JP5142071B2 - Liquid silicone rubber coating composition, curtain airbag and method for producing the same - Google Patents

Description

  The present invention is suitable for manufacturing 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 is particularly mounted on a driver seat or a passenger seat. Unlike air bags that are used, curtain air bags that are housed along the roof side from the front pillar and are required to maintain a constant inflation time in order to protect the head and prevent popping out in the event of a collision or vehicle fall The present invention relates to a liquid silicone rubber coating agent composition suitable for production, a curtain airbag having a silicone rubber coating layer comprising a cured product of the composition, and a method for producing the curtain airbag.

Conventionally, the following are known as a silicone rubber composition for an air bag for the purpose of forming a rubber coating on the fiber surface. For example, Patent Document 1 discloses a liquid silicone rubber coating for an air bag having excellent adhesion to a base fabric, which is obtained by adding an inorganic filler, an organopolysiloxane resin, and an epoxy group-containing organosilicon compound to an addition-curable composition. An agent composition is disclosed. In Patent Document 2, excellent adhesiveness to a base fabric is obtained by heating in a short time, which is obtained by adding an inorganic filler, an organopolysiloxane resin, an organic titanium compound, and an alkyl silicate or an alkyl polysilicate to an addition-curable composition. A liquid silicone rubber coating agent composition for an air bag that expresses the above is disclosed. Patent Document 3 discloses a silicone rubber coating composition for an air bag excellent in thin film coatability in which the viscosity of a vinyl group-containing organopolysiloxane is limited to 8000 centipoise or less. In Patent Document 4, a silicone rubber coating having a reduced sticky feeling is obtained by adding wet silica having an average specific surface area of 150 to 250 m ² / g by BET method and an average particle size of 20 μm or less to a rubber coating composition. A liquid silicone rubber composition for coating used in the production of a base fabric is disclosed.

  However, these compositions, when used for curtain airbag applications, are all poor in adhesion to the airbag fabric, so that the inflation time can be satisfactorily maintained by suppressing leakage of the inflator gas. There wasn't.

JP-A-5-214295 JP 2002-138249 A JP 2001-287610 A JP 2001-59052 A

  The present invention has been made in view of the above circumstances, and in particular, when used for curtain airbag applications, a liquid silicone rubber coating composition having excellent adhesion to a base fabric for airbags, It is an object of the present invention to provide a curtain airbag having a silicone rubber coating layer made of a cured product of the composition on at least one surface, and a method for producing the curtain airbag.

As a result of intensive studies to achieve the above object, the present inventor has found that (A) an organopolysiloxane containing two or more alkenyl groups bonded to silicon atoms in one molecule, and (B) silicon in one molecule. Organohydrogenpolysiloxane having a specific structure 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) 1 molecule A liquid silicone rubber coating composition comprising an organosilicon compound having an epoxy group and a silicon atom-bonded alkoxy group therein, and (F) a titanium compound and a zirconium compound, or both, When used as a silicone rubber coating layer, the coating layer has adhesion to an air bag base fabric. For excellent, suppressing the leakage of the inflator gas, it found that the inflation of the curtain airbag can be maintained constant time, 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) The following general formula (1) having at least two hydrogen atoms bonded to silicon atoms in one molecule

（式中、Ｒ^１は脂肪族不飽和結合を含まない互いに同一又は異種の非置換もしくは置換の一価炭化水素基を表し、Ｘは独立に水素原子又はＲ^１を表し、ｐは１〜５０の整数、ｑは０〜５０の整数であり、ただし、式：ｔ＝ｐ／（ｐ＋ｑ）で示されるｔが０．２≦ｔ≦１を満たし、ｐが１のとき、少なくとも一方のＸは水素原子を表わす。）
で表されるオルガノハイドロジェンポリシロキサン：本（Ｂ）成分中に含まれるケイ素原子に結合した水素原子の数が（Ａ）成分中のケイ素原子結合アルケニル基１個当たり１〜１０個となる量、
（Ｃ）付加反応触媒：有効量、
（Ｄ）比表面積が５０ｍ²／ｇ以上の微粉末シリカ：０〜５０質量部、
（Ｅ）１分子中にエポキシ基とケイ素原子結合アルコキシ基とを有する有機ケイ素化合物：０．１〜１０質量部、
ならびに
（Ｆ）チタニウム化合物およびジルコニウム化合物のいずれか一方または両方：０．１〜５質量部
を含有してなる液状シリコーンゴムコーティング剤組成物を提供する。

