JP2009221364A - Liquid silicone rubber coating composition, air bag, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid silicone rubber coating composition which provides a cured product excellent in insulation properties and antistatic properties not only before exposure to high temperatures but also after the exposure, and in particular, which can be suitably used to manufacture an air bag, an air bag having a silicone rubber coating layer composed of a cured product of the composition, and a method for producing the air bag. <P>SOLUTION: Provided is a liquid silicone rubber coating composition, including predetermined quantities of (A) an organopolysiloxane containing 2 or more Si atom-bonded alkenyl groups, (B) an organohydrogenpolysiloxane containing 2 or more SiH groups, (C) an addition reaction catalyst, (D) a finely powdered silica with a specific surface area of at least 50 m<SP>2</SP>/g, (E) an organosilicon compound containing an epoxy group and a Si atom-bonded alkoxy group and/or a hydrosilyl group, and (F) a titanium compound and/or a zirconium compound, and (G) an ion conductive antistatic agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is suitable for producing an air bag of a vehicle or the like in which a silicone rubber coating film is formed on a fiber cloth such as 6,6-nylon, 6-nylon, and polyester, and particularly only before exposure to a high temperature. Liquid silicone rubber coating agent composition suitable for producing an air bag excellent in insulation and antistatic properties even after exposure, an air bag having a silicone rubber coating layer comprising a cured product of the composition, and a method for producing the same About.

  Since the cured product of the liquid silicone rubber coating composition has excellent properties such as weather resistance, heat resistance, and cold resistance, the silicone rubber coating layer made of the cured product is widely used in airbags. .

  The liquid silicone rubber coating composition is generally supplied in a state containing an organopolysiloxane having a high polymerization degree and a reinforcing filler. This composition is prepared by mixing a reinforcing filler and various dispersants with a raw material polymer containing organopolysiloxane using a mixing apparatus such as a dough mixer or a two-roll mill. Reinforcing fillers such as organopolysiloxane and silica are electrically insulating materials. Therefore, the liquid silicone rubber coating composition obtained by blending these and the cured product thereof are charged by contact with various substances, generating static electricity and adsorbing dust in the air. There is.

  Conventionally, an antistatic rubber uses a polyether compound (Patent Document 1) and carbon black (Patent Documents 2 and 3) as an antistatic agent. When a polyether-based compound is used as an antistatic agent, the polyether-based compound is decomposed at a high temperature, and the resulting cured product not only exhibits an antistatic effect but also has reduced physical properties. . When carbon black is used as an antistatic agent, the obtained cured product has problems that it is difficult to maintain electrical insulation or that the color is limited to black.

  Patent Document 4 describes a silicone rubber composition for a semiconductive roller in which a lithium salt is blended with a thermosetting organopolysiloxane composition, but the invention described in the patent document does not relate to an insulating material. Absent. Further, in order to make the cured product of the composition semi-conductive by adding an ionic conductive agent, it is necessary to add a large amount of ionic conductive agent, so that the resulting cured product has a large decrease in rubber properties.

Special Table 2002-500237 Special table 2002-507240 gazette JP 2002-327122 A JP 2003-82232 A

  The present invention has been made in view of the above circumstances, and provides a cured product excellent in insulation and antistatic properties not only before exposure to high temperatures but also after exposure, and in particular, for producing an air bag. It is an object of the present invention to provide a liquid silicone rubber coating composition that can be suitably used, an air bag having a silicone rubber coating layer comprising a cured product of the composition, and a method for producing the air bag. .

As a result of intensive studies to achieve the above object, the present inventor has (A) an organopolysiloxane containing two or more alkenyl groups bonded to a silicon atom in one molecule, and (B) silicon in one molecule. Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to atoms, (C) addition reaction catalyst, preferably (D) fine powder silica having a specific surface area of 50 m ² / g or more, (E) epoxy in one molecule Containing silicon group-bonded alkoxy group and / or hydrosilyl group (SiH group), (F) titanium compound and / or zirconium compound, and (G) ion conductive antistatic agent The cured product of the liquid silicone rubber coating composition thus obtained has an insulating property not only before exposure but also after exposure. Found that excellent fine antistatic property, the present invention has been accomplished.

