JP3121757B2 - Film-forming emulsion-type silicone composition for airbag and airbag - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base fabric for an air bag, which is capable of safely adjusting the viscosity corresponding to various coating methods to the environment and the human body without using a harmful organic solvent, and having excellent coating properties. A film-forming emulsion-type silicone composition for an airbag capable of forming a rubber cured film having good adhesiveness and airtightness and a reduced tackiness on the surface, and a cured film of the film-forming emulsion-type silicone composition were formed. The present invention relates to an airbag formed by sewing an airbag base fabric.

[0002]

BACKGROUND ART In recent years, a so-called airbag device has been widely used as a safety device provided in front of an automobile seat. This airbag device is configured to include a bag-shaped airbag, a sensor that senses an impact given to an automobile, and an inflator that instantaneously sends gas into the airbag by the sensor to inflate the airbag. ing. The airbag is
Normally, it is folded and stored inside the steering wheel etc., but if the car receives a strong impact due to a collision accident etc., the sensor arranged at the center of the dashboard floor and the front floor detects the impact, In the inflator, a gas generating agent containing sodium azide or the like as a main component is reacted to generate nitrogen gas, and the nitrogen gas is fed into the airbag to instantly inflate the airbag. That is, the airbag device senses an impact at the time of occurrence of a car accident and instantaneously inflates the airbag. With the inflated airbag, the impact to the occupant at the time of occurrence of the car accident is effectively reduced. It has a crucial role in protecting the occupant's body. Generally, an airbag of such an airbag device is provided with chloroprene rubber (Japanese Patent Application Laid-Open No. 49-55028) on one side (the inner side of the airbag) of a woven fabric made of a synthetic resin such as a nylon resin. )
The cloth material on which a silicone rubber coating (Japanese Patent Application Laid-Open No. 2-270654) is formed is cut into a predetermined shape, and a plurality of the obtained base fabrics are sewn in a bag shape. In addition, the coating formed on the inner surface of the bag imparts airtightness to the woven fabric, and at the moment the airbag is deployed, the nylon woven fabric is directly exposed to a high-temperature gas that is pressed into the airbag at a stretch. This prevents the nylon resin from melting and deteriorating, and has a function of protecting the occupant from high-temperature gas. Therefore, this coating is required to have some heat resistance. On the other hand, airbags usually need to be folded and stored in a handle or the like, and since it is desired to save space in the storage part, the airbag can be folded as compactly as possible. It is desirable that Therefore, initially, chloroprene rubber was mainly used as the coating. However,
Chloroprene rubber has insufficient heat resistance and durability, and has a drawback of shortening the life of the airbag. In addition, in order to avoid the effects of fire and blast generated when a vehicle or the like collides, it is necessary to impart flame retardancy to the airbag. The chloroprene rubber has insufficient flame retardancy, and a silicone flame retardant has been further applied to the surface to be exposed to the blast. In contrast, in the case of an airbag coated with silicone rubber, it is possible to impart a flame retardancy to the coating film itself by applying a known flame retardant to the silicone, thereby eliminating the need to coat the flame retardant. . For this reason, silicone rubber coating agents which are more excellent in heat resistance and weather resistance than chloroprene rubber have been attracting attention.

An airbag coated with silicone rubber is usually stored in a handle or the like, and is inflated by a blast when colliding. At this time, the coating film also elongates instantaneously following the elongation of the base fabric, so that the silicone rubber coating film also requires mechanical strength and elongation. For this purpose, a base polymer having a large degree of polymerization and a high viscosity is used, and a reinforcing agent, a flame retardant, an adhesion aid, and the like are further compounded. However, these silicone compositions are generally high viscosity, it is difficult to apply the required amount 30 to 100 g / m ² by knife coating or the like, a knife diluted with an organic solvent in this order such as toluene or xylene A process is adopted in which the viscosity is adjusted so as to be easily coated with a coating or the like, and after application, the solvent is cured while evaporating the solvent with a dryer. Therefore, when the rubber airbag, generally knives used for rubber coated roll, with a coating of gravure, it is difficult to apply normally 30 to 100 g / m ² coating amount is required, It is common practice to dilute these rubbers with an organic solvent, adjust the viscosity to an appropriate value, and use the resulting rubber. However, these organic solvents may not only ignite due to static electricity, but also harm the health of workers due to suction and skin contact, or require a large cost for recovery after the solvent is volatilized. Further, if not collected, there is a problem that it leads to air pollution and the like, and in recent years, the regulation of organic solvents is being enforced in all fields.
In addition, in order to make the coating composition easy to coat with knife coating or the like without using an organic solvent, there is a method of lowering the degree of polymerization of the base polymer of the coating composition and lowering the viscosity. Also, the mechanical strength of the cured film formed on the base fabric is not sufficient, and a high temperature blast when the airbag is opened may cause cracks in the coating surface, causing air to leak and the bag not to expand sufficiently. Further, the conventional rubber coating composition has a problem that the cured film surface has high tackiness and the coating surfaces are easily blocked.

