JPH11158380A - Silicone aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicone aqueous emulsion composition capable of forming a high-strength rubber elastic film by removing water and further suitable as a textile treating agent. SOLUTION: This composition consists essentially of (A) an organopolysiloxane represented by the formula R<1> s are each the same or different substituted or unsubstituted monovalent hydrocarbon group; Xs are each hydroxyl group or an alkoxy group; Z is the same or different group represented by the formula [OSi(R<1> )2 ]k -X; (k) and (n) are each an integer of >=0; (m) is an integer of >=1}, (B) an organopolysiloxane containing at least two groups represented by the formula R<2> SiR<3> a X3-a [R<2> is a bivalent hydrocarbon group; R<3> is an unsubstituted monovalent hydrocarbon group; X is hydroxyl group or an alkoxy group; (a) is 0 or 1] and present in the molecule, (C) a fine powdery silica and (D) a curing accelerator and is an aqueous emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous silicone emulsion composition and, more particularly, to an aqueous silicone emulsion composition which forms a rubber film by removing moisture.

[0002]

2. Description of the Related Art Numerous compositions have been proposed as aqueous silicone emulsion compositions which form a rubber film by removing moisture. For example, a silicone emulsion composition comprising a silanol group-containing diorganopolysiloxane, colloidal silica and an organotin compound and having a pH in the range of 9 to 11.5 has been proposed (see JP-A-56-16553). . However, this composition has a problem that various restrictions are imposed on its use because the composition itself is alkaline. Further, an organopolysiloxane latex composition obtained by emulsion-polymerizing a cyclic organosiloxane and an aminoalkyl trialkoxysilane in the presence of a sulfonic acid-based or quaternary ammonium salt-based surfactant (JP-A-54-13661) ), Silanol group-containing organopolysiloxane emulsion, reaction product of amino group-containing organosilane and acid anhydride, epoxy group-containing organosilane, organosilane such as isocyanate group-containing organosilane,
A silicone aqueous emulsion composition comprising colloidal silica and a curing catalyst (JP-A-5-98579) has been proposed. However, these compositions have a problem that the film strength after curing is low in all cases. Further, an aqueous emulsion composition comprising a silanol group-containing diorganopolysiloxane, a silicon atom-bonded hydrogen atom-containing organopolysiloxane, colloidal silica, an amide group and a carboxyl group-containing organoalkoxysilane, an epoxy group-containing organoalkoxysilane, and a curing accelerating catalyst. Has been proposed (see JP-A-8-85405). However, this composition has a problem that a silanol group and a silicon atom-bonded hydrogen atom undergo a condensation reaction, and hydrogen gas is generated, thereby damaging a storage container.
It could not be used depending on the application.

[0003]

The present inventors have conducted intensive studies to solve the above problems, and as a result, when two specific types of organopolysiloxanes are used in combination as the main components of the aqueous emulsion composition, The inventors have found that the above problems are solved, and have reached the present invention. That is, the object of the present invention is to
It is an object of the present invention to provide a silicone aqueous emulsion composition which forms a high-strength rubber film by removing water, and to provide a silicone aqueous emulsion composition which is suitable as a fiber treatment agent.

[0004]

The present invention provides (A) a compound represented by the following general formula:

Embedded image (Wherein, R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group, X is a hydroxyl group or an alkoxy group, and Z is a group represented by the formula:
-[OSi (R ¹ ) ₂ ] _k -X are the same or different groups. k and n are integers of 0 or more, and m is an integer of 1 or more. An organopolysiloxane represented by the formula (B):
R ² SiR ³ _a X _3-a (wherein, R ² is a divalent hydrocarbon group, R ³ is an unsubstituted monovalent hydrocarbon group, X is a hydroxyl group or an alkoxy group, and a is 0 or 1). (C) an organopolysiloxane having at least two groups shown in a molecule thereof,
The present invention relates to an aqueous silicone emulsion composition comprising finely divided silica and a curing accelerator (D) as main components and being an aqueous emulsion.

