Liquid silicone rubber coating composition, curtain air bag, and method of producing same

The present invention is suitable for producing airbags for vehicles or the like in which a silicone rubber coating film is formed on a fiber cloth such as 6,6-nylon, 6-nylon, or polyester, and is particularly mounted on a driver's seat or a passenger's seat. Unlike airbags that are used, curtain airbags that are stored along the roof side from the front pillars and are required to maintain a certain inflatable time to protect the head and prevent popping out in the event of a collision or a vehicle tipping over. The present invention relates to a liquid silicone rubber coating agent composition suitable for production, a curtain airbag having a silicone rubber coating layer composed of a cured product of the composition, and a method for producing the same.

Conventionally, the following silicone rubber compositions for airbags have been known for the purpose of forming a rubber film on the surface of a fiber cloth. For example, Patent Document 1 describes a liquid silicone rubber coating for an air bag, which is formed by adding an inorganic filler, an organopolysiloxane resin, and an epoxy group-containing organosilicon compound to an addition-curable composition and has excellent adhesiveness to a base cloth. The agent composition is disclosed. Patent Document 2 states that an inorganic filler, an organopolysiloxane resin, an organic titanium compound and an alkyl silicate or an alkyl polysilicate are added to an addition-curable composition, and excellent adhesion to a base fabric is obtained by heating for a short time. 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 having an excellent thin film coating property in which the viscosity of a vinyl group-containing organopolysiloxane is limited to 8000 cmpoise or less. Patent Document 4 states that the rubber coating composition has an average specific surface area of 150 to 250 m by the BET method.²A liquid silicone rubber composition for coating, which is obtained by adding wet silica having an average particle size of 20 μm or less at / g and used for producing a silicone rubber coating base fabric having a reduced adhesive feeling, is disclosed.

However, when these compositions are used for curtain airbag applications, they are all inferior in adhesiveness to the airbag base fabric, so that the leakage of inflator gas can be suppressed and the expansion time can be maintained satisfactorily. There wasn't.

Additive-curable compositions containing a zirconium compound related to the present invention are disclosed in Patent Documents 5 to 8. However, the zirconium compounds exemplified in these are 4-ligand compounds, and the oxyzirconium compound of the present invention is not shown.

<patcit num="1"><text>Japanese Patent Application Laid-Open No. 5-214295</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 2002-138249</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2001-287610</text></patcit><patcit num="4"><text>Japanese Unexamined Patent Publication No. 2001-59052</text></patcit><patcit num="5"><text>Japanese Patent Application Laid-Open No. 62-240361</text></patcit><patcit num="6"><text>Japanese Unexamined Patent Publication No. 4-178461</text></patcit><patcit num="7"><text>Japanese Unexamined Patent Publication No. 4-246466</text></patcit><patcit num="8"><text>Japanese Unexamined Patent Publication No. 8-269337</text></patcit>

<p> The present invention has been made in view of the above circumstances, and is a liquid silicone rubber coating agent composition, which suppresses leakage of inflator gas when the airbag is deployed and provides an airbag having excellent durability of expansion time. It is an object of the present invention to provide a curtain airbag using the cured product of the above, and a method for manufacturing the curtain airbag.</p>

<p> As a result of diligent studies to achieve the above object, the present inventor (A) is an organopolysiloxane containing two or more alkenyl groups bonded to a silicon atom in one molecule, and (B) silicon in one molecule. Organohydrogenpolysiloxane containing at least two atom-bonded hydrogen atoms, (C) addition reaction catalyst, preferably (D) specific surface area of 50 m²A liquid silicone rubber coating composition containing (E) an organosilicon compound having an epoxy group and a silicon atom-bonded alkoxy group in one molecule, and (F) an oxyzirconium compound. When the cured product is used as a silicone rubber coating layer of a curtain air bag, it has been found that leakage of inflator gas can be suppressed and the expansion of the curtain air bag can be maintained for a certain period of time, and the present invention has been made.</p><p> 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 this composition is in the component (A). Amount of 1 to 10 per silicon atom-bonded alkenyl group, (C) Addition reaction catalyst: effective amount, (D) Specific surface area is 50m²Fine powder silica of / 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) Oxyzirconium compound: 0.1 to 5 parts by mass To provide a liquid silicone rubber coating agent composition containing the above.</p><p> Secondly, the present invention A base material made of fiber cloth and A silicone rubber coating layer composed of a cured product of the above composition and formed on at least one surface of the base material. Provide curtain airbags with.</p><p> Thirdly, the present invention The above composition is applied to at least one surface of a base material made of a fiber cloth. By curing the composition, a silicone rubber coating layer made of the cured product of the composition is formed on at least one surface of the base material. Provided is a method for manufacturing the above-mentioned curtain airbag including the above.</p>