(Wherein R ¹ represents an identical or different unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, X independently represents a hydrogen atom or R ¹ , and p represents ¹ to 50) Q is an integer of 0 to 50, provided that t represented by the formula: t = p / (p + q) satisfies 0.2 ≦ t ≦ 1, and when p is 1, at least one X is Represents a hydrogen atom.)
The amount by which the number of hydrogen atoms bonded to silicon atoms contained in the component (B) is 1 to 10 per silicon atom-bonded alkenyl group in the component (A) ,
(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 in one molecule: 0.1 to 10 parts by mass
And (F) One or both of a titanium compound and a zirconium compound: A liquid silicone rubber coating composition comprising 0.1 to 5 parts by mass is provided.

  Second, the present invention applies the above composition to at least one surface of a substrate made of a fiber cloth, and cures the composition to cure at least one surface of the substrate. A method for producing a curtain airbag comprising forming a silicone rubber coating layer made of a material is provided.

Third, the present invention
A substrate made of fiber cloth;
And a silicone rubber coating layer comprising a cured product of the composition, wherein the silicone rubber coating layer provides a curtain airbag formed on at least one surface of the substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid silicone rubber coating agent composition excellent in the adhesiveness with respect to the base fabric for airbags is obtained. A curtain airbag having a silicone rubber coating layer made of a cured product of the composition on at least one surface of the substrate can satisfactorily maintain the inflation time by suppressing leakage of the inflator gas.

  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 agent composition of the present invention comprises the following components (A) to (F) 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 two or more alkenyl groups bonded to silicon atoms in one molecule and is a base polymer of the composition of the present invention. 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, and branched chains. The main chain basically consists of repeating diorganosiloxane units, and both ends of the molecular chain are triorganosiloxy groups. It is preferably a linear diorganopolysiloxane blocked with (this organo group may also include an alkenyl group). 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%.

  (A) As an organic group couple | bonded with silicon atoms other than the alkenyl group of a component, for example, it is the same or different mutually unsubstituted or substituted normally 1-12 carbon atoms, Preferably it is about 1-10 carbon atoms. Of monovalent hydrocarbon groups. 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 (2)
R _a SiO _{(4-a) / 2} (2)
(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 ² ₃ SiO _0.5 and siloxane unit represented by the formula: R ² ₂ R ³ SiO _0.5 and siloxane unit represented by the formula: R ² ₂ SiO And an organosiloxane copolymer comprising a siloxane unit represented by the formula: SiO ₂ , a siloxane unit represented by the formula: R ² ₃ SiO _0.5 and a siloxane unit represented by the formula: R ² ₂ R ³ SiO _0.5 and a formula: SiO organosiloxane consisting of siloxane units represented by ₂ An organosiloxane copolymer comprising a siloxane unit represented by the formula: R ² ₂ R ³ SiO _0.5 , a siloxane unit represented by the formula: R ² ₂ SiO, and a siloxane unit represented by the formula: SiO ₂ Organosiloxane copolymers comprising a siloxane unit represented by the formula: R ² R ³ SiO and a siloxane unit represented by the formula: R ² SiO _1.5 or a siloxane unit represented by the formula: R ³ SiO _1.5 , and their organopoly The mixture which consists of 2 or more types of siloxane is mentioned.

