JPH09228255A - Fiber treatment agent - Google Patents

Abstract

(57) [Abstract] [Problem] Generation of oil spots on a fiber material is almost prevented, and highly durable water repellency, waterproofness, flexibility, smoothness, wrinkle resistance and compression recovery are applied to the fiber material. To provide, at a low cost, a fiber treatment agent which is excellent in mechanical stability, dilution stability, compounding stability, and stability over time as well as being imparted. A general formula _{R n SiO (4-n)} / 2 (R is a substituted or unsubstituted monovalent hydrocarbon radical, n is an integer of 0 to 3) of low molecular weight having a structural unit represented by organo Obtained by emulsion polymerization of siloxane in the presence of a surfactant, a catalyst component and water, and further having a viscosity at 25 ° C. of 500,
The present invention relates to a fiber treatment agent, which comprises a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group of 000 cP or more as a main component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treatment agent containing a silicone emulsion obtained by emulsion-polymerizing a low molecular weight organosiloxane as a main component, and more specifically a viscosity at 25 ° C. of 500,000 cP or more. By using a silicone emulsion containing a polyorganosiloxane with a terminal hydroxyl group as the main component, oil spots on fiber materials are almost prevented, and highly durable water repellency, waterproofness, flexibility, smoothness, and wrinkle resistance. And imparts compression recovery to the fiber material, as well as mechanical stability,
The present invention relates to a fiber treatment agent having excellent dilution stability, compounding stability, and stability over time.

[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 In order to impart recoverability and the like, various fiber treating agents containing silicone emulsion as a main component have been used.

However, the conventional fiber treating agents cannot satisfy the above-mentioned characteristics satisfactorily because the blended silicone has a small molecular weight, and the washing resistance is low. The peach was low.

Therefore, the advent of a fiber treating agent containing a high molecular weight silicone, particularly a high molecular weight polyorganosiloxane, has been awaited.

By the way, when a high-molecular-weight polyorganosiloxane is blended with a fiber treating agent, the emulsification technique is an important factor for satisfying the above-mentioned characteristics, but generally, the polyorganosiloxane emulsification method is used. Is a mechanical emulsification method.

The mechanical emulsification method is a polyorganosiloxane,
In this method, mechanical energy is applied to a mixture of a surfactant and water to uniformly emulsify and disperse these components to obtain a desired stable emulsion. A colloid mill, a homomixer, a homogenizer, a combimix, a sand grinder, etc. are generally used for imparting mechanical energy.

For example, in the method described in US Pat. No. 2,755,194, polydimethylsiloxane of 350 cSt and a surfactant are mixed at 25 ° C., a small amount of water is added to this mixture, and the mixture is emulsified and dispersed in a colloid mill. After that, the desired emulsion is obtained by further continuously adding water. However, in the mechanical emulsification method, only polyorganosiloxane within the range of the mechanical energy applied from the equipment used can be used, and at most 5
Only polyorganosiloxanes with viscosities up to about 0,000 cP could be emulsified (JP-A 63-125530).
No. 56-109227). Therefore, when an emulsion containing a polyorganosiloxane emulsified by a mechanical emulsification method is used as a fiber treatment agent, a sticky feeling remains, which is not satisfactory as a fiber treatment agent. In addition, the emulsion thus obtained generally has a large particle size of suspended fine particles composed of polyorganosiloxane, and has stability (mechanical properties) in the processes such as stirring, circulation and squeezing of the processing liquid, which are required during fiber processing. Stability), dilution (20-10 with water)
The stability at the time of dilution (about 0 times) (dilution stability) or the stability in combination with various additives (blending stability) is insufficient, so when applied to a fiber treatment agent, the emulsion There is a problem in that the polyorganosiloxane is destroyed and floats on the treatment bath to form oil droplets (oil spots) on the fiber material, resulting in stains.

Further, in the mechanical emulsification method, a method of emulsifying / dispersing a highly viscous fluid or resin, which is difficult to mechanically emulsify, by dissolving it in an organic solvent such as benzene, toluene or xylene, is also proposed. (See JP-B-63-45748, JP-A-60-1258 and JP-A-60-1259). However, this method has a problem that it is difficult to use it as a fiber treatment agent since it uses an organic solvent and thus has a problem of danger due to solvent odor and flammability of the solvent.

Further, in a mechanically emulsified emulsion, a method of improving stability with time by micronizing suspended fine particles by using polyorganosiloxane in combination with polyoxyalkylene group-containing polyorganosiloxane is also proposed. (JP-A-60-126209, 60)
-197610 gazette). However, since the polyoxyalkylene group-containing polyorganosiloxane used in this method is expensive, it is not general, and the upper limit of the viscosity of the polyorganosiloxane applicable to this method is only about 1000 cP at most. However, there is a problem in that it is difficult to provide a fiber treatment agent containing a polyorganosiloxane having a high viscosity.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and substantially prevents the generation of oil spots on a fiber material and has high durability such as water repellency, waterproofness, flexibility and smoothness. It is an object of the present invention to provide a fiber treatment agent which is excellent in mechanical stability, dilution stability, compounding stability and stability over time, at the same time as imparting a property, wrinkle resistance and compression recovery property to a fiber material.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, in the presence of an anionic surfactant or a cationic surfactant and a catalyst component, Emulsion polymerization of an organosiloxane in water to produce a fiber treatment agent mainly composed of a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group and having a viscosity of 500,000 cP or more at 25 ° C. Without giving rise to high durability water repellency, waterproofness, flexibility, smoothness, wrinkle resistance and compression recovery, the mechanical stability, dilution stability, compounding stability and temporal stability It has been found that it has excellent properties, and has completed the present invention.