On the other hand, as for 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, Japanese Patent Publication No. Sho 38-860 discloses a structure composed of polydiorganosiloxane, polyorganohydrogensiloxane, polyalkyl silicate and a tin salt of a fatty acid in which both molecular terminals are blocked with hydroxyl groups.
Japanese Patent Publication No. 57063/1982 discloses a polydiorganosiloxane in which both ends of a molecular chain are blocked with a hydroxyl group, which is composed of a tri- or higher functional silane and a tin salt of a fatty acid.
Japanese Patent Publication No. 226 discloses a composition composed of polydiorganosiloxane, polyorganohydrogensiloxane and a platinum compound in which both molecular chain terminals are blocked with a vinyl group.
JP-A-54-131661 proposes a product obtained by emulsion polymerization of a cyclic organosiloxane and a functional group-bonded organoalkoxysilane. However, elastomeric substances formed from these emulsion compositions are excellent in heat resistance, water repellency, weather resistance, transparency, etc., but are inferior in mechanical strength, and for example, are not suitable for use as a coating agent. It was inappropriate. Therefore, in order to improve the mechanical strength, some means for adding colloidal silica as a reinforcing material have been proposed. Japanese Patent Application Laid-Open No. 54-52160 discloses a polydiorganosiloxane, a polyorganohydrogensiloxane containing a vinyl group at the molecular chain terminal or on the side chain. It is described that colloidal silica is added to an emulsion composed of a platinum compound (catalyst). JP-A-56-36546 discloses that an emulsion composed of a polydiorganosiloxane, a polyorganohydrogensiloxane and a platinum compound (catalyst) each having a vinyl group at both ends of a molecular chain is heated to form a crosslinked structure. Later, a method of adding colloidal silica is disclosed. However, elastomeric substances formed by removing water from these emulsion compositions are not sufficiently bonded to colloidal silica and polyorganosiloxane, that is, have poor interfacial adhesion and poor uniform dispersibility of colloidal silica. Therefore, it is not possible to sufficiently impart the reinforcing property of silica to silicone.

On the other hand, the crosslinking method is different from the above case,
In order to solve the above-mentioned problems, JP-A-61-16929 and JP-A-61-271352 disclose a diorganosiloxane having a low degree of polymerization and having both hydroxyl groups blocked at both ends in the presence of acidic colloidal silica. There is disclosed a method for producing an emulsion in which emulsion polymerization is performed with an alkoxysilane having a property higher than that of the emulsion. However, it is difficult to include the raw material siloxane and colloidal silica in the same micelle in the initial homogenization. As a result, in addition to the condensation of siloxane and silica in the micelle, siloxane and silica not involved in this condensation It becomes a coexisting emulsion and does not lead to improvement in mechanical strength.

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention has excellent adhesiveness, airtightness, etc. to an airbag base fabric, and further comprises a colloidal silica-silicone core-shell body as a main component and mechanical properties by removing water. Provided is a film-forming emulsion-type silicone composition for an airbag which does not use a harmful organic solvent by using an emulsion-type silicone composition capable of forming an elastomeric material excellent in quality, and an airbag formed with a cured film thereof. With the goal.

[0007]