R ² in the above formula is the same or different unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Alkyl groups such as 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; chloromethyl group, 3-chloropropyl group, 3, 3 And halogenated alkyl groups such as 3-trifluoropropyl group. R ³ in the above formula is an alkenyl group, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.

[Component (B)]
In the organohydrogenpolysiloxane of component (B), silicon atom-bonded hydrogen atoms (that is, SiH groups) in the molecule form a crosslinked structure by the hydrosilylation addition reaction with the alkenyl groups in component (A) to cause curing. It is an essential component as a crosslinking agent for giving a cured silicone rubber having a practically sufficient strength. The organohydrogenpolysiloxane is represented by the following general formula (1).

（式中、Ｒ^１は脂肪族不飽和結合を含まない互いに同一又は異種の非置換もしくは置換の一価炭化水素基を表し、Ｘは独立に水素原子又はＲ^１を表し、ｐは１〜５０の整数、ｑは０〜５０の整数であり、ただし、式：ｔ＝ｐ／（ｐ＋ｑ）で示されるｔが０．２≦ｔ≦１を満たし、ｐが１のとき、少なくとも一方のＸは水素原子を表わす。）

(Wherein R ¹ represents an identical or different unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, X independently represents a hydrogen atom or R ¹ , and p represents ¹ to 50) Q is an integer of 0 to 50, provided that t represented by the formula: t = p / (p + q) satisfies 0.2 ≦ t ≦ 1, and when p is 1, at least one X is Represents a hydrogen atom.)

R ¹ in the general formula (1) is an identical or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 8, not containing an aliphatic unsaturated bond. . Specific examples of R ¹ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, decyl group; phenyl group, tolyl group, Aryl groups such as xylyl group and naphthyl group; cycloalkyl groups such as cyclohexyl group; aralkyl groups such as benzyl group and phenylethyl group; halogen-substituted hydrocarbon groups such as chloromethyl group, bromoethyl group and trifluoropropyl group; cyanoethyl group And cyano-substituted hydrocarbon groups such as Of these, like the component (A), a methyl group and a phenyl group are preferable. In the general formula (1), an organohydrogenpolysiloxane in which all R ¹ is a methyl group or a phenyl group, and an organohydrogenpolysiloxane in which a part of R ¹ is a methyl group and the rest is a phenyl group are synthesized. Is easy and has good chemical stability.

  Moreover, p in General formula (1) is 1-50, Preferably it is 2-25, More preferably, it is 3-25, More preferably, it is an integer of 5-20, Most preferably, it is an integer of 10-20, q is q. 0 to 50, preferably 0 to 20, more preferably an integer of 0 to 10, provided that t satisfies 0.2 ≦ t ≦ 1, preferably 0.5 ≦ t ≦ 1, and p is 1. , At least one X represents a hydrogen atom.

  Specific examples of the organohydrogenpolysiloxane of component (B) include trimethylsiloxy group-capped methylhydrogen polysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, and dimethylhydrogen at both ends. Siloxy group-blocked methylhydrogenpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group Blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane at both ends Methylphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends dimethyl Hydrogensiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogen Among the siloxane / dimethylsiloxane / methylphenylsiloxane copolymers, those satisfying the condition of the general formula (1) are listed. It is.

  In the present invention, the organohydrogenpolysiloxane represented by the above formula (1) may be used alone or in combination of two or more.

  The viscosity of the organohydrogenpolysiloxane represented by the above formula (1) at 25 ° C. is preferably 1 to 500 mPa · sec, more preferably 5 to 100 mPa · sec.