<p> According to the present invention, a liquid silicone rubber coating agent composition having excellent adhesiveness to a base cloth for an airbag can be obtained. A curtain airbag composed of a base material made of a fiber cloth and a cured product of the composition and having a silicone rubber coating layer formed on at least one surface of the base material suppresses leakage of inflator gas and has an expansion time. Can be satisfactorily sustained.</p>

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

&lt;Liquid silicone rubber coating composition&gt; The liquid silicone rubber coating composition of the present invention contains the following components (A) to (F) and is liquid at room temperature (meaning 25 ° C. The same applies hereinafter). is there. Hereinafter, each component will be described in detail.

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

Examples of the molecular structure of the component (A) include linear, cyclic, branched chain, and three-dimensional network, but the main chain basically consists of repeating diorganosiloxane units, and both ends of the molecular chain are It is preferably a linear diorganopolysiloxane sealed with a triorganosyloxy group (note that these organogroups can also include alkenyl groups). When the molecular structure of the organopolysiloxane of the 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 terminal and the molecular chain. Either one or both of them may be in the middle (that is, the non-terminal of the molecular chain). Particularly preferably, the component (A) is a linear diorganopolysiloxane containing at least an alkenyl group 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 substituents as each other, usually having 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%, particularly about 0.01 to 5 mol%, based on the total monovalent organic group bonded to the silicon atom. Is preferable.

As a monovalent organic group bonded to a silicon atom other than the alkenyl group of the component (A), for example, an aliphatic unsaturated bond, which is the same or different from each other and is unsubstituted or substituted, usually has 1 carbon atom. Examples thereof include a monovalent hydrocarbon group having a carbon atom number of about 1 to 12, preferably about 1 to 10. When the monovalent hydrocarbon group is substituted, an example thereof is a halogen-substituted one. Specific examples of the organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and a heptyl group; a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and the like. Aryl groups; aralkyl groups such as benzyl group and phenethyl group; alkyl halide groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group can be mentioned, and in particular, methyl group and phenyl group can be mentioned. It is preferably a group.

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

As a preferable example of the component (A), the following average composition formula (1) R_aSiO_{(4-a) / 2} (1) (In the formula, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8, which are identical or different from each other, and a is 1.5 to 2.8, preferably 1.8 to 2.5. It is preferably a positive number in the range of 1.95 to 2.05, but 0.001 to 10 mol%, preferably 0.01 to 5 mol% of the total R is an alkenyl group.) Organopolysiloxane represented by. Specific examples of R include the alkenyl group specifically mentioned above as the alkenyl group bonded to the silicon atom in the component (A), and the monovalent organic group bonded to the silicon atom other than the alkenyl group of the component (A). Examples of the organic group specifically mentioned above can be mentioned.

Specific examples of the organopolysiloxane of the component (A) include a trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the molecular chain, trimethylsiloxy group-blocked methylvinylpolysiloxane at both ends of the molecular chain, and trimethyl at both ends of the molecular chain. Syroxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both-ended dimethylvinylsyloxy group-blocked dimethylpolysiloxane, molecular chain double-ended dimethylvinylsyloxy group-blocked methylvinylpolysiloxane, molecular chain double-ended dimethylvinyl Syroxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both-ended dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain double-ended divinylmethylsiloxy group-blocked dimethylpolysiloxane, molecule Divinylmethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the chain, trivinylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, trivinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the molecular chain, Expression: R¹₃SiO_0.5Siloxane unit and formula: R¹₂R²SiO_0.5Siloxane unit and formula: R¹₂Siloxane unit represented by SiO and formula: SiO₂Organosiloxane copolymer consisting of siloxane units represented by, formula: R¹₃SiO_0.5Siloxane unit and formula: R¹₂R²SiO_0.5Siloxane unit and formula: SiO₂Organosiloxane copolymer consisting of siloxane units represented by, formula: R¹₂R²SiO_0.5Siloxane unit and formula: R¹₂Siloxane unit represented by SiO and formula: SiO₂Organosiloxane copolymer consisting of siloxane units represented by, formula: R¹R²Siloxane unit represented by SiO and formula: R¹SiO_1.5Siloxane unit represented by or formula: R²SiO_1.5Examples thereof include an organosiloxane copolymer composed of the siloxane unit represented by (1) and a mixture composed of two or more kinds of these organopolysiloxanes.