The present inventors have conducted intensive studies to achieve the above object, and as a result, by using a film-forming emulsion containing a specific colloidal silica-silicone core-shell body as a main component, various airbag base fabrics have been developed. Shows excellent adhesiveness, airtightness and mechanical properties, and can be adjusted to a viscosity suitable for knife, roll gravure coating, etc. without using harmful organic solvents. By forming a roughened surface state, there are various advantages such as reducing tackiness on the rubber surface, improving workability when sewing as an airbag, or preventing blocking when rubber surfaces come into contact with each other. Heading that
The present invention has been completed. That is, the present invention, (A) (a) colloidal core 80 to 5% by weight of silica (b) the average compositional formula ^{_{R 1 a SiO (4-a}} ) / 2 ... (I) ( wherein, R ¹ is carbon A substituted or unsubstituted monovalent hydrocarbon group of the formulas 1 to 8, a is a number of 1.80 to 2.20, and 0.01 to 25 mol% of R ¹ is a group containing an ethylenically unsaturated group) 100 parts by weight of a colloidal silica-silicone core shell composed of 20 to 95% by weight of a shell of polyorganosiloxane, (B) 0.1 to 5 parts by weight of an organic peroxide, (C) 1 to 20 parts by weight of an emulsifier, and (D) water 50 to 1000 parts by weight of a film-forming emulsion-type silicone composition for an airbag, and an airbag obtained by sewing an airbag base fabric having a cured film of the emulsion-type silicone composition formed thereon. . Here, the colloidal silica-silicone core-shell body has, as a main component, a structure in which colloidal silica is used as a core and at least a part of the core is coated with silicone, and a small amount of separated silicone particles may be included. Thus, the emulsion type silicone composition according to the present invention can be manufactured as follows. That is, (A) (a) colloidal silica and (b-1) a general formula R ² _n SiO _{(4-n) / 2} ... (II) (wherein R ² is a carbon atom containing no ethylenically unsaturated group) Number 1
8 is a substituted or unsubstituted monovalent organic group, and n is an integer of 0 to 3. A) an organosiloxane having 2 to 10 silicon atoms, having a structural unit represented by formula (1) and containing no hydroxyl group;
(b-2) General formula R ³ _l R ⁴ _m SiO _{(4-lm) / 2} ... (III) (wherein, R ³ has 1 to 1 carbon atoms not containing an ethylenically unsaturated group)
8, a substituted or unsubstituted monovalent organic group, R ⁴ is a group containing an ethylenically unsaturated group, l is 0 to 2, m is 1 to 3, l + m =
Shows an integer of 1 to 3. A) an organosiloxane having an ethylenically unsaturated group having 2 to 10 silicon atoms having no structural group and having no hydroxyl group, or (a) and (b-2) in an aqueous medium. An aqueous emulsion of a colloidal silica-silicone core-shell body is prepared by polycondensation in the presence of an emulsifier, and then obtained by adding an organic peroxide (B). Since the silicone aqueous emulsion composition according to the present invention is mainly composed of a core-shell body in which a silicone shell covers a colloidal silica core via a siloxane bond, the reinforcing property of the colloidal silica is sufficiently and effectively brought out. It is possible to evaporate volatile substances such as water at room temperature or by heating the same to obtain an elastomer cured product having excellent mechanical strength.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the components constituting the aqueous silicone emulsion composition according to the present invention will be described.
Colloidal silica of component (A) used in the present invention
The silicone core-shell body is a component that forms a cured elastomer after water is removed. One of the colloidal silica particles of the component (a) is covered with the polyorganosiloxane of the component (b). More specifically, the core-shell body is composed of 1) a polyorganosiloxane in which both ends are bonded to a silica surface via a siloxane bond, and 2) one end of the polyorganosiloxane is a silica surface. And a siloxane bond, and the other end is blocked with a hydroxyl group. 3) Polyorganosiloxane is blocked with a hydroxyl group at both ends and does not have a siloxane bond with the silica surface. It was done. The combination of trifunctional and tetrafunctional alkoxysilanes and chain stoppers increases the types of these forms and makes them complex. The polyorganosiloxane shell part of the component (b) in the colloidal silica-silicone core shell of the component (A) is selected in the range of 20 to 95% by weight. If it is less than 20% by weight, the elasticity and the like are greatly reduced, and a cured product lacking elastomeric properties is obtained. On the other hand, 95
If the amount is more than 10% by weight, the reinforcing property of colloidal silica cannot be sufficiently imparted to the polyorganosiloxane, resulting in a cured elastomer having poor mechanical properties. The organic group bonded to the silicon atom of the polyorganosiloxane shell as 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. , Of which 0.01 to 25 mol% is a group containing an ethylenically unsaturated group. Examples of the unsubstituted hydrocarbon group containing no ethylenically unsaturated group include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a hexadecyl group, a straight-chain or branched alkyl group such as an octadecyl group, Examples include an aryl group such as a phenyl group, a naphthyl group, and a xenyl group, an aralkyl group such as 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 cyclopentyl group. Examples of the substituted hydrocarbon group containing no ethylenically unsaturated group include a group in which the hydrogen atom of the unsubstituted organic group exemplified above is substituted with a halogen atom such as fluorine or chlorine. , 3,3,3-trifluoropropyl group, 3-fluoropropyl group and the like. Further, the group containing an ethylenically unsaturated group is a group that remains without participating in a radical reaction, but as an ethylenically unsaturated group, a group represented by the general formula

[0009]

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[0010] In addition, examples of the group containing an ethylenically unsaturated group include those represented by the general formula CH ₂ CHCH— (CH ₂ ) _n − (VII). However, the above (IV) to (VI
In the formula (I), n represents an integer of 0 to 10. Examples of the group containing ethylenic unsaturation represented by the above formula (IV) include a vinyloxypropyl group, a vinyloxyethoxypropyl group, a vinyloxyethyl group, a vinyloxyethoxyethyl group, and the like, preferably a vinyloxypropyl group, It is a vinyloxyethoxypropyl group. When the ethylenically unsaturated group is represented by the above formula (V), R ⁵ is a hydrogen atom or a carbon atom
To 6 alkyl groups, preferably a hydrogen atom or 1 carbon atom
Or 2 alkyl groups, more preferably a hydrogen atom or a methyl group. Examples of the group containing the ethylenically unsaturated group represented by the formula (V) include a vinylphenyl group, 1-
(Vinylphenyl) ethyl group, 2- (vinylphenyl)
Ethyl group, (vinylphenyl) methyl group, isopropenylphenyl group, 2- (vinylphenoxy) ethyl group,
Examples thereof include a-(vinylbenzoyloxy) propyl group and a 3- (isopropenylbenzoylamino) propyl group, preferably a vinylphenyl group, a 1- (vinylphenyl) ethyl group, and a 2- (vinylphenyl) ethyl group. When the ethylenically unsaturated group is represented by the above formula (VI), R ⁶ is a hydrogen atom or a methyl group. R ⁷ is an alkylene group having 1 to 6 carbon atoms, a group represented by —O—, —S—, and —N (R ⁸ ) R ⁹ −, and R ⁸ is a hydrocarbon having 1 to 6 carbon atoms. A group or a (meth) acryloyl group, and R ⁹ is an alkylene group having 1 to 6 carbon atoms. Examples of the group containing an ethylenically unsaturated group represented by the formula (VI) include a γ-acryloxypropyl group,
γ-methacryloxypropyl group, N-methacryloyl-
N-methyl-γ-aminopropyl group, N-acryloyl-N-methyl-γ-aminopropyl group, N, N-bis-
(Methacryloyl) -γ-aminopropyl group and the like, and preferably N-methacryloyl-N-methyl-γ.
-Aminopropyl group, N-acryloyl-N-methyl-
γ-aminopropyl group. Examples of the group containing an ethylenically unsaturated group represented by the above formula (VII) include a vinyl group,
Examples include an allyl group, a homoallyl group, a 5-hexenyl group, and a 7-octenyl group, and a vinyl group and an allyl group are preferable. Groups containing such carbon functional groups and ethylenically unsaturated groups, based on the average composition formula R ¹ total _{a SiO (4-a) /} 2 for R ¹ in formula (I) is usually 0.02 to 10 mol% ,Preferably
It is in the range of 0.05 to 5 mol%. At less than 0.02 mol%,
The effect of improving the adhesiveness (adhesion or fixation) when applied to the base material of the airbag is small, and if it exceeds 10 mol%, the final cured product may be too hard.

