JP6892200B2 - A silicone rubber composition containing a block polyisocyanate composition, a method for producing a coating product, and a coating product. - Google Patents

Description

The present invention relates to a silicone rubber composition containing a blocked polyisocyanate composition and a curable silicone rubber composition.
It is an unrefined or refined hydrolyzable woven fabric that is coated on a woven fabric having an oil content of 5% by mass or less based on the weight of the woven fabric. The present invention relates to a silicone rubber composition that maintains adhesiveness even after long-term storage under high humidity, a method for producing a coating product, and a coating product. The present invention relates, in particular, to silicone rubber compositions suitable for airbags, methods of producing coatings and coatings.

Coatings produced by coating a curable silicone rubber composition with a resin or the like and curing it are used in many fields, but if a large amount of spinning oil agent at the time of production remains in the woven fabric, the silicone rubber composition There was a problem that the cured product and the woven fabric did not adhere to each other. Patent Document 1 describes a process control method for solving the problem, but it takes time and effort.

On the other hand, in the silicone rubber composition, in order to increase the adhesive force, Patent Document 2 discloses an isocyanate compound exhibiting a strong adhesive-imparting action, but the compatibility with the silicone rubber composition is poor and it is dispersed. As a result, it was not possible to adhere to a woven fabric having a large amount of residual oil, especially in an unrefined or insufficiently scoured woven fabric, due to separation or poor dispersion.
Further, from the viewpoint of the environment, the blending of organic solvents is not preferred, and those having a small amount of solvent and, by extension, those containing almost no solvent are required.

Further, since the isocyanate group has high reactivity, the reaction proceeds in the silicone rubber composition and the adhesiveness gradually decreases, so that the composition kit cannot be prepared by blending in advance. Therefore, even if the isocyanate compound is added at the time of blending the silicone rubber composition kit, the adhesiveness is lost with the passage of time, so that the pot life is short, and industrial production is practically impossible. As a substance capable of controlling the reactivity of the isocyanate group, for example, Non-Patent Document 1 describes a completely solvent-free low-viscosity block polyisocyanate composition, but there is also a description about blending with a silicone rubber composition. No findings have been shown.

In general, hydrolyzable woven fabrics easily absorb moisture, and deterioration is accelerated under high temperature and high humidity. As a result, in woven fabrics in which deterioration has progressed, there is a serious problem that the cured product of the silicone rubber composition is peeled off. .. As a method for solving this, for example, Patent Document 3 discloses a method for improving the hydrolysis resistance of polyester yarn, but it is economically disadvantageous to perform a special treatment, and further, this method is disadvantageous. Even with such yarns, in a woven fabric having a large amount of oil, it is difficult to adhere at the time of curing, and peeling due to deterioration is worse than when the amount of oil is small.

As described above, the silicone rubber composition containing the conventional block polyisocyanate composition and the curable silicone rubber composition is an unrefined or refined hydrolyzable woven fabric, and the amount of oil is 5 of the weight of the woven fabric. It is a problem to coat a woven fabric of mass% or less, to be able to adhere strongly even if it is cured, and to maintain the adhesiveness even after long-term storage of the obtained coated material under high temperature and high humidity. There has been a demand for a silicone rubber composition that realizes such a situation.

Japanese Unexamined Patent Publication No. 2012-177220 JP-A-2007-186596 Japanese Unexamined Patent Publication No. 2014-65493

"Coating Time Signal" 2015 No. No. 235 (Asahi Kasei Chemicals Co., Ltd.)

The present invention has been made in view of the above circumstances, and is an unrefined or refined hydrolyzable woven fabric with respect to a silicone rubber composition containing a blocked polyisocyanate composition and a curable silicone rubber composition. , The amount of oil is 5% by mass or less of the weight of the woven fabric, and it adheres strongly even when cured, and maintains the adhesiveness even after the obtained coated material is stored for a long time under high temperature and high humidity. It is an object of the present invention to provide a silicone rubber composition suitable for an airbag, in particular.

As a result of diligent studies, the present inventors have made a block polyisocyanate composition containing a polyisocyanate and a heat-dissociable blocking agent, particularly low viscosity, and the amount of the heat-dissociation blocking agent is determined to be isocyanate in the polyisocyanate composition. It has been found that the present object can be achieved by setting an appropriate amount with respect to the basic amount, and the present invention has been completed.

That is, the present invention is a silicone rubber composition , (A) 100 parts by mass of organopolysiloxane having 1.8 or more alkenyl groups bonded to silicon atoms on average in one molecule, (B) aliphatic. A polyisocyanate obtained from at least one diisocyanate selected from the group consisting of diisocyanates and aliphatic diisocyanates and a heat-dissociable blocking agent are contained, and the heat-dissociable blocking agent is applied to 1 mol of isocyanate groups in the polyisocyanate. 0.01 to 5 parts by mass of a blocked polyisocyanate composition containing an amount of 1 mol or more, substantially free of an organic solvent, and a viscosity at 60 ° C. of 100,000 mPa · s or less, (C) Addition curing. With respect to the alkenyl group of the organohydrogenpolysiloxane component (A), which has an effective amount of catalyst, (D) two or more hydrogen atoms bonded to silicon atoms on average in one molecule, hydrogen atoms bonded to silicon atoms are present. It is characterized by containing an amount of 0.5 to 20 mol.