That is, the fiber treating agent of the present invention is represented by the general formula R _n SiO _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3). Obtained by emulsion polymerization of a low molecular weight organosiloxane having a structural unit represented by a surfactant, a catalyst component, and water.
Furthermore, it is characterized in that the main component is a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group-blocking property and a viscosity at 25 ° C. of 500,000 cP or more.

Here, the structural unit is a monofunctional type, which is a terminal unit of the molecule, M unit, a bifunctional type, which is a linear structural unit, a D unit, a trifunctional type, or a tetrafunctional type, which is a network structural factor. It is a concept that includes a certain T unit or Q unit.

The catalyst component is a substance added to polymerize a low molecular weight organosiloxane in the presence of water, and the surfactant itself may have this function like trimethylsulfonic acid. Therefore, it is not necessary to add it.

In the fiber treatment agent of the present invention, the viscosity of the silicone emulsion as the main component is 500,00.
0 cP or more, preferably 600,000 to 20,000
20,000 cP, particularly preferably 1,000,000 to
A silicone emulsion containing 10,000,000 cP of polyorganosiloxane in the suspended fine particles in an amount of about 5 to 60% is used. Furthermore, the weight average molecular weight of the polyorganosiloxane is 100,000 to 1,
, 000,000, especially 200,000 to 500,000
Are preferred. The viscosity of polyorganosiloxane is
If it is less than 500,000 cP, the sticky feeling is strong, and
Fiber treatability becomes insufficient. The suspended fine particles are fine particles dispersed in a dispersion medium of an emulsion, and in the present invention, fine particles made of polyorganosiloxane or the like obtained by emulsion polymerization.

The fiber treating agent of the present invention is mainly composed of a silicone emulsion containing the above-mentioned polyorganosiloxane having a terminal hydroxyl group blocked, and the silicone emulsion in the fiber treating agent is used as a silicone component in the fiber treating agent. It is obtained by blending 01 to 50% by weight, preferably 0.1 to 20% by weight. The fiber-treating agent may be used as it is, but if necessary, an arbitrary amount of any component may be added to the fiber-treating agent so long as the object of the present invention is not impaired. When the optional component is added, preferably 0.1 to 99.9% by weight of the optional component is added to the fiber treatment agent.

Hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane, and olefin oligomers as optional components; isopropyl palmitate, stearyl stearate, octyldodecyl myristate, triglyceride 2-ethylhexanoate, and the like; Higher alcohols such as lauryl alcohol, cetyl alcohol and stearyl alcohol; paramitic acid,
Higher fatty acids such as stearic acid; resin processing agents such as glyoxal resin, melamine resin, urea resin, polyester resin and acrylic resin; solvents such as ethanol; water; various surfactants described below; bactericides; fragrances; coloring agents, etc. Can be mentioned. Further, in order to cure the polyorganosiloxane having a terminal hydroxyl group blocked into an elastomer, methylhydrogen silicone, alkoxysilane, or the like may be used as a crosslinking agent, or tin or a titanium compound may be used in combination as a catalyst.

To add the above-mentioned optional components to the fiber treating agent of the present invention, the silicone emulsion, which is the main agent containing the polyorganosiloxane having a terminal hydroxyl group blocked, and other optional components are simply mixed uniformly. Alternatively, the components other than the silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group blocked may be previously emulsified by a homogenizer, colloid mill, line mixer or the like, or uniformly mixed by a stirrer, and then added to this. A silicone emulsion containing a polyorganosiloxane having terminal hydroxyl groups may be added.

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 is usually in the range of 0.01 to 10% by weight in terms of polyorganosiloxane with respect to the fiber material. 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.

As the fiber material to be treated, natural fibers such as cotton, hemp, silk, wool, angora, and mohair, regenerated fibers such as rayon and bemberg, semi-synthetic fibers such as acetate, and polyester are used. Synthetic fiber, such as fiber, polyamide fiber, polyacrylonitrile fiber, polyvinyl chloride fiber, polyvinyl alcohol fiber, polyethylene fiber, polypropylene fiber, spandex
Inorganic fibers such as glass fiber, carbon fiber and silicon carbide fiber can be used. 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.