(A) Another monovalent organic group in the component (b) includes an organic functional group composed of a carbon atom, a hydrogen atom, and at least one of nitrogen and oxygen. Containing such an organic functional group (A)
The emulsion composition using the component is advantageous in adhesiveness (adhesion or fixation) when applied to a base material of an airbag. Such organic functional groups include, for example,

[0012]

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And the like.

The organic peroxide of the component (B) induces and accelerates the curing of the polyorganosiloxane shell of the component (A) and the component (b) by a radical reaction, and includes diacyl peroxide, dialkyl peroxide, Oxyketal, alkylperoxyketal, peroxydicarbonate and the like are exemplified. In the present invention, those having a one-hour half-life temperature in the range of 25 to 100 ° C. are preferable,
For example, benzoyl peroxide, O-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, acetyl peroxide, acetylcyclohexanesulfonyl peroxide, 2,4,
4-trimethylpentylperoxyphenoxyacetate, t-butylperoxyneodecanoate, di-3-
Methoxybutyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t
-Butylcyclohexyl) peroxydicarbonate,
Diisopropyl peroxydicarbonate and the like are suitable. The amount of the organic peroxide as the component (B) is usually 0.1 to 5 parts by weight based on 100 parts by weight of the colloidal silica-silicone core-shell body as the component (A). If the amount is less than 0.1 part by weight, the curing speed is low and the strength of the cured product is low. On the other hand, if it exceeds 5 parts by weight, the composition tends to increase in viscosity or gel in a short time, and the workability of coating the airbag base fabric is deteriorated.

The emulsifier of the component (C) is colloidal silica
It plays a role of allowing the silicone core-shell body to stably exist in water and a role of a polycondensation catalyst when forming the core-shell body, and is an anionic emulsifier or a cationic emulsifier. Examples of the anionic emulsifier include an aliphatic substituted benzenesulfonic acid, an aliphatic substituted naphthalenesulfonic acid, an aliphatic sulfonic acid, a silylalkylsulfonic acid, and an aliphatic substituted benzenesulfonic acid having a carbon chain having a carbon atom length of 6 to 18. Organic sulfonic acid-based emulsifiers such as substituted diphenyl ether sulfonic acid are exemplified, and aliphatic substituted benzene sulfonic acid is more preferable. However, when the colloidal silica-silicone core-shell emulsion is prepared, it is used in the form of these sulfonic acids, but is neutralized later with an alkali, and therefore exists in the form of a sulfonic acid salt in the composition of the present invention. Examples of the cationic emulsifier include alkyltrimethylammonium salts such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride;
For example, dialkyldimethylammonium salts such as dioctadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride, didodecyldimethylammonium chloride, and quaternary compounds such as benzalkonium chloride such as octadecyldimethylbenzylammonium chloride and hexadecyldimethylbenzylammonium chloride An ammonium salt type emulsifier can be used. The mixing ratio of the emulsifier of the component (C) is usually 1 to 20 parts by weight based on 100 parts by weight of the colloidal silica-silicone core-shell body of the component (A). If the amount is less than 1 part by weight, it is difficult to form stable micelles. If the amount is more than 20 parts by weight, the emulsion viscosity increases, and all of them become unstable emulsions. If necessary, a nonionic emulsifier may be used in combination as the component (C). Examples of the nonionic emulsifier include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene (hereinafter abbreviated as POE) alkyl ether, POE sorbitan fatty acid ester, POE glycerin fatty acid ester, POE alkylphenol ether, and POE polyoxypropylene block copolymer. And the like.

The amount of the water component (D) is usually in the range of 50 to 1000 parts by weight per 100 parts by weight of the core shell body of the component (A). If the component (D) is less than 50 parts by weight or more than 1000 parts by weight, the emulsified state is poor and the emulsion becomes unstable.