The blending amount of component (B) is such that the number of silicon atom-bonded hydrogen atoms in component (B) is usually 1 to 10, particularly preferably, for one silicon atom-bonded alkenyl group in component (A). The amount is in the range of 1 to 7. When the blending amount is such that one silicon atom-bonded alkenyl group in component (A) is less than one silicon-bonded hydrogen atom in component (B), the resulting composition is cured. It tends to be insufficient. Further, when the blending amount is more than 10 silicon atom-bonded hydrogen atoms in the component (B) with respect to one silicon atom-bonded alkenyl group in the component (A), the heat resistance of the resulting silicone rubber It tends to be extremely inferior.
In the composition of the present invention, an organohydrogenpolysiloxane other than the component (B) and the component (E) described later can be blended as an optional component. In this case, the component (B), ( The number of SiH groups contained in the whole organohydrogenpolysiloxane other than the component (E) and the components (B) and (E) is 1 to 10 per one silicon-bonded alkenyl group in the component (A). In particular, the number is preferably 1 to 7, and the molar ratio of the number of SiH groups in the component (B) to the total number of SiH groups is preferably about 0.5 to 1, particularly about 0.7 to 1.

[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 as an addition reaction catalyst, and is preferably in the range of 1 to 500 ppm in terms of the mass of the catalytic metal element with respect to the total mass of the components (A) and (B). More preferably, it is the range of 10-100 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 the component (E), any organosilicon compound can be used as long as it is an organosilicon compound having an epoxy group and a silicon atom-bonded alkoxy group in one molecule. However, from the viewpoint of adhesion development, at least one An organosilicon compound having an epoxy group and at least two silicon-bonded alkoxy groups, for example, silane, or a cyclic or linear siloxane having 2 to 30 silicon atoms, preferably about 4 to 20 silicon atoms. Thus, it preferably has at least one epoxy group and at least two silicon-bonded alkoxy groups. (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 a functional group other than an epoxy group and a silicon atom-bonded alkoxy group in one molecule, for example, an alkenyl group such as a vinyl group, a (meth) acryloxy group, and a hydrosilyl group (SiH group). It may have at least one functional group selected from the group consisting of:

  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-based condensed compounds such as organic zirconium chelate compounds such as zirconium monobutoxyacetylacetonate bis (ethylacetoacetate) and zirconium tetraacetylacetonate 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 be deteriorated in 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.

[Other ingredients]
In addition to the components (A) to (F), the composition of the present invention can 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.

[Airbag]
The liquid silicone rubber coating composition thus obtained is excellent in adhesion to the airbag fabric, and is stored along the roof side from the front pillar. It is suitable for producing a curtain airbag that is required to maintain a constant expansion time in order to prevent popping out.

  In the present invention, a known structure is used as an air bag, particularly a curtain air bag, on which a silicone rubber coating layer made of a cured product of the above composition is formed. Specific examples thereof include 6,6-nylon. , 6-nylon, polyester fiber, aramid fiber, various polyamide fibers, various synthetic fibers, such as various woven fabrics of the base fabric, the outer periphery of two plain weave base fabrics coated with rubber on the inner surface And air bags of the type produced by stitching together the adhesive layers (hereinafter abbreviated as plain weave type), and bag weaving type air bags in which the woven fabric is used as a base fabric and a bag portion is formed by weaving. It is done.

  The liquid silicone rubber coating composition is applied to at least one surface of a substrate made of a fiber cloth, in particular, one surface, and is heated in a hot air drying oven and cured to cure the silicone rubber coating. A layer can be formed. A curtain airbag can be manufactured using the silicone rubber coating base fabric for curtain 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 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 .

  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.

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

[Example 1]
Both ends of the molecular chain are blocked with a vinyldimethylsiloxy group, and 65 parts by mass of dimethylpolysiloxane having a viscosity at 25 ° C. of about 30,000 mPa · s, 8 parts by mass of hexamethyldisiloxane, 2 parts by mass of water, and BET method 40 parts by mass of fumed silica (Aerosil (registered trademark) 300, manufactured by Nippon Aerosil Co., Ltd.) having a measured specific surface area of about 300 m ² / g was put into a kneader at room temperature 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).