According to the present invention, the silicone rubber composition containing the block polyisocyanate composition and the curable silicone rubber composition is an unrefined or refined hydrolyzable woven fabric, and the amount of oil is 5% by mass or less based on the weight of the woven fabric. It coats the woven fabric, which adheres strongly even when cured, and maintains the adhesiveness even after the obtained coated material is stored for a long period of time under high temperature and high humidity, so that the workload of the scouring process is greatly increased. It can be reduced and the durability of the coated material can be greatly improved.

The details of the silicone rubber composition according to the present invention will be described below.

The curable silicone rubber composition of the present invention comprises at least one or more kinds of silicone rubber composition composition kits, and these composition kits are mixed and cured by a reaction to finally form a silicone rubber composition. Any can be used as long as a cured product can be obtained. Such curing method, an addition curing, suitable curing method of the present invention, the organopolysiloxane having an alkenyl group bonded to a silicon atom in a molecule, organohydrogenpolysiloxane Si- crosslinking system heating or at room temperature with H groups by addition reaction catalyst, a method of activating an addition reaction catalyst in the ultraviolet is how to crosslink the like.

(Ingredient (A))
The component (A) is a main component constituting the curable silicone rubber composition, and is a main material of the silicone rubber composition for obtaining excellent rubber physical characteristics after curing.
When the curable silicone rubber composition of the present invention is an addition-curable type, the component (A) is the component (A-1) shown below.
The component (A-1) is an organopolysiloxane containing 1.8 or more alkenyl groups bonded to silicon atoms in one molecule on average, and the average composition formula is usually as follows. It is represented by the formula (1).
R ² _a SiO _{(4-a) / 2} (1)
(However, in the formula (1), R ² is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon atoms 1 to 18, and a is 1.7 to 2.1. is there.)

Here, at least two or more of the monovalent hydrocarbon groups represented by R ² are alkenyl such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group and cyclohexenyl group. Selected from the groups, the other groups are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, specifically methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. Group, tert-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. Among aryl groups such as cycloalkyl group, phenyl group, trill group, xsilyl group, biphenyl group and naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group, and hydrocarbon groups thereof. Halogen such as chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, cyanoethyl group in which some or all of the hydrogen atoms of It is selected from a substituted alkyl group, a cyano-substituted alkyl group and the like.

In the selection R ^2, preferably a vinyl group as the two or more necessary alkenyl groups, other examples of the group methyl, phenyl, 3,3,3 - trifluoropropyl groups are preferred. Moreover, it least 70 mol% of all R ² is a methyl group, preferably in terms of physical properties and economy of the cured product, usually is used those having more than 80 mol% is methyl groups.

The organopolysiloxane of the component (A-1) may be linear or branched. The molecular structure is as follows: dimethylpolysiloxane with both ends of the molecular chain dimethylvinylsiloxy group-blocked, dimethylvinylsiloxy group-sealed dimethylsiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane at both ends of the molecular chain. Copolymer, dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group at both ends of molecular chain, dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of molecular chain, some of the methyl groups of these organopolysiloxanes Or an alkyl group such as an ethyl group or a propyl group; an aryl group such as a phenyl group or a tolyl group; an organopolysiloxane substituted with an alkyl halide group such as a 3,3,3-trifluoropropyl group, and these organosane. A mixture of two or more types of polysiloxane is exemplified, but a linear organopolysiloxane having vinyl groups at both ends of the molecular chain is preferable because of its availability.

The component (A-2) is an organopolysiloxane having a hydroxy group bonded to a silicon atom at both ends of the molecular chain, and / or an organopolysiloxane having an alkoxy group bonded to a silicon atom at both ends of the molecular chain. It may be linear or branched. Examples of the alkoxy group include a methoxy group and an ethoxy group, but a methoxy group is preferable from the viewpoint of reactivity. Except for the hydroxy group and the alkoxy group, it is preferably an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon atoms of 1 to 18, specifically, a methyl group, an ethyl group and a propyl group. , Isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other alkyl groups, cyclopentyl group. , Cycloalkyl group such as cyclohexyl group, cycloheptyl group, aryl group such as phenyl group, tolyl group, xsilyl group, biphenyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group. Or, a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, or a 3-chloro in which some or all of the hydrogen atoms in these hydrocarbon groups are substituted with a halogen atom, a cyano group, or the like. It is selected from halogen-substituted alkyl groups such as propyl group and cyanoethyl group, cyano-substituted alkyl groups and the like, but in the present invention, a methyl group is preferable from the viewpoint of physical properties and economic efficiency of the cured product, and usually 80 mol of methyl group is used. Those having% or more are used.

The organopolysiloxane of the component (A) is produced by a method known to those skilled in the art, and has a viscosity at 25 ° C. of preferably 50 to 1,000,000 mPa · s, more preferably 200 to 500,000 mPa · s, and particularly of viscosity. It is preferable to use two or more different types because the viscosity of the final silicone rubber composition can be easily adjusted. The viscosity can be measured with a rotational viscometer or the like.

