TWI829907B - Addition hardening liquid polysiloxane rubber composition for airbags and airbag - Google Patents

Abstract

The invention provides an addition hardening liquid polysiloxane rubber composition for airbags and an airbag. An addition-hardening liquid polysiloxane rubber composition for airbags, characterized by containing the following components (A) to (F) as essential components, (A) containing two or more bonds in one molecule Organopolysiloxane with an alkenyl group bonded to silicon atoms and a weight average degree of polymerization of 100 to 1,000, (B) One molecule contains 0 to 3 alkenyl groups bonded to silicon atoms and a weight average degree of polymerization of 2,000 to 10,000 Organopolysiloxane, (C) Organohydrogenated polysiloxane containing at least 2 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, (D) BET method specific surface area of 50m ² /g or more Silica fine powder, (E) a hydrosilylation reaction catalyst, (F) an organosilicon compound containing an adhesive functional group (however, component (A), (B), and (C) are not included ).

Description

Addition hardening liquid polysiloxane rubber composition for airbags and airbag

The present invention relates to an addition hardening liquid polysiloxane rubber composition for airbags suitable for making airbags and an airbag.

The purpose of the silicone rubber composition for air bags that has been proposed in the past is to form a rubber film on the fiber surface. Airbags with a silicone rubber film are suitable for use as airbags in automobiles and the like because they have excellent air tightness and low combustion rate properties.

As a method for manufacturing such a polysiloxy-coated base fabric for airbags, it has been disclosed that a cross-linking agent having hydrogenated silyl groups at both ends of the molecular chain is combined with a cross-linking agent having hydrogenated silyl groups in the branch chain. A method of manufacturing a polysilicone-coated airbag with excellent internal pressure retention by coating the resulting addition-hardening liquid polysilicone rubber composition onto a base cloth and heating and curing it (Patent Document 1: Japanese Patent Publication No. 2013-531695); or liquid polysiloxane produced by mixing the siloxane component with silicon dioxide, surface treatment agent, and water in advance, containing resinous polysiloxane. The composition is coated on the fiber surface to obtain an airbag (Patent Document 2: Japanese Patent Application Laid-Open No. 2013-209517) and the like.

However, airbags manufactured according to these methods have significantly poor blocking resistance because the unique adhesive feeling of silicone rubber remains. As a measure for this improvement, powder such as talc, which is rich in adhesion, sliding properties, etc., is applied to the rubber surface. However, in addition to high cost, this method also has the risk of adverse effects on the human body due to dust. In addition, since the powder is only adhered to the surface of the rubber coating cloth, the powder easily falls off and the effect cannot be stably exerted.

As a method to solve these problems, it has been disclosed that polysiloxane containing an adhesive is coated on a base fabric for airbags, and the polysiloxane is hardened by irradiating electron beams to create anti-caking properties. , a method of coating a base fabric with polysilicone that has excellent internal pressure retention (Patent Document 3: Japanese Patent Application Publication No. 2015-085271); or coating liquid polysilicone rubber on a base fabric for airbags After the composition is cured by heating, the polysilicone coating is irradiated with vacuum ultraviolet rays to produce a polysilicone-coated base fabric with excellent low friction properties (Patent Document 4: Japanese Patent Publication No. 2018-511687) wait.

However, since these manufacturing methods require the use of electronic rays or ultraviolet rays, there are concerns about the impact on the health of workers. In addition, if the coating amount of polysilicone is small, since the filaments will be more exposed on the surface than the polysilicone rubber layer, electronic rays or ultraviolet rays will cause the base fabric to deteriorate. Problems such as deterioration in the strength of the base fabric. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2013-531695 [Patent Document 2] Japanese Patent Application Publication No. 2013-209517 [Patent Document 3] Japanese Patent Application Publication No. 2015-085271 [Patent Document 4] Japanese Patent Publication No. 2018-511687

[Problem to be solved by the invention]

The present invention was made in view of the above-mentioned circumstances, and its object is to provide an addition-hardening liquid polysiloxane rubber composition for airbags that is excellent in caking resistance and adhesion to the base fabric for airbags and a safety product. air bag. [Means to solve the problem]

As a result of intensive research in order to achieve the above object, the inventors found that, like an addition-hardening liquid polysiloxane rubber composition containing components (A) to (F) described below, by combining (B) An organopolysiloxane containing 0 to 3 alkenyl groups bonded to silicon atoms in the molecule and a weight average degree of polymerization of 2,000 to 10,000 is used. The composition is applied to the surface of the airbag base fabric and heated to harden. , the obtained polysiloxane-coated base fabric for airbag manufacturing was excellent in caking resistance and adhesion to the base fabric, and thus the present invention was completed.

Therefore, the present invention provides the following addition curing liquid polysilicone rubber composition for airbags and an airbag. [1] An addition-hardening liquid polysiloxane rubber composition for airbags, characterized by containing the following components (A) to (F) as essential components. (A) contains 2 components in one molecule The above organopolysiloxane with alkenyl groups bonded to silicon atoms and a weight average degree of polymerization of 100 to 1,000: 100 parts by mass, (B) One molecule contains 0 to 3 alkenyl groups bonded to silicon atoms and the weight Organopolysiloxane with an average degree of polymerization of 2,000 to 10,000: 1 to 20 parts by mass, (C) Organohydrogenated polysiloxane containing at least 2 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: The SiH group contained in this component is in an amount of 1 to 10 moles per 1 mol of the total alkenyl groups bonded to silicon atoms contained in component (A) and component (B), (D) Silica fine powder with a BET method specific surface area of 50 m ² /g or more: 1 to 50 parts by mass, (E) Catalyst for hydrosilylation reaction: relative to the total mass of components (A) to (D), The mass conversion of the catalyst metal element is 1 to 500 ppm, (F) contains an organosilicon compound that provides an adhesive functional group (but does not include component (A), component (B), and component (C)): 0.1 to 10 mass share. [2] The addition-hardening liquid polysiloxane rubber composition for airbags according to [1], which further contains at least 1 compound selected from the group consisting of organic titanium compounds, organic zirconium compounds, and organic aluminum compounds as the component (G). kind of condensation catalyst, and the component (G) is 0.1 to 5 parts by mass relative to 100 parts by mass of the component (A). [3] The addition-hardening liquid polysiloxane composition for air bags according to [1] or [2], further containing a powdery three-dimensional network organopolysiloxane as the component (H) Resin (however, the molecule of the organopolysiloxane resin does not contain hydrogen atoms bonded to silicon atoms, and does not include component (A) or component (B)), and relative to 100 parts by mass of component (A), ( H) component is 0.1~100 parts by mass. [4] The addition-hardening liquid polysiloxane rubber composition for airbags according to any one of [1] to [3], wherein component (F) contains epoxy groups and bonded silicon atoms. An organic silicon compound that provides an adhesive functional group at least one of an alkoxy group (alkoxysilyl group), a hydrogenated silyl group, an isocyanate group, an acryl group, and a methacrylyl group. [5] An airbag characterized by having a hardened film of the addition-hardening liquid polysiloxane rubber composition for airbags as described in any one of [1] to [4] on a base fabric for airbags . [Effects of the invention]

According to the present invention, it is possible to provide an addition-hardening liquid polysiloxane rubber composition for airbags and an airbag that are excellent in caking resistance and adhesion to the base fabric for airbags.

