JP2003160758A - Film-formable emulsion type silicone composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-formable emulsion type silicone composition having excellent adhesion and hermeticity to various base materials and capable of forming an elastomeric substance excellent in mechanical strength by removing water. <P>SOLUTION: The film-formable emulsion type silicone composition is composed of, respectively by a specified quantity, (A) a colloidal silica-silicone core shell body composed of (a) a core of the colloidal silica of 80-5 wt.% and (b) a shell of polyorganosiloxane of 20-95 wt.% where an end of a molecule is blocked with a hydroxyl group, (B) one or more of silicone containing a specified end hydoxyl group, (C) a specified polyorganohydrogen siloxane, (D) a curing catalyst, (E) an emulsifying agent and (F) water. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is capable of adjusting viscosity corresponding to various coating methods safely to the environment and human body without using harmful organic solvents, and has excellent coatability, and particularly adhesiveness to fibers and airtightness. The present invention relates to a film-forming emulsion type silicone composition capable of forming a rubber-cured film having good properties and reduced surface tackiness, and a fiber having a cured film formed from the film-forming emulsion type silicone composition.

[0002]

2. Description of the Related Art As a film-forming type emulsion type silicone composition, various silicone aqueous emulsion compositions which form an elastomeric substance after removing water have been proposed. For example, in Japanese Examined Patent Publication No. 38-860, there is disclosed, in Japanese Examined Patent Publication No. Sho 57-860, a polydiorganosiloxane having both molecular chain ends blocked with hydroxyl groups, a polyorganohydrogensiloxane, a polyalkyl silicate and a tin salt of a fatty acid. −
57063 discloses a polydiorganosiloxane in which both ends of a molecular chain are blocked with hydroxyl groups, a compound composed of a trifunctional or higher functional silane and a tin salt of a fatty acid.
In JP-A-6-131661, there is disclosed a resin composed of a polydiorganosiloxane, polyorganohydrogensiloxane and a platinum compound, both ends of which are blocked with vinyl groups. A product obtained by emulsion-polymerizing an organosiloxane and a functional group-bonded organoalkoxysilane has been proposed.

However, the elastomeric substance formed from these emulsion compositions is excellent in heat resistance, water repellency, weather resistance, transparency, etc., but is inferior in mechanical strength, for example, as a coating agent. It was unsuitable for use. Therefore, in order to improve the mechanical strength, some means for adding colloidal silica as a reinforcing material have been proposed. As for the addition method using a hydrosilylation reaction, firstly, Japanese Patent Laid-Open No. 54216/1979
Japanese Patent Laid-Open Publication No. 0-58242 describes adding colloidal silica to an emulsion composed of a polydiorganosiloxane containing a vinyl group at the terminal or side chain of the molecular chain, a polyorganohydrogensiloxane and a platinum compound (catalyst). ing. Further, in JP-A-56-36546, an emulsion composed of polydiorganosiloxane, polyorganohydrogensiloxane with a vinyl group blocked at both ends of a molecular chain, and a platinum compound (catalyst) is heated to form a crosslinked structure. Later, a method of adding colloidal silica is disclosed. However, the elastomeric substance formed by removing water from these emulsion compositions has insufficient bonding between the colloidal silica and the polyorganosiloxane, that is, the interfacial adhesion is poor, and the uniform dispersibility of the colloidal silica is also poor. Therefore, it is not possible to sufficiently impart the reinforcing property of silica to silicone.

On the other hand, although the crosslinking method is different from the above case,
In order to improve the above-mentioned problems, JP-A-61-162929 and JP-A-61-271352 disclose in the presence of acidic colloidal silica, a diorganosiloxane having a low degree of polymerization and blocked at both terminal hydroxyl groups, and a trifunctional compound. Disclosed is a method for producing an emulsion, in which emulsion polymerization is performed with an alkoxysilane having a property or higher. However, in the initial homogenization, it is difficult to include the raw material siloxane and colloidal silica in the same micelle, and as a result, in addition to the condensation of siloxane and silica in the micelle, siloxane and silica that are not involved in this condensation are It becomes a coexisting emulsion and does not improve the mechanical strength.

Further, in Japanese Patent Laid-Open No. 10-14860, a film-forming emulsion type silicone composition containing a colloidal silica-core shell as a main component is obtained, but although this method certainly improves mechanical strength to some extent, Not enough yet.

[0006]

Therefore, the present invention uses a colloidal silica-silicone core shell body and a cross-linking type silicone emulsion, which has excellent adhesiveness and airtightness to various substrates, especially fibers. By using an emulsion-type silicone composition capable of forming an elastomeric substance having excellent mechanical properties by removing water, a film-forming emulsion-type silicone composition for fibers that does not use harmful organic solvents and a cured film thereof The purpose of the present invention is to provide a fiber formed with.