(Component (B))
The block polyisocyanate composition of the component (B) is a woven fabric having unrefined or refined hydrolysis, and is used for strongly adhering to a woven fabric having an oil content of 5% by mass or less based on the weight of the woven fabric. It is an essential ingredient. The conventional blocked polyisocyanate compound has a drawback that it is difficult to handle because the viscosity of urethane groups and urea groups generated when the raw material polyisocyanate is reacted with the blocking agent becomes very high due to strong intramolecular hydrogen bonds. there were. In addition, since the isocyanate content in the molecule is low, it was necessary to increase the blending amount in order to strongly adhere to the base fabric, but the viscosity is high and it is difficult to handle, and it is incompatible with the curable silicone rubber composition. Therefore, sufficient adhesiveness could not be obtained due to separation or poor dispersion. As a result of diligent studies, the present inventors have conducted thermal dissociation by containing a polyisocyanate obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and a heat-dissociable blocking agent. A low-viscosity block containing a sex blocking agent in an amount of 1 mol or more per 1 mol of isocyanate groups in polyisocyanate, substantially free of organic solvents, and a viscosity at 60 ° C. of 100,000 mPa · s or less. When the polyisocyanate composition is used, the compatibility with the curable silicone rubber composition is significantly improved as compared with the conventional case, and as a result, the dispersion of the blocked polyisocyanate composition is improved and the adhesiveness of the silicone rubber composition is improved over time. The silicone rubber composition is coated on an unrefined or refined hydrolyzable fabric having an oil content of 5% by mass or less based on the weight of the fabric, and strongly adheres even when cured. Moreover, it has been found that the obtained coating material has a surprising effect of maintaining adhesiveness even after being stored for a long period of time under high temperature and high humidity.

Examples of the aliphatic diisocyanate include butane diisocyanate, pentane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Among these, hexamethylene diisocyanate is preferable because of its easy availability in the industry. These aliphatic diisocyanates may be used alone or in combination of two or more. Examples of the alicyclic diisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,4-cyclohexane diisocyanate. Among these, isophorone diisocyanate is preferable because of its easy availability in the industry. These alicyclic diisocyanates may be used alone or in combination of two or more.

Either of the aliphatic diisocyanate and the alicyclic diisocyanate may be used alone, or two or more kinds of the aliphatic diisocyanate and the alicyclic diisocyanate may be used in combination.

The blocking agent is not particularly limited as long as it is thermally dissociable and meets the object of the present invention. Since the blocking agent protects the isocyanate groups, prevents the isocyanate groups from being deactivated by water and the like, and prevents the curing catalyst from being poisoned by the isocyanate groups, it can be stabilized and maintained even in the silicone composition. The "thermal dissociation" property here means that the blocking agent bonded to the isocyanate group is dissociated by heating, and the temperature required for dissociation varies depending on the structure of the blocking agent, for example, 40 ° C. to 300 ° C. Is. The isocyanate group can act as an adhesive immediately after the blocking agent is dissociated.
From the viewpoint of industrial availability, it is preferable to use one selected from oxime-based, acid-amide-based, amine-based, active methylene-based and pyrazole-based compounds, alone or in combination, and methyl ethyl ketooxime and acetoxime. , Methanol, ethanol, acetoanilide, acetate amide, ε-caprolactam, diphenylamine, aniline, ethyl acetoacetate, 3-methylpyrazole, 3.5-dimethylpyrazole and the like.

The amount of the heat-dissociating block agent is preferably 1 mol or more with respect to 1 mol of the isocyanate group in the polyisocyanate. As a result, almost all the isocyanate groups are blocked and stabilized in the silicone composition, so that not only the adhesiveness is not lost even after the silicone rubber composition is formulated, but also the oil agent is present in the woven fabric. Can also be cured and strongly adhered. Further, since the heat dissociative blocking agent is present in excess with respect to the isocyanate groups, the isocyanate groups not consumed in the initial curing reaction are maintained in a stabilized state in the cured product. As a result, when the coating material is exposed to high temperature and high humidity, the heat dissociative blocking agent dissociates again and the isocyanate group starts the reaction again, so that the progress of moisture absorption and hydrolysis to the woven fabric is suppressed and the coating material is coated. Can be prevented from peeling off. Therefore, by adjusting the timing of thermal dissociation according to the type and amount of the thermal dissociative blocking agent, it is possible to control the suppression of hydrolysis and the acquisition of strong adhesive force with respect to various substrates. Therefore, the thermal dissociation temperature of the blocking agent is preferably in the range of 40 to 300 ° C. in view of the conditions under which the coating material is normally expected to be exposed, but since many woven fabrics have heat resistance restrictions, 40 ° C. to 200 ° C. ℃ is more preferable.

The blocked polyisocyanate composition of the present invention does not substantially contain an organic solvent, but "substantially free" means that the content of the organic solvent in the blocked polyisocyanate composition is 5% by mass or less. Further, from the viewpoint of reducing the environmental load, 3% by mass or less is preferable, and 1% by mass or less is more preferable. The lower the viscosity, the better the compatibility. Therefore, from the viewpoint of ease of handling, the viscosity is preferably 100,000 mPa · s or less at 60 ° C., and from the ease of mixing, the viscosity is 30,000 mPa · s or less at 60 ° C. More preferred. For viscosity measurement, an E-type viscometer can be used up to 25,600 mPa · s, and a rheometer (RS-1 manufactured by HAAKE) can be used above that. Further, the rotor can be selected according to the viscosity.

The blending amount of the component (B) is preferably 0.01 part by mass to 5 parts by mass, and more preferably 0.02 part by mass to 3 parts by mass with respect to 100 parts by mass of the component (A). If it is 0.01 part or less, the proportion of isocyanate groups exposed from the initial stage becomes large, so that it is deactivated by moisture or the like, so that it is difficult to obtain an adhesive effect, and if it is 5 parts by mass or more, curing becomes slow, which is not preferable.