Next, a method for producing the aqueous silicone emulsion composition according to the present invention will be described. The silicone aqueous emulsion composition of the present invention contains (A) the colloidal silica of the component (a), the organosiloxane of the component (A) (b-1) and the ethylenically unsaturated group of the component (A) (b-2). A colloidal silica-silicone core-shell emulsion is prepared by polycondensing an organosiloxane or (a) component and (b-2) component in an aqueous medium in the presence of an effective amount of an emulsifier or an emulsifier mixture. And then (B)
The main point is to add an organic peroxide as a component.
The (A) (a) component of the colloidal silica used in the present invention, there is referred finger in water dispersions of SiO ₂ as a basic unit, in the present invention 4～300Nm, particularly preferably
Those having an average particle diameter of 30 to 150 nm are suitable. As such colloidal silica, there are both acidic side and alkaline side, and they are appropriately selected according to conditions. For example, when emulsion polymerization is performed under acidic conditions using an anionic emulsifier, the use of acidic colloidal silica is preferred.

The organosiloxane of component (A) (b-1) and the organosiloxane having an ethylenically unsaturated group of component (A) (b-2) used in the present invention are represented by the above formulas (II) and (II), respectively. (III) having a structural unit represented by the formula and having no silicon atom and having 1 to 10 silicon atoms. The structure is not particularly limited, such as linear, branched or cyclic. Having one is preferred. Here, when the number of silicon atoms exceeds 10, when emulsion polymerization is performed, since it is difficult to incorporate colloidal silica particles into the siloxane micelles, there are some which cannot participate in the formation of the core-shell body, and as a result, in addition to the target core-shell body, An emulsion is obtained in which free colloidal silica and polyorganohydrogensiloxane micelles coexist. In the case of hydroxyl group-containing siloxane, a polycondensation reaction occurs at the initial stage of emulsification, and the number of silicon atoms is 10
Is not preferable because of the above problems. 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,
Examples include cyclic compounds such as 1,3,5-tris (3,3,3-trifluoropropyl) trimethylcyclotetrasiloxane, which are used alone or as a mixture of two or more.

As the organosiloxane containing an ethylenically unsaturated group as the component (A) (b-2), 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 3,5-trivinyltrimethylcyclotrisiloxane, 1,3,5,7-tetraallyltetramethylcyclotetrasiloxane, 1,3,5,7-tetra (5-hexenyl) tetramethylcyclotetrasiloxane, 1,3 , 5,7-tetra (7-octenyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (vinyloxypropyl) tetramethylcyclotetrasiloxane,
1,3,5,7-tetra (vinyloxyethoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (p-vinylphenyl) 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-vinylbenzoyloxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p
-Isopropenylbenzoylamino) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (γ
-Acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7 -tetra (γ-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7
-Tetra (N-methacryloyl-N-methyl-γ-aminopropyl) tetramethylcyclotetrasiloxane, 1,
3,5,7-tetra (N-acryloyl-N-methyl-γ-
Aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N, N-bis (methacryloyl) -γ-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N , N-bis (acryloyl) -γ-aminopropyl] tetramethylcyclotetrasiloxane and the like, and these may be used alone or as a mixture of two or more. In addition, a linear or branched organosiloxane may be used in addition to the cyclic compounds exemplified above. However, in the case of a linear or branched siloxane, the molecular terminal is 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, a 3,3,3 Those blocked with a trifluoropropyldimethylsilyl group or the like are preferred.

In the present invention, if necessary, (b-3)
An alkoxysilane having both a group containing an ethylenically unsaturated group and an alkoxy group, or an organic functional group and an alkoxy group can be blended. Examples of the alkoxysilane having both a group containing an ethylenically unsaturated group and an alkoxy group include (vinyloxypropyl) methyldimethoxysilane,
(Vinyloxyethoxypropyl) methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1-
(M-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyl Dimethoxysilane, 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, γ-acryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyl Dimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
N-methacryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, N, N
-Bis (methacryloyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis (acryloyl) -γ-
Aminopropylmethyldimethoxysilane, N-methacryloyl-N-methyl-γ-aminopropylphenyldiethoxysilane, 1- (3-methacryloxypropyl)-
1,1,3-trimethyl-3,3-dimethoxydisiloxane,
Silane compounds such as vinylmethyldimethoxysilane, vinylethyldiisopropoxysilane, vinyldimethylethoxysilane, allylmethyldimethoxysilane, 5-hexenylmethyldiethoxysilane, 7-octenylethyldiethoxysilane and siloxane compounds obtained by hydrolyzing the same And these may be used alone or as a mixture of two or more. On the other hand, examples of the alkoxysilane having both an organic functional group and an alkoxy group include 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-diethylenetriaminepropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3-mercaptopropylmethyl A silane compound such as dimethoxysilane and a siloxane compound obtained by hydrolyzing it.

The above-mentioned organosiloxane (A) (b-1), the ethylenically unsaturated group-containing organosiloxane (A) (b-2), and (A) (b-3) The component alkoxysilane has a polyorganosiloxane shell portion in the colloidal silica-silicone core-shell body of the composition according to the present invention of 20 to 95% by weight, and has an average compositional formula R ¹ _a SiO _{(4- a) / 2} (wherein, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, a is a number of 1.80 to 2.20, and 0.01 to 25 mol% of R ¹ is ethylenically unsaturated. (A group containing a saturated group).