As an emulsion polymerization method for a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group, which is used in the fiber treating agent of the present invention, for example, first, an anionic surfactant or a cationic surfactant is used. optionally a surfactant and a catalyst component such as potassium hydroxide dissolved in water, then the general formula R _n SiO _{(4-
n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3), and a low molecular weight organosiloxane is added with stirring. This is roughly emulsified by using an emulsifying machine such as a homomixer, a colloid mill or a line mixer, and further emulsified through an emulsifying machine such as a pressure homogenizer or an ultrasonic homogenizer to obtain an emulsion. Then, as a first reaction step, the emulsion is maintained at 70 to 90 ° C. for 1 to 15 hours, and then as a second reaction step, at 0 to 40 ° C. for 1 to 50.
The emulsion polymerization is promoted by maintaining it for 0 hour, and the polymerization is stopped when the desired polymer viscosity is reached.

When stopping 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 to neutralize the medium. By suspending the polymerization by the addition, it is possible to obtain a silicone emulsion in which the main component of the suspended fine particles is a polyorganosiloxane having a high degree of polymerization and having a terminal hydroxyl group blocking, and a by-product, a low molecular weight organosiloxane. it can.

In the first reaction step of the method for producing a silicone emulsion of the present invention, when the reaction temperature is lower than 70 ° C. or the reaction time is shorter than 1 hour, sufficient heat energy is imparted to the low molecular weight organosiloxane. Therefore, it is impossible to produce a satisfactory emulsion because the reaction conversion rate of the low molecular weight organosiloxane as a raw material is low, or the polymerization rate of the polyorganosiloxane produced is slow. On the other hand, when the reaction temperature is higher than 90 ° C, water is evaporated and the emulsion becomes unstable and breaks. Therefore, the reaction temperature is preferably 70 to 90 ° C.
Is set in the range. Further, even if the reaction time exceeds 15 hours, there is no further improvement effect on the polymerization rate, which is disadvantageous in terms of production efficiency. Therefore, the reaction time is preferably set to 2 to 10 hours.

In the second reaction step, when the reaction temperature is out of the range of 0 to 40 ° C., the polymerization rate of the polyorganosiloxane produced is slow, which is disadvantageous in terms of production efficiency. Therefore, the reaction temperature is preferably 5 to
It is set in the range of 35 ° C. Moreover, since the viscosity of the polyorganosiloxane in the emulsion becomes higher, a fiber treating agent having good characteristics can be obtained,
The reaction time is set to 1 to 500 hours, preferably 2 to 300 hours.

Examples of the alkaline substance used for neutralization include inorganic substances such as sodium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate and potassium acetate, and amines such as ammonia and triethanolamine. Examples of the acidic substance used for this neutralization include organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid and glycolic acid, and inorganic acids.

In the emulsion polymerization method of a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group, which is used in the fiber treating agent of the present invention, the general formula R _n SiO _{(4-n) / 2} (R Is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 0 to 3) and the low molecular weight organosiloxane is not particularly limited, but cyclic polyorganosiloxane, the molecular chain end of which is blocked with a hydroxyl group or an alkoxyl group. A stopped linear or branched polyorganosiloxane or a mixture thereof can be preferably used, and usually has a molecular weight of 100 to 100.
Those of 5,000, preferably 200 to 1,000 are used.

As the cyclic polyorganosiloxane, the following general formula 1 (wherein R ¹ and R ² are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group,
It is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms such as an allyl group or a phenyl group, and m is an average number of 3 to 8), and specifically, hexamethylcyclotrisiloxane. , Octamethylcyclotetrasiloxane,
1,3,5,7-tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1 , 2, 3,
4-tetravinyl-1,2,3,4-tetramethylcyclotetrasiloxane, 1,2,3,4-tetramethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, 1,2,3,4-tetramethyl- 1, 2, 3,
4-tetraphenylcyclotetrasiloxane etc. are illustrated.

[0028]

Embedded image The linear or branched polyorganosiloxane is represented by the following general formulas 2 and 3 (wherein R ³ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group, an allyl group or phenyl). A monovalent hydrocarbon group having 1 to 8 carbon atoms such as a group, R ⁴ is a hydrogen atom, a methyl group, an ethyl group,
A propyl group, a vinyl group, an allyl group, a phenyl group or another monovalent hydrocarbon group having 1 to 8 carbon atoms, a hydroxyl group or an alkoxy group, and n and l are 0 to 50). Preferably, specifically, α, ω-dihydroxypolydimethylsiloxane, α, ω-dimethoxypolydimethylsiloxane, tetramethyl-1,3-dihydroxydisiloxane, octamethyl-1,7-dihydroxytetrasiloxane, hexamethyl-1,5. -Diethoxytrisiloxane and the like are exemplified, and in addition, crosslinking agents such as methyltrimethoxysilane, trimethoxysilane, and tetraethoxysilane can also be used.

Embedded image

Embedded image The amount of the low molecular weight organosiloxane used is not particularly limited, but the concentration of the low molecular weight organosiloxane in the reaction system during the emulsion polymerization is 5 to 60% by weight, particularly 10 to 50% by weight. It is preferable that the content be 5% by weight or less, and if it is less than 5% by weight, the efficiency of emulsification becomes poor, and if it exceeds 60% by weight, the viscosity of the emulsion increases and it is not preferable because it is inconvenient for work.