R in the above formula¹Is the same or heterologous unsubstituted or substituted monovalent hydrocarbon group having preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, which does not contain an aliphatic unsaturated bond, and examples thereof include. , Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group and other alkyl groups; phenyl group, trill group, xsilyl group, naphthyl group and other aryl groups; benzyl group, phenethyl group Aralkyl groups such as; chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group and other alkyl halide groups. Also, R in the above formula²Is an alkenyl group having the same or different substituents, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, and examples thereof include vinyl group, allyl group, butenyl group, and pentenyl. Examples include a group, a hexenyl group, a heptenyl group and the like.

[(B) component] The organohydrogenpolysiloxane of the component (B) undergoes a hydrosilylation addition reaction with the component (A) and acts as a cross-linking agent. The organohydrogenpolysiloxane of the component (B) may be used alone or in combination of two or more. The molecular structure of the component (B) is not particularly limited, and various conventionally produced organohydrogenpolysiloxanes such as linear, cyclic, branched chain, and three-dimensional network structures (resin) are used. can do.

The number of organohydrogenpolysiloxane (B) component is at least 2 (usually about 2 to 300), preferably 3 or more (usually 3 to 200, preferably about 3 to 100) in one molecule. It has a hydrogen atom (ie, a hydrosilyl group or SiH) bonded to the silicon atom of. When the organohydrogenpolysiloxane of the component (B) has a linear structure, these SiH groups are located only at either the end of the molecular chain or the middle of the molecular chain (that is, the non-terminal of the molecular chain). Or may be located in both.

The number of silicon atoms (degree of polymerization) in one molecule of the component (B) is preferably 2 to 300, more preferably 3 to 200, and even more preferably about 4 to 150. Further, 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 500 mPa · s. Degree.

As the component (B), for example, an organohydrogenpolysiloxane represented by the following average composition formula (2) can be used. R³_{b b}H_cSiO_{(4-bc) / 2} (2) (In the formula, R³Is a monovalent hydrocarbon group bonded to a silicon atom, which does not contain an aliphatic unsaturated bond and has the same or different heterogeneous substituents or substitutions, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Yes, b and c are preferably 0.7 b 2.1, 0.001 c 1.0 and 0.8 b + c 3.0, more preferably 1.0 b 2.0, 0.01 c 1.0 and 1.5 b. It is a positive number that satisfies + c 2.5. )

R above³Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group and the like. Alkyl group; aryl group such as phenyl group, trill group, xsilyl group, naphthyl group; aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group; some or all of hydrogen atoms in these hydrocarbon groups are fluorine. Examples thereof include a group substituted with a halogen atom such as an atom, a bromine atom and a chlorine atom, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group and the like. R³Is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.

Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, and tris (hydrogen). Dimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain Methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane, methylhydrogensiloxane, methylphenylsiloxane copolymer at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane, methylhydrogensiloxane, diphenylsiloxane at both ends of the molecular chain Polymer, dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane at both ends of the molecular chain Copolymer, dimethylhydrogensiloxy group-blocked dimethylhydrogensiloxy group at both ends of molecular chain, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer at both ends of molecular chain, dimethylhydrogen at both ends of molecular chain Syloxy group-blocking methylphenylpolysiloxane, molecular chain double-ended dimethylhydrogen siloxy group-blocking diphenylpolysiloxane, in each of these exemplary compounds, some or all of the methyl groups are replaced with other alkyl groups such as ethyl groups and propyl groups. Organohydrogenpolysiloxane, Formula: R³₃SiO_0.5Siloxane unit and formula: R³₂HSiO_0.5Siloxane unit and formula: SiO₂Organosiloxane copolymer consisting of siloxane units represented by, formula: R³₂HSiO_0.5Siloxane unit and formula: SiO₂Organosiloxane copolymer consisting of siloxane units represented by, formula: R³Siloxane unit represented by HSiO and formula: R³SiO_1.5Siloxane unit and formula: HSiO_1.5Examples thereof include an organosiloxane copolymer consisting of either one or both of the siloxane units represented by (1) and a mixture consisting of two or more of these organopolysiloxanes. R in the above formula³Is the same as described above.