Therefore, the present invention firstly
(A) Organopolysiloxane containing two or more alkenyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: The total number of hydrogen atoms bonded to silicon atoms contained in the composition is An amount of 1 to 10 silicon atom-bonded alkenyl groups,
(C) addition reaction catalyst: effective amount,
(D) Fine powder silica having a specific surface area of 50 m ² / g or more: 0 to 50 parts by mass,
(E) Organosilicon compound having an epoxy group and a silicon atom-bonded alkoxy group and / or a hydrosilyl group in one molecule: 0.1 to 10 parts by mass,
And (F) any one or both of a titanium compound and a zirconium compound: 0.1 to 5 parts by mass (G) an ionic conductive antistatic agent: a liquid silicone rubber coating agent containing 0.0001 to 5 parts by mass A composition is provided.

The present invention secondly,
A substrate made of fiber cloth;
An air bag comprising a cured product of the above composition and having a silicone rubber coating layer formed on at least one surface of the substrate.

Third, the present invention
Applying the above composition to at least one surface of a substrate made of fiber cloth,
There is provided a method for producing the above-described airbag, which comprises forming a silicone rubber coating layer comprising a cured product of the composition on at least one surface of the substrate by curing the composition.

  According to the present invention, a liquid silicone rubber coating composition that provides a cured product excellent in insulation and antistatic properties not only before exposure to high temperature but also after exposure can be obtained. By using the composition of the present invention, an air bag excellent in insulation and antistatic properties can be obtained not only before exposure but also after exposure by the production method of the present invention.

  Hereinafter, the present invention will be described in more detail. In the present invention, the viscosity is a value measured with a rotational viscometer.

<Liquid silicone rubber coating composition>
The liquid silicone rubber coating composition of the present invention contains the following components (A) to (G), and is liquid at room temperature (meaning 25 ° C., hereinafter the same). . Hereinafter, each component will be described in detail.

[(A) component]
The organopolysiloxane of component (A) contains 2 or more (usually 2 to 50) alkenyl groups bonded to silicon atoms in one molecule, preferably about 2 to 20, and is a composition of the present invention. The base polymer of the product. The (A) component organopolysiloxane may be used alone or in combination of two or more.

  Examples of the molecular structure of the component (A) include linear, cyclic, branched, and three-dimensional networks, but the main chain is basically composed of repeating diorganosiloxane units, and both ends of the molecular chain are A linear diorganopolysiloxane blocked with a triorganosiloxy group is preferred (note that these organo groups may include alkenyl groups). Further, when the molecular structure of the organopolysiloxane of component (A) is linear or branched, the position of the silicon atom to which the alkenyl group is bonded in the molecule of the organopolysiloxane is the molecular chain end and molecular chain. Either one of them may be used on the way (non-terminal molecular chain). Particularly preferably, the component (A) is a linear diorganopolysiloxane containing 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 those having the same or different unsubstituted or substituted, usually 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, a heptenyl group, and the like, and a vinyl group is particularly preferable.

  The content of the alkenyl group bonded to the silicon atom in the component (A) is preferably 0.001 to 10 mol% with respect to the total monovalent organic group bonded to the silicon atom, particularly 0.01 to It is preferably about 5 mol%.

  Examples of the monovalent organic group bonded to the silicon atom other than the alkenyl group as component (A) include, for example, the same or different unsubstituted or substituted non-aliphatic unsaturated bond, usually 1 carbon atom. -12, preferably a monovalent hydrocarbon group having about 1 to 10 carbon atoms. When the monovalent hydrocarbon group is substituted, examples thereof include halogen-substituted ones. Specific examples of the organic group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group; phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aryl groups; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group, etc. It is preferably a group.

  The viscosity of component (A) at 25 ° C. is preferably in the range of 100 to 500,000 mPa · s, particularly preferably in the range of 300 to 100,000 mPa · s. When the viscosity is within this range, the workability of the resulting composition is good, and the physical properties of the resulting silicone rubber are good.

As a preferable example of the component (A), the following average composition formula (1)
R _a SiO _{(4-a) / 2} (1)
(In the formula, R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and a is 1.5 to 2.8, preferably 1 0.8 to 2.5, more preferably a positive number in the range of 1.95 to 2.05, provided that 0.001 to 10 mol%, preferably 0.01 to 5 mol% of the total R is an alkenyl group. .)
The organopolysiloxane shown by these is mentioned. Specific examples of R include alkenyl groups specifically mentioned above as alkenyl groups bonded to silicon atoms in component (A), and organic groups bonded to silicon atoms other than alkenyl groups in component (A) above. And organic groups specifically mentioned in the above.