[The best way to implement the invention]

Hereinafter, the present invention will be described in more detail. However, in this manual, the viscosity is the value measured with a rotational viscometer at 25°C based on the method described in JIS K 7117-1:1999. In addition, the degree of polymerization is a value obtained by using toluene as a developing agent and using the weight average degree of polymerization (weight average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis.

＜Addition hardening liquid polysiloxane rubber composition＞ The addition-hardening liquid polysiloxane rubber composition for airbags of the present invention contains the following components (A) to (F), and is liquid at room temperature (25°C). Each component is described in detail below.

[(A) ingredient] The organopolysiloxane of component (A) contains two or more alkenyl groups bonded to silicon atoms in one molecule and is liquid at 25°C. It is the matrix in the composition related to the present invention. Polymer (main agent).

Examples of the molecular structure of component (A) include linear, cyclic, and branched chains. However, the main chain is basically composed of repeating diorganosiloxane units, and both ends of the molecular chain are formed by triorganosiloxane units. Linear diorganopolysiloxanes terminated with siloxy groups are preferred. In addition, when the molecular structure of the organopolysiloxane of component (A) is linear or branched, the position of the silicon atom bonded to the alkenyl group in the molecule of the organopolysiloxane may be: At the end of the molecular chain (i.e., triorganosiloxane oxygen group) and in the middle of the molecular chain (i.e., the bifunctional diorganosiloxane unit or the trifunctional monoorganosesquioxane unit located at the non-terminal end of the molecular chain) Either one, or both. Particularly preferred components (A) are linear diorganopolysiloxanes containing at least alkenyl groups bonded to silicon atoms at both ends of the molecular chain.

Examples of the alkenyl group bonded to the silicon atom in the component (A) include usually an alkenyl group having 2 to 8 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms. Specific examples include vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, heptenyl, and the like, and vinyl is particularly preferred.

(A) The content of the alkenyl group bonded to the silicon atom in the component is 0.001 to 10 mol based on the total monovalent organic group (i.e., unsubstituted or substituted monovalent hydrocarbon group) bonded to the silicon atom. Mol % is preferred, especially about 0.01 to 5 mol %.

Examples of the monovalent organic group bonded to the silicon atom other than the alkenyl group of component (A) include unsubstituted or substituted ones that are the same as or different from each other and usually have 1 to 12 carbon atoms (preferably 1 to 12 carbon atoms). 10) Monovalent hydrocarbon group. Specific examples of the monovalent organic group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and heptyl; phenyl, tolyl, xylyl, Aryl groups such as naphthyl; aralkyl groups such as benzyl and phenethyl; halogen-substituted alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc., especially those with Methyl is preferred.

The weight average degree of polymerization of component (A) is 100 to 1,000, and preferably 150 to 900. If the weight average degree of polymerization is less than 100, the mechanical properties of the resulting polysilicone rubber will deteriorate. On the other hand, if the weight average degree of polymerization exceeds 1,000, the viscosity of the resulting polysilicone rubber composition will deteriorate. becomes higher, the coating workability may deteriorate. (A) The viscosity of the component is 50~100,000mPa‧s at 25℃, preferably 100~50,000mPa‧s.

Specific examples of the organopolysiloxane of component (A) include trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymer at both ends of the molecular chain, Terminal trimethylsiloxy-terminated methylvinylpolysiloxane, both ends of the molecular chain trimethylsiloxy-terminated dimethylsiloxane‧methylvinylsiloxane‧methylphenylsiloxane Oxane copolymer, dimethylvinylsiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, methylvinylpolysiloxane terminated by dimethylvinylsiloxy groups at both ends of the molecular chain, Dimethylvinylsiloxane-methylvinylsiloxane copolymer terminated with dimethylvinylsiloxy groups at both ends of the molecular chain, Dimethylsiloxy terminated with dimethylvinylsiloxy groups at both ends of the molecular chain Alkyl‧methylvinylsiloxane‧methylphenylsiloxane copolymer, divinylmethylsiloxane at both ends of the molecular chain, divinylmethyl polysiloxane at both ends of the molecular chain Silanoxy-terminated dimethylsiloxane‧methylvinylsiloxane copolymer, trivinylsiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, trivinylsiloxane at both ends of the molecular chain Silyloxy-terminated dimethylsiloxane·methylvinylsiloxane copolymer, and a mixture containing two or more kinds of these organopolysiloxanes.

(A) The organopolysiloxane type of component may be used individually by 1 type, and may be used in combination of 2 or more types.

[(B)Component] The organopolysiloxane of component (B) contains 0 to 3 alkenyl groups bonded to silicon atoms in one molecule and is oily or rubbery at 25°C for caking resistance. And an adhesion improver for the base fabric is formulated into the composition.

Examples of the molecular structure of component (B) include linear, cyclic, and branched chains. However, the main chain is basically composed of repeats of diorganosiloxane units, and both ends of the molecular chain utilize triorganosiloxane units. A linear diorganopolysiloxane terminated with a silanoxy group or a dimethylvinylsiloxy group is preferred. In addition, when the molecular structure of the organopolysiloxane of component (B) is linear or branched, the position of the silicon atom bonded to the alkenyl group in the molecule of the organopolysiloxane may be: At the end of the molecular chain (i.e., triorganosiloxane oxygen group) and in the middle of the molecular chain (i.e., the bifunctional diorganosiloxane unit or the trifunctional monoorganosesquioxane unit located at the non-terminal end of the molecular chain) Either one, or both.

Examples of the alkenyl group bonded to the silicon atom in the component (B) include usually an alkenyl group having 2 to 8 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms. Specific examples include vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, heptenyl, and the like, and vinyl is particularly preferred.

The content of alkenyl groups bonded to silicon atoms in component (B) is preferably 0 to 3 in one molecule of the polymer. If the alkenyl group content exceeds 4 in one polymer molecule, sufficient adhesion improvement effect cannot be obtained.

Examples of the monovalent organic group bonded to the silicon atom other than the alkenyl group of component (B) include, for example, unsubstituted or substituted ones that are the same as or different from each other and usually have 1 to 12 carbon atoms (preferably 1 to 12 carbon atoms). 10) Monovalent hydrocarbon group. Specific examples of the monovalent organic group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and heptyl; phenyl, tolyl, xylyl, Aryl groups such as naphthyl; aralkyl groups such as benzyl and phenethyl; halogen-substituted alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc., especially those with Methyl is preferred.