As for the blending amount of the component (B), the number of silicon atom-bonded hydrogen atoms in the present composition is usually 1 to 10, particularly preferably 1 for one silicon atom-bonded alkenyl group in the component (A). It is an amount that falls within the range of ~ 5. When the blending amount is such that the number of silicon atom-bonded hydrogen atoms in the present composition is less than one with respect to one silicon atom-bonded alkenyl group in the component (A), the obtained composition is sufficiently cured. It may not be. Further, when the blending amount is such that the number of silicon atom-bonded hydrogen atoms in the present composition exceeds 10 with respect to one silicon atom-bonded alkenyl group in the component (A), the heat resistance of the obtained silicone rubber Is likely to be extremely inferior.

The component (E) described later to be included in the composition of the present invention can also optionally have a hydrogen atom bonded to a silicon atom. Further, the composition of the present invention can contain an organohydrogenpolysiloxane other than the component (B) and the component (E) as an optional component. In this case, the number of SiH groups contained in the total organohydrogenpolysiloxane, which is the sum of the components (B) and (E) and the organohydrogenpolysiloxanes other than the components (B) and (E), is ( A) The number of silicon atom-bonded alkenyl groups in the component is preferably 1 to 10, particularly 1 to 5, and the molar ratio of the number of SiH groups in the component (B) to the total number of SiH groups is It is desirable that it is about 0.5 to 1, especially about 0.7 to 1. When organohydrogenpolysiloxane is not contained in the component (B), the number of silicon atom-bonded hydrogen atoms in the component (B) is 1 to 1 for each silicon atom-bonded alkenyl group in the component (A). The number is 10, preferably 1 to 5.

[(C) component] As the addition reaction catalyst of the component (C), any catalyst is used as long as it promotes the hydrosilylation addition reaction between the silicon atom-bonded alkenyl group in the component (A) and the SiH group in the component (B). May be good. The component (C) may be used alone or in combination of two or more. Examples of the component (C) include platinum group metals such as platinum, palladium and rhodium, platinum chloride acid, alcohol-modified platinum chloride acid, a coordination compound between platinum chloride acid and olefins, vinylsiloxane or an acetylene compound, and tetrakis (tetrakis). Examples thereof include platinum group metal compounds such as triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, and platinum compounds are particularly preferable.

The blending 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 mass of the catalyst metal element with respect to the total mass of the components (A) and (B). More preferably, it is in the range of 10 to 100 ppm. When the blending amount is within this range, the addition reaction is likely to be sufficiently promoted, curing is likely to be sufficient, and the rate of the addition reaction is likely to be improved as the blending amount is increased, which is economical. It is also easy to be advantageous.

[(D) component] If necessary, the fine powder silica of the component (D) optionally used in the present invention acts as a reinforcing agent. That is, it imparts high tear strength to the cured product of the composition of the present invention. By using the fine powder silica of the component (D) as a reinforcing agent, a coating film having excellent tear strength characteristics can be formed. Fine powder silica of component (D) has a specific surface area of usually 50 m.²/ g or more, preferably 50-400m²/ g, especially preferably 100-300m²/ g. When the specific surface area is within this range, it is easy to impart excellent tear strength characteristics to the obtained cured product. The specific surface area is measured by the BET method. The component (D) may be used alone or in combination of two or more.

As the fine powder silica of the component (D), known ones conventionally used as a reinforcing filler for silicone rubber can be used as long as the specific surface area is within the above range. Precipitated silica and the like can be mentioned.

These fine powder silicas may be used as they are, but in order to facilitate imparting better fluidity to the composition of the present invention, methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane; dimethyl Polysiloxane; It is preferable to use it as hydrophobic fine powder silica by surface hydrophobizing treatment with an organosilicon compound such as hexaorganodisilazane such as hexamethyldisilazane, divinyltetramethyldisilazane, and dimethyltetravinyldisilazane. ..