Specific examples of the organopolysiloxane of component (A) include: a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of a molecular chain, a trimethylsiloxy group-capped methylvinylpolysiloxane with a molecular chain at both ends, and a trimethylsiloxy group with both ends of a molecular chain. Siloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, dimethylvinylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, dimethylvinylsiloxy group-blocked methylvinylpolysiloxane at both ends of the molecular chain, dimethylvinyl at both ends of the molecular chain Siloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain Terminal divinylmethylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends divinylmethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trivinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends trivinylsiloxy group Blocked dimethylsiloxane / methylvinylsiloxane copolymer, siloxane unit represented by the formula: R ¹ ₃ SiO _0.5 and siloxane unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and siloxane unit represented by the formula: R ¹ ₂ SiO And an organosiloxane copolymer comprising a siloxane unit represented by the formula: SiO ₂ , a siloxane unit represented by the formula: R ¹ ₃ SiO _0.5 and a siloxane unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and a formula: SiO organosiloxane copolymers consisting of siloxane units represented by ₂ , Wherein: the siloxane units represented by the formula R ^{1 ₂} R ₂ SiO _0.5: siloxane units represented by the formula R ¹ ₂ SiO: organosiloxane copolymers consisting of siloxane units represented by SiO _2, wherein: R ¹ Organosiloxane copolymers comprising a siloxane unit represented by R ² SiO and a siloxane unit represented by the formula: R ¹ SiO _1.5 or a siloxane unit represented by the formula: R ² SiO _1.5 , and two types of these organopolysiloxanes The mixture which consists of the above is mentioned.

R ¹ in the above formula is an identical or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, which does not contain an aliphatic unsaturated bond. Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and heptyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group Aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group; R ² in the above formula is an unsubstituted or substituted alkenyl group having 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, which is the same or different from each other. , Allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and the like.

[Component (B)]
The (B) component organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with the (A) component and acts as a crosslinking agent. The (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more. There is no restriction | limiting in particular in the molecular structure of (B) component, For example, any structure of a linear form, cyclic | annular form, a branched form, and a three-dimensional network shape may be sufficient.

  The organohydrogenpolysiloxane of component (B) contains at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms (ie, hydrosilyl group or SiH) in one molecule. When the organohydrogenpolysiloxane of component (B) has a linear structure, these SiH groups are located only at either the molecular chain end or in the middle of the molecular chain (that is, the molecular chain non-terminal). Or both.

  The number (degree of polymerization) of silicon atoms in one molecule of the component (B) is preferably 2 to 300, more preferably about 4 to 150. Furthermore, the component (B) is preferably liquid at room temperature (25 ° C.), and the viscosity of the component (B) at 25 ° C. is preferably 0.1 to 1,000 mPa · s, more preferably 0.5 to It is about 500 mPa · s.

As the component (B), for example, represented by the following average composition formula (2), at least 2 (usually 2 to 300), preferably 3 or more, more preferably 3 to 150 silicon in one molecule An organohydrogenpolysiloxane having an atom-bonded hydrogen atom is preferably used.
R ³ _b H _c SiO _{(4-bc) / 2} (2)
(In the formula, R ³ is a monovalent carbon atom bonded to a silicon atom having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, which is the same or different, unsubstituted or substituted, and does not contain an aliphatic unsaturated bond. A hydrogen group, b is a positive number from 0.7 to 2.1, c is a positive number from 0.001 to 1.0, and b + c is a positive number from 0.8 to 3.0. .)

Examples of the monovalent hydrocarbon group for R ³ include the same groups as those exemplified for R ¹ . Further, b is preferably a positive number of 0.8 to 2.0, c is preferably a positive number of 0.01 to 1.0, and b + c is preferably a positive number of 1.0 to 2.5. It is.

Examples of the organohydrogenpolysiloxane of component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrogensiloxane cyclic polymer, methyl Hydrogensiloxane / dimethylsiloxane cyclic copolymer, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy Block-capped dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy-capped dimethylpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy-capped methyl with molecular chain at both ends Idrogen polysiloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxane at both ends Siloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units And a copolymer comprising SiO _4/2 units and (C ₆ H ₅ ) SiO _3/2 units.