[0007]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that an emulsion containing a specific colloidal silica-silicone core-shell body dispersed therein, an epoxy silicone emulsion containing a terminal hydroxyl group, and a terminal hydroxyl group. Excellent adhesiveness and airtightness to various fibers by using as the main component a film-forming emulsion composed of an amino silicone emulsion containing dimethyl silicone emulsion containing at least one terminal hydroxyl group And mechanical properties, and can be adjusted to a viscosity suitable for knife, roll gravure coating, etc. without using harmful organic solvents, and by forming a surface condition along the irregularities of the base fabric, the rubber surface The feeling of tackiness was reduced and the rubber surfaces contacted each other. It found that there are various advantages such that does not cause blocking, leading to the completion of the present invention.

That is, the present invention relates to (A) (a) core 80 to 5% by weight of colloidal silica (b) average composition formula R ¹ _a SiO _{(4-a) 2} (I) (wherein R ¹ Is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is a number of 1.80 to 2.20). From 20 to 95% by weight of a shell of polyorganosiloxane whose molecular end is blocked with a hydroxyl group. Colloidal silica-silicone core shell body
1 to 50 parts by weight, (B) the general formula Z _b R ² _c SiO _{[4- (b + c)] / 2} (II) (wherein Z is an epoxy group-containing organic group, N- (β-amino) Ethyl) -γ-aminopropyl group or γ-aminopropyl group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, b represents an integer of 0 to 2, and c is 0 to represents an integer 2, b + c is 1 or more terminal hydroxyl groups-containing silicone represented by a 1 to 3) of integers, 1 to 90 parts by weight, (C) the general formula _{^{R 3 d H e SiO [4-}} ( _{d + e)] / 2} (III) (In the formula, R ³ may be the same as or different from each other, and a substituted or unsubstituted monovalent hydrocarbon group having no ethylenically unsaturated bond, d is A polyorganohydrogensiloxane having at least two units represented by the formula (e) is an integer of 0 to 2, e is an integer of 1 or 2, and d + e is an integer of 1 to 3) (A) + For 100 parts by weight of component (B) And the unit represented by the general formula (III) is 0.001 to 100.
1 x 1 to 100 parts by weight of (D) curing catalyst and (A) + (B) components so that the amount is parts by weight.
0 ^{-6 to} 5 parts by weight, 1 to 20 parts by weight with respect to 100 parts by weight of the (E) emulsifier and (A) + (B) components
Parts by weight, (F) water, and 30 to 1000 parts by weight per 100 parts by weight of the components (A) + (B), a film-forming emulsion type silicone composition, and the above emulsion type silicone composition. It is a fiber on which a cured film of a material is formed.

Here, the colloidal silica-silicone core-shell body is mainly composed of colloidal silica as a core and at least part of which is coated with silicone.
Some of the separated silicone particles may be included.

The emulsion type silicone composition according to the present invention can be manufactured as follows. That is, (A) (a) colloidal silica and (b-1) general formula R ⁴ _n SiO _{(4-n) / 2} (IV) (wherein, R ⁴ is a substituted or non-substituted one having 1 to 18 carbon atoms). Substituted monovalent hydrocarbon group, n represents a structural unit represented by 0), and has 2 hydroxyl-free silicon atoms.
~ 10 polyorganosiloxane, and optionally (b-2) a silane compound having 1 to 4 alkoxy groups,
An aqueous medium, polycondensation in the presence of an emulsifier, to prepare a colloidal silica-silicone core-shell aqueous emulsion, further (B) siloxane of the general formula (II) by emulsion polymerization in the presence of an emulsifier, or At least one terminal hydroxyl group-containing silicone emulsion obtained by mechanical emulsification, and (C)
An emulsion prepared by mechanically emulsifying the polyorganohydrogensiloxane containing the general formula (III) in the presence of an emulsifier is prepared separately, and then mixed, and then the curing catalyst of the component (D) is added. , Obtained by mixing.

The silicone aqueous emulsion composition according to the present invention is mainly composed of a core-shell body in which a core of colloidal silica is covered with a silicone shell through a siloxane bond, and a combination of a hydroxyl group-containing silicone and a terminal hydroxyl group-containing silicone. Therefore, it becomes possible to bring out the reinforcing property of the colloidal silica sufficiently and effectively. By evaporating volatile substances such as water at room temperature or by heating it, the cured elastomer finally obtained is mechanical. Exhibits excellent performance in strength. Furthermore, the adhesiveness with the fiber is remarkably excellent due to the functional group in the main component.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, the components constituting the silicone aqueous emulsion composition according to the present invention will be described.
(A) component colloidal silica used in the present invention-
The silicone core-shell body is a component that forms an elastomer cured product after water is removed, and one colloidal silica particle as the component (a) is covered with the polyorganosiloxane as the component (b). This core-shell product is a simpler type and more specifically, 1) polyorganosiloxane has both ends bound to the silica surface through siloxane bonds, and 2) one end of the polyorganosiloxane has a silica surface. It is bonded in the form of a siloxane bond and the other end is blocked with a hydroxyl group, and 3) polyorganosiloxane has both ends blocked with a hydroxyl group and does not have a siloxane bond with the silica surface. It was done. The combined use of trifunctional and trifunctional alkoxysilanes and chain stoppers increases the types of these forms and makes them complicated.