The blending amount of the component (D) is 50 parts by mass or less (that is, 0 to 50 parts by mass) with respect to 100 parts by mass of the organopolysiloxane of the component (A). If the blending amount exceeds 50 parts by mass, the fluidity of the composition tends to decrease, and the coating workability tends to deteriorate. 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 impart a particularly good high tear strength to the cured product of the composition of the present invention.

[(E) component] As the component (E), an organic having an epoxy group and a silicon atom-bonded alkoxy group (for example, as an alkoxysilyl group such as a trialkoxysilyl group, an organodialkoxysilyl group, or a diorganoalkoxysilyl group) in one molecule. Any organic silicon compound can be used as long as it is a silicon compound, but from the viewpoint of adhesion development, an organic silicon compound having at least one epoxy group and at least two silicon atom-bonded alkoxy groups, for example, at least one. A silane having 1 epoxy group and at least 2 silicon atom-bonded alkoxy groups, or having 2 to 30 silicon atoms, preferably about 4 to 20, at least 1 epoxy group and at least 2 silicon atoms. It is preferably a cyclic or linear siloxane having a silicon atom-bonded alkoxy group. The component (E) may be used alone or in combination of two or more.

The epoxy group is, for example, a silicon atom in the form of 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 bound to. A silicon atom-bonded alkoxy group is bonded to a silicon atom to form, for example, a trialkoxysilyl group such as a trimethoxysilyl group or a triethoxysilyl group; a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, or an ethyldiethoxy group. It is preferable to form an alkyldialkoxysilyl group such as a silyl group.

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

Examples of the organosilicon compound of the component (E) include an organosilicon compound represented by the following chemical formula, a mixture of two or more of these, a partial hydrolysis condensate of one or more of these, and the like. ..

<chemistry num="1"><img file="JP5115906B2_D0001.tif" /></chemistry>(In the formula, n is an integer from 1 to 10, m is an integer from 0 to 100, preferably an integer from 0 to 20, p is an integer from 1 to 100, preferably an integer from 1 to 20, and q is an integer from 1 to 10. It is an integer.)

The blending amount of the component (E) is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount is less than 0.1 parts by mass, the obtained composition may not exhibit sufficient self-adhesiveness. If the blending amount exceeds 10 parts by mass, the physical properties of the obtained cured product tend to deteriorate.

[(F) component] The component (F) is an oxyzirconium compound, which acts as a condensation aid catalyst for promoting adhesion and greatly affects the airtightness. The component (F) may be used alone or in combination of two or more. Examples of the oxyzirconium compound of the component (F) include oxyzirconium having two identical or different monovalent organooxy groups in the molecule represented by the following chemical formula, and a part of the organooxy group remaining in organosiloxane. Examples include compounds substituted with groups. ZrO (OR⁴)₂ZrO (OC (= O) R⁴)₂ZrO (OC (R)⁴) = CHC (= O) R⁵)₂

In the above formula, R⁴Is the same or heterologous unsubstituted or substituted monovalent hydrocarbon group having preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, which does not contain an aliphatic unsaturated bond.⁵Is usually 1 to 20, more preferably 1 to 10 monovalent hydrocarbon groups, each of the same or heterologous unsubstituted or substituted, which does not contain an aliphatic unsaturated bond, or inside the monohydric hydrocarbon group. It is a hydrocarbon oxy group that may have ~ 2 etheric oxygens.

R above⁴And R⁵Examples of the hydrocarbon group represented by (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group and octyl group. Alkyl groups such as nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group; aryl groups such as phenyl group, trill group, xylyl group and naphthyl group; benzyl group and phenylethyl group , Aralkyl groups such as phenylpropyl group; groups in which some or all of the hydrogen atoms in these hydrocarbon groups are replaced with halogen atoms such as fluorine atom, bromine atom, chlorine atom, for example, chloromethyl group. , Chloropropyl group, bromoethyl group, trifluoropropyl group and the like. Also, R⁵Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, and tert-butoxy group may have ethereal oxygen in the group represented by. , Methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, alkoxy-substituted alkoxy group such as ethoxyethoxy group and the like. R⁴Is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group. R⁵Is preferably an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or a methoxy group. , Ethoxy group. R⁴And R⁵Is a linear, cyclic, or branched monovalent organopolysiloxane residue in which some of the hydrogen atoms bonded to carbon atoms are usually 1 to 20 silicon atoms, preferably 2 to 10 silicon atoms. It may be replaced.