The weight average degree of polymerization of component (B) is 2,000 to 10,000, and preferably 3,000 to 9,000. If the weight average degree of polymerization is less than 2,000, sufficient improvement in caking resistance and adhesion may not be obtained. On the other hand, if the weight average degree of polymerization exceeds 10,000, the resulting polysilicone rubber composition may have The viscosity will increase and coating workability will deteriorate.

The compounding amount of component (B) is 1 to 20 parts by mass, preferably 2 to 18 parts by mass, and more preferably 3 to 15 parts by mass relative to 100 parts by mass of component (A). If the blending amount of component (B) is less than 1 part by mass, sufficient improvement effects on caking resistance and adhesion may not be obtained. On the other hand, if the blending amount exceeds 20 parts by mass, the resulting polymer may not be fully improved. The viscosity of the silicone rubber composition will increase, which may deteriorate the coating workability.

[(C)Component] The organohydrogenated polysiloxane of component (C) mainly performs a hydrosilylation addition reaction with the alkenyl groups in component (A) and (B) to function as a cross-linking agent (hardening agent). Examples of the molecular structure of component (C) include various structures such as linear, cyclic, branched chain, and three-dimensional network (resin-like) structures. However, one molecule must have at least two (preferably) 3 or more) hydrogen atoms (SiH groups) bonded to silicon atoms, usually 2 to 300, preferably 3 to 200, and preferably 4 to 100 SiH groups, and used in It is liquid at 25℃. Such SiH groups can be located at any position at the end of the molecular chain, in the middle of the molecular chain, or at both positions.

As this organohydrogenated polysiloxane, one represented by the following average composition formula (1) can be used. 【Chemical 1】

In formula (1), R ¹ is an aliphatic unsaturated bond that is the same as or different from each other but does not include an alkenyl group, etc., and is preferably an unsubstituted or substituted monovalent hydrocarbon group with a carbon number of 1 to 10 bonded to a silicon atom, Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, etc. , aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc., aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc., or a part or all of the hydrogen atoms of these groups are replaced by fluorine, Examples of those substituted by halogen atoms such as bromine and chlorine include chloromethyl, chloropropyl, bromoethyl, and trifluoropropyl. ^R1 is preferably an alkyl group or an aryl group, and more preferably a methyl group. Also, a is 0.7~2.1, b is 0.001~1.0, and a+b is a positive number satisfying 0.8~3.0; preferably, a is 1.0~2.0, b is 0.01~1.0, and a+b is a positive number satisfying 1.5~ 2.5 is a positive number.

Examples of the organohydrogenated polysiloxane as the component (C) include 1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane. Alkane, ginseng (hydrogenated dimethylsiloxane) methylsiloxane, ginseng (hydrogenated dimethylsiloxane) phenylsiloxane, methylhydrogenated cyclopolysiloxane, methylhydrogenated siloxane‧dimethylsiloxane Oxane cyclic copolymer, trimethylsiloxy-terminated methyl hydrogenated polysiloxane at both ends of the molecular chain, dimethylsiloxane‧methylhydrogenated silicone terminated by trimethylsiloxy groups at both ends of the molecular chain Oxane copolymer, trimethylsiloxy-terminated dimethylsiloxane‧methylhydrogensiloxane‧methylphenylsiloxane copolymer at both ends of the molecular chain, trimethylsiloxy terminated at both ends of the molecular chain Group-terminated dimethylsiloxane‧methylhydrogenatedsiloxane‧diphenylsiloxane copolymer, dimethylhydrogenated siloxane at both ends of the molecular chain, methylhydrogenated polysiloxane terminated by molecular chains Terminal dimethylhydrogenated silyloxy-terminated dimethylpolysiloxane, both terminal dimethylhydrogenated silyloxy-terminated dimethylsiloxane and methylhydrogenated siloxane copolymer, molecular chain terminal-terminated dimethylsiloxane Dimethylsiloxane‧Methylphenylsiloxane copolymer end-capped with dimethyl hydrogenated silyloxy groups, dimethylsiloxane‧diphenyl end-capped with dimethyl hydrogenated silyloxy groups at both ends of the molecular chain Siloxane copolymer, dimethylhydrogenated silyloxy-terminated methylphenyl polysiloxane at both ends of the molecular chain, dimethylhydrogenated silanoxy-terminated diphenyl polysiloxane at both ends of the molecular chain, or Each of these exemplary compounds has a siloxane unit represented by the formula: R ² ₃ SiO _0.5 , in which part or all of the methyl group is substituted with other alkyl groups such as ethyl or propyl. The formula: R ² An organosiloxane copolymer composed of siloxane units represented by ₂ HSiO _0.5 and the formula: SiO ₂ , containing siloxane units represented by the formula: R ² ₂ HSiO _0.5 and the formula: Organosiloxane copolymer composed of siloxane units represented by SiO ₂ , containing siloxane units represented by formula: R ² HSiO and siloxane units represented by formula: R ² SiO _1.5 or formula: HSiO Organosiloxane copolymers composed of siloxane units represented by _1.5 , and mixtures containing two or more types of organopolysiloxanes. Incidentally, R ² in the above formula is a monovalent hydrocarbon group other than an alkenyl group.

The compounding amount of component (C) is the SiH group contained in component (C) relative to 1 mol (or units) of the total alkenyl groups bonded to silicon atoms contained in component (A) and component (B). The amount is 1 to 10 moles (or pieces), preferably 1.2 to 9 moles (or pieces), and more preferably 1.5 to 8 moles (or pieces). If the SiH group contained in component (C) is less than 1 mole relative to 1 mole of the total alkenyl groups bonded to silicon atoms contained in component (A) and component (B), the composition will not be able to If it is fully hardened, and if it exceeds 10 moles, the heat resistance of the obtained cured polysilicone rubber will be extremely poor. The organohydrogenated polysiloxane of component (C) may be used individually by 1 type, or may be used in combination of 2 or more types.

[(D)Component] The silica fine powder of component (D) functions as a reinforcing filler. That is, by using silica fine powder as a reinforcing filler to provide strength to the cured polysilicone rubber obtained from the composition related to the present invention, a coating capable of satisfying the strength required by the present invention can be formed. Cloth film. The above-mentioned silica fine powder needs to have a specific surface area (BET method) of 50m ² /g or more, preferably 50~400m ² /g, and preferably 100~300m ² /g. If the specific surface area is less than 50m ² /g, it cannot provide the required strength characteristics.

As such silica fine powder, provided that the specific surface area is within the above-mentioned range, well-known ones conventionally used as a reinforcing filler for polysilicone rubber may be used. Examples thereof include fumed silica. (Fumed silica), precipitated silica (wet silica), etc.