  The blending amount of the component (B) is such that the number of silicon atom-bonded hydrogen atoms in the composition is usually 1 to 10, particularly preferably 1 with respect to one silicon atom-bonded alkenyl group in the component (A). It is an amount that falls within the range of ˜7. When the blending amount is such that the number of silicon-bonded hydrogen atoms in the composition is less than 1 for one silicon-bonded alkenyl group in component (A), the resulting composition is not cured. It tends to be enough. Further, when the blending amount is more than 10 silicon atom-bonded hydrogen atoms in the present composition with respect to one silicon atom-bonded alkenyl group in the component (A), the heat resistance of the resulting silicone rubber Tends to be extremely inferior.

  The component (E) described later contained in the composition of the present invention can also optionally have a hydrogen atom bonded to a silicon atom. Furthermore, in the composition of the present invention, an organohydrogenpolysiloxane other than the component (B) and the component (E) can be blended as an optional component. In this case, the number of SiH groups contained in the total organohydrogenpolysiloxane obtained by summing up the (B) component, the (E) component, and the organohydrogenpolysiloxane other than the (B) component and the (E) component is (A). The number of SiH groups in the component (B) relative to the total number of SiH groups is preferably 1 to 10, particularly 1 to 7 with respect to one silicon atom-bonded alkenyl group in the component. It is desirable to be about 5 to 1, particularly about 0.7 to 1. When the organohydrogenpolysiloxane is not included in addition to the component (B), the number of silicon-bonded hydrogen atoms in the component (B) is 1 to 1 for one silicon-bonded alkenyl group in the component (A). Ten, preferably 1-7.

[Component (C)]
As the addition reaction catalyst for component (C), any catalyst can be used as long as it promotes the hydrosilylation addition reaction between the silicon-bonded alkenyl group in component (A) and the SiH group in component (B). Also good. (C) A component may be used individually by 1 type, or may use 2 or more types together. Examples of the component (C) include platinum group metals such as platinum, palladium and rhodium, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, coordination compounds of vinylsiloxane or acetylene compounds, tetrakis ( Platinum group metal compounds such as triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium may be mentioned, with platinum compounds being particularly preferred.

  The compounding amount of the component (C) may be an effective amount (so-called catalyst amount) as an addition reaction catalyst, and is usually 0.5 to 5 in terms of the mass of the catalytic metal element with respect to the total mass of the components (A) and (B). 1,000 ppm, preferably in the range of 1 to 500 ppm, more preferably in the range of 10 to 100 ppm. If the blending amount is within this range, the addition reaction is likely to be sufficiently promoted, the curing is likely to be sufficient, and the rate of the addition reaction is easily improved as the blending amount increases. It tends to be advantageous.

[(D) component]
The finely divided silica of component (D) optionally used in the present invention as required functions as a reinforcing agent. That is, high tear strength is imparted to the cured product of the composition of the present invention. By using fine powder silica of component (D) as a reinforcing agent, a coating film having excellent tear strength characteristics can be formed. The fine powder silica of component (D) has a specific surface area of usually 50 m ² / g or more, preferably 50 to 400 m ² / g, particularly preferably 100 to 300 m ² / g. When the specific surface area is in this range, it is easy to impart excellent tear strength characteristics to the resulting cured product. The specific surface area is measured by the BET method. (D) A component may be used individually by 1 type, or may use 2 or more types together.

  As the fine powder silica of component (D), as long as the specific surface area is within the above range, known ones conventionally used as reinforcing fillers for silicone rubber can be used. For example, fumed silica, Examples include precipitated silica.

  These finely divided silicas may be used as they are, but in order to easily give better fluidity to the composition of the present invention, methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane; dimethyl Polysiloxane; preferably used as hydrophobic fine powder silica by subjecting it to surface hydrophobization treatment with an organosilicon compound such as hexaorganodisilazane such as hexamethyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane, etc. .

  (D) The compounding quantity of a component is 50 mass parts or less (namely, 0-50 mass parts) with respect to 100 mass parts of (A) component organopolysiloxane. When the blending amount exceeds 50 parts by mass, the fluidity of the composition tends to be lowered and the coating workability tends to be deteriorated. The blending amount is preferably 0.1 to 50 parts by mass, more preferably 1 to 50 parts by mass, and particularly preferably 5 to 40 parts by mass. When the blending amount is within this range, it is easy to give particularly good high tear strength to the cured product of the composition of the present invention.