Also, -OR⁴, -OC (= O) R⁴, -OC (R⁴) = CHC (= O) R⁵A compound in which a part of the monovalent organooxy group represented by the above is substituted with a siloxane residue is one or two Rs in the molecule in each of the above chemical formulas.⁴Group, OR⁴Group, OC (= O) R⁴Group or R⁵A part of the hydrogen atom bonded to the carbon atom of the above is usually replaced with a linear, cyclic or branched organopolysiloxane structure having 1 to 20 silicon atoms, preferably 2 to 10 silicon atoms, etc. Can be mentioned. Specific examples of these (F) components include the following compounds in addition to the compounds A and B used in the examples.<img file="JP5115906B2_D0002.tif" />

The blending amount of the component (F) is in the range of 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount is less than 0.1 parts by mass, the adhesiveness of the obtained composition and the airtightness of the obtained airbag tend to decrease. If the blending amount exceeds 5 parts by mass, the heat resistance of the obtained cured product tends to decrease.

[Other ingredients] In addition to the above-mentioned components (A) to (F), any other component may be added to the composition of the present invention 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 The reaction control agent is not particularly limited as long as it is a compound having a curing inhibitory effect on the addition reaction catalyst of the component (C), and conventionally known ones 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 compounds such as acetylene alcohols; and two or more alkenyl groups. Compounds; hydroperoxy compounds; maleic acid derivatives and the like.

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

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, layered mica, and carbon. Inorganic fillers such as black, diatomaceous earth, and glass fiber; fillers in which these inorganic fillers are surface-hydrophobicized with organic silicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds. ; Silicone rubber powder; Silicone resin powder and the like.

Other ingredients In addition, for example, an organopolysiloxane containing one silicon atom-bonded hydrogen atom in one molecule and no other functional group, and another molecule containing one silicon atom-bonded alkenyl group in one molecule. Organic polysiloxanes that do not contain functional groups, non-functional organopolysiloxanes that do not contain silicon atom-bonded hydrogen atoms, silicon atom-bonded alkenyl groups, or other functional groups, organic solvents, creep hardening inhibitors, plasticizers, A thixophilic imparting agent, a pigment, a dye, an antifungal agent 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 stored along the roof side from the front pillars and can maintain a constant expansion time to protect the head and prevent popping out in the event of a collision or a vehicle tipping over. It is suitable for producing the required curtain airbag.

In the present invention, an air bag having a known structure is used as an air bag on which a silicone rubber coating layer made of a cured product of the above composition is formed, particularly a curtain air bag, and specific examples thereof are 6,6-nylon. , 6-Nylon, polyester fiber, aramid fiber, various polyamide fibers, various polyester fibers, and other synthetic fiber woven fabrics are used as the base fabric, and the outer circumferences of two plain woven fabrics with rubber coating on the inner surface are glued together. Examples thereof include an air bag of a type (hereinafter abbreviated as a plain weave type) manufactured by laminating and sewing the adhesive layers thereof, and a bag weaving type air bag in which a bag portion is formed by weaving the woven fabric as a base cloth. ..

The liquid silicone rubber coating agent composition is applied to at least one surface of a base material made of a fiber cloth, particularly one surface, and is heated and cured in, for example, a hot air drying furnace on the surface. A silicone rubber coating layer can be formed. Using the silicone rubber-coated base cloth for a curtain airbag thus obtained, a curtain airbag can be manufactured.

Here, examples of the base material made of the fiber cloth include a base material based on the above-mentioned woven fabric of various synthetic fibers. Further, as a method of coating the base material with the above 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 15-80g / m², Even more preferably 20-60 g / m²Degree.

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.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1] &lt;Preparation of composition&gt; Both ends of the molecular chain are sealed with vinyldimethylsiloxy groups, and the viscosity at 25 ° C is about 30,000 mPa · s. 60 parts by mass of dimethylpolysiloxane, 8 parts by mass of hexamethyldisiloxane, 2 parts by mass of water, by BET method. Measured specific surface area is about 300m²40 parts by mass of fumed silica (Aerosil® 300, manufactured by Aerosil Japan, Inc.) of / 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 continued to mix for 2 hours. The mixture was cooled to room temperature, and the mixture was sealed with vinyldimethylsiloxy groups at both ends of the molecular chain, and the viscosity at 25 ° C was about 30,000 mPa · s. 24 parts by mass of dimethylpolysiloxane, both ends of the molecular chain. Is sealed with a trimethylsiloxy group, and 5 parts by mass of dimethylpolysiloxane, which contains 5 mol% of vinylmethylsiloxane group units in the diorganosiloxane unit of the main chain and has a viscosity of about 700 mPa · s at 25 ° C, is added. And mixed until uniform to give base compound (I).