As the above-mentioned reinforcing silica fine powder, for example, silica fine powder whose surface is hydrophobized with a surface treatment agent described below can be used. In this case, these silica fine powders can be used in a pre-powder state and directly undergo surface hydrophobization treatment with a surface treatment agent. They can also be used in combination with polysiloxane oil. (For example, the alkenyl group-containing organopolysiloxane of the above-mentioned component (A)) is added with a surface treatment agent during kneading to perform surface hydrophobization treatment.

As a common treatment method for component (D), surface treatment can be carried out by well-known techniques. For example, the above-mentioned untreated silica fine powder is placed in a sealed mechanical kneading device or fluidized bed under normal pressure. Mix with the surface treatment agent at room temperature (25°C) or heat treatment (heating) in the presence of inert gas as required. Depending on the situation, water or catalysts (hydrolysis accelerators, etc.) can be used to promote surface treatment. After kneading, surface-treated silica fine powder can be produced by drying. The amount of the surface treatment agent to be prepared may be an amount or more calculated from the coverage area of the surface treatment agent.

Specific examples of the surface treatment agent include silazones such as hexamethyldisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, and butyltrimethoxysilane. Oxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane Silane coupling agents such as vinyl silane, vinyl silane (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and chloropropyltrimethoxysilane , polymethylsiloxane, etc., those used for surface treatment can be used as hydrophobic silica fine powder. As the surface treatment agent, silane coupling agents or silazanes are particularly preferred.

Furthermore, it is preferable if the silica fine powder of component (D) is in a pre-powdered state and is directly surface hydrophobized with a surface treatment agent containing an alkenyl group. : "With respect to 1 mol of the total alkenyl groups bonded to silicon atoms contained in the surface treatment agent of component (A), component (B), and component (D) in the composition, component (C) contains The SiH group is 1 to 10 moles (or pieces), preferably 1.2 to 9 moles (or pieces), and more preferably 1.5 to 8 moles (or pieces)." This is because if there is less than 1 mole of SiH groups per mole of alkenyl groups bonded to silicon atoms in the composition, the composition may not be sufficiently hardened and may not exhibit sufficient adhesion. On the other hand, if the SiH group exceeds 10 moles, the heat resistance of the obtained cured polysiloxane rubber will be extremely poor.

The compounding amount of component (D) is 1 to 50 parts by mass, preferably 10 to 30 parts by mass relative to 100 parts by mass of the organopolysiloxane of component (A). If the blending amount is less than 1 part by mass, the strength required by the present invention cannot be obtained. If the blending amount exceeds 50 parts by mass, the viscosity of the composition will increase and the fluidity will decrease, thereby worsening the coating operation.

(D) The fine powder silica system of component may be used individually by 1 type, or may be used in combination of 2 or more types.

[(E)INGREDIENT] The catalyst for the hydrosilylation reaction of component (E) is mainly used to promote the addition reaction between the alkenyl groups bonded to silicon atoms in components (A) and (B) and the SiH groups in component (C). By. The catalyst for the hydrosilylation reaction is not particularly limited, and examples include platinum group metals such as platinum, palladium, and rhodium; chloroplatinic acid; alcohol-modified chloroplatinic acid; chloroplatinic acid and olefins, and vinylsiloxanes. Or coordination compounds of acetylene compounds; platinum group metal compounds such as quaternary (triphenylphosphine) palladium, chloroparaben (triphenylphosphine) rhodium, etc., preferably platinum group metal compounds.

The compounding amount of component (E) is sufficient as long as it is an effective amount that can serve as a catalyst. It is preferably 1 to 500ppm, preferably 10~100ppm. If the blending amount is less than 1ppm, the addition reaction will be significantly slowed down and the composition may not be hardened. If the blending amount exceeds 500ppm, the heat resistance of the cured product will be reduced.

(E) The addition reaction catalyst system of component (E) may be used individually by 1 type, or may be used in combination of 2 or more types.

[(F)INGREDIENT] The component (F) is an organosilicon compound containing an adhesive functional group. Examples of the adhesive functional group include an epoxy group, an alkoxy group (alkoxysilyl group) bonded to a silicon atom, a hydrogenated silyl group, Isocyanate group, acryl group, methacryl group, etc. are added in order to demonstrate and improve the adhesion of the polysilicone rubber composition to the airbag base fabric. As the organosilicon compound, any organosilicon compound can be used as long as it has such an adhesive functional group. However, each of the organosilicon compounds must have at least one epoxy group and at least one bonded silicon in one molecule. Organosilicon compounds with alkoxy atoms are preferred. In particular, from the viewpoint of exhibiting adhesion, an alkoxy group having at least one epoxy group and at least one bonded silicon atom (for example, trialkoxysilyl group, organic dialkoxy group silane group, etc.), or a cyclic or linear organosiloxane with about 1 to 100 silicon atoms (preferably 1 to 50) and having at least 1 epoxy group Alkoxy group with at least 2 bonded silicon atoms.

Epoxy groups include glycidoxyalkyl groups such as glycidoxypropyl group; epoxy-containing groups such as 2,3-epoxycyclohexylethyl group, 3,4-epoxycyclohexylethyl group, etc. It is preferred to bond to the silicon atom in the form of a cyclohexyl alkyl group or the like. The alkoxy group bonded to the silicon atom is preferably a trialkoxysilyl group bonded to the silicon atom to form, for example, trimethoxysilyl group, triethoxysilyl group, etc.; methyldimethoxysilyl group, Alkyl dialkoxysilyl groups such as ethyldimethoxysilyl group, methyldiethoxysilyl group, ethyldiethoxysilyl group, and the like.

In addition, component (F), as a functional group other than the epoxy group and the alkoxy group bonded to the silicon atom, may have in one molecule, for example, an alkenyl group selected from the group consisting of vinyl, acryl group, (methyl group, etc.) ) At least one functional group selected from the group consisting of an acryloxy group, an isocyanate group and a hydrogenated silyl group (SiH group).

Examples of the organosilicon compound as the component (F) include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, (3,4-epoxy (3,4-epoxycyclohexylethyl)trimethoxysilane, (3,4-epoxycyclohexylethyl)triethoxysilane, (3,4-epoxycyclohexylethyl)methyldimethoxysilane , (3,4-epoxycyclohexylethyl)methyldiethoxysilane, (2,3-epoxycyclohexylethyl)triethoxysilane, (2,3-epoxycyclohexyl) Epoxy-containing silane coupling agents (i.e., epoxy functional based organoalkoxysilane); vinyl-containing silane coupling agents such as vinyltrimethoxysilane; acrylyl-containing silane coupling agents such as 3-acrylyloxypropyltrimethoxysilane; 3- Isocyanate group-containing silane coupling agents such as isocyanate propyl ethoxysilane; silane coupling agents such as methoxysilyl modified products of triallyl isocyanurate; cyclic organic compounds represented by the following chemical formula Organic silicon compounds such as polysiloxane or linear organopolysiloxane; mixtures of two or more of these, or partial hydrolysis condensates of one or two or more of these, etc. The main content is shown below.