(Component (C))
Any of the curing catalysts of the present invention can be used as long as it is used for curing the curable silicone rubber composition. The catalyst used for the addition reaction is a catalyst known to those skilled in the art that promotes the addition curing reaction between the alkenyl group and the hydrogen atom bonded to the silicon atom. Specifically, platinum group metals such as platinum, rhodium, palladium, osmium, iridium, and ruthenium, or those obtained by fixing these to a fine-grained carrier material (for example, activated carbon, aluminum oxide, silicon oxide), and a platinum compound. Examples thereof include platinum halide, platinum-olefin complex, platinum-alcohol complex, platinum-alcolate complex, platinum-vinylsiloxane complex, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride and the like. Will be done.

Further, for economic reasons, a metal compound catalyst other than the noble metal may be used. Specifically, as the hydrosilylated iron catalyst, an iron-carbonyl complex catalyst, an iron catalyst having a cyclopentadienyl group as a ligand, etc. A terpyridine-based ligand, an iron catalyst having a terpyridine-based ligand and a bistrimethylsilylmethyl group, an iron catalyst having a bisiminopyridine ligand, an iron catalyst having a bisiminoquinolin ligand, and an aryl group are coordinated. An iron catalyst having a child, an iron catalyst having a cyclic or acyclic olefin group having an unsaturated group, and an iron catalyst having a cyclic or acyclic olefinyl group having an unsaturated group. In addition, hydrosilylated cobalt catalysts, vanadium catalysts, ruthenium catalysts, iridium catalysts, samarium catalysts, nickel catalysts, manganese catalysts and the like are exemplified.

The catalyst can also be used in the form of microencapsulation in a fine particle solid or the like. In this case, the fine particle solid containing the catalyst and insoluble in the organopolysiloxane is, for example, a thermoplastic resin (for example, a polyester resin or a silicone resin). The catalyst can also be used in the form of clathrate compounds, for example in cyclodextrin.

An effective amount of the catalyst is used according to the desired curing temperature and curing time, but usually, the concentration of the catalyst metal element is 0.5 to 1,000 ppm with respect to the total mass of the silicone rubber composition. It may be preferably in the range of 1 to 500 ppm, more preferably in the range of 1 to 100 ppm. If the blending amount is less than 0.5 ppm, curing may be significantly slowed or not cured, while if it exceeds 1,000 ppm, the cost increases, which is economically unfavorable.

Examples of the catalyst used for the reaction with organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-chlorobenzoyl peroxide, p-methylbenzoyl peroxide, and o-methylbenzoyl. Peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-bis (2,5-t-butylperoxy) hexane, di-t-butyl peroxide, t-butylperbenzoate, 1,1- Bis (t-butylperoxycarboxy) hexane and the like are exemplified, and these organic peroxides are used in the range of 0.1 to 5 parts by mass per 100 parts by mass of the component (A-1).

Examples of the catalyst used in the condensation reaction include dibutyltin diacetate, bis (acetoxydibutyltin) oxide, bis (lauroxydibutyltin) oxide, dibutyltin bisacetylacetonate, dibutyltin bismaleic acid monobutyl ester, and dioctyl bismaleic acid monobutyl ester. Examples thereof include organotin catalysts, and these condensation reaction catalysts are used in the range of 0.1 to 20 parts by mass per 100 parts by mass of the component (A-2).

(Component (D))
The component (D) is an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule on average, and reacts with the component (A) to act as a cross-linking agent. Specifically, methylhydrogenpolysiloxane, dimethylsiloxane / methylhydrogenpolysiloxane copolymer, methylphenylsiloxane / methylhydrogenpolysiloxane copolymer, cyclic methylhydrogenpolysiloxane, dimethylhydrogensiloxy unit and SiO _Examples thereof include a copolymer composed of 4/2 units. The blending amount of this organohydrogenpolysiloxane is preferably an amount in which the hydrogen atom bonded to the silicon atom is 0.5 to 20 mol based on the total number of alkenyl groups of the component (A-1). If it is less than 0.5 mol, the hardness is remarkably lowered, and if it is more than 20 mol, it becomes too hard and the cured film is easily cracked or peeled off, which is not preferable.

The viscosity of the organohydrogenpolysiloxane of the component (D) at 25 ° C. is preferably 1 to 100,000 mPa · s, more preferably 2 to 5,000 mPa · s, and these may be used alone or in combination of two or more. You may.

In particular, when it is desired to improve the elongation of the cured product of the silicone rubber composition to follow the elastic woven fabric, an organohydrogen having hydrogen atoms bonded to silicon atoms only at both ends of the molecular chain. It is preferable to contain polysiloxane. These are preferably linear, and high elongation can be easily obtained by relatively easily increasing the molecular chain length of the organopolysiloxane having the alkenyl group of the component (A-1) by a curing reaction.

Further, from the viewpoint of elongation and adhesiveness, both ends of the molecular chain and those containing hydrogen atoms other than both ends may be contained, and specifically, as represented by the following general formula (2). A linear organohydrogenpolysiloxane is exemplified.