Both ends of the molecular chain are sealed with vinyldimethylsiloxy groups in 64 parts by mass of the base compound (I), and 0.18 mol% of vinylmethylsiloxane group units are contained in the diorganosiloxane units of the main chain, and the viscosity at 25 ° C. 8 parts by mass of dimethylpolysiloxane, which is about 30,000 mPa · s, 23 parts by mass of dimethylpolysiloxane, which has a viscosity at 25 ° C of about 30,000 mPa · s, with both ends of the molecular chain sealed with vinyl dimethylsiloxy groups. Both ends of the chain are sealed with vinyl dimethylsiloxy groups, and the viscosity at 25 ° C is about 100,000 mPa · s, 35 parts by mass of dimethylpolysiloxane, and the viscosity at 25 ° C is 10 mPa · s. Molecular chain with silicon atom-bonded hydrogen atom Both ends trimethylsiloxy group-sealed dimethylsiloxane / methylhydrogensiloxane copolymer (silicon atom-bonded hydrogen atom content = 0.82% by mass) 3 parts by mass, 1-ethynylcyclohexanol 0.02 part by mass , 0.25 parts by mass of dimethylpolysiloxane solution containing 1% by mass of platinum chloride / 1,3-divinyltetramethyldisiloxane complex as platinum atom content, 0.14 parts by mass of tetramethyltetravinylcyclotetrasiloxane, γ-glycidoxy Composition A was prepared by mixing 0.7 parts by mass of propyltrimethoxysilane and 0.32 parts by mass of the following oxyzylozane compound A.

&lt;Airtightness test&gt; This composition is coated on the bag-woven airbag base fabric (80 g / m) so that it can be coated evenly and evenly with a coater.²), Heated in an oven at 170 ° C. for 1 minute and cured to prepare a bag-woven airbag. An airtightness test was conducted using this airbag. The airtightness test was performed by inflating the airbag at a pressure of 140 kPa and measuring the residual pressure after 30 seconds, and the airtightness was evaluated by the measured residual pressure value. The results are shown in Table 1.

&lt;Scott fir test&gt; The Scott fir test was performed using a Scott fir tester. After performing a rubbing test 300 times with a pressing force of 4 kgf on the above-mentioned bag-woven air bag, the peeling state of the silicone rubber-coated thin film from the base cloth was visually confirmed. The evaluation was performed according to the following criteria. The results are shown in Table 1. Pass: Passed if the coating film did not peel off from the base cloth. Fail: Fail if there is peeling of the coating film from the base fabric.

[Example 2] Composition B was prepared in the same manner as in Example 1 except that 0.25 parts by mass of the following oxyzirconium compound B was used instead of 0.32 parts by mass of the oxyzirconium compound A in Example 1, and the airtightness test and Scott fir were performed. The test was conducted. These results are shown in Table 1.

[Comparative example 1] Composition C was prepared in the same manner as in Example 1 except that 0.4 parts by mass of the following zirconium tetraacetylacetone compound C was used instead of 0.32 parts by mass of the oxyzirconium compound A in Example 1, and an airtightness test was performed. , Scott fir test was performed. These results are shown in Table 1.

[Comparative example 2] Composition D was prepared in the same manner as in Example 1 except that 0.4 parts by mass of the following zirconium dibutoxybis (ethylacetacetate) compound D was used instead of 0.32 parts by mass of the oxyzirconium compound A in Example 1. Then, an airtightness test and a Scott fir test were conducted. These results are shown in Table 1.

Compound A:

<chemistry num="2"><img file="JP5115906B2_D0003.tif" /></chemistry>Compound B:

<chemistry num="3"><img file="JP5115906B2_D0004.tif" /></chemistry>Compound C:

<chemistry num="4"><img file="JP5115906B2_D0005.tif" /></chemistry>Compound D:

<chemistry num="5"><img file="JP5115906B2_D0006.tif" /></chemistry>

<tables num="1"><img file="JP5115906B2_D0007.tif" /></tables>