  64 parts by mass of base compound (I), 31 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, and both ends of the molecular chain are vinyl 35 parts by mass of dimethylpolysiloxane blocked with a dimethylsiloxy group and having a viscosity at 25 ° C. of about 100,000 mPa · s, a viscosity at 25 ° C. of 5 mPa · s, and a silicon-bonded hydrogen atom on the side chain of the molecular chain Molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom content = 1.28% by mass, t = 1) 1.65 parts by mass, 1-ethynylcyclohexanol 0.07 parts by mass, Di containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content 0.25 parts by chill polysiloxane solution, .gamma.-glycidoxypropyltrimethoxysilane 0.65 parts by weight, were mixed 0.85 parts by weight of zirconium tetra acetylacetonate, a composition was prepared A.

<Hardness, elongation at break, tensile strength, tear strength>
The composition A is press-cured at 150 ° C. for 5 minutes and then post-cured at 150 ° C. for 1 hour to prepare a sheet according to JIS K 6249. The sheet is hardened according to JIS K 6249, and stretched when cut. The tensile strength and tear strength were measured. The results are shown in Table 1.

<Peel adhesive strength>
The composition A was uniformly coated on a 6,6-nylon base fabric for an air bag with a coater (60 g / m ² ) and cured by heating in an oven at 170 ° C. for 1 minute to obtain a silicone rubber-coated nylon base fabric. Obtained. The peel adhesive strength of the silicone rubber coating layer to the nylon base fabric was measured as follows. Two pieces of silicone rubber-coated nylon base cloth having a width of 50 mm are bonded together with the adhesive so that the thickness of the addition curing type room temperature curing type silicone adhesive X-32-2600A / B becomes 0.6 mm, The adhesive was allowed to cure for 24 hours. Next, the two bonded silicone rubber-coated nylon base fabrics were cut to produce a 20 mm wide piece, and a T-shaped peel test was performed on this piece at a pulling rate of 200 mm / min. The results are shown in Table 1.

<Scott itch test>
The Scott stagnation test was conducted using a Scott stagnation tester. After performing 200 stagnation tests on the above silicone rubber-coated nylon base cloth with a pressing pressure of 5 kgf, visually check the coating part for destruction, and if the silicone rubber coating layer does not peel off the coating surface The case where it peeled and peeled was evaluated as disqualified. The results are shown in Table 1.

[ Reference Example 1 ]
To 78 parts by mass of the base compound (I) obtained in Example 1, 35 parts by mass of dimethylpolysiloxane having both molecular chain ends blocked with vinyldimethylsiloxy groups and a viscosity at 25 ° C. of about 5,000 mPa · s, 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 and (CH ₃ ) ₂ (CH ₂ ═CH) SiO ₁ Molecule having 10 parts by mass of an organopolysiloxane resin consisting of 6.5 mol% of _{/ 2} units and 54 mol% of SiO ₂ units, having a viscosity of 45 mPa · s at 25 ° C., and having a silicon atom-bonded hydrogen atom in the molecular chain side chain Trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer with both chain ends (silicon atom-bonded hydrogen atom content = 1.08 mass%, t = 0.7) 6.4 Parts by mass, 0.09 parts by mass of 1-ethynylcyclohexanol, 0.38 parts by mass of a dimethylpolysiloxane solution containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as a platinum atom content, γ -Composition B was prepared by mixing 0.3 part by mass of glycidoxypropyltrimethoxysilane and 0.2 part by mass of titanium tetra-2-ethylhexoxide.

  About the hardened | cured material of the composition B, it carried out similarly to Example 1, and measured the hardness, elongation at the time of cutting, tensile strength, tear strength, and peel adhesive force, and the Scott sag test. The results are shown in Table 1.