HR ³ ₂ SiO- (HR ³ SiO) _m- (R ³ ₂ SiO) _n -SiR ³ ₂ H (2)

In formula (2), R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms of the same or different species, which does not independently have an aliphatic unsaturated bond, and m is 1 to 1. A positive number of 50, n is a positive number of 0 or 1 to 150, and t represented by the formula: t = m / (m + n) satisfies 0.01 ≦ t ≦ 1.0. M in the formula (2) is more preferably 1 to 20, n is more preferably 10 to 100, t is 0.02 ≦ t ≦ 1.0, and even more preferably t is 0. 02 ≦ t ≦ 0.2. When m is 50 or more, the elongation at break does not increase, and when n is 150 or more, the hardness of the cured product decreases, which is not preferable. Further, when t is 0.01 or less, the hardness of the cured product is lowered, which is not preferable, and when t is 0.1 or more, the elongation of the cured product at break is difficult to increase, which is not preferable.

From the viewpoint of adhesiveness and heat resistance, both ends of the molecular chain of the organohydrogenpolysiloxane have a trimethylsiloxy group, and contains an organohydrogenpolysiloxane containing at least one aromatic group in the molecule. Also, for economic reasons, the aromatic group is preferably a phenyl group. Further, when these are used in combination with an organohydrogenpolysiloxane having trimethylsiloxy groups at both ends of the molecular chain and containing no aromatic group in the molecule and having a hydrogen content of 5 mmol / g or more. , It is preferable because the adhesiveness is further promoted.

(Component (E))
The silica of the component (E) is a component having a function as a reinforcing material, and examples thereof include fumed silica, silica fume, precipitated silica, calcined silica, colloidal silica, and diatomaceous earth having hydrophilicity or hydrophobicity. , particularly preferably having their fine powder, less 100μm particle size, and the ratio more preferably at least ^{50 m} 2 / g surface area, 150 meters ² / g or more is more preferable. Further, silica which has been surface-treated in advance with organosilane, organosilazane, organocyclopolysiloxane and the like can also be preferably used. The amount of the component (E) added is usually in the range of 0.5 to 50 parts by mass, preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the component (A). These may be used alone or in combination of a plurality of types. If the blending amount is too small, the desired physical properties such as tear strength cannot be obtained, and if it is too large, the fluidity of the silicone rubber composition is lowered, the desired thickness of the cured product cannot be obtained, and the coating workability is lowered. To do.

When hydrophilic fine powder silica is used, it is preferable to hydrophobize the surface of the silica with a hydrophobizing agent, if necessary. Examples of the hydrophobizing agent include organosilazanes such as hexamethyldisilazane, halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane, and these halogen atoms are alkoxy groups such as methoxy group and ethoxy group. Substituted organoalkoxysilanes and the like, or dimethylsilicone oils can be mentioned, with hexamethyldisilazane being preferred.

(Component (F))
Component (F) is a component which imparts serves to improve the strength of the cured product of the silicone rubber composition, and siloxane units having a vinyl group in the molecule, T siloxane of the formula R ¹ SiO _3/2 Units (wherein R ¹ are unsubstituted or substituted monovalent hydrocarbon groups having 1-18 carbon atoms that are the same or different from each other) and / or represented by the formula SiO _4/2 . An organopolysiloxane resin containing a siloxane unit having a Qsiloxane unit is preferable. These preferably contain 0.1 to 50 parts by mass with respect to 100 parts by mass of the component (A). If it is 0.1 part by mass or less, the effect of improving the adhesiveness is not observed, and if it is 50 parts by mass or more, the cured product becomes too hard, or the surface of the cured product becomes tacky and blocking is likely to occur, which is not preferable.

(Ingredient (G))
The organosilicon compound of the component (G) is a component that imparts a function of further improving the adhesiveness of the silicone rubber composition of the present invention, and is an organosilicon having an epoxy group and a silicon atom-bonded alkoxy group in one molecule. Any organosilicon compound can be used as long as it is a compound, but it is preferably an organosilicon compound having at least one epoxy group and at least two or more alkoxy groups having a silicon atom bond. Such epoxy groups include silicon in the form of glycidoxyalkyl groups such as glycidoxypropyl groups, epoxy-containing cyclohexylalkyl groups such as 2,3-epoxidecyclohexylethyl groups and 3,4-epoxidecyclohexylethyl groups. It is preferably bonded to an atom, and an epoxy group containing 2 to 3 epoxy groups in one molecule may be used. The silicon atom-bonded alkoxy group includes a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, and an ethyldiethoxysilyl group, and an alkyldialkoxysilyl group. Etc. are preferable. Further, as the functional group other than the above, a functional group selected from an alkenyl group such as a vinyl group, a (meth) acryloxy group and a hydrosilyl group (SiH group) may be used.

(Ingredient (H))
The component (H) is a component having a function as a condensation co-catalyst for promoting adhesion, and comprises an element selected from B, Al, Ti, and Zr as a metal atom, a metal alkoxide, a metal salt salt, and a metal. One or more compounds selected from the chelating group. Examples of such organic metal compounds include boron-based condensation catalysts such as boron isopropoxide; organic titanium alkoxides such as tetraisopropyl titanate, tetranormal butyl titanate, tetraterchary butyl titanate, tetraoctyl titanate, and tetrastearyl titane. Organic titanium acylate such as titanium isostearate, diisopropoxy (acetylacetonate) titanium, diisopropoxy (ethylacetacetate) titanium, tetraacetylacetonate titanium, titanium-1,3-propanedioxybis (ethylacetate) Titanium-based condensation co-catalysts such as (acetate) and other organic titanium chelate compounds; organic zirconates such as tetraisopropyl zirconate, tetranormal butyl zirconate, tetratershally butyl zirconate, tetraoctyl zirconate, tetrastearyl zirconate. Alkoxide, organic zirconium acylate such as zirconium isostearate, zirconium diisopropoxy (acetylacetate), zirconium diisopropoxy (ethylacetate acetate), zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetate A zirconium-based condensation co-catalyst represented by an organic zirconium chelate compound such as nate, an oxozirconium compound such as zirconium bis (2-ethylhexanoate) oxide, and zirconium acetylacetonate (2-ethylhexanoate) oxide; Aluminum alkoxides such as triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate); aluminum chelate compounds such as diisopropoxyaluminum (ethylacetate acetate) aluminum tris (ethylacetacetate), aluminum tris (acetylacetonate) An aluminum-based condensation catalyst represented by an aluminum asyloxy compound such as hydroxyaluminum bis (2-ethylhexanoate), etc. is exemplified.