In the emulsion polymerization method of a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group, which is used in the fiber treatment agent of the present invention, a siloxane unit (structural unit) is further added to the above low molecular weight organosiloxane. 10 mol% or less, particularly 0.1 to 5 mol%
It is no problem to add an amount of a hydrolyzable organosilane having an organic functional group or an organosiloxane oligomer having a siloxane unit having an organic functional group to an extent that does not impair the object of the present invention and to emulsify these. By adding, it is possible to introduce an organic functional group into the resulting polyorganosiloxane.

In this case, examples of the hydrolyzable organosilane include methyltrimethoxysilane, methyldimethoxysilane, dimethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane and Ν- (2 -Aminoethyl) -3-
Aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane , Trifluoropropyltrimethoxysilane,
3-carboxypropylmethyldimethoxysilane, (vinyloxypropyl) methyldimethoxysilane, (vinyloxyethoxypropyl) methyldimethoxysilane, p-
Vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane,
2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylphenoxy) propyltriethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (p-vinylphenyl) ethyl Methyldimethoxysilane, 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] phenyldipropoxysilane , N-methacryloyl-N-methyl-3-
Aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-3-aminopropylmethyldimethoxysilane, N, N-bis (methacryloyl) -3-aminopropyltrimethoxysilane, N, N-bis (acryloyl) -3- Aminopropylmethyldimethoxysilane, N-methacryloyl-N-methyl-3-aminopropylphenyldiethoxysilane, 1-methacryloxypropyl-1,1,3-trimethyl-3,3-dimethoxydisiloxane, vinylmethyldimethoxysilane, Vinylethyldiisopropoxysilane, allylmethyldimethoxysilane, 5-hexenylmethyldiethoxysilane, 3
-Octenylethyldiethoxysilane and the like can be mentioned, and these are used alone or as a mixture of two or more kinds.

Examples of the organosiloxane oligomer having a siloxane unit having an organic functional group include trimethyltriphenylcyclotrisiloxane, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane, 1,3,5. , 7-Tetra (3-aminopropyl) tetramethylcyclotetrasiloxane,
1,3,5,7-Tetra [N- (2-aminoethyl)-
3-Aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-mercaptopropyl) tetramethylcyclotetrasiloxane, 1,3,3
5,7-Tetra (3-glycidoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (3-acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-carboxypropyl) tetramethylcyclotetrasiloxane, 1,3,3
5,7-Tetra (vinyloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (vinyloxyethoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (p-vinyl) Phenyl) tetramethylcyclotetrasiloxane, 1,3
5,7-Tetra [1- (m-vinylphenyl) methyl]
Tetramethylcyclotetrasiloxane, 1,3,5,7
-Tetra [2- (p-vinylphenyl) ethyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-vinylphenoxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5 , 7-Tetra [3- (p-pinylbenzoyloxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra- [3- (p-isopropenylbenzoylamino) propyl] tetramethylcyclotetra Siloxane, 1,
3,5,7-Tetra (N-methacryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-acryloyl-
N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N, N-
Bis (methacryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [Ν, N-bis (acryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,3
5,7-tetravinyltetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 1,3,
5-trivinyltrimethylcyclotrisiloxane, 1,
3,5,7-Tetraallyltetramethylcyclotetrasiloxane, 1,3,5,7-tetra (5-hexenyl)
Tetramethylcyclotetrasiloxane, 1,3,5,7
Examples include cyclic compounds such as -tetra (7-octenyl) tetramethylcyclotetrasiloxane, and these can be used alone or as a mixture of two or more kinds. In addition to this, an organosiloxane oligomer having a linear or branched organic functional group may be used.

However, when an organosiloxane oligomer containing a linear or branched organic functional group is used,
The terminal of the molecular chain is not particularly limited, but from the viewpoint of easy handling and introduction of the organic functional group into the polyorganosiloxane to be formed, the terminal of the molecular chain is an organic group other than a hydroxyl group, for example, an alkoxy group. , Trimethylsilyl group, dimethylvinylsilyl group, methylphenylvinylsilyl group, methyldiphenylsilyl group, or 3,3,3-
It is preferably blocked with a trifluoropropyldimethylsilyl group or the like.

Next, as anionic surfactants that can be used as the surfactant, aliphatic substituted benzenesulfonic acids, aliphatic hydrogen sulfates, or unsaturated aliphatic sulfones represented by the following general formulas 4 to 7 are used. A mixture of acid and hydroxyaliphatic sulfonic acid is preferably used.