Hereinafter, the present invention will be described in detail. The component (A) used in the present invention has a general formula:

Embedded image Wherein R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group, X is a hydroxyl group or an alkoxy group, and Z is a group represented by the formula:
The same or different groups represented by [OSi (R ¹ ) ₂ ] _k -X. k and n are integers of 0 or more, and m is an integer of 1 or more. )). In the above formula, R ¹ is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, saturated aliphatic hydrocarbon group such as dodecyl group,
Vinyl group, allyl group, unsaturated aliphatic hydrocarbon group such as hexenyl group, cyclopentyl group, saturated alicyclic hydrocarbon group such as cyclohexyl group, phenyl group, tolyl group, aromatic hydrocarbon group such as naphthyl group, and And / or the same or different hydrogen atoms bonded to carbon atoms of these groups are exemplified by groups partially substituted by halogen atoms or organic groups including epoxy groups, carboxyl groups, amino groups, methacryl groups and the like. Examples include a substituted or unsubstituted monovalent hydrocarbon group. X is a hydroxyl group or an alkoxy group. As the alkoxy group, a methoxy group, an ethoxy group,
Examples thereof include a propoxy group. Z is-[OSi (R ¹ )
₂ ] The same or different groups represented by _k- X. k, n
Is an integer of 0 or more, and m is an integer of 1 or more. In these preferred ranges, k is an integer of 0 to 1,000, m is an integer of 100 to 10,000, and n is an integer of 0 to 1,000. Examples of such an organopolysiloxane include the following compounds.

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[0006] Such an organopolysiloxane can be synthesized by a conventionally known method. For example,
In the presence of a catalyst such as an alkali metal hydroxide, a cyclic siloxane such as octamethyltetrasiloxane and α, ω-
It can be obtained by re-equilibrating a hydroxyl polysiloxane oligomer or an organoalkoxysilane. Further, the organopolysiloxane of the component (A) of the present invention is prepared by emulsion polymerization as an emulsion, that is, by emulsifying a cyclic siloxane, an organoalkoxysilane or the like in water using an anionic surfactant or a cationic surfactant in advance. After dispersing, if necessary,
It can be easily synthesized by adding a catalyst such as an acid or an alkaline substance to carry out a polymerization reaction. Organoalkoxysilane in emulsion polymerization is represented by the general formula R ¹ _qS
i (OR ³ ) _4-q (wherein R ¹ and R ³ are the same as above, and q is 1 or 2), and specific examples include methyldimethoxysilane, dimethyldiethoxysilane, and methyltrimethoxysilane. , Methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane and the like. (A)
The component organopolysiloxane is preferably used in the present invention in the form of an emulsion.

The component (B) has the formula: —R ² SiR ³ _a X _3-a (wherein R ² is a divalent hydrocarbon group, R ³ is an unsubstituted monovalent hydrocarbon group,
X is a hydroxyl group or an alkoxy group, a is an organopolysiloxane having at least two groups represented by 0 or 1) in the molecule, and is a component that functions as a crosslinking agent for the organopolysiloxane of the component (A). The organopolysiloxane of the component (B) is specifically, for example, a compound represented by the following general formula:

Embedded image Is an organopolysiloxane represented by In the above formula,
R ¹ and X are the same as described above. R ² is a divalent hydrocarbon group, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group; — (CH ₂ ) ₂ C ₆ H ₄
Examples thereof include an alkylene arylene group represented by-. R ³ is an unsubstituted monovalent hydrocarbon group. A is R ¹ or a group selected from the group represented by the formula: R ² SiR ³ _a X _3-a . a is 0 or 1. x and y are integers of 0 or more, and when y is 0 or 1, A is represented by the formula:
It is a group represented by R ² SiR ³ _a X _3-a .

An example of such an organopolysiloxane is an organopolysiloxane represented by the following formula.

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[0009] Such an organopolysiloxane can be synthesized by a known method. For example, the formula: (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _x [CH ₃ HSiO]
_y Si (CH ₃ ) ₃ (where x and y are integers), an organopolysiloxane having a silicon-bonded hydrogen atom in a side chain and vinyltrimethoxysilane in an amount of 10 to 20 ppm. By reacting in the presence of a platinum-based catalyst, an organopolysiloxane represented by the following formula can be obtained.

Embedded image The organopolysiloxane (B) is preferably used in the form of an aqueous emulsion.