[(E) component]
As component (E), an epoxy group and a silicon atom-bonded alkoxy group (for example, as an alkoxysilyl group such as trialkoxysilyl group, organodialkoxysilyl group, diorganoalkoxysilyl group) and / or hydrosilyl in one molecule Any organosilicon compound can be used as long as it is an organosilicon compound having a group (SiH group). From the viewpoint of adhesion development, at least one epoxy group and at least two silicon-bonded alkoxy groups and / or Or an organosilicon compound having a hydrosilyl group (SiH group), for example, a silane having at least one epoxy group and at least two silicon atom-bonded alkoxy groups, or 2 to 30 silicon atoms, preferably 4 ~ 20, at least one epoxy group and at least 2 It is preferable for the silicon-bonded alkoxy groups and / or hydrosilyl groups is a cyclic or linear siloxane having (SiH group) and. (E) A component may be used individually by 1 type, or may use 2 or more types together.

  The epoxy group is a silicon atom in the form of, for example, a glycidoxyalkyl group such as a glycidoxypropyl group; an epoxy-containing cyclohexylalkyl group such as a 2,3-epoxycyclohexylethyl group or a 3,4-epoxycyclohexylethyl group. It is preferable that it is couple | bonded with. A silicon atom-bonded alkoxy group is bonded to a silicon atom, for example, a trialkoxysilyl group such as a trimethoxysilyl group or a triethoxysilyl group; a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldiethoxy An alkyl dialkoxysilyl group such as a silyl group is preferably formed.

  The component (E) is composed of, for example, an alkenyl group such as a vinyl group, an acryloxy group, or a methacryloxy group as a functional group other than an epoxy group, a silicon atom-bonded alkoxy group, and a hydrosilyl group (SiH group) in one molecule. It may have at least one functional group selected from the group.

  Examples of the organosilicon compound of component (E) include organosilicon compounds represented by the following chemical formula, mixtures of two or more of these, or one or more partially hydrolyzed condensates of these. .

（式中、ｎは１〜１０の整数、ｍは０〜１００の整数、好ましくは０〜２０の整数、ｐは１〜１００の整数、好ましくは１〜２０の整数、ｑは１〜１０の整数である。）

(In the formula, n is an integer of 1 to 10, m is an integer of 0 to 100, preferably an integer of 0 to 20, p is an integer of 1 to 100, preferably an integer of 1 to 20, and q is an integer of 1 to 10. (It is an integer.)

  (E) The compounding quantity of component is 0.1-10 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, Preferably it is 0.5-5 mass parts. When the blending amount is less than 0.1 parts by mass, the resulting composition may not have sufficient adhesive strength. When the blending amount exceeds 10 parts by mass, even if the blending amount is increased, the resulting composition is difficult to improve adhesive force, tends to be expensive, and is uneconomical.

[(F) component]
The component (F) is one or both of a titanium compound (particularly, an organic titanium compound) and a zirconium compound (particularly, an organic zirconium compound), and acts as a condensation promoter for promoting adhesion. (F) A component may be used individually by 1 type, or may use 2 or more types together. Examples of the component (F) include organic titanates such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra-2-ethylhexoxide, titanium diisopropoxy bis (acetylacetonate), titanium diiso Titanium-based condensation promoters such as organic titanium chelate compounds such as propoxybis (ethyl acetoacetate) and titanium tetraacetylacetonate, organic zirconium esters such as zirconium tetranormal propoxide and zirconium tetranormal butoxide, zirconium tributoxy monoacetylacetonate , Zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate), zirconium tetraacetylacetonate and other zirconium compounds such as organic zirconium chelate compounds Co-catalyst, and the like.

  (F) The compounding quantity of a component is 0.1-5 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 0.2-2 mass parts. When the blending amount is less than 0.1 parts by mass, the obtained cured product is likely to have poor adhesion durability under high temperature and high humidity. If the blending amount exceeds 5 parts by mass, the resulting cured product is likely to be deteriorated in heat resistance.