(In the formula, h is an integer from 1 to 10, k is an integer from 0 to 40, preferably an integer from 0 to 20, p is an integer from 1 to 40, preferably an integer from 1 to 20, and q is 1~ an integer of 10)

The compounding amount of component (F) is 0.1 to 10 parts by mass, preferably 0.25 to 5 parts by mass relative to 100 parts by mass of the organopolysiloxane of component (A). If the blending amount is less than 0.1 parts by mass, the resulting composition may not exhibit sufficient adhesive strength. If the compounding amount exceeds 10 parts by mass, the thixotropy of the composition will increase and the fluidity will decrease, and the coating workability may deteriorate.

However, when the component (F) contains an alkenyl group and/or a SiH group, the component (F) is preferably: "relative to the components (A), (B) and (F) in the composition. The total number of alkenyl groups bonded to silicon atoms (or nitrogen atoms) is 1 mole (or pieces), and the total number of SiH groups contained in component (C) and (F) is 1 to 10 moles (or pieces). ), preferably 1.2 to 9 moles (or pieces), and more preferably 1.5 to 8 moles (or pieces)." This is because if there is less than 1 mole of SiH groups per mole of alkenyl groups bonded to silicon atoms in the composition, the composition may not be sufficiently hardened and may not exhibit sufficient adhesion. On the other hand, if the SiH group exceeds 10 moles, the heat resistance of the obtained cured polysiloxane rubber will be extremely poor.

(F) Component system may be used individually by 1 type, and may be used in combination of 2 or more types.

[Other ingredients] In the composition related to the present invention, in addition to the aforementioned components (A) to (F), other arbitrary components may be blended within the scope that does not impair the object of the present invention. Specific examples include the following. These other components may be used individually by 1 type, or may be used in combination of 2 or more types.

[(G)INGREDIENT] The condensation catalyst of component (G) is at least one selected from the group consisting of organic titanium compounds, organic zirconium compounds, and organic aluminum compounds. It is used to promote adhesion and serves as a condensation auxiliary catalyst for imparting adhesive functional groups in component (F). to play a role. Specific examples of component (G) include titanium tetraisopropoxide, titanium tetranormal butoxide, and titanium tetra-2-ethylhexoxide. Among organic titanium chelate compounds such as organic titanate, diisopropoxybis(ethyl acetyl acetate) titanium, diisopropoxy bis(ethyl acetyl acetate) titanium, tetraacetyl acetonate titanium, etc. Similar titanium-based condensation auxiliary catalysts (titanium compounds); organic zirconium esters such as zirconium tetra-n-propoxide and zirconium tetra-n-butoxide, zirconium tributoxy monoacetylpyruvate, bis-monobutoxyacetylpyruvate Zirconium-based condensation auxiliary catalysts (zirconium compounds) such as zirconium (ethyl acetate), zirconium tetraacetylpyruvate and other organic zirconium chelates; organic aluminum such as aluminum secondary butoxide Aluminum-based condensation auxiliary catalysts (aluminum compounds) such as acid esters, aluminum ethyl acetate, aluminum monoacetyl pyruvate, aluminum ethyl acetate, etc. .

The organic titanium compound, organic zirconium compound and organic aluminum compound of the component (G) are any components prepared according to the needs. The blending amount is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the component (A), and Preferably, it is 0.2~4 parts by mass. When the blending amount is within the range of 0.1 to 5 parts by mass, the resulting cured product will have excellent bonding durability or heat resistance under high temperature and high humidity.

(G) Component may be used individually by 1 type, and may be used in combination of 2 or more types.

[(H) Component] (H) Component is an organopolysiloxane resin with a three-dimensional network (resin-like) structure that is powdery at 25° C., and is preferably composed essentially of R ⁴ SiO ₃ selected from trifunctional It is composed of at least one branched chain siloxane unit / ₂ unit and tetrafunctional SiO ₂ unit. If necessary, it may also contain monofunctional R ⁴ ₃ SiO _1/2 unit and/or 2 An organopolysiloxane resin with a three-dimensional network structure of functional R ⁴ ₂ SiO _2/2 units (the organic group here may also include an alkenyl group), and functions as a flame resistance improving agent. However, this organopolysiloxane resin does not contain hydrogen atoms (SiH groups) bonded to silicon atoms. Furthermore, the organopolysiloxane resin has a three-dimensional network (resin-like) structure and is in powder form at 25°C, which is in contrast to the organopolysiloxane resin which has a substantially linear structure and is liquid at 25°C ( A) component, or oily or rubbery component (B), is clearly different. The organic polysiloxane resin in powder form is preferably spherical or slightly spherical.

R ⁴ in the above formula is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms) that is the same as or different from each other. Examples thereof include those in the component (A) above. Examples of alkenyl groups and monovalent organic groups (unsubstituted or substituted monovalent hydrocarbon groups) are the same, and specific examples include vinyl, allyl, propenyl, butenyl, pentenyl, and hexene. Alkenyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, etc.; phenyl, tolyl, xylene, etc. Aryl groups such as benzyl and naphthyl groups; aralkyl groups such as benzyl and phenethyl groups; halogen-substituted alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc., especially Therefore, methyl and vinyl are preferred.

(H) The content of the alkenyl group bonded to the silicon atom in the component, relative to the entire monovalent organic group (i.e., unsubstituted or substituted monovalent hydrocarbon group) bonded to the silicon atom, is in the range of 0 to 10 moles Mol % is preferred, especially about 2 to 8 mol %.

The organopolysiloxane resin of component (H) contains R ⁴ SiO _3/2 units and/or SiO ₂ units. The total amount in the organopolysiloxane resin of component (H) is 20 to 75 mol%. , in particular, it is better to set it to 30~60 mol%. Here, the organopolysiloxane resin of component (H) may optionally contain R ⁴ ₃ SiO _1/2 units and/or R ⁴ ₂ SiO _2/2 units as described above, and the total content is ( The H) component of the organopolysiloxane resin is 0 to 70 mol%, and particularly preferably 0 to 50 mol%. If the total amount of R ⁴ SiO _3/2 units and/or SiO ₂ units in the organopolysiloxane resin of component (H) is in the range of 20 to 75 mol%, a sufficient flame resistance improvement effect can be obtained , so it is suitable.

In addition, the organopolysiloxane resin of component (H) was determined by using toluene as a developing agent and using the weight average degree of polymerization (weight average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis. The price range is 2,000~50,000, especially 4,000~20,000 is better. When the weight average degree of polymerization is in the range of 2,000 to 50,000, a sufficient flame resistance improvement effect can be obtained and the viscosity of the liquid polysiloxane rubber composition can be improved with good coating workability.

