyorganosiloxane having a viscosity of 0,000,000 cSt is used as a main ingredient, and the object of the present invention has been achieved.

On the other hand, the fiber treating agents of Comparative Examples 4 and 5 have a higher temperature in the second stage of the emulsion polymerization, and therefore the cationic polyorganosiloxane containing a polyorganosiloxane having a viscosity of less than 10,000 cSt. This is an example in which a siloxane emulsion was used as a main ingredient, and the object of the present invention could not be achieved.

Examples 5 to 9 and Comparative Examples 6 and 7 Some of the raw materials used in the production of the intermediate anionic polyorganosiloxane emulsion were changed in order to confirm the effects of the introduction of crosslinking points and organic functional groups. Example 1 except that
In the same manner as in the above, a cationic polyorganosiloxane emulsion was prepared. Then, the degree of swelling and gel content of the emulsions of Examples 5 and 6 and Comparative Example 6 in which a crosslinking point was introduced were measured, and the emulsions of Examples 7 to 9 and Comparative Example 7 in which an organic functional group was introduced. Is ¹
The content of the organic functional group was measured by H-NMR.
Table 4 shows the raw material composition and production conditions of each emulsion. In addition, the characteristics of the emulsion, the analysis results of the polymer,
Table 5 shows the test results as a fiber treatment agent carried out in the same manner as in Example 1.

[0086]

[Table 4]

[0087]

[Table 5]

As is clear from Tables 4 and 5, the fiber treating agents of Examples 5 to 9 were 10,000 to 10,000.
This is an example in which a cationic polyorganosiloxane emulsion having a viscosity of 000 cSt is used as a main ingredient,
The object of the present invention has been achieved. Furthermore, by introducing crosslinking points and organic functional groups, the feeling and water repellency and
The waterproofness and durability became better.

On the other hand, the fiber treating agent of Comparative Example 7
By the introduction of the 3-aminopropyl group, the feeling of the treated cloth is
It is better than the treated cloths according to Comparative Examples 4 to 6 in which the organic functional groups are not introduced, but is not sufficient, and furthermore, the water repellency, waterproofness and durability are inferior, and the object of the present invention is achieved. Could not.

Examples 10 to 15 A cationic polyorganosiloxane emulsion was prepared in the same manner as in Example 1 except that the miscible surfactant or the cationic surfactant was changed. Table 6 shows the raw material composition and production conditions of each emulsion. Also, the properties of the emulsion, the analysis results of the polymer, and Example 1
Table 7 shows the test results as a fiber treatment agent carried out in the same manner as in Example 1.

[0091]

[Table 6]

[0092]

[Table 7]

As is clear from Tables 6 and 7, the fiber treatment agents of Examples 10 to 15 using various miscible surfactants or cationic surfactants were all stable and treated. Both properties attained the object of the present invention.

Claims (2)

[Claims] (A) 10,000 to 1 at 25 ° C.
A high molecular weight polyorganosiloxane having a viscosity of 0,000,000 cSt; (b) an aliphatic hydrocarbon sulfonic acid and an aliphatic hydrocarbon sulfuric acid having 1 to 20 carbon atoms and optionally substituted by a hydroxyl group, and having 6 carbon atoms Anionic surfactants or salts thereof selected from the group consisting of arylsulfonic acids of -30 to 30 and alkylarylsulfonic acids of 7 to 50 carbon atoms; (c) a miscible interface having a hydrophilic-lipophilic ratio of 9 to 25; An activator; and (d) bis (polyoxyethylene) hydrocarbylmethyl quaternary ammonium halide or sulfate;
A cationic interface selected from the group consisting of alkyltrimethylammonium halides or sulfates having 8 to 30 carbon atoms in the alkyl group; and benzylalkyldimethylammonium halides or sulfates having 8 to 16 carbon atoms in the alkyl group. A fiber treating agent mainly comprising a stable cationic silicone oil-in-water emulsion containing an activator. 2. The method of claim 2, wherein (c) the miscible surfactant is polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkyl ether having 6 to 40 carbon atoms in the alkyl group, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, 6 carbon atoms in the alkyl group
To 40 polyoxyethylene alkylamines, polyoxyethylene alkylamides having 6 to 40 carbon atoms in the alkyl group, polyoxyethylene lanolin, lauryl dimethylaminoacetic acid betaine, coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, 2-alkyl-N The fiber treating agent according to claim 1, which is selected from the group consisting of -carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauroyl sarcosine sodium and a quaternary ammonium salt lanolin derivative.