R ⁵ C ₆ H ₄ SO ₃ H ・ ・ ・ 4 R ⁵ OSO ₃ H ・ ・ ・ 5 R ⁶ CH = C Η (C Η ₂ ) _n SO ₃ H ・ ・ ・ 6 R ⁶ CH C Η (OH) (C Η ₂ ) _m SO ₃ H 7 (wherein R ⁵ is a monovalent aliphatic hydrocarbon group having ^{6 to} 30 carbon atoms, R ⁶ is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms) A hydrogen group, and n and m are integers such that the total number of carbon atoms in the surfactants of formulas 6 and 7 is 6 to 30).

Here, R ⁵ in the formulas 4 and 5 is a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, preferably 6 to 18, such as hexyl group, octyl group, decyl group,
Examples thereof include dodecyl group, cetyl group, stearyl group, myricyl group, oleyl group, nonenyl group, octynyl group, phytyl group and pentadecadienyl group.

Further, R ⁶ in the formulas 6 and 7 is a monovalent aliphatic hydrocarbon group having 1 or more carbon atoms, preferably 6 to 18, and for example, a monovalent aliphatic hydrocarbon group similar to R ⁵ is used. A hydrogen group is mentioned.

Such 4 or 5 anionic surfactants include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, octylsulfate, laurylsulfate, oleylsulfate, cetyl. Examples include sulfate and the like.

Examples of the anionic surfactant of formula 6 or 7 include so-called α-olefin sulfonic acid and the like.

Further, an anionic surfactant having a weak catalytic action can also be used in combination with the polymerization catalyst. As such an anionic surfactant, the above-mentioned 4
Formula aliphatic substituted benzene sulfonic acid, sodium salt, potassium salt, ammonium salt of aliphatic hydrogen sulphates of formula 5, and the like, specifically, dodecyl benzene sulfonate sodium, octyl benzene sulfonate sodium, dodecyl benzene sulfone Examples thereof include ammonium acid, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate and the like.

In addition to the above-mentioned anionic surfactants of formula 4 or 5, for example, polyoxyethylene (4) lauryl ether sulfate, polyoxyethylene (1
3) polyoxyethylene alkyl ether sulfate such as cetyl ether sulfuric acid, polyoxyethylene (6) stearyl ether sulfuric acid, polyoxyethylene (4) sodium lauryl sulfate, polyoxyethylene (4) octylphenyl ether ammonium sulfate Its salt, polyoxyethylene (3) lauryl ether carboxylic acid,
Polyoxyethylene (3) stearyl ether carboxylic acid, polyoxyethylene (6) sodium lauryl ether carboxylate, polyoxyethylene (6) sodium octyl ether carboxylate and other polyoxyethylene alkyl ether ether carboxylic acid esters or salts thereof, etc. One kind or two or more kinds can be used,
It is not limited to these.

The polymerization catalyst to be used in combination with the anionic surfactant is usually an aliphatic-substituted benzenesulfonic acid, an aliphatic hydrogensulfate, or an unsaturated aliphatic sulfone which is used as a polymerization catalyst for low molecular weight organosiloxanes. A mixture of acid and hydroxyaliphatic sulfonic acid, acidic catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid and the like are preferably used, but not limited thereto, and polymerizes a low molecular weight organosiloxane in the presence of water. Any catalyst can be used as long as it can be used.

The amount of the anionic surfactant used is 0.1% by weight based on 100 parts by weight of the above low molecular weight organosiloxane.
The amount is more preferably 5 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight. If the amount is less than 0.5 parts by weight, the stability of the emulsion may be poor and separation may occur. The emulsion may thicken and the fluidity may deteriorate. When the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but it is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the low molecular weight organosiloxane.

Further, as the cationic surfactant that can be used as the surfactant, the following general formula 8 (in the formula,
R ⁷ is a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, R
Preferred is a quaternary ammonium salt-based surfactant represented by each of ⁸ , ^9, and ¹⁰ being a monovalent organic group, and Χ being a hydroxyl group, a chlorine atom or a bromine atom.

[0044]

Embedded image In formula 8, R ⁷ has 6 or more carbon atoms, preferably 8
To 18 aliphatic hydrocarbon groups, for example, hexyl group, octyl group, decyl group, dothesyl group, cetyl group, stearyl group, myricyl group, oleyl group, hexadecyl group, nonenyl group, octynyl group, phytyl group, pental group. Examples thereof include a decadienyl group. R ⁸ , R ⁹ and R ¹⁰ 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. Group, xenyl group, aryl group such as naphthyl group, cycloalkyl group such as cyclohexyl group, and the like.

Examples of such a quaternary ammonium salt type surfactant of formula 8 are lauryl trimethyl ammonium hydroxide, stearyl trimethyl ammonium hydroxide, dioctyl dimethyl ammonium hydroxide, distearyl dimethyl ammonium hydroxide, lauryl trimethyl chloride. Ammonium, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, benzalkonium chloride, stearyl dimethyl benzyl ammonium chloride, etc. are mentioned, These 1 type, or 2 or more types are used. be able to.

Since the above-mentioned cationic surfactant has a weak catalytic action, it is preferably used in combination with a polymerization catalyst. As the polymerization catalyst used in combination, a hydroxylation usually used as a polymerization catalyst for a low molecular weight organosiloxane is used. Examples thereof include alkali metal hydroxides such as lithium, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. When the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but it is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the low molecular weight organosiloxane.