The polyorganosiloxane shell part of the component (b) in the colloidal silica-silicone core shell body of the component (A) is selected in the range of 20 to 95% by weight. If it is less than 20% by weight, the elastic modulus and the like are significantly reduced, and a cured product lacking elastomeric properties can be obtained. On the other hand, if it exceeds 95% by weight, the reinforcing property of colloidal silica cannot be sufficiently imparted to the polyorganosiloxane, resulting in an elastomer cured product lacking mechanical properties. Further, the organic group bonded to the silicon atom of the polyorganosiloxane shell which is the component (b) in the core-shell body of the component (A) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. is there. As the unsubstituted organic group, a linear or branched alkyl group such as methyl group, ethyl group, propyl group, hexyl group, octyl group, decyl group, hexadecyl group, octadecyl group, phenyl group, naphthyl group, xenyl group, etc. Examples thereof include an aralkyl group such as an aryl group, a benzyl group, a β-phenylethyl group, a methylbenzyl group and a naphthylmethyl group, and a cycloalkyl group such as a cyclohexyl group and a cyclobenzyl group. Examples of the substituted organic group include groups obtained by substituting the hydrogen atom of the above-mentioned non-substituted organic group with a halogen atom such as fluorine or chlorine, and as such, 3,3,3
Examples thereof include a trifluoropropyl group and a 3-fluoropropyl group. Another monovalent organic group in the components (A) and (b) includes a carbon functional group, which contains such an organic group.
The emulsion composition using the component (A) is excellent in adhesiveness (adhesion or adhesion) when applied to fibers and is advantageous.

The carbon functional group as used herein means a carbon atom, a hydrogen atom, and at least one of nitrogen and oxygen.
An organic group composed of species atoms, for example,

[0015]

[Chemical 1]

And the like.

The molecular structure of the polyorganosiloxane which is the component (A) (b) is preferably substantially linear, and this meaning is a generic term for linear or slightly branched linear.

The amount of the component (A) compounded is usually in the range of 1 to 50 parts by weight, preferably 10 to 40 parts by weight. This is because if it is less than 1 part by weight or exceeds 50 parts by weight, the reinforcing property of the colloidal silica cannot be sufficiently imparted to the polyorganosiloxane, and the cured product of the elastomer lacks mechanical properties.

The component (B) used in the present invention is one or more of the terminal hydroxyl group-containing silicones represented by the following general formula (II). Like the component (A), after the water is removed, the elastomer is cured. It is a component that forms a substance, and is a component that further imparts rubber elasticity of the elastomer.

The general formula Z _b R ² _c SiO _{[4- (b + c)] / 2} (II) (In the formula, Z, b and c are as described above) 1 to 90 parts by weight, preferably 30
Within the range of up to 80 parts by weight. If it is less than 1 part by weight, the elastic modulus and the like are greatly reduced and a cured product lacking elastomeric properties is obtained. On the other hand, if it exceeds 90 parts by weight
The reinforcing property of the colloidal silica-silicone core shell body of the component (A) cannot be sufficiently imparted to the polyorganosiloxane, resulting in an elastomer cured product lacking mechanical properties.

The component (C) used in the present invention have the general formula ^{_{R 3 d H e SiO [4-}} (d + e)] / 2 ... (III) ( wherein, R ^3, d and e are described above As described above), a polyorganohydrogensiloxane having at least two units represented by the formula (1), in which a hydrogen atom bonded to a silicon atom is bonded to a silicon atom at a molecular end in the components (A) and (B). It has a function of contributing as a cross-linking agent for performing a dehydrogenation reaction with the hydroxyl group.

If the component (C) has two or more hydrogen atoms directly bonded to a silicon atom in one molecule,
The molecular structure is not particularly limited, and those having a linear, cyclic, or branched siloxane skeleton can be used, but due to the ease of synthesis, the linear one or R ³ ₂ HSiO _1/2 A polyorganohydrogensiloxane composed of units and SiO ₂ units is preferred. R ^{3 s} may be the same or different from each other and are a substituted or unsubstituted monovalent hydrocarbon group having no ethylenically unsaturated bond, and examples of such a group include methyl, ethyl, propyl and butyl. Alkyl groups such as hexyl, octyl, decyl, dodecyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; and substituted such as chloromethyl, 3,3,3-trifluoropropyl, chlorophenyl A monovalent hydrocarbon group can be mentioned, and a methyl group is preferable from the viewpoint of ease of synthesis.

[0023] In (C) in component (III) siloxane units other than the unit represented by the formula, the organic groups bonded to silicon atoms may be the same or different from each other, those similar to R ³ For example, a methyl group is preferable from the viewpoint of ease of synthesis. The blending amount of the component (B) is 0.001 to 100 parts by weight in terms of the unit represented by the general formula (III) with respect to 100 parts by weight of the components (A) + (B), The amount is preferably 0.1 to 10 parts by weight. General formula (II
If the unit represented by I) is less than 0.001 part by weight, the number of crosslinks is small and the mechanical strength of the cured film decreases, and if it exceeds 100 parts by weight, changes in physical properties (particularly heat resistance) after curing increase. Is.