[(G) component]
The ion conductive antistatic agent of component (G) is not an electronic conductive material such as carbon black but an ion conductive material. The component (G) is not particularly limited as long as it is an ion conductive material, but is preferably a lithium salt.

Specific examples of the component _{(G), LiBF 4, LiClO 4, LiPF} 6, LiAsF 6, LiSbF 6, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiSO 3 C 4 F 9, LiC (SO 2 _{CF 3) 3, LiB (C} 6 H 5) 4 and the like.
(G) A component may be used individually by 1 type and may use 2 or more types together.

  The form of the ion conductive antistatic agent of component (G) is not particularly limited, and component (G) alone may be used, but component (G) is more uniformly dispersed in the composition of the present invention, resulting in a more stable effect. A paste containing the component (G) and the organopolysiloxane is preferable so as to exert the effect. In this case, the organopolysiloxane may be the same as or different from the component (A), and may be in the form of raw rubber or oil. The organopolysiloxane is preferably dimethylpolysiloxane or methylvinylpolysiloxane, and both ends of the molecular chain are preferably blocked with dimethylvinylsiloxy groups and trimethylsiloxy groups. Moreover, in order to improve workability | operativity, you may add fillers, such as reinforcing silica and diatomaceous earth, to this paste. The concentration of the component (G) in the paste is preferably 2 to 90% by mass, more preferably 5 to 80% by mass, and particularly preferably 10 to 50% by mass.

  Component (G) is usually added in an amount of 0.0001 to 5 parts by weight, preferably 0.0005 to 3 parts by weight, more preferably 0.001 to 1 part by weight per 100 parts by weight of component (A). Especially preferably, it is 0.001-0.5 mass part. If the amount added is less than 0.0001 part by mass, the resulting silicone rubber tends to have an insufficient antistatic effect. When the addition amount is more than 5 parts by mass, the resulting silicone rubber may not maintain insulation properties, or may adversely affect heat resistance and other physical properties.

[Other ingredients]
In addition to the components (A) to (G), the composition of the present invention may contain other optional components as long as the object of the present invention is not impaired. Specific examples thereof include the following. Each of these other components may be used alone or in combination of two or more.

-Reaction control agent A reaction control agent will not be specifically limited if it is a compound which has a hardening inhibitory effect with respect to the addition reaction catalyst of the said (C) component, A conventionally well-known thing can also be used. Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene-based compounds such as acetylene alcohols; and containing two or more alkenyl groups. Compounds; hydroperoxy compounds; maleic acid derivatives and the like.

  Since the degree of the effect of inhibiting the curing by the reaction control agent varies depending on the chemical structure of the reaction control agent, it is preferable to adjust the addition amount of the reaction control agent to an optimum amount for each reaction control agent to be used. By adding an optimal amount of the reaction control agent, the composition has excellent long-term storage stability at room temperature and curability.

Inorganic filler Examples of the inorganic filler include crystalline silica, hollow filler, silsesquioxane, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, Inorganic fillers such as layered mica, carbon black, diatomaceous earth, and glass fibers; these inorganic fillers are hydrophobized with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds. Treated filler; silicone rubber powder; silicone resin powder and the like.

Other components In addition, for example, an organopolysiloxane containing one silicon atom-bonded hydrogen atom in one molecule and no other functional group, and one silicon atom-bonded alkenyl group in one molecule Organopolysiloxanes containing no other functional groups, non-functional organopolysiloxanes containing neither silicon-bonded hydrogen atoms, silicon-bonded alkenyl groups, or other functional groups, organic solvents, creep hardening inhibitors , Plasticizers, thixotropic agents, pigments, dyes, fungicides and the like can be blended.

[Preparation method]
The liquid silicone rubber coating composition of the present invention can be prepared by mixing the above components according to a conventional method.

<Hardened product>
The coating agent composition of the present invention can be cured by a known curing method under known curing conditions. Specifically, for example, the composition can be cured by heating at 120 to 180 ° C. for 1 to 10 minutes.

  The volume resistivity of the obtained cured product is preferably 1 GΩ · m or more, and particularly preferably 2 GΩ · m or more. When the volume resistivity is within this range, the insulation of the airbag having the silicone rubber coating layer made of the cured product is practically sufficient.