(Component (I))
As the component (I), any component (I) may be blended as long as it is a component that further improves the dispersion of the blocked polyisocyanate composition of the component (B), but the density is 2.0 g / cm ³ The above powder is preferable. Since the dispersion of the blocked polyisocyanate composition is further improved as the oil absorption amount increases, 15 ml / 100 g or more is preferable, and the average particle size is preferably 100 μm or less from the viewpoint of ease of blending. Specifically, powders such as sedimentary barium sulfate and talc are exemplified.

In the silicone rubber composition of the present invention, any conventionally known additive for silicone rubber may be used as an optional component other than the above components (A) to (I) as long as the object of the present invention is not impaired. Good. Examples of such additives include viscosity modifiers, reinforcing fillers, non-reinforcing fillers, adhesion-imparting agents, pigments, dyes, curing inhibitors, heat-resistant imparting agents, flame-retardant agents, antistatic agents, conductivity-imparting agents, and airtightness. A property improver, a radiation shield, an electromagnetic wave shield, a preservative, a stabilizer, an organic solvent, a plasticizer, a fungicide, or a silicon atom-bonded hydrogen atom or an alkenyl group contained in one molecule, and others. Examples thereof include an organopolysiloxane containing no functional group, a non-functional organopolysiloxane or an organopolysiloxane resin containing no silicon atom-bonded hydrogen atom or alkenyl group. These may be used alone or in combination of two or more.

The viscosity adjusting material may be any material as long as it imparts a function of controlling a change in the viscosity of the silicone rubber composition, and specifically, at least one silanol group in one molecule (that is, that is). , A silane containing a hydroxyl group bonded to a silicon atom) is preferable. These may be used alone or in combination, and specific examples thereof include trimethylsilanol, triethylsilanol, triisopropylsilanol, triphenylsilanol, dimethylphenylsilanol, vinylphenylmethylsilanol, dimethylvinylsilanol, etc., but are industrially available. From the viewpoint of ease of use, trimethylsilanol, triethylsilanol, triisopropylsilanol, and triphenylsilanol are preferable.

As the adhesiveness-imparting agent, a silane coupling agent containing no epoxy group may be further blended. The organic functional group preferably contains one or more selected from a vinyl group, a methacryl group, an acrylic group and an isocyanate group, and is preferably 3-methacryloxypropyltrimethoxysilane or 3-methacryloxypropyltriethoxysilane. And methacryloxysilane such as 3-trimethoxysilylpropyl succinate anhydride, frangion such as dihydro-3- (3- (triethoxysilyl) propyl) -2,5-frangion, and the like are exemplified. The organic functional group may be bonded to the silicon atom via another group such as an alkylene group. These are preferably used in combination with the component (H) because the effect is further promoted. Specifically, a titanium chelate compound is used in combination with a methacryloxy group-containing organoalkoxysilane, and / or zirconium. Concomitant use of chelate compounds and / or concomitant use of aluminum chelate compounds, or concomitant use of dihydro-3- (3- (triethoxysilyl) propyl) -2,5-furandion with titanium chelate compounds and / or Combinations such as a combination of zirconium chelate compounds and / or a combination of aluminum chelate compounds are exemplified.

Pigments include titanium oxide, alumina silicic acid, iron oxide, zinc oxide, carbon black, rare earth oxides, chromium oxide, cobalt pigments, ultramarine, cerium silanolate, aluminum oxide, aluminum hydroxide, titanium yellow, carbon black, and phthalocyanine. Blue and mixtures thereof are exemplified.

As the curing inhibitor, all conventionally known compounds having a curing inhibitory effect can be used, and phosphorus-containing compounds such as acetylene compounds, hydrazines, triazoles, phosphins, mercaptans, and triphenylphosphine can be used. Nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylene-based compounds, compounds containing two or more alkenyl groups, hydroperoxy compounds, maleic acid derivatives, silanes having amino groups, and silicone compounds. Etc. are exemplified.

More specifically, various "en-in" systems such as 3-methyl-3-penten-1-in and 3,5-dimethyl-3-hexene-1-in; 3,5-dimethyl- Acetylene alcohols such as 1-hexyne-3-ol, 1-ethynyl-1-cyclohexanol, and 2-phenyl-3-butyne-2-ol; well-known dialkyl, dialkenyl, and dialkoxyalkyl fumarate and maleate. Such as maleate and phenylate; and those containing cyclovinylsiloxane are exemplified.

Examples of the heat-resistant imparting agent include cerium hydroxide, cerium oxide, iron oxide, fume titanium dioxide, and mixtures thereof.

Examples of the flame retardant include metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, diatomaceous earth and calcium carbonate.