The component (D) curing catalyst is for dehydrogenating the silicon atom-bonded hydrogen atoms of the component (C) and the silicon atom-bonded hydroxyl groups at the molecular ends of the components (A) and (B). There are metal organic acid salts such as alkyltin organic acid salts and zinc organic acid salts, cobalt, rhodium, nickel, palladium and platinum compounds, organic metal alcoholates such as tetrabutoxytitanium, amines such as n-butylamine and imidazole. Is exemplified. In the present invention, alkyltin organic acid salts, zinc organic acid salts and organic titanium alcoholates are preferable, and dialkyltin dicarboxylates such as dibutyltin dilaurate and dioctyltin dilaurate are particularly suitable.

The compounding amount of the curing catalyst as the component (D) is (A) +
It is usually 1 × 10 ^{−6 to} 5 parts by weight with respect to 100 parts by weight of the component (B). If the blending amount is less than 1 × 10 ^-6 parts by weight, the curing rate is slow and the strength of the cured product is low. On the other hand, if the amount exceeds 5 parts by weight, the composition tends to increase in viscosity or gel in a short time and the workability of coating on the fiber is deteriorated.

The emulsifier of the component (E) plays a role of allowing the colloidal silica-silicone core shell of the component (A) and the hydroxyl group-containing silicone of the component (B) to exist stably in water, and forms the core shell of the component (A). The polycondensation catalyst plays a role as a polycondensation catalyst and a polycondensation catalyst of the component (B), and is an anionic emulsifier or a cationic emulsifier.

As the anionic emulsifier, an aliphatic substituted benzenesulfonic acid, an aliphatic substituted naphthalenesulfonic acid, an aliphatic sulfonic acid, a silylalkylsulfonic acid whose aliphatic substituent has a carbon chain of 6 to 18 carbon atoms. , Aliphatic substituted diphenyl ether sulfonic acid, alkyl sulfuric acid, alkyl ether sulfuric acid and the like, among which aliphatic substituted benzene sulfonic acid is more preferable. However,
These sulfonic acids are used in the preparation of the colloidal silica-silicone core-shell emulsion, but they are neutralized with an alkali later, so that they are present in the form of sulfonate in the composition of the present invention. Examples of the cationic emulsifier include alkyl trimethyl ammonium salts such as octadecyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride, and dialkyl dimethyl ammonium salts such as dioctadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride and didodecyl dimethyl ammonium chloride. Examples include salts, for example, quaternary ammonium salt type emulsifiers such as benzalkonium chloride such as octadecyldimethylbenzylammonium chloride and hexadecyldimethylbenzylammonium chloride.

The mixing ratio of the (E) component emulsifier is
It is usually 1 to 20 parts by weight with respect to 100 parts by weight of the components (A) + (B). If the amount is less than 1 part by weight, it is difficult to form stable micelles. If the amount exceeds 20 parts by weight, the emulsion viscosity increases and an unstable emulsion is formed, and the curing system is impaired. When emulsifying the polyorganohydrogensiloxane of component (B) and component (C) when emulsion polymerization is not used, a nonionic emulsifier may be used in combination as component (E), and only component (C) is emulsified. It is preferable to use a nonionic emulsifier. Examples of the nonionic emulsifier include glycerin fatty acid ester, sorbitan fatty acid ester,
Examples thereof include polyoxyethylene (hereinafter abbreviated as POE) alkyl ether, POE sorbitan fatty acid ester, POE glycerin fatty acid ester, POE alkylphenol ether, POE polyoxypropylene block copolymer, and the like.

The amount of water as the component (F) is (A) + (B)
It is usually in the range of 30 to 1000 parts by weight with respect to 100 parts by weight of the component. If the amount of component (F) is less than 30 parts by weight or more than 1000 parts by weight, the emulsified state is poor and the emulsion becomes unstable.

Next, the method for producing the silicone aqueous emulsion composition according to the present invention will be described. The silicone water-based emulsion of the present invention, as described above, (A) (a) component colloidal silica and (A) (b-1) component organosiloxane, if necessary, further (A) (b-2) component To produce a colloidal silica-silicone core-shell emulsion by polycondensing an alkoxysilane of 1. in an aqueous medium in the presence of an effective amount of an emulsifier or a mixture of emulsifiers, and then a hydroxyl group-containing silicone emulsion of component (B) The above was prepared by a conventional method in an aqueous medium, and (A) and
After mixing with (B), an aqueous emulsion prepared by mechanically emulsifying (C) component polyorganohydrogensiloxane in the presence of an effective amount of an emulsifier or an emulsifier mixture by a conventional method, and (D) It is obtained by adding a component curing catalyst and mixing.

The colloidal silica as the component (A) (a) used in the present invention refers to an aqueous dispersion containing SiO ₂ as a basic unit, and in the present invention, it is 4 to 300 nm, particularly Those having an average particle diameter of 30 to 150 nm are preferable. As such colloidal silica, there are those on both the acidic side and the alkaline side, which are appropriately selected and used according to the conditions, for example, when performing emulsion polymerization under acidic conditions using an anionic emulsifier. It is more preferable to use acidic colloidal silica.