The amount of the cationic surfactant used is 0. 100 parts by weight based on 100 parts by weight of the above-mentioned low molecular weight organosiloxane.
5 to 50 parts by weight, particularly 1 to 20 parts by weight is preferable, and if it is less than 0.5 parts by weight, the cationic property of the emulsion itself is insufficient, and the stability of the emulsion may be poor and separation may occur. If it exceeds 50 parts by weight, the emulsion may thicken and lose its fluidity. In the reaction system using the cationic surfactant, Si-
The use of a low molecular weight organosiloxane having a H-bond causes a dehydrogenation reaction, and thus the use of a low molecular weight organosiloxane having a Si-H bond is not preferable.

Further, in order to improve the stability of the silicone emulsion obtained by emulsion polymerization, a nonionic surfactant is added to the above-mentioned surfactant before or after the emulsion polymerization within a range not impairing the object of the present invention. You may use it together. As such nonionic surfactants, those having an HLB value of 6 to 20 are preferable, and examples thereof include polyoxyethylene (6) lauryl ether, polyoxyethylene (7) cetyl ether, and polyoxyethylene (7) cetyl ether. Oxyethylene (20) stearyl ether, polyoxyethylene (3) octylphenyl ether, polyoxyethylene (18) nonylphenyl ether, polyethylene glycol monostearate (EO14), polyethylene glycol distearate (EE 80), polyoxyethylene (20 ) Hydrogenated castor oil, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene monostearate (6)
Sorbitan, polyoxyethylene trioleate (2
0) sorbitan, polyoxyethylene tetraoleate (40) sorbit, polyoxyethylene (15) glyceryl monooleate, polyoxyethylene (15) glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene (10) behenyl ether , Polyoxyethylene (10) phytosterols, polyoxyethylene (1) polyoxypropylene (4) cetyl ether, polyoxyethylene (5) stearylamine,
Examples thereof include polyoxyethylene (8) stearyl propylene diamine and polyoxyethylene (5) cetyl ether sodium phosphate, but are not limited thereto.

The amount of these nonionic surfactants to be used is such that, when they are used in combination before emulsion polymerization, the above surfactant 1 is used.
If it exceeds 500 parts by weight with respect to 00 parts by weight, it may be a factor that hinders the polymerization reaction of the low molecular weight organosiloxane.
It is preferably 0 parts by weight.

[0050]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, in which parts and% are
Unless otherwise specified, they are parts by weight and% by weight.

The average particle size of the suspended fine particles in the obtained silicone emulsion is the laser particle size analysis system LPA-3 manufactured by Otsuka Electronics Co., Ltd., which adopts the dynamic light scattering method.
It was measured using 000S / 3100. The nonvolatile content of the obtained silicone emulsion was measured by heating the silicone emulsion at 105 ° C. for 3 hours to evaporate the nonvolatile content. Further, for measuring the swelling degree and gel content of the polyorganosiloxane having a cross-linking point introduced, a polyorganosiloxane obtained by dropping a silicone emulsion into isopropyl alcohol, coagulating and drying is used. Went by. That is, the degree of swelling was 2 for polyorganosiloxane.
It was determined as a value obtained by dividing the weight of toluene occluded by the polyorganosiloxane when immersed in toluene at 3 ° C. for 48 hours by the weight of the polyorganosiloxane before immersion. The gel content was determined by subjecting polyorganosiloxane to extraction treatment in toluene at 23 ° C. for 48 hours. Also,
The measurement of the organic functional group content of the polyorganosiloxane introduced with an organic functional group, the polyorganosiloxane obtained by coagulation and drying by the same method as the swelling degree measurement,
Nippon Bruker Co., Ltd. Nuclear Magnetic Resonance Spectrometer AM-
It was carried out by performing 1Η-ΝMR analysis using 300.

Example 1 100 parts of octamethylcyclotetrasiloxane was added to a mixed solution of 2 parts of n-dodecylbenzene sulfonic acid (manufactured by Nissan Chemical Industries, Ltd., Soft Oarai 5S) and 150 parts of distilled water. , After pre-stirring with a homomixer, 300 kgf / with a pressure homogenizer
The mixture was emulsified and dispersed by passing it twice at a pressure of cm ² . The emulsion was transferred to a separable flask equipped with a condenser, nitrogen inlet and stirrer and heated at 85 ° C. for 5 hours with stirring and mixing, then 2 hours over 3 hours.
After gradually cooling and stirring to 5 ° C., the mixture was further cooled and stirred at 25 ° C. for 5 hours to promote the polymerization reaction. Subsequently, the emulsion was adjusted to pH 7 with 10% aqueous sodium carbonate solution.
A polydimethylsiloxane emulsion was obtained by neutralizing the solution to stop the polymerization reaction. Emulsion A
And

The nonvolatile content of the obtained emulsion A is 3
It was 6.5%, and the average particle size of the suspended fine particles was 275 nm.