The airtightness improving agent may be any agent as long as it has an effect of reducing the air permeability of the cured product, and may be an organic substance or an inorganic substance. Specifically, polyvinyl alcohol, polyisobutylene, isobutylene-isoprene copolymers, mica, glass flakes, boehmite, powders having a flat shape such as various metal foils and metal oxides, silicone rubber powders and silicone resins. Powders and mixtures thereof are exemplified.

A method known to those skilled in the art can be used to produce the silicone rubber composition of the present invention, and the method is not limited. For example, the component (A), the component (B), the component (C), and the component (E) are mixed in advance, or the component (A), the component (D), and the component (E) are mixed with a stirrer, or 2 After preparing a silicone rubber base by uniformly kneading with a high shear type mixer such as this roll, kneader mixer, pressure kneader mixer, loss mixer, extruder, continuous extruder, etc., the components ( It may be produced by blending any one of F) to component (I). Further, for example, a known method may be used in which the component (A) and the component (C), or the component (A) and the component (D) are produced in advance by an emulsifier using an emulsifier. In addition, the silicone rubber composition of the present invention may be stored in an organic solvent such as toluene, xylene, hexane, white spirit, or a mixture thereof.

The present invention particularly relates to a silicone rubber composition for a fiber base cloth used for an airbag of an automobile or the like. The airbag is a bag-shaped stitch of an airbag base cloth, and is mainly used for an automobile. It is a device that is installed in the vehicle and inflates the bag in the event of a collision to ensure the safety of the driver and passengers. The airbag base fabric is usually a woven fabric woven with synthetic fibers such as polyamide and polyethylene terephthalate, and the silicone rubber composition of the present invention is coated on these synthetic fiber woven fabrics. Specifically, polyamide fiber woven fabrics such as nylon 6, nylon 66, and nylon 46, aramid fiber woven fabrics, polyester fiber woven fabrics typified by polyalkylene terephthalate, polyetherimide fiber woven fabrics, sulfone fiber woven fabrics, carbon fiber woven fabrics, or Although a mixture of these is used, the present invention is particularly effective for polyester fiber woven fabrics and polyamide fiber woven fabrics in which hydrolysis is likely to proceed. The silicone rubber composition is coated on a woven fabric having a shape such as plain weave, bag shape, hose shape, etc. using a thread having a thickness of 10 to 5,000 decitex, but from the viewpoint of workability and economy, 50 to 1 Woven fabrics using 000 decitex yarns are preferred.

The woven fabric may be in either an unrefined state or a refined state, but in the case of an unrefined fabric, the refining step can be omitted by directly coating. The type and composition of the oil agent are not particularly limited, but the amount of the oil agent is preferably 5% by mass or less and more preferably 3% by mass or less based on the weight of the woven fabric from the viewpoint of ease of production.

The silicone rubber compositions of the present invention can be coated by commonly used methods, such as dipping and pazing, brushing, sinking, spraying, roller coating, gravure coating, commas. Coaters, printing, knife coating, Meyerbar, airbrush, slop padding, roll coating, etc. are used, and coating is performed individually or in combination depending on the situation. Further, the coating does not necessarily have to be performed once, and may be performed a plurality of times until the desired coating state is obtained. Therefore, the cured film after coating does not necessarily have to be one layer, and may be composed of a plurality of cured films. Further, on the surface of the cured film after coating, for example, the desired component is added to the silicone rubber composition or coated for the purpose of imparting effects such as antifouling, antistatic, slipperiness and blocking prevention. Alternatively, the surface may be processed after curing, or a cured layer having such a function may be further formed.

Drying and curing after coating is usually performed in a heating device that can be heated by hot air, infrared, near infrared, gas burners, heat exchangers or other energy sources. In addition to the commonly used heating device, any device that can achieve the purpose can be used, for example, a heating roll calendar, a heatable laminating press, and a heatable step press. Alternatively, high temperature contact rolls, hot air dryers, microwave dryers are exemplified.

At the time of curing, in order to avoid the formation of bubbles in the cured film, it is preferable to provide the heating device with a plurality of temperature zones having different temperatures, for example, 60 to 150 ° C., preferably 80 to 130 in the first temperature zone. Pre-drying can be performed at a temperature of ° C., more preferably 90-120 ° C., followed by curing at a temperature of 300 ° C. or lower in the second and subsequent temperature zones, but many fibers have heat resistance restrictions in processing. Therefore, it is preferably 250 ° C. or lower.

Even when it is difficult to provide a plurality of temperature zones in the process, it is preferable to pre-dry the substrate to be cured so that the temperature reaches at least 170 ° C. or higher even once. The residence time required for curing varies depending on the weight of the coating, the thermal conductivity of the woven fabric, the thermal conductivity of the coated woven fabric, etc., but is preferably about 0.5 to 30 minutes, and is preferably at room temperature. If so, it may be carried out by leaving it for 10 minutes to several hours.

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. In addition, each part in each example shows a mass part. The results of this example and comparative example are shown in Tables 1 and 2.

<Test base cloth>
The base fabric is a polyester plain weave fabric composed of threads with a thickness of 470 decitex. The base fabric has an oil content of 0.04% by mass by scouring, and the unrefined base fabric has an oil content of the woven fabric weight. Two types of base fabrics of 1.2% by mass were used.