Specific examples of the organopolysiloxane resin as the component (H) include siloxane units represented by the formula: R' ₃ SiO _0.5 and siloxane represented by the formula: R' ₂ R"SiO _0.5 . Alkane unit, an organosiloxane copolymer composed of a siloxane unit represented by the formula: R' ₂ SiO and a siloxane unit represented by the formula: SiO ₂ ; containing silicon represented by the formula: R' ₃ SiO _0.5 Oxane unit, formula: R' ₂ R" An organosiloxane copolymer composed of a siloxane unit represented by SiO _0.5 and a siloxane unit represented by the formula: SiO ₂ ; containing the formula: R' ₂ R" An organosiloxane copolymer composed of a siloxane unit represented by SiO _0.5 and the formula: R' ₂ A siloxane unit represented by SiO and a siloxane unit represented by the formula: SiO ₂ ; containing the formula: R' An organosiloxane copolymer composed of a siloxane unit represented by R”SiO and a siloxane unit represented by the formula: R′SiO _1.5 or a siloxane unit represented by the formula: R”SiO _1.5 ; and, A mixture containing two or more types of these organopolysiloxanes.

R' in the above formula is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms) that is the same as or different from each other other than an alkenyl group. Examples of this include methane Alkyl groups such as base, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, etc.; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; benzyl, phenethyl, etc. Aralkyl groups; halogenated alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc., especially methyl is preferred. In addition, R" in the above formula is an alkenyl group. Examples thereof include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, etc., with vinyl being particularly preferred. .

The compounding amount of component (H) is 0.1 to 100 parts by mass, preferably 1 to 90 parts by mass, and particularly preferably 3 to 80 parts by mass relative to 100 parts by mass of the organopolysiloxane of component (A). When the blending amount is in the range of 0.1 to 100 parts by mass, sufficient flame resistance improvement effect can be obtained, and the cost-effectiveness is also excellent.

However, when the component (H) contains an alkenyl group, the component (H) is preferably: "relative to the bonded silicon contained in the component (A), (B) and (H) in the composition. The total number of atomic alkenyl groups is 1 mol, and the SiH group contained in component (C) is 1 to 10 moles (or pieces), preferably 1.2 to 9 moles (or pieces), and preferably 1.2 to 9 moles (or pieces). The amount is 1.5~8 moles (or pieces)."

Furthermore, if additional explanation is given, when the (D) component, (F) component, and (H) component containing an alkenyl group are used in combination, the total number of SiH groups of each component in the composition may be considered. The ratio of the number of ears to the total number of alkenyl groups per mole is then adjusted. For example, if the silica fine powder of component (D) is used in a preliminarily powdered state and is directly surface hydrophobized with a surface treatment agent containing an alkenyl group, component (H) contains When the component (F) contains an alkenyl group and/or a SiH group, it is preferably: "With respect to the (A) component, (B) component, (D) component, and (H) in the composition The total of the alkenyl groups bonded to the silicon atoms (or nitrogen atoms) contained in the component and (F) is 1 mol, and the total of the SiH groups contained in the component (C) and (F) is 1 to 10 mol. ears, preferably 1.2~9 moles, and more preferably 1.5~8 moles." The reason for this is that if the total number of SiH groups is less than 1 mole relative to the total 1 mole of alkenyl groups bonded to silicon atoms in the composition, the composition may not be sufficiently hardened and may not exhibit sufficient strength. In the case of adhesive force, on the other hand, if the SiH group exceeds 10 moles, the heat resistance of the resulting cured polysilicone rubber will be extremely poor.

(H) The three-dimensional network organopolysiloxane resin system of component (H) may be used individually by 1 type, and may be used in combination of 2 or more types.

‧Reaction control agent The reaction control agent is not particularly limited as long as it is a compound that has an effect of inhibiting hardening of the hydrosilylation reaction catalyst of component (E), and a well-known compound can be used. Specific examples include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; and acetylene-based compounds such as acetylene alcohols. Compounds; compounds containing two or more alkenyl groups; hydrogen peroxide compounds; maleic acid derivatives, etc.

The degree of the effect of inhibiting hardening by a reaction control agent will vary depending on the chemical structure of the reaction control agent. Therefore, the amount of the reaction control agent added is preferably determined according to the type of reaction control used. dosage to adjust to the most suitable amount. By adding an optimal amount of reaction control agent, the composition has excellent long-term storage stability and hardening properties at room temperature.

‧Non-reinforcing filler Examples of fillers other than the silica fine powder of component (D) include: crystalline silica (for example, quartz powder with a BET method specific surface area of less than 50 m ² /g), organic Resin hollow fillers, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, carbon black, diatomaceous earth, talc, kaolinite, glass fiber, etc.; Fillers obtained by subjecting these fillers to surface hydrophobic treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds, etc.; polysilica Oxygen rubber powder, etc.

‧Other ingredients In addition, it can also be formulated, for example: organopolysiloxane containing one hydrogen atom bonded to a silicon atom in one molecule but no other functional groups; one alkenyl group containing one alkenyl group bonded to a silicon atom in one molecule Organopolysiloxanes with a weight average polymerization degree of less than 2,000 but containing no other functional groups; none containing hydrogen atoms bonded to silicon atoms, alkenyl groups bonded to silicon atoms, or other functional groups Functional organic polysiloxane (so-called dimethylpolysiloxane oil); organic solvents; anti-creep hardeners; plasticizers; thixotropic agents; pigments; dyes; antifungal agents, etc.

＜Preparation of addition-hardening liquid polysilicone rubber composition＞ The above-mentioned components (A) to (F), components (G) and (H) other than these, and other components prepared according to the needs are uniformly mixed to prepare an addition hardening type. Liquid polysilicone rubber composition. The viscosity of the addition-hardening liquid polysiloxane rubber composition obtained in this manner is measured at 25°C based on the method described in JIS K 7117-1: 1999. The composition is liquid at 25°C. It is 1~1,000Pa‧s, preferably 10~300Pa‧s. If the viscosity is within the range of 1 to 1,000 Pa‧s at 25°C, when applied to the base fabric for airbags, uneven coating or insufficient adhesion to the base fabric after hardening is unlikely to occur, so it is suitable for use. .

＜Base fabric for airbags＞ Generally, as the airbag base fabric (base material containing fiber cloth) formed with a polysilicone rubber layer, a well-known fabric can be used. Specific examples include 6,6-nylon, 6-nylon, and aromatic fabric. Base fabrics of various polyamide fibers such as polyamide fibers, various polyester fibers such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and other synthetic fibers .

＜How to manufacture airbags＞ The above-mentioned addition curing liquid polysiloxane rubber composition is coated on at least one surface of the airbag base cloth (a base material containing fiber cloth), especially on one surface, and then by It is heated and hardened using a drying oven or the like to form a polysilicone rubber layer (hardened material layer). An airbag can be manufactured using the silicone rubber-coated base fabric for airbags obtained in this way.