The organosiloxane of the component (A) (b-1) used in the present invention has a structural unit represented by the above formula (IV) and has 2 to 10 silicon atoms containing no hydroxyl group. This structure is not particularly limited and may be linear, branched or cyclic, but preferably has a cyclic structure. Here, when the number of silicon atoms exceeds 10, when performing emulsion polymerization,
Since it is difficult to incorporate the colloidal silica particles into the siloxane micelles, some particles cannot participate in the formation of the core-shell body, and as a result, an emulsion in which the free colloidal silica and the polyorganosiloxane micelles coexist in addition to the target core-shell body. Further, a hydroxyl group-containing siloxane is not preferred because it causes a polycondensation reaction at the initial stage of emulsification to form a siloxane having more than 10 silicon atoms, which causes the above problems. Examples of the substituted or unsubstituted monovalent organic group contained in the organosiloxane of the component (A) (b-1) include the same organic groups as those in the polyorganosiloxane shell in the colloidal silica-silicone core shell body. .

As the organosiloxane of the component (A) (b-1), hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5,7-tetramethyl-1, 3,5,7-Tetraphenylcyclotetrasiloxane, 1,3,5,7-tetrabenzyltetramethylcyclotetrasiloxane, 1,3,5
Examples thereof include cyclic compounds such as -tris (3,3,3-trifluoropropyl) trimethylcyclotetrasiloxane and compounds in which these substituents are substituted with the above organic groups.
In addition to the cyclic compounds exemplified above, a linear or branched organosiloxane may be used. However, in the case of linear or branched siloxane, the molecular end has an organic group other than a hydroxyl group, for example, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, 3,3,3 Those blocked with a trifluoropropyldimethylsilyl group or the like are preferable.

Further, the alkoxysilane as the component (A) (b-2), which is used if necessary, serves as one component for forming the shell portion, but the interface between the core of colloidal silica and the shell of the organosiloxane is used. It is also effective as a mediator of binding. Examples of the organic silane compound having 1 to 4 such alkoxy groups include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane and methyltriethoxysilane. Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxy. Silane, dimethyldipropoxysilane, dimethyldibutoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, methylethyldimethoxysilane, methylpropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc. , Fluoroalkylalkoxysilanes and other fluorinated alkoxysilanes.

The organosiloxane as the component (A) (b-1) and the alkoxysilane as the component (A) (b-2) as described above are the colloidal silica-silicone core shell bodies in the composition according to the present invention. The polyorganosiloxane shell in the above is 20 to 95% by weight, and the average composition formula R ¹ _a SiO _{(4-a) 2 of the} formula (I) (wherein, R ¹ is a substituted or unsubstituted C 1-8 group _). Is a monovalent hydrocarbon group, a is a number of 1.80 to 2.20).

When the component (A) (b-2) containing an alkoxy group and a carbon functional group is blended, the adhesiveness (adhesion) of the elastomer cured product formed from the composition of the present invention to the fiber It is advantageous in that it can improve (or sticking). However, the compounding amount thereof may be 0.02 to 10 mol%, more preferably 0.05 to 5 mol% based on the total amount of the organic groups bonded to the silicon atom of the average composition formula (I). desirable.

Organosilicon compounds having both a carbon functional group and an alkoxy group include 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane and N- (2-aminoethyl ) -3-Aminopropylmethyldimethoxysilane, N
-Diethylenetriaminepropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, 3,4
-Epoxycyclohexylethyltrimethoxysilane,
γ-mercaptopropylmethyldimethoxysilane and the like can be mentioned, and these are used alone or as a mixture of two or more kinds.

As described above, the colloidal silica-silicone core shell emulsion of component (A) according to the present invention comprises the colloidal silica of component (A) and (a) and (A) (b-1).
It can be prepared by shear-mixing the component organosiloxane and, if necessary, the component (A) (b-2) alkoxysilane in an aqueous medium in the presence of an emulsifier using a homogenizer and the like to cause polycondensation. This emulsifier is mainly (A) (b-1)
At the same time playing the role of a surfactant for emulsifying the components, (A) (a) component, (A) (b-1) component and (A) (b-2) component of the polycondensation reaction It acts as a catalyst, where an organic sulfonic acid emulsifier is used as the anionic emulsifier.
Further, as the cationic emulsifier, a quaternary ammonium salt type is preferable. However, in the case of the quaternary ammonium salt type, the catalytic action is low depending on the type, so it is desirable to add and use an alkali catalyst such as sodium hydroxide or potassium hydroxide. The amount of this emulsifier used is (A) and (a) components,
The total amount of components (A) (b-1) and (A) (b-2) is usually 1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight. Moreover, you may use together a nonionic emulsifier as needed.

In the preparation of the colloidal silica-silicone core shell body, in order to keep the colloidal silica in a stable state, a combination of acidic colloidal silica-anionic emulsifier and alkaline colloidal silica-cationic emulsifier is selected. . The amount of water used at this time is
Total amount of (A) (a) component and (A) (b-1) and (A) (b-2) components 100
Usually 50 to 1000 parts by weight, preferably 100 to 100 parts by weight.
It is 500 parts by weight, and the condensation temperature is usually 5 to 100 ° C.