The finely powdered silica as the component (C) is a component for improving the strength of a cured film formed after removing water. As such silica, colloidal silica is generally used, and resinous silica obtained by hydrolyzing and condensing alkoxysilane can also be used. This component is also preferably used in a form dispersed in water using a surfactant. Further, after mixing in advance with the organopolysiloxane of the component (A) or the component (B), the mixture may be dispersed in water using a surfactant. The amount of the component (C) is not particularly limited, but is preferably 0.5 to 100 parts by weight based on 100 parts by weight of the component (A). A more preferred range is 1 to 50 parts by weight.

The catalyst for accelerating the curing of the component (D) is blended to crosslink the treating agent component used in the present invention. Specifically, for example, dibutyltin dilaurate,
Organic acid metal salts such as dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, tin octylate, zinc stearate, zinc octylate, iron octylate, and amine compounds such as n-hexylamine and guanidine. Can be. It is desirable that these curing promoting catalysts be emulsified or dispersed in water in advance using a surfactant, except when they are water-soluble. The amount of the component (D) is not particularly limited, but is preferably 0.01 to 10 parts by weight per 100 parts by weight of the component (A).
It is preferably in parts by weight. A more preferred range is
0.1 to 5 parts by weight. As a surfactant used to form each of the above components in the form of an emulsion or dispersion,
Although not particularly limited, for example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, and sorbitan fatty acids Examples thereof include nonionic surfactants such as esters, cationic surfactants such as quaternary ammonium salts and alkylamine acetates, and amphoteric surfactants such as alkyl betaines and alkyl imidazolines.

The aqueous silicone emulsion composition of the present invention comprises the above components (A) to (D). In addition to these components, a thickener, an antifoaming agent, a penetrant, an antistatic agent Addition of inorganic powders, preservatives, silane coupling agents, etc. may be added as long as the object of the present invention is not impaired.

Since the composition of the present invention as described above forms a rubber film by removing moisture, it is used for applications requiring such properties. In particular, it is suitable as a fiber treatment agent. Here, when used as a fiber treatment agent, the material to which the composition of the present invention can be applied, and the fiber material include natural fibers such as wool, silk, hemp, angora, mohair, and asbestos; rayon, Bemberg, and the like. Regenerated fiber; semi-synthetic fiber such as acetate; synthetic fiber such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, and spandex; inorganic fiber such as glass fiber, carbon fiber, and silicon carbide fiber. Is exemplified. Examples of the form include a knitted fabric, a woven fabric, a nonwoven fabric, and paper.

[0014]

Next, the present invention will be described with reference to examples. In the examples, the characteristics of the cured film were examined by the following methods. ○ Characteristics of cured film Put the aqueous silicone emulsion composition in an aluminum dish,
The film was allowed to stand at room temperature for 24 hours to evaporate water, and the surface state, film strength and elasticity of the film obtained were examined. The silicone aqueous emulsion composition was placed in an aluminum dish,
The coated film was allowed to stand for 10 minutes in a hot-air circulating oven at a temperature of 10 ° C., and the surface state, film strength and elasticity of the cured film obtained by evaporating water were examined.

[0015]

REFERENCE EXAMPLE 1 Preparation of Component (A) 40 parts by weight of octamethyltecyclotetrasiloxane and γ-glycidide prepared by uniformly dissolving 3 parts by weight of dodecylbenzenesulfonic acid in 55 parts by weight of water and separately prepared A mixture with 2 parts by weight of xypropyltrimethoxysilane was added with stirring. This was passed twice at 450 kg / cm ² using a homogenizer emulsifier to obtain an emulsion. This was heated at 80 ° C. for 2 hours, kept at 10 ° C. for 24 hours, and then neutralized with an aqueous sodium carbonate solution to obtain Emulsion A.

[0016]

Reference Example 2 Preparation of Component (B) Average molecular formula:

Embedded image Is reacted with 85 parts by weight of an organopolysiloxane containing a silicon-bonded hydrogen atom represented by the following formula and 15 parts by weight of vinyltrimethoxysilane in the presence of chloroplatinic acid.