Here, as a method of applying the addition curing liquid polysilicone rubber composition to the airbag base fabric, a conventional method can be used, and application by a blade coater is preferred. The thickness of the coating layer (or surface coating amount) can generally be set to 10~100g/ ^m2 , preferably 12~90g/ ^m2 , and still more preferably 15~80g/ ^m2 .

The addition-hardening liquid polysiloxane rubber composition can be hardened under well-known curing conditions and by a well-known curing method. Specifically, the composition can be hardened by heating at 100 to 200° C. for 1 to 30 minutes.

When the base fabric for airbags (polysilicone rubber-coated base fabric for airbags) produced in this way and having a silicone rubber layer on at least one surface is processed into an airbag, the following can be used The manufacturing method is as follows: At least the inner side of the airbag is bonded with an adhesive between the outer peripheral parts of two pieces of plain woven fabric coated with polysiloxane rubber, and the adhesive layers are sewn together to create a safety Air bag method. Alternatively, the following production method may be adopted: on both outer sides of the airbag base fabric that has been woven in advance, addition-hardening liquid polysilica is coated in a specified coating amount as described above. A method of hardening an oxygen rubber composition under specified hardening conditions. Incidentally, as the adhesive used here, well-known ones can be used, but in terms of adhesion strength, adhesion durability, etc., a polysiloxane-based adhesive called a seam sealant is suitable. [Example]

Hereinafter, the present invention will be specifically explained by showing the preparation examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. However, the viscosity is measured at room temperature (25°C) with a rotational viscometer. In addition, the average degree of polymerization means the weight average degree of polymerization.

[Preparation Example 1] Into the kneading machine: Dimethylpolysilica, which has a viscosity of 30,000 mPa‧s at 25°C and an average degree of polymerization of 750, is terminated with vinyldimethylsilyloxy groups at both ends of the molecular chain. 60 parts by mass of oxane (A1), 8 parts by mass of hexamethyldisilazane, 2 parts by mass of water, silica fine powder (D) with a specific surface area measured by the BET method of 300 m ² /g (Aerosil 300, (manufactured by Japan Aerosil Co., Ltd.) 40 parts by mass, and mixed at room temperature for 1 hour. After that, 8 parts by mass of hexamethyldisilazane was added and mixed for another hour. The temperature was then increased to 150°C and mixing was continued for a further 2 hours. Then, after cooling to room temperature, add: 25 parts by mass of dimethyl polysiloxane (A1), which has a viscosity of 30,000 mPa‧s at 25°C and is terminated with vinyldimethylsiloxy groups at both ends of the molecular chain; Dimethyl-vinylmethyl polysiloxane (A2), which has a viscosity of 700 mPa‧s at 25°C and an average degree of polymerization of 200, is terminated with trimethylsiloxy groups at both ends of the molecular chain (this constitutes the main chain The 2-functional diorganosiloxane unit contains 5 mol% of vinylmethylsiloxane units and 95 mol% of dimethylsiloxane units) 5 parts by mass, and is mixed until uniform to obtain Matrix compound (1).

[Example 1] 75 parts by mass of the matrix compound (1) obtained in Preparation Example 1 was mixed with vinyldimethylsiloxy-terminated vinyl dimethylsiloxy groups at both ends of the molecular chain with a viscosity of approximately 1,000 mPa‧s at 25°C and an average degree of polymerization of 200. 58.5 parts by mass of methylpolysiloxane (A3) and 8 parts by mass of dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000, which are terminated at both ends of the molecular chain with trimethylsiloxy groups, as a cross-linking agent The viscosity at 25℃ is 45mPa‧s and the molecular chain branches have hydrogen atoms bonded to silicon atoms at both ends of the molecular chain. Trimethylsiloxy-terminated dimethylsiloxane‧methylhydrogenated siloxane copolymer 5 parts by mass of substance (C) (content of hydrogen atoms bonded to silicon atoms = 0.0108 mol/g), 0.28 parts by mass of γ-glycidoxypropyltrimethoxysilane (F), 1-ethynylcyclohexane 0.05 parts by mass of alcohol and 0.23 parts by mass of a dimethylpolysiloxane solution (E) containing a chloroplatinic acid/1,3-divinyltetramethyldisiloxane complex with a platinum atom content of 1% by mass. , and mixed for 1 hour to prepare composition A (SiH group/vinyl group in the entire composition = 5.1 mol/mol, viscosity 35 Pa‧s).

<Adhesion test> Using a blade coater, apply composition A to 66 nylon base fabric (210 denier) and PET base fabric (495 denier) for ^airbags so that the surface coating amount becomes 25~30g/m2 denier), and then heat and harden it in a dryer at 200°C for 1 minute to produce an airbag base fabric coated with a cured polysilicone rubber material. For the above-mentioned polysilicone rubber-coated nylon base fabric and PET base fabric, a Scott rubbing tester (device name: Scott rub resistance wear tester, Toyo Seiki Manufacturing Co., Ltd.) was used according to the method described in JIS K 6404-6: 1999. company system) to evaluate adhesion. After conducting a 500-time rubbing test with a pressing pressure of 19.6N, visually confirm the damage of the coated part. If the polysilicone rubber layer does not peel off from the coated surface, it is evaluated as qualified; if it does peel off, , it is evaluated as unqualified.

＜Caking resistance test＞ A test was conducted to evaluate the adhesive feeling on the surface of the rubber coating layer. The prepared silicone rubber-coated base fabric for airbags is cut into a width of 100mm x a length of 200mm, and the silicone rubber-coated surface of the obtained film-forming cloth is connected to the glass in a manner that prevents air from entering. The board is tight. The glass plate closely adhered to the film-forming cloth was placed vertically, and the elapsed time until the film-forming cloth naturally fell off the glass plate was measured, and the evaluation was performed based on the following evaluation criteria. As mentioned above, if the glass plate tightly adhered to the film-forming cloth is placed vertically, and the elapsed time from the vertical placement until the film-forming cloth falls off the glass plate is less than 1 second, it is evaluated as "good" ; If it is more than 1 second and less than 6 seconds, it is evaluated as "OK"; if it is more than 6 seconds, it is evaluated as "Bad".

[Example 2] In addition to using dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000 to terminate both ends of the molecular chain in Example 1 with trimethylsiloxy groups, the same mass parts of dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000 were used. The composition B was prepared in the same manner except that the terminal vinyl dimethyl siloxane group was capped with dimethyl polysiloxane (B2) (B2) for substitution (SiH group/vinyl group in the entire composition = 5.0 mol /mol, viscosity 25 Pa‧s), and the adhesion test and caking resistance test were conducted in the same manner as in Example 1, and the results are shown in Table 1.