  Further, as the antistatic performance of the cured product, the surface of the silicone rubber molded product made of the cured product was charged with 6 kV of static electricity by corona discharge using a static honestometer (manufactured by Sisid Electric Co., Ltd.) The time for half the charged voltage (half-life) is preferably within 2 minutes, and particularly preferably within 1 minute.

[Airbag]
The liquid silicone rubber coating composition thus obtained is suitable for producing an air bag excellent in insulation and antistatic properties not only before exposure to high temperatures but also after exposure.

  In the present invention, as an air bag on which a silicone rubber coating layer formed of a cured product of the above composition is formed, one having a known configuration is used. Specific examples thereof include 6,6-nylon, 6-nylon, Examples include air bags based on woven fabrics of various synthetic fibers such as polyester fibers, aramid fibers, various polyamide fibers, and various polyester fibers.

  The liquid silicone rubber coating agent composition is applied to at least one surface of a substrate made of a fiber cloth, in particular, one surface, for example, heated in a hot air drying oven and cured by heating. A silicone rubber coating layer can be formed. An airbag can be manufactured using the silicone rubber coating base fabric for airbags obtained in this way.

Here, as a base material which consists of fiber cloths, the base material which makes the base fabric the woven fabric of the various synthetic fibers mentioned above is mentioned. In addition, as a method of coating the substrate with the composition, a conventional method can be adopted, but the thickness (or surface coating amount) of the coating layer is preferably 10 to 150 g / m ² , more preferably. Is 15 to 80 g / m ² , more preferably about 20 to 60 g / m ² .

  EXAMPLES Hereinafter, although a preparation example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Preparation Example 1] Preparation of antistatic agent paste Antistatic agent pastes 1 and 2 were prepared as follows.

・ Antistatic paste 1
42 parts by weight of dimethylpolysiloxane raw rubber sealed at both ends with dimethylvinylsiloxy groups, hydrophobized fumed silica with a specific surface area of 110 m ² / g (trade name: R-972, Nippon Aerosil Co., Ltd.) 8) parts by mass) and 50 parts by mass of a 20% by mass adipic acid ester solution of LiN (SO ₂ CF ₃ ) ₂ were kneaded to prepare an antistatic agent paste 1.

・ Antistatic agent paste 2
42 parts by weight of dimethylpolysiloxane raw rubber sealed at both ends with dimethylvinylsiloxy groups, hydrophobized fumed silica with a specific surface area of 110 m ² / g (trade name: R-972, Nippon Aerosil Co., Ltd.) 8) parts by mass and 50 parts by mass of a polyether-modified silicone oil (trade name: KF351F, manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 75 mm ² / s at 25 ° C. 2 was prepared.

[Preparation Example 2] Preparation of base compound (I) 65 parts by mass of dimethylpolysiloxane having both molecular chain ends blocked with vinyldimethylsiloxy groups and a viscosity at 25 ° C of about 30,000 mPa · s, hexamethyldisiloxane 8 parts by mass, 2 parts by mass of water, 40 parts by mass of fumed silica (trade name: Aerosil (registered trademark) 300, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of about 300 m ² / g measured by the BET method at room temperature It was put in and mixed for 1 hour to obtain a mixture. The mixture was heated to 150 ° C. and subsequently mixed for 2 hours. The mixture was cooled to room temperature, and 19 parts by mass of dimethylpolysiloxane having both molecular chain ends blocked with vinyldimethylsiloxy groups and a viscosity at 25 ° C. of about 30,000 mPa · s were added to the mixture. 5 parts by weight of dimethylpolysiloxane containing 5 mol% of vinylmethylsiloxane units with respect to all diorganosiloxane units and having both molecular chain ends blocked with trimethylsiloxy groups and having a viscosity at 25 ° C. of about 700 mPa · s Was added and mixed until uniform to obtain a base compound (I).