[Comparative Example 1]
Composition C was prepared in the same manner as in Example 1 except that zirconium tetraacetylacetonate was not used in Example 1. About the hardened | cured material of the composition C, it carried out similarly to Example 1, and measured the hardness, elongation at the time of cutting, tensile strength, tear strength, and peel adhesive force, and the Scott sag test. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, the viscosity at 25 ° C. is 5 mPa · s, and the molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane having a silicon atom-bonded hydrogen atom in the molecular chain side chain (silicon atom-bonded hydrogen atom content = 1.28% by mass, t = 1) Instead of 1.65 parts by mass, a trimethylsiloxy group blocked at both ends of a molecular chain having a viscosity of 10 mPa · s at 25 ° C. and having silicon-bonded hydrogen atoms in the side chain of the molecular chain Except for using 7.75 parts by mass of a dimethylsiloxane / methylhydrogensiloxane copolymer (silicon-bonded hydrogen atom content = 0.15% by mass, t = 0.1), the same as in Example 1, Composition D was prepared. About the hardened | cured material of the composition D, it carried out similarly to Example 1, and measured the hardness, elongation at the time of cutting, tensile strength, tear strength, and peel adhesive force, and the Scott sag test. The results are shown in Table 1.

[Comparative Example 3]
In Reference Example 1 , a dimethylsiloxane / methylhydrogensiloxane copolymer blocked with a trimethylsiloxy group blocked at both ends of a molecular chain having a viscosity at 25 ° C. of 45 mPa · s and having a silicon atom-bonded hydrogen atom in the molecular chain side chain (silicon atom bond) Hydrogen atom content = 1.08% by mass, t = 0.7) A molecule having a viscosity at 25 ° C. of 10 mPa · s instead of 6.4 parts by mass and having silicon-bonded hydrogen atoms in the molecular chain side chain chain terminals blocked with trimethylsiloxy groups dimethylsiloxane-methylhydrogensiloxane copolymer but using (silicon-bonded hydrogen atom content = 0.15 wt%, t = 0.1) 11.00 parts by weight, reference Composition E was prepared as in Example 1 . About the hardened | cured material of the composition E, it carried out similarly to Example 1, and measured hardness, elongation at the time of cutting | disconnection, tensile strength, tear strength, and peel adhesive force, and the Scott sag test. The results are shown in Table 1.

Claims (4)

(A) Organopolysiloxane containing two or more alkenyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) The following general formula (1) having at least two hydrogen atoms bonded to silicon atoms in one molecule

(Wherein R ¹ represents an identical or different unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, X independently represents a hydrogen atom or R ¹ , and p represents ¹ to 50) Q is an integer of 0 to 50, provided that t represented by the formula: t = p / (p + q) satisfies 0.2 ≦ t ≦ 1, and when p is 1, at least one X is Represents a hydrogen atom.)
The amount by which the number of hydrogen atoms bonded to silicon atoms contained in the component (B) is 1 to 10 per silicon atom-bonded alkenyl group in the component (A) ,
(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 in one molecule: 0.1 to 10 parts by mass
And (F) organozirconium compound: a liquid silicone rubber coating composition for curtain airbags based on a woven fabric of 6,6-nylon or 6-nylon containing 0.1 to 5 parts by mass. The organic zirconium compound is an organic zirconium esters, organic zirconium chelate compound, or Ri these Kumiawasedea, the composition according to claim 1 the base fabric Ru dough der woven of nylon 6,6. 6,6-coating a composition according to claim 1 or 2 on at least one surface of the base fabric comprising a woven fabric of nylon or 6-nylon, by curing the composition, of the base fabric at least A method for producing a curtain airbag using 6,6-nylon or 6-nylon woven fabric as a base fabric, comprising forming a silicone rubber coating layer comprising a cured product of the composition on one surface. A base fabric made of 6,6-nylon or 6-nylon woven fabric ;
A curtain airbag having a silicone rubber coating layer comprising a cured product of the composition according to claim 1, wherein the silicone rubber coating layer is formed on at least one surface of the base fabric .