Embedded image An organopolysiloxane represented by the following formula was obtained. After 40 parts by weight of this organopolysiloxane and 4 parts by weight of polyoxyethylene dodecyl ether (EO 6 mol adduct) were mixed, 4 parts by weight of water was added and uniformly mixed. Next, the mixture was treated with a colloid mill, and 52 parts by weight of water was further added and uniformly mixed to obtain an emulsion B.

[0017]

[Reference Example 3] Preparation of component (D) 30 parts by weight of dioctyltin dilaurate and polyoxyethylene nonylphenyl ether (EO 10 mol adduct) 5
After uniformly mixing the parts by weight with a homomixer, 65 parts by weight of water was gradually added and emulsified and dispersed in water. Next, this was passed twice at 300 kg / cm ² using a homogenizer emulsifier to obtain an emulsion D.

[0018]

[Reference Example 4] Preparation of emulsion for comparative example Average molecular formula:

Embedded image Was mixed with 5 parts by weight of polyoxyethylene dodecyl ether (EO 6 mol adduct), and 5 parts by weight of water was added and mixed uniformly. Next, the mixture was treated with a colloid mill, and 50 parts by weight of water was added and mixed uniformly to obtain an emulsion.

[0019]

Example 1 Emulsion A60 obtained in Reference Example 1
After uniformly mixing the parts by weight of the emulsion B obtained in Reference Example 2 with 10 parts by weight of colloidal silica (Nissan Chemical Co., Ltd .: Snowtex 30; active ingredient 30% by weight) as the component (C) under stirring. Then, 1 part by weight of the emulsion D obtained in Reference Example 3 was added and uniformly mixed to prepare a silicone aqueous emulsion composition. The properties of the cured films of these silicone aqueous emulsion compositions were examined, and the results are shown in Table 1. For comparison, a silicone aqueous emulsion composition was prepared in the same manner as above except that the emulsion B was not used (Comparative Example 1). A silicone aqueous emulsion composition was prepared in the same manner as described above except that colloidal silica was not blended (Comparative Example 2). Emulsion D
A silicone aqueous emulsion composition was prepared in the same manner as described above, except that was not blended (Comparative Example 3). The properties of these compositions were measured in the same manner as described above, and are shown in Table 1.

[0020]

[Table 1]

[0021]

Example 2 The silicone aqueous emulsion composition prepared in Example 1 was placed in a polyethylene container, allowed to stand at room temperature for one month in a state where the lid was closed and sealed. One month later,
The silicone aqueous emulsion composition was taken out and its properties were examined. The properties were the same as those of the silicone emulsion composition immediately after production, and no change was observed.
Was found to be stable. No change was observed in the container.

[0022]

COMPARATIVE EXAMPLE 4 The silicone aqueous emulsion composition for comparative example obtained in Reference Example 4 was put in a polyethylene container, allowed to stand for one month at room temperature in a closed state with a lid closed. 1
A month later, when trying to remove the silicone aqueous emulsion composition, the polyethylene container was swollen,
At the same time as opening the lid, there was a loud popping sound. Generation of hydrogen gas was observed.

[0023]

The aqueous silicone emulsion composition of the present invention comprises the components (A) to (D), and particularly contains two kinds of organopolysiloxanes of the component (A).
It has the characteristic that a high-strength rubber film is formed by removing water.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Isao Ona 2-2 Chikusa Beach, Ichihara-shi, Chiba Dow Corning Silicone Co., Ltd.

Claims (2)

[Claims] (A) A general formula: (Wherein, R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group, X is a hydroxyl group or an alkoxy group, and Z is a group represented by the formula:
-[OSi (R ¹ ) ₂ ] _k -X are the same or different groups. k and n are integers of 0 or more, and m is an integer of 1 or more. An organopolysiloxane represented by the formula (B):
R ² SiR ³ _a X _3-a (wherein, R ² is a divalent hydrocarbon group, R ³ is an unsubstituted monovalent hydrocarbon group, X is a hydroxyl group or an alkoxy group, and a is 0 or 1). (C) an organopolysiloxane having at least two groups shown in a molecule thereof,
An aqueous silicone emulsion composition comprising finely divided silica and (D) a curing accelerator as main components and being an aqueous emulsion. 2. The aqueous silicone emulsion composition according to claim 1, which is a fiber treating agent.