As described above, the silicone emulsion composition according to the present invention comprises the above-mentioned colloidal silica of the component (A) (a), the organosiloxane of the component (A) (b-1), and the component (A) (b- 2)
Component ethylenically unsaturated group-containing organosiloxane and, optionally, (A) component (b-3) component alkoxysilane, or (A) component (a) and component (A) (b-2) component and (A ) (b-3) component,
In an aqueous medium, in the presence of an emulsifier, shear-mix using a homogenizer or the like, and prepare a colloidal silica-silicone core-shell body by polycondensation, and then (B)
It can be produced by adding an organic peroxide as a component. This emulsifier mainly plays the role of a surfactant for emulsifying the (A) (b-1) component and the (A) (b-2) component and the resulting colloidal silica-silicone core-shell body, (A) (a) component, (A) (b-1) component, (A) (b-2) component,
(A) It functions as a catalyst for the polycondensation reaction with the component (b-3). Here, an organic sulfonic acid emulsifier is used as an anionic emulsifier, and a quaternary ammonium salt is used as a cationic emulsifier. Is preferred. However, in the case of the quaternary ammonium salt type, the catalytic action is low depending on the type, and therefore, the combined use of an alkali catalyst such as sodium hydroxide or potassium hydroxide is desired. The amount of the emulsifier used is (A)
Component (a), (A) (b-1), (A) (b-2) and (A) (b-3) The total amount of the component 100 parts by weight, usually 1 to 20 parts by weight, preferably Is about 1 to 10 parts by weight. If necessary, a nonionic emulsifier may be used in combination. In preparing the colloidal silica-silicone core-shell body, a combination of an acidic colloidal silica-anionic emulsifier and an alkaline colloidal silica-cationic emulsifier is selected in order to keep the colloidal silica in a stable state. The amount of water used at this time is 100 parts by weight of the total amount of the components (A) (a) and (A) (b-1), (A) (b-2) and (A) (b-3). Usually 50 ~
It is 1000 parts by weight, preferably 100 to 500 parts by weight, and the condensation temperature is usually 5 to 100 ° C.

In preparing the colloidal silica-silicone core shell in the composition according to the present invention, a crosslinking agent may be added as a fourth component to improve the strength of the silicone shell. As this crosslinking agent,
Trifunctional crosslinks such as trimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane And a tetrafunctional crosslinking agent such as tetraethoxysilane. The amount of the crosslinking agent added is usually 10% by weight or less, preferably 10% by weight, based on the total amount of the components (A) (b-1), (A) (b-2) and (A) (b-3). 5
% By weight or less.

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 must be neutralized with an alkali or acid to maintain long-term stability. As the alkaline substance, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine and the like are used, and as the acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like are used. Finally, the organic peroxide of the component (B) is added to the colloidal silica-silicone core-shell body, followed by stirring and mixing, whereby the production of the aqueous silicone emulsion composition of the present invention is completed. As the organic peroxide used in the present invention, bis (4
(T-butylcyclohexyl) peroxydicarbonate and the like are preferable. When using these organic peroxides, it is desirable to use an emulsifier and water by an ordinary method in advance to form an O / W or W / O emulsion. Furthermore, the addition and stirring and mixing temperature of the curing catalyst is preferably in the range of 5 to 25 ° C.

The aqueous silicone emulsion according to the present invention is stable for about two months after production or preparation, but when it is to be stored for a long period of time, the organic peroxide is separately stored as a separate component, and immediately before use. Mixing is preferred. In addition, the use of reinforcing fillers, stabilizers, pigments, modifiers, flame retardants, etc. does not interfere, and even if a thickener is used to make the viscosity easy to coat, or diluted with water No problem.

For example, examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc carbonate and the like. Furthermore, in order to improve the adhesion of the emulsion composition according to the present invention to an airbag base fabric, a known adhesion aid such as an organosilicon compound having both a carbon functional group and a hydrolyzable group in one molecule. Can be added to the composition of the present invention. Such organosilicon compounds include 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

[0027]

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And the like. These organosilicon compounds can be used alone or in combination of two or more.

Further, the treatment of the substrate of the composition of the present invention comprises
It is applied to various airbag base fabrics by a method such as dip coating, spray coating, brush coating, knife coating, roll coating, and the like, and water is removed by drying and left at room temperature for 10 minutes to several hours, or The mixture is hardened by slightly heating it accordingly.

[0030]

According to the film-forming emulsion type silicone composition for an airbag of the present invention, the viscosity of the coating liquid when treated to various airbag base fabrics is lower than that of a conventional silicone rubber coating composition. As a result, workability during coating is improved. In addition, since the water gradually evaporates, even in a complicated shape, a rubber coating conforming to the shape of the surface is formed, and blocking does not occur when the rubber surfaces come into contact with each other. Further, a cured film having excellent mechanical strength is provided as compared with a conventional film-forming emulsion. In addition, since no harmful organic solvent is used, the viscosity at the time of work is excellent, and the viscosity can be adjusted to be suitable for various coatings without impairing the worker's health.