Further, the emulsion A was destroyed with isopropyl alcohol, the silicone polymer was taken out, and IR
As a result of analysis, it was confirmed that this was a dimethyl silicone polymer having hydroxyl groups sealed at both ends, and the viscosity at 25 ° C. was measured and found to be 98,000 cP.

Next, 518 parts of water was added to 30 parts of emulsion A to prepare a fiber treating agent having a silicone concentration of 2% by weight.

400 ml of the prepared fiber treatment agent
Samples were placed in a 20 cm x 35 cm x 3 cm square bat made of stainless steel, and two rubber rollers with a diameter of 6 cm (nip pressure 0.5 kg / cm ² ) assembled vertically were placed on the bottom bat. 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 to determine the mechanical stability of the fiber treatment agent by the roller treatment as the state of oil adhered to the rubber roll.
It evaluated based on the evaluation criteria shown below.

○: No oil adhered.

Δ: Oil is partially adhered to the surface of the rubber roll to cause repellency.

X: Oil adhered to the surface of the rubber roll Next, 25 ml of the fiber treatment agent after the roller treatment was sampled,
Centrifugation was performed at a speed of 2500 rpm for 30 minutes, and mechanical stability of the fiber treatment agent by centrifugation was evaluated according to the following evaluation criteria.

○: It was a completely uniform aqueous solution, and there was no oil floating.

Δ: The surface is glaring, and some floating of oil is recognized.

X: A large amount of oil floating was observed on the surface.

Emulsion A was diluted to adjust the fiber treatment agent so that the silicone concentration was 5% by weight.

Then, 500 ml of the prepared fiber treatment agent
Put in a household mixer for 60 at a speed of 4000 rpm
Stirring was performed for a minute, and the stability of the fiber treatment agent by the mixer treatment was evaluated according to the following evaluation criteria.

O ... No oil adhered to the blades of the mixer or the glass wall.

Δ: A slight amount of oil was found on the blades of the mixer and the glass wall.

X: Oil adheres to the blades of the mixer and the glass wall, and the oil floats on the surface.

Further, using a simple hair spray,
Spray the beige dyed nylon naphtha with the fiber treatment agent after the mixer treatment, dry it at room temperature, and heat it for 3 minutes at 150 ° C. It evaluated according to the evaluation criteria shown in.

(Presence or absence of oil spot) O ... No oil spot.

Δ: There is a slight oil spot.

X: There are many oil spots.

(Feeling) ○ ... Very good without feeling slimy, and good in flexibility, impact resilience and smoothness. Δ: Slight slimy feel, good flexibility, impact resilience and smoothness.

X: Strong slimy feeling, poor flexibility, impact resilience and smoothness.

Further, the surface condition of the treated cloth after spraying water on the surface of the treated cloth was observed, and the volatility and waterproofness were evaluated according to the following evaluation criteria.

⊚ ... No wetness or water droplets on the surface.

O ... Wet with small water droplets on the surface.

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

×: Only the surface is totally wet.

XX: The entire front and back surfaces are wet.

Further, the treated cloth was placed in a washing bath in which 5 g of sodium alkylbenzenesulfonate and 2 g of sodium carbonate were added to 1000 ml of water, and the bath temperature was 50: 1 by using a household electric washing machine at a bath ratio of 100: 1. ℃,
After washing for 15 minutes, the above-mentioned "feel" and "volatility and waterproofness" tests were carried out to obtain a durability test. In addition, "feel" and "volatile and waterproof" evaluation,
As described above.

The results are shown in Table 1.

(Comparative Example 1) Polydimethylsiloxane (viscosity 1,000,000 cP) 100 with hydroxyl groups blocked at both ends
Part, polyoxyethylene (9) lauryl ether (manufactured by Nikko Chemicals Co., Ltd., NIKKOL BL-9EX) 1
After uniformly mixing 0 parts and 20 parts of water, the mixture was emulsified using a colloid mill and uniformly dispersed in 160 parts of water to obtain a mechanically emulsified emulsion (referred to as emulsion B). . The nonvolatile content of the obtained emulsion B was 37.5%, and the average particle size of suspended fine particles was 820 n.
m. Moreover, when the viscosity at 25 ° C. was measured,
It was 1,000,000 cP.

Then, the emulsion B was tested under the same conditions as in Example 1 and evaluated in the same manner.

The results are shown in Table 1.

Example 2 30% Cetyltrimethylammonium Chloride Aqueous Solution (manufactured by Kao Corporation, Kotamine 6)
0 W, active ingredient 30%) 6.7 parts, polyoxyethylene (18) nonyl phenyl ether (manufactured by Nikko Chemicals, NIKKOL NP-18TX; Η LΒ1
9) 4 parts, 0.5 parts potassium hydroxide and 150 distilled water
100 parts of octamethylcyclotetrasiloxane was added to the mixed solution of 1 part and after preliminarily stirring with a homomixer,
The mixture was emulsified and dispersed by passing it twice through a pressure homogenizer at a pressure of 300 kgf / cm ² .