When preparing the colloidal silica-silicone core-shell body in the composition according to the present invention, a component serving as a crosslinking agent may be added to improve the strength of the silicone shell portion. Among the above-mentioned silane compounds, trifunctional compounds are exemplified,
Trifunctional cross-links such as trimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane And tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of the crosslinking agent added is usually 10% by weight or less, preferably 5% by weight or less, based on the total amount of the components (A) (b-1) and (A) (b-2).

Since the colloidal silica-silicone core shell emulsion in the composition according to the present invention obtained as described above is acidic or alkaline, it is necessary to neutralize with an alkali or an acid in order to maintain long-term stability. As the alkaline substance, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, etc. are used, and as the acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, etc. are used.

The hydroxyl group-containing siloxanes of the component (B) used in the present invention have two or more structural units represented by the above formula (II) in one molecule, and have a hydroxyl group at the terminal. If so, its molecular structure is not particularly limited, straight-chain,
Either branched form can be used. As a method for producing the same, an ordinary method can be used, and either an emulsion polymerization method in which polymerization is performed in an aqueous medium or a mechanical emulsification method in which a silicone oil is produced and then emulsified may be used. As a more specific component (B), it is desirable to use the terminal hydroxyl group-containing epoxy silicone alone or in combination with the branched terminal hydroxyl group-containing epoxy silicone and the linear terminal dimethyl silicone.

The organohydrogensiloxane of the component (C) used in the present invention has a molecular structure as long as it has two or more structural units represented by the above formula (III) in one molecule. There is no particular limitation, and those having a linear, cyclic, or branched siloxane skeleton can be used, but for the sake of ease of synthesis, a linear one, or R ³ ₂ HSiO _1/2 unit and Si
A branched polyorganohydrogensiloxane composed of O ₂ units is preferred.

The component (C) is sheared and mixed in advance in an aqueous medium in the presence of an emulsifier using a homogenizer or the like by a conventional method to prepare an aqueous emulsion of the component (C).
It is desirable to mix with the emulsion of component (A) and the emulsion of component (B). The emulsifier in this case is mainly (B)
A nonionic emulsifier is preferable because it plays a role of a surfactant for emulsifying the components, and the anionic emulsifier needs to be finally neutralized. Examples of the nonionic emulsifier include those mentioned above, and among them, POE alkylphenol ether is preferable. The amount of the emulsifier used and the amount of water used are within the ranges described above in combination with those used in the components (A) and (B), preferably 100 parts by weight of the component (C). 1 to 10 parts by weight and 100 to 500 parts by weight of water are used, and the emulsification temperature is usually 5 to 100 ° C.

An emulsion of the above component (A) and (B)
The required amount of the component (C) is added to the emulsion mixture as it is, or the emulsion and the curing catalyst of the component (D) are added and mixed by stirring to complete the production of the silicone aqueous emulsion composition of the present invention. To do. As the curing catalyst used in the present invention, dialkyltin dicarboxylate and the like are preferable as described above. Also,
When using these curing catalysts, it is desirable to use an emulsifier and water by an ordinary method in advance to prepare an O / W type or W / O type emulsion. Further, the temperature for adding and stirring and mixing the curing catalyst is preferably in the range of 5 to 25 ° C.

The silicone aqueous emulsion according to the present invention is stable for about two months after its production or preparation, but when it is stored for a long period of time, the curing catalyst is separately stored as a separate component and mixed immediately before use. It is preferable. In addition, there is no problem in using reinforcing fillers, stabilizers, pigments, modifiers, flame retardants, and the like in combination. Furthermore, there is no problem even if a thickener is used to make the viscosity easy to coat or it is diluted with water. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc carbonate and the like. Furthermore, in order to improve the adhesiveness of the emulsion composition according to the present invention to fibers, a known adhesion aid such as an organosilicon compound having a carbon functional group and a hydrolyzable group in one molecule may be used. There is no problem even if it is added to the emulsion composition. As such an organosilicon compound, 3-
Glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3,4-
Epoxycyclohexylethyltrimethoxysilane, 3
-Mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and an organosilicon compound represented by the following structural formula

[0047]

[Chemical 2]

And the like. These organosilicon compounds may be used alone or as a mixture of two or more kinds, and are prepared as they are or as an emulsion separately from the components (A) and (B) with an emulsifier, and are mixed in the emulsion composition of the present invention. do it. Further, the treatment of the substrate of the composition of the present invention, various fibers are applied by a method such as dip coating, spray coating, brush coating, knife coating, roll coating, etc., water is removed by drying, and 10 minutes at room temperature. -Leave it for several hours or heat it slightly depending on the substrate to cure it.

[0049]

According to the film-forming emulsion type silicone composition of the present invention, when various fibers are treated, the viscosity of the coating liquid is lowered as compared with the conventional silicone rubber coating composition. Time workability is improved. Moreover, due to the gradual evaporation of water, even in a complicated shape, a rubber film conforming to the shape of the surface is formed, and blocking does not occur when the rubber surfaces contact each other. Furthermore, it provides a cured film with better mechanical strength than conventional film-forming emulsions. Further, since no harmful organic solvent is used, it is possible to adjust the viscosity to be suitable for various coatings, with excellent safety at the time of work and without impairing the health of the worker.