[Example 3] In Example 1, except for adding 0.3 parts by mass of zirconium tetraethylpyruvate (G), the composition C was prepared in the same manner (SiH group/vinyl group in the entire composition = 5.1 mol/mol, viscosity 25Pa·s), and the adhesion test and caking resistance test were conducted in the same manner as in Example 1, and the results are shown in Table 1.

[Example 4] For 100 parts by mass of the matrix compound (1) obtained in Preparation Example 1, vinyldimethylsilane at both ends of the molecular chain having a viscosity of approximately 1,000 mPa‧s at 25°C and an average degree of polymerization of 200 was mixed. 97.5 parts by mass of oxygen-terminated dimethylpolysiloxane (A3), and 10 parts by mass of dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000 at both ends of the molecular chain using trimethylsiloxy groups. , a powder containing 39.5 mol% of (CH ₃ ) ₃ SiO _1/2 unit, 6.5 mol% of (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 unit and 54 mol% of SiO ₂ unit 25 parts by mass of organopolysiloxane resin (H) (weight average molecular weight: 6,000) with a three-dimensional network structure, a cross-linking agent with a viscosity of 45 mPa‧s at 25°C, and a molecular chain branch with bonded silicon Trimethylsiloxy-terminated dimethylsiloxane-methylhydrogenated siloxane copolymer (C) at both ends of the molecular chain of hydrogen atoms (content of hydrogen atoms bonded to silicon atoms = 0.0108 mol/ g) 17 parts by mass, 0.9 parts by mass of γ-glycidoxypropyltrimethoxysilane (F), 0.09 parts by mass of 1-ethynylcyclohexanol, chloroplatinic acid with a platinum atom content of 1% by mass/1 , 0.45 parts by mass of dimethylpolysiloxane solution (E) of 3-divinyltetramethyldisiloxane complex and 0.3 parts by mass of zirconium tetraacetylpyruvate (G), and mixed for 1 hour After that, composition D was prepared (SiH group/vinyl group in the entire composition = 5.1 mol/mol, viscosity 25 Pa‧s), and the adhesion test and caking resistance test were conducted in the same manner as in Example 1, and the results were compared Shown in Table 1.

[Comparative example 1] In addition to dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000, in which both ends of the molecular chain of Example 1 are terminated with trimethylsiloxy groups, the viscosity of the same mass part at 25°C is about 1,000mPa ‧s, except that vinyldimethylsiloxy-terminated dimethylpolysiloxane (A3) at both ends of the molecular chain with an average degree of polymerization of 200 is used for substitution, the rest are prepared in the same way as composition E (composition SiH group/vinyl group in the entire material = 4.8 mol/mol, viscosity 10 Pa·s), and the adhesion test and caking resistance test were conducted in the same manner as in Example 1. The results are shown in Table 1.

[Comparative example 2] In addition to using dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000 to terminate both ends of the molecular chain in Example 1 using trimethylsiloxy groups, using the same mass parts of both ends of the molecular chain using trimethylsiloxane The composition F was prepared in the same manner except that dimethylpolysiloxane with an average polymerization degree of 1,500 at the end of the oxygen group was substituted (SiH group/vinyl group in the entire composition = 5.1 mol/mol, viscosity 15 Pa·s), and the adhesion test and caking resistance test were conducted in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative example 3] In addition to using dimethylpolysiloxane (B1) with an average degree of polymerization of 6,000 to terminate both ends of the molecular chain in Example 1 using trimethylsiloxy groups, using the same mass parts of both ends of the molecular chain using trimethylsiloxane Dimethyl-vinylmethylpolysiloxane with an oxygen-terminated average degree of polymerization of 6,000 (the bifunctional diorganosiloxane units constituting the main chain contain 0.25 mol% of vinylmethylsiloxane Except for the substitution of alkane units and 99.75 mol% dimethylsiloxane units, composition G was prepared in the same manner (SiH group/vinyl group in the entire composition = 4.9 mol/mol, viscosity 22 Pa ‧s), and the adhesion test and caking resistance test were conducted in the same manner as in Example 1, and the results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Composition A B C D E F G ＜Adhesion test＞ Nylon 66 base fabric qualified qualified qualified qualified Unqualified qualified qualified PET base fabric qualified qualified qualified qualified Unqualified Unqualified Unqualified ＜Caking resistance test＞ good good good good Can Can Can

Claims (5)

An addition-hardening liquid polysiloxane rubber composition for airbags, characterized by containing the following components (A) to (F) as essential components, and (A) contains at both ends of the molecular chain in one molecule Linear diorganopolysiloxane with two or more alkenyl groups bonded to silicon atoms and a weight average degree of polymerization of 100 to 1,000: 100 parts by mass, (B) One molecule contains 0 to 3 bonded to Organopolysiloxane with an alkenyl group of silicon atoms and a weight average degree of polymerization of 3,000 to 10,000: 1 to 20 parts by mass, (C) containing at least 2 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule Organohydrogenated polysiloxane: The number of SiH groups contained in this component is 1 to 10 moles per 1 mol of the total alkenyl groups bonded to silicon atoms contained in component (A) and component (B). The amount of an ear, (D) Silica fine powder with a BET method specific surface area of 50 m ² /g or more: 1 to 50 parts by mass, (E) Catalyst for hydrosilylation reaction: relative to (A) component ~ (D ) The total mass of the components, converted to 1 to 500 ppm based on the mass of the catalytic metal element, (F) contains an organosilicon compound that provides an adhesive functional group (but does not include (A) component, (B) component, (C) Ingredients): 0.1~10 parts by mass. The addition-hardening liquid polysiloxane rubber composition for airbags according to Claim 1, which further contains as component (G) a condensation of at least one selected from the group consisting of an organic titanium compound, an organic zirconium compound, and an organic aluminum compound. Catalyst, and relative to 100 parts by mass of component (A), component (G) is 0.1 to 5 parts by mass. For example, the addition-hardening liquid polysiloxane rubber composition for airbags according to claim 1 or 2 further contains a powdery three-dimensional network organopolysiloxane resin as the component (H) (however, the The molecule of the organopolysiloxane resin does not contain hydrogen atoms bonded to silicon atoms, and does not include component (A) or component (B)), and (H) component is 0.1 with respect to 100 parts by mass of component (A) ~100 parts by mass. For example, the addition-hardening liquid polysiloxy rubber composition for airbags according to claim 1 or 2, wherein component (F) contains an alkoxy group (alkoxysilane) selected from an epoxy group and a silicon atom-bonded group. An organic silicon compound that provides an adhesive functional group at least one of a group), a hydrogenated silyl group, an isocyanate group, an acryl group, and a methacrylate group. An airbag, characterized by having a hardened film of the addition-hardening liquid polysiloxane rubber composition for airbags according to any one of claims 1 to 4 on a base fabric for airbags.