The emulsion was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer,
Heat at 85 ° C. for 10 hours with stirring and mixing, then cool to 25 ° C. over 3 hours, then cool at 168 ° C. at 168
The polymerization reaction proceeded by holding for a time. continue,
This emulsion was neutralized to pΗ7 with acetic acid to terminate the polymerization reaction, to obtain a polydimethylsiloxane emulsion (referred to as emulsion C).

The nonvolatile content of the obtained emulsion C is 3
It was 6.2%, and the average particle size of the suspended fine particles was 203 nm. Furthermore, this emulsion C is destroyed with isopropyl alcohol, the silicone polymer is taken out, and
As a result of analysis, it was confirmed that this was a dimethyl silicone polymer with both end hydroxyl groups blocked, and the viscosity at 25 ° C. was measured and found to be 845,000 cP.

Then, the emulsion C was tested under the same conditions as in Example 1 and evaluated in the same manner.

The results are shown in Table 1.

[0090]

[Table 1] As is clear from Table 1, the fiber treating agents of Examples 1 and 2 are examples in which a polyorganosiloxane emulsion having a viscosity of 500,000 cP or more was used as a main component, and the object of the present invention was sufficiently obtained. There is.

On the other hand, the fiber treating agent of Comparative Example 1 is an example in which a polyorganosiloxane emulsion having a viscosity of 500,000 cP or less, which is emulsified by a mechanical emulsification method, is used as a main component, and the object of the present invention is obtained. I couldn't do that.

(Examples 3 to 6 and Comparative Examples 2 to 3) An emulsion was prepared in the same manner as in Example 1 except that the raw materials used and some of the production conditions were changed. Table 2 shows the raw material composition, production conditions and characteristics of each emulsion. In addition, Table 2 also shows the evaluation of test results performed in the same manner as in Example 1. The second
In the table, all columns of composition are expressed as parts by weight.

[0093]

[Table 2] As is clear from Table 2, the fiber treating agents of Examples 3 to 6 are examples in which polyorganosiloxane emulsions having terminal hydroxyl groups blocked and having a viscosity of 500,000 cP or more are used as the main component, and the object of the present invention is to It has been obtained enough.

On the other hand, the fiber treatment agents of Comparative Examples 2 to 3 were not capped with terminal hydroxyl groups, or 500,0.
This is an example in which a polyorganosiloxane emulsion having a viscosity of 00 cP or less is used as a main component, and the object of the present invention could not be obtained. (Examples 7 to 11 and Comparative Examples 4 to 5) In order to confirm the effect of introducing a crosslinking point or an organic functional group, the same procedure as in Example 1 was performed except that a part of the raw materials used was changed. , Silicone emulsions G to P were prepared. Then, the degree of swelling and gel content were measured for the emulsion having the cross-linked points introduced, and the content of the organic functional group was measured by ¹ H-NMR for the emulsion having the organic functional group introduced. Table 3 shows the raw material composition of each emulsion, the production conditions and the characteristics thereof. In addition, Table 3 also shows evaluation of test results performed in the same manner as in Example 1. In addition,
In Table 3, all compositional columns are expressed as parts by weight.

[0095]

[Table 3] As is clear from Table 3, the fiber treatment agents of Examples 7 to 11 are examples in which polyorganosiloxane emulsions having terminal hydroxyl groups blocked and having a viscosity of 500,000 cP or more are used as the main agent, and the object of the present invention is to Is sufficiently obtained.

On the other hand, the fiber treating agents of Comparative Examples 4 to 5 are examples in which a polyorganosiloxane emulsion having a viscosity of 500,000 cP or less is used as a main component, and the object of the present invention cannot be obtained. It was In addition, the introduction of cross-linking points and organic functional groups improved the texture, volatility, waterproofness and durability of the treated cloth.

[0097]

As described above, according to the present invention, since the main component is a silicone emulsion containing a polyorganosiloxane having a high-viscosity terminal hydroxyl group, oil spots are not generated on the fiber material. It is possible to provide a fiber treatment agent capable of imparting water repellency, waterproofness, flexibility, smoothness, wrinkle resistance, and compression recovery, which are almost prevented and have high durability, to a fiber material. Also,
It is possible to provide a fiber treatment agent having high durability of these effects even when an operation such as washing is performed on the fiber material. Further, it is possible to inexpensively provide a fiber treatment agent which is excellent in mechanical stability against stirring, circulation and the like, dilution stability against water and the like, and compounding stability with various additives, and also excellent stability over time. Therefore, the present invention
It is very useful industrially.

[0098]

Claims (1)

[Claims] 1. A low molecular weight compound having a structural unit represented by the general formula R _n SiO _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 0 to 3). It is obtained by emulsion polymerization of an organosiloxane in the presence of a surfactant, a catalyst component and water, and further has a viscosity at 25 ° C. of 500,
A fiber treatment agent comprising a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group of 000 cP or more as a main component.