[0050]

The present invention will be described in detail below with reference to examples and comparative examples. All "parts" in the examples are "parts by weight".
"%" Means "% by weight". Preparation Example 1 Acid colloidal silica Snowtex OL (manufactured by Nissan Chemical Industries, Ltd., average particle size 84 nm, SiO ₂ 20.66%, Na ₂ O 0.019
%, PH 2.78) 1000 parts, distilled water 200 parts, dodecylbenzene sulfonic acid 8.4 parts in a mixed solution, add 50 parts of octamethylcyclotetrasiloxane, and after preliminarily stirring with a homomixer, 300 kgf / cm ² of with a homogenizer. The mixture was emulsified and dispersed by passing it twice under pressure. The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and heated with stirring at 85 ° C. for 5 hours and cooled at 5 ° C. for 48 hours to complete the polymerization. Next, this polyorganosiloxane emulsion was neutralized to pH 7 with an aqueous sodium carbonate solution to terminate the polymerization and obtain an emulsion a. The polymerization rate of octamethylcyclotetrasiloxane in the obtained polyorganosiloxane was 99.6%.

Further, the polyorganosiloxane is
Idal silica-Silicone core shell body
And particle size analysis and electron microscopy based on dynamic light scattering
It was confirmed by observation. That is, the laser particle size analysis system
Grains using a stem (LPA-3000 S / 3100 manufactured by Otsuka Electronics Co., Ltd.)
When the diameter was analyzed, it was found to be around 84 nm of the raw material colloidal silica.
The monodisperse particle size distribution with peaks disappeared completely, 153n
A new monodisperse particle size distribution with a peak near m
It was Furthermore, when observed with an electron microscope,
Only the cone particle image was confirmed, and the raw silica particle image was completely
Not observed. On the other hand, this core shell body
Pour some of the resin into a large amount of acetone to
After being precipitated and separated by filtration, dried in a vacuum dryer at 50 ° C for 12 hours,
A core-shell aggregate was obtained. And this core shell body
Elemental analysis of aggregates, IR and¹H, ²⁹Results of Si-NMR analysis
As a result, the ratio of the silicone shell part was 49.2%. Well
When the core-shell body is regarded as a graft polymer
Grafting rate and grafting efficiency of 40.2%
It was.

Next, octamethyltetrasiloxane 60
Part, 2.0 parts of dodecylbenzenesulfonic acid, and 40 parts of water were added, and the resulting mixture was first emulsified with a homomixer and then second emulsified under a pressure of 400 kgf / cm ² using a high pressure homogenizer.
Polymerization was carried out at 0 ° C. for 3 hours and at room temperature for 3 hours for a total of 6 hours.
It was neutralized with 0.8 part of triethanolamine to obtain an emulsion b containing a terminal hydroxyl group-containing dimethyl silicone having a polymer viscosity of 150,000 cP.

Further, 34 parts of octamethyltetrasiloxane,
60 parts of water was added to 0.5 parts of dodecylbenzene sulfonic acid, which was first emulsified with a homomixer, then second emulsified under a pressure of 400 kgf / cm ² using a high pressure homogenizer, and at 80 ° C for 3 hours at room temperature. Polymerization was carried out for 3 hours for a total of 6 hours. Then, 3.3 parts of γ-glycidoxytrimethoxysilane was added, and the mixture was polymerized at room temperature for 1 hour. Subsequently, it was neutralized with 0.2 part of triethanolamine to give a polymer viscosity of 250,000 cP.
An emulsion c containing the terminal hydroxyl group-containing epoxy silicone was obtained.

Also, polyoxyethylene (18) nonyl phenyl ether (manufactured by Nikko Chemicals Co., NIKKOL NP-18
TX: HLB 19) Linear polymethyl hydrogen siloxane with a degree of polymerization of 50 in a mixture of 2.0 parts and 400 parts of distilled water 200
Parts were added, and after preliminarily stirring with a homomixer, the mixture was emulsified and dispersed by passing through a homogenizer twice at a pressure of 300 kgf / cm2 to obtain an emulsion d.