[0031]

The present invention will be described in detail below with reference to examples and comparative examples. In the examples, all “parts” are “parts by weight”.
, And all “%” indicate “% by weight”. Preparation Example 1 Acidic colloidal silica Snowtex OL (manufactured by Nissan Chemical Industries, Ltd., average particle diameter 84 nm, SiO ₂ 20.66%, Na ₂ O 0.019
%, PH 2.78) In a mixture of 1000 parts, 470 parts of distilled water and 8.4 parts of dodecylbenzenesulfonic acid, 210 parts of octamethylcyclotetrasiloxane and 1.2 parts of 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane And preliminarily stirred with a homomixer, and then with a homogenizer.
It was emulsified and dispersed by passing twice at a pressure of 300 kgf / cm ² . The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and cooled at 5 ° C. for 48 hours to complete the polymerization. Then, the polyorganosiloxane emulsion was washed with an aqueous solution of sodium carbonate to a pH of 7.
To complete the polymerization. The polymerization rate of octamethylcyclotetrasiloxane and 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane in the obtained polyorganosiloxane was 99.4%. In addition, it was confirmed that the polyorganosiloxane was a colloidal silica-silicone core-shell body by particle size analysis based on a dynamic light scattering method and observation with an electron microscope. In other words, a laser particle size analysis system (LPA-
When the particle size analysis was performed using 3000 S / 3100), the monodisperse particle size distribution with a peak near 84 nm of the raw colloidal silica completely disappeared, and the monodisperse particle size with a peak near 153 nm. A new distribution appears. Furthermore, when observed with an electron microscope, only the silicone particle image was confirmed,
No raw silica particle image was observed. On the other hand, a part of the core-shell emulsion was poured into a large amount of acetone to precipitate a core-shell body, separated by filtration, and dried with a vacuum dryer at 50 ° C. for 12 hours to obtain a core-shell aggregate. And elemental analysis of this core-shell aggregate, IR and
As a result of ¹ H, ²⁹ Si-NMR analysis, the ratio of the silicone shell portion was 49.7%. Further, when the core-shell body was regarded as a graft polymer, the graft ratio and the graft efficiency were 41.7%, respectively. Next, the colloidal silica-silicone core-shell aqueous emulsion prepared above
25 parts of 25% aqueous emulsion of bis (4-t-butylcyclohexyl) peroxydicarbonate per 100 parts (solid content 24.0%) [Perkadox 16 (trade name, manufactured by Kayaku Akzo) 25 parts, NIKKOL OP-5 (Prepared with 25 parts of Nikko Chemicals Co., Ltd. and 50 parts of distilled water) 1.0 part, thickener
HPC (hydroxypropylcellulose (grade M) manufactured by Nippon Soda Co., Ltd.) 1.2 parts and 3-glycidoxypropyltrimethoxysilane 3 parts are added at 25 ° C., and the mixture is stirred and mixed to obtain a silicone aqueous emulsion composition. This was used as Preparation 1.

Preparation Example 2 As an acidic colloidal silica, Snowtex OZL (manufactured by Nissan Chemical Industries, Ltd., average particle size 122 nm, SiO ₂ 21.14)
%, Na ₂ O 0.101%, pH 2.02)
A polyorganosiloxane emulsion was prepared under the same composition and under the same conditions as in the above case. The obtained polyorganosiloxane was confirmed to be a colloidal silica-silicone core-shell body having a monodisperse particle size distribution by particle size analysis based on dynamic light scattering and observation with an electron microscope (proportion of silicone shell portion). 49.3%, graft ratio (%)
And graft efficiency (%) 40.3% each). Next, with respect to 100 parts of the aqueous colloidal silica-silicone core-shell emulsion prepared above (solid content: 24.0%), Preparation Example 1
0.24 parts of the same organic peroxide as above, a thickener HPC (hydroxypropylcellulose grade M, Nippon Soda Co., Ltd.)
1.0 part and an organosilicon compound represented by the following formula:

[0033]

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By adding 2.5 parts at 25 ° C. and mixing and stirring, a silicone aqueous emulsion composition was obtained.

Preparation Example 3 In a mixture of 2.0 parts of dodecylbenzenesulfonic acid and 320 parts of distilled water, 100 parts of octamethylcyclotetrasiloxane was added.
The mixture was preliminarily stirred with a homomixer, and then passed twice with a homogenizer at a pressure of 300 kgf / cm ² to emulsify and disperse. The emulsified and dispersed liquid was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and heated at 85 ° C for 5 hours while stirring and mixing.
And then cooled to pH 7 with a 10% aqueous sodium carbonate solution.
To complete the condensation, and used as the main ingredient. This one is
As a result of GPC measurement, the number average molecular weight was Mn = 2.93 × 10 ⁵ . On the other hand, a mixed solution of 2.0 parts of dodecylbenzenesulfonic acid and 320 parts of distilled water has a viscosity of 25 cSt represented by the following formula.
100 parts of polymethylhydrogensiloxane

[0036]

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After the mixture was preliminarily stirred with a homomixer, the mixture was passed twice with a homogenizer at a pressure of 300 kgf / cm ² to emulsify and disperse to obtain a curing agent. next,
To 100 parts of the base material, 5 parts of the curing agent, 0.1 part of a 50% aqueous emulsion of dibutyltin dilaurate (prepared with 50 parts of dibutyltin dilaurate, 5 parts of sodium dodecylbenzenesulfonate, and 45 parts of distilled water), 3-glycidoxypropyltriethyl Methoxysilane 3.0 parts and thickener HPC
(Hydroxypropylcellulose grade M; manufactured by Nippon Soda Co., Ltd.) (4 parts) was added at 25 ° C., and the mixture was stirred with stirring to obtain a silicone aqueous emulsion composition.