[Example 1]
-Preparation of composition 35 parts by mass of dimethylpolysiloxane having 78 parts by mass of base compound (I), both ends of the molecular chain blocked with vinyldimethylsiloxy groups, and a viscosity at 25 ° C of about 5,000 mPa · s. Both ends of the chain are blocked with vinyldimethylsiloxy groups, and 15 parts by mass of dimethylpolysiloxane having a viscosity at 25 ° C. of about 1,000 mPa · s, 39.5 mol% of (CH ₃ ) ₃ SiO _1/2 units ( CH ₃ ) ₂ (CH ₂ ═CH) 10 parts by mass of an organopolysiloxane resin consisting of 6.5 mol% of SiO _1/2 units and 54 mol% of SiO ₂ units, the viscosity at 25 ° C. is 45 mPa · s, Dimethylsiloxane / methylhydrogensiloxane copolymer with a trimethylsiloxy group blocked at both ends of the molecular chain having silicon-bonded hydrogen atoms in the side chain (Hydrogen atom content = 1.08 mass%) 6.4 mass parts, 1-ethynylcyclohexanol 0.09 mass parts, chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content 1 mass % Dimethylpolysiloxane solution 0.38 parts by mass, γ-glycidoxypropyltrimethoxysilane 0.3 parts by mass, titanium tetra-2-ethylhexoxide 0.2 parts by mass, and antistatic agent paste 10 .05 parts by weight were mixed to prepare a composition.

-Charge amount measurement The above composition was poured into a 70 mm x 50 mm x 6 mm (depth) mold and cured by heating at 150 ° C for 5 minutes to obtain a molded product. The molded product was placed in an oven at 200 ° C. for 4, 50, 100, or 400 hours, and then static electricity was applied to the surface by using a static honest meter (manufactured by Sisid Electrostatic Co., Ltd.) by corona discharge. The time (half-life) at which the charged voltage was halved was measured. The results are shown in Table 1.

-Volume resistivity measurement The above composition was poured into a 170 mm x 130 mm x 1 mm (depth) mold and cured by heating at 150 ° C for 5 minutes to obtain a molded product. The molded product was placed in an oven at 200 ° C. for 4 hours, 50 hours, 100 hours or 400 hours, and then its volume resistivity was measured based on JIS K 6249. The results are shown in Table 1.

[Example 2]
The charge amount and volume resistivity were measured in the same manner as in Example 1 except that the addition amount of the antistatic agent paste 1 in Example 1 was changed from 0.05 parts by mass to 0.01 parts by mass.

[Comparative Example 1]
The charge amount and volume resistivity were measured in the same manner as in Example 1 except that the antistatic agent paste 1 was not added in Example 1.

[Comparative Example 2]
The charge amount and volume resistivity were measured in the same manner as in Example 1 except that the antistatic agent paste 2 was used instead of the antistatic agent paste 1 in Example 1.

Claims (8)

(A) Organopolysiloxane containing two or more alkenyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: The total number of hydrogen atoms bonded to silicon atoms contained in the composition is An amount of 1 to 10 silicon atom-bonded alkenyl groups,
(C) addition reaction catalyst: effective amount,
(D) Fine powder silica having a specific surface area of 50 m ² / g or more: 0 to 50 parts by mass,
(E) Organosilicon compound having an epoxy group and a silicon atom-bonded alkoxy group and / or a hydrosilyl group in one molecule: 0.1 to 10 parts by mass,
(F) One or both of a titanium compound and a zirconium compound: 0.1 to 5 parts by mass, and (G) an ionic conductive antistatic agent: a liquid silicone rubber coating containing 0.0001 to 5 parts by mass Agent composition.   The content of the component (B) is such that the number of hydrogen atoms bonded to the silicon atom contained in the component (B) is 1 to 10 per silicon atom-bonded alkenyl group in the component (A). The composition according to claim 1.   The composition according to claim 1 or 2, wherein the component (G) is a lithium salt. The component (G) is LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiSO ₃ CF ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiSO ₃ C ₄ F ₉ , LiC (SO ₂ CF ₃ ) ₃ , and LiB (C ₆ H ₅₎ 1, two or more in a composition according to claim 1 selected from the group consisting of _4.   The composition according to any one of claims 1 to 4, wherein the volume resistivity of the cured product is 1 GΩ · m or more.   The composition which concerns on any one of Claims 1-5 used for an airbag. A substrate made of fiber cloth;
The airbag which consists of a hardened | cured material of the composition of any one of Claims 1-6, and has a silicone rubber coating layer formed in the at least one surface of this base material. The composition according to any one of claims 1 to 6 is applied to at least one surface of a substrate made of a fiber cloth,
The method for producing an air bag according to claim 7, further comprising forming a silicone rubber coating layer made of a cured product of the composition on at least one surface of the substrate by curing the composition.