Next, 30 parts of the emulsion a prepared above (solid content 20%) and emulsion b (solid content 60%) 60
And 100 parts of a mixture of 10 parts of emulsion c (solid content 35%), 0.5 part of emulsion d (33% solid content)
Addition amount of 0.004 parts of the unit represented by the general formula (II) to 100 parts), 50% dibutyltin dilaurate aqueous emulsion (50 parts dibutyltin dilaurate, 5 parts sodium dodecylbenzenesulfonate and 45 parts distilled water) Preparation) 0.8 parts, thickener HPC (hydroxypropyl cellulose grade M, 1.0 part by Nippon Soda Co., Ltd.) at 25 ° C
Was added and mixed and stirred to obtain a silicone aqueous emulsion composition, which was designated as Preparation Liquid 1. Preparation Example 2 To 34 parts of octamethyltetrasiloxane, 3.3 parts of aminoethylaminopropyldimethoxysilane and 2.0 parts of stearyldimethylammonium chloride, 60 parts of water was added, which was first emulsified with a homomixer and then 400 kgf / using a high pressure homogenizer. Secondary emulsification was carried out under a pressure of cm ² , 0.2 part of potassium hydroxide was added, and polymerization was carried out at 80 ° C. for 5 hours. Then, it is neutralized with 0.7 part of acetic acid to obtain a polymer viscosity of 2,000 c.
Emulsion e containing P-containing amino group-containing siloxane
Got A prepared liquid 2 having the composition shown in Table 1 was prepared in the same manner except that this emulsion e was changed to the emulsion c of Preparation Example 1. Preparation Example 3 A preparation liquid 3 having the composition shown in Table 1 was obtained in the same manner except that the emulsions b and c of Example 1 were omitted. Preparation Example 4 30 parts of dimethyl silicone containing hydroxyl groups at both ends having a degree of polymerization of 3500, 0.3 parts of methyl hydrogen silicone having a degree of polymerization of 50, 1 part of dibutyltin laurate, and 70 parts of toluene were mixed and stirred with a disper at room temperature. Then, a preparation liquid 4 (toluene solution a) was obtained. Examples 1-2, Comparative Examples 1-2 Coating compositions obtained in Preparation Examples 1-4 (Preparation liquid 1
~ 4) is cast on a fluorine-coated plate and kept at room temperature 25 ° C for 48 hours.
After leaving for a while, a rubber-like sheet was obtained. The properties of the obtained rubber film (elongation rate, maximum tensile stress) were measured. Further, it was cast on cotton and polyester taffeta, the wettability was observed, and the adhesiveness and mechanical strength after standing for 48 hours at room temperature of 25 ° C. were measured by the following methods. The results are shown in Table 1. -Wetability When coated on cotton and polyester taffeta, the easiness of coating and spreading of the rubber coating composition on the cloth was observed, and the following four grades were evaluated. ◎: Easy to spread and apply smoothly ○: Easy to apply △: Slightly difficult to apply ×: Difficult to apply ・ Adhesiveness and mechanical strength Adhesiveness and mechanical strength (coating) of rubber film coated on cotton and polyester taffeta to cloth Strongly squeeze the cotton and polyester taffeta cloth with your fingers, and if the adhesion is poor or the mechanical strength is poor, peel and fall off from the rubber film on the coated surface) did. ◎: The rubber film does not come off from the coating surface, and exhibits excellent adhesiveness and mechanical strength. △: The rubber film slightly comes off and peels off from the coating surface.

[0056]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J038 DL031 DL041 DL051 DL061                       GA07 GA08 GA09 GA12 GA13                       HA066 HA446 JA26 JA57                       JB01 JB38 JC09 JC13 JC30                       JC38 JC39 KA04 KA09 KA21                       MA08 MA10 NA08 NA24 PC10

Claims (4)

[Claims] 1. A core of colloidal silica (A) (a) 80 to 5% by weight (b) Average composition formula R ¹ _a SiO _{(4-a) 2} (I) (wherein R ¹ is a carbon number 1 To 8 substituted or unsubstituted monovalent hydrocarbon groups, a is a number from 1.80 to 2.20) Colloidal silica comprising 20 to 95% by weight of a shell of polyorganosiloxane having a molecular end blocked with a hydroxyl group. Silicone core shell body,
1 to 50 parts by weight, (B) the general formula Z _b R ² _c SiO _{[4- (b + c)] / 2} (II) (wherein Z is an epoxy group-containing organic group, N- (β-amino) Ethyl) -γ-aminopropyl group or γ-aminopropyl group, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, b represents an integer of 0 to 2, and c is 0 to represents an integer 2, b + c is 1 or more terminal hydroxyl groups-containing silicone represented by a 1 to 3) of integers, 1 to 90 parts by weight, (C) the general formula _{^{R 3 d H e SiO [4-}} ( _{d + e)] / 2} (III) (In the formula, R ³ may be the same as or different from each other, and a substituted or unsubstituted monovalent hydrocarbon group having no ethylenically unsaturated bond, d is A polyorganohydrogensiloxane having at least two units represented by the formula (e) is an integer of 0 to 2, e is an integer of 1 or 2, and d + e is an integer of 1 to 3) (A) + For 100 parts by weight of component (B) And the unit represented by the general formula (III) is 0.001 to 100.
The amount of (D) curing catalyst, (A) + (B) component
1 × 10 ^{−6 to} 5 parts by weight per 100 parts by weight, (E) an emulsifier,
1 to 20 parts by weight per 100 parts by weight of the components (A) + (B) and
A film-forming emulsion type silicone composition comprising (F) water and 30 to 1000 parts by weight per 100 parts by weight of components (A) + (B). 2. The film-forming emulsion type silicone composition according to claim 1, wherein the component (B) is a terminal hydroxyl group-containing epoxy silicone or a combination of a terminal hydroxyl group-containing epoxy silicone and a terminal dimethyl silicone. 3. The film-forming emulsion type silicone composition according to claim 1, which is used in a fiber treatment composition. 4. A fiber on which a cured film of the film-forming emulsion type silicone composition according to claim 1 is formed.