Preparation Example 4 15 parts of fumed silica were uniformly mixed with 100 parts of α, ω-divinylpolymethylsiloxane base polymer having a viscosity of 10,000 cP, and then a solution of chloroplatinic acid in isopropanol was used as a platinum amount. An amount of 20 ppm based on the polymer was uniformly dispersed to obtain a main ingredient. On the other hand, an α, ω-divinylpolymethylsiloxane base polymer having a viscosity of 10,000 cP
Mix 100 parts with 15 parts of fumed silica so as to make uniform, and then add 5.0 parts of polymethyl hydrogen siloxane having a viscosity of 25 cSt represented by the following formula.

[0039]

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And 0.2 part of a silicon compound having an acetylenically unsaturated group represented by the following formula:

[0041]

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Was uniformly dispersed to obtain a curing agent. 50 parts of the main agent and the curing agent and 3 parts of an organosilicon compound represented by the following formula

[0043]

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Was mixed and stirred to obtain a rubber component 4.

Examples 1-2 and Comparative Examples 1-4 Preparations 1-3 and rubber components 4 obtained in Preparations 1-4
Then, various diluents shown in Table 1 were added in amounts shown in Table 1 to obtain a coating composition. 6,6
- amount of rubber to nylon cloth (420D) was coated so as to become a 60~80g / m ^2. Next, the cloth was treated in an oven as follows to obtain a cloth having a cured silicone rubber film.

90 ° C. × 5 min → 170 ° C. × 2 min The surface condition of the rubber coating film of the obtained film-forming cloth is visually observed and evaluated according to the following criteria. It measured on condition of.・ Coating film surface condition evaluation criteria Film thickness ◎; uniform ○; almost uniform △; slight unevenness ×; uneven ・ Surface dynamic friction coefficient measurement conditions 150g load, speed 100mm / min, temperature 25 ℃, humidity 60% RH ・ paint Properties 6,6-Observe the ease of application and spread of the rubber coating composition on the cloth when coated on nylon cloth,
Evaluation was made in the following four stages. ◎: Easy to spread and spread smoothly ○: Easy to apply △; Slightly difficult to apply ×: Difficult to apply ・ Permeability As in the case of evaluation of wettability, the coating composition was treated with 6,6-
The ease with which the coating composition soaked into the cloth when coated on a nylon cloth was observed and evaluated according to the following four grades. ◎: Good penetration, the entire surface becomes uniform from the surface of the cloth to the inside. ○: Somewhat difficult to penetrate, but uniform from the surface of the cloth to the inside. △: A large amount remains on the surface of the cloth and penetrates sufficiently into the inside. No ×: Only the surface of the cloth does not penetrate into the inside. ・ Adhesiveness and mechanical strength 6,6 －Adhesiveness and mechanical strength of rubber film coated on nylon cloth to nylon cloth (coated nylon cloth Was strongly squeezed with a finger, and those having poor adhesion or poor mechanical strength were peeled off and dropped off from the rubber film on the coating surface), and evaluated by the following three steps. ◎: No rubber film is detached from the coated surface, and excellent adhesion and mechanical strength are exhibited. △: Rubber film is slightly detached and peeled from the coated surface. ×: Rubber film is detached from the coated surface.

[0047]

[Table 1]

────────────────────────────────────────────────── (5) References JP-A-4-110351 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 183/07 B60R 21/16 C09D 1 / 00 CA (STN) CAOLD (STN) REGISTRY (STN) WPIDS (STN)

Claims (2)

(57) [Claims] 1. A (A) (a) a core 80 to 5% by weight of colloidal silica (b) the average compositional formula ^{_{R 1 a SiO (4-a}} ) / 2 ... (I) ( wherein, R ¹ is the number of carbon atoms 1-8 substituted or unsubstituted monovalent hydrocarbon groups, a is a number of 1.80-2.20, and 0.01-25 mol% of R ^{1 is} a group containing an ethylenically unsaturated group) 100 parts by weight of a colloidal silica-silicone core shell composed of 20 to 95% by weight of an organosiloxane shell, (B) 0.1 to 5 parts by weight of an organic peroxide, (C) 1 to 20 parts by weight of an emulsifier, and (D) water 50 1 to 1000 parts by weight of a film-forming emulsion type silicone composition for an airbag. 2. An airbag obtained by sewing an airbag base fabric on which a cured film of the emulsion-type silicone composition according to claim 1 is formed.