<Coating method>
In order to confirm the passage of time of adhesiveness, the silicone rubber composition after formulation was left at room temperature for 5 hours or more before coating. The coating was performed using a knife coater, and the curing was performed at a temperature of 190 ° C. and a curing time of 45 seconds.

<Adhesion test method for coated materials>
The adhesiveness of the cured product was confirmed by a kneading test. A coating cloth having a length of 10 cm and a width of 5 cm was prepared, and a load of 10 N was applied onto the cured film for measurement. The test equipment used was a scrub tester INC-1507-A (manufactured by Imoto Seisakusho Co., Ltd.), and the test was conducted in accordance with ISO 5981.
The measurement was performed on the coated cloth left at room temperature for 24 hours and the one stored at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours, respectively. Those in which no peeling or peeling was observed were regarded as acceptable.

<Example 1>
As the component (A-1), 60 parts of dimethylpolysiloxane containing both terminal vinyl groups having a viscosity of about 20,000 mPa · s and 8 parts of dimethylpolysiloxane containing both terminal vinyl groups having a viscosity of about 100,000 mPa · s. And 7.8 parts of dimethylpolysiloxane containing vinyl groups at both ends with a viscosity of about 1,000 mPa · s, and dimethylpolysiloxane (vinyl group) containing vinyl groups at both ends with a viscosity of about 10 mPa · s and in the molecule. A mixture of 0.5 parts with a content of 3 mmol / g), and as a component (B), a thermally dissociable block with Duranate X2252 (manufactured by Asahi Kasei Co., Ltd.) having a viscosity of 20,000 mPa · s at 60 ° C. 0.3 part of methyl ethyl ketooxime adjusted to be 2 with respect to the number of moles of isocyanate groups as an agent, and platinum-divinyltetramethyldisiloxane complex as a component (C) with a platinum content of 1 0.3 part of dimethylpolysiloxane solution containing%, and as component (I), precipitated barium sulfate powder (density 4.0 g / cm ³ , oil absorption 18 ml / 100 g, average particle size 0.3 μm) 0.3 The rubber base was adjusted by adding the parts and mixing well with a stirring mixer.

^{To 77 parts of the rubber base, 5.9 parts of fumed silica having a specific surface area of 300 m 2} / g measured by the BET method as a component (E) and 0.1 part of ethynylcyclohexanol as a curing inhibitor were added. And mixed well with a stirring mixer. Further, as the component (D), 0.6 parts of both-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane (hydrogen content 1.6%) having a viscosity at 25 ° C. of 30 mPa · s and a viscosity at 25 ° C. of 70 mPa. 3 parts of both-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane (hydrogen content 0.8%), which is s, and both-terminal trimethylsiloxy group-blocking methylphenylhydrogenpolysiloxane having a viscosity of 40 mPa · s at 25 ° C. Organohydrogenpolysiloxane (hydrogen content) having 0.2 parts (hydrogen content 0.8%) and hydrogen atoms that bond with silicon atoms only at both ends of the molecular chain having a viscosity of 50 mPa · s at 25 ° C. 0.05%) 5 parts and 0.3 part of trimethylsilanol were added and mixed well with a stirring mixer.

Further, the component (F) is 6 parts of an organopolysiloxane resin having a vinyl group unit and a Qsiloxane unit in the molecule, and the component (G) is 0.8 parts of 3-glycidoxypropyltrimethoxysilane. As (H), 0.5 part of diisopropoxy (ethylacetacetate) titanium was added and mixed well with a stirring mixer to prepare the silicone rubber composition of Example 1. The molar ratio of total Si—H groups to total vinyl groups in this silicone rubber composition was 3.3. This was left at room temperature for 5 hours ^{, then coated on a scoured polyester cloth at about 35 g / m 2} , left at room temperature for 24 hours, and stored at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours. Later, an adhesion test was performed.

The coated cloth of Example 1 showed good adhesiveness without pinholes or peeling even after 2,000 times after being left for 24 hours. In addition, when stored for 500 hours at a temperature of 80 ° C. and a relative humidity of 95%, several pinholes were observed at 2,000 times, but there were no pinholes or peeling up to 1800 times, and good adhesiveness was obtained. Was shown, and the judgment of adhesiveness was acceptable.

<Example 2>
The silicone rubber composition of Example 1 left at room temperature for 5 hours ^{was coated on an unrefined polyester cloth at 35 g / m 2} to prepare a coated cloth in the same manner as in Example 1. After leaving for 24 hours, despite the increase in the amount of oil, there was no pinhole or peeling even after 2,000 times, and those stored for 500 hours at a temperature of 80 ° C and a relative humidity of 95% were pinned at 2,000 times. Although several holes were found, there were no pinholes or peeling up to 1,800 times, and the judgment of adhesiveness was acceptable.

<Comparative example 1>
A product containing no blocked polyisocyanate composition, which is the component (B) of the formulation of Example 1, was prepared and used as Comparative Example 1. Then, after leaving it at room temperature for 5 hours, the refined polyester cloth was ^{coated at 36 g / m 2} to prepare a coated cloth in the same manner as in Example 1. After leaving for 24 hours, no pinholes or peeling were observed up to 600 times, but peeling was observed after 800 times, so the test was discontinued. In addition, those stored at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours did not show pinholes or peeling up to 200 times, but peeling was observed after 300 times, so the test was stopped. Therefore, the judgment of adhesiveness was unacceptable.

<Comparative example 2>
The formulation prepared in Comparative Example 1 left at room temperature for 5 hours ^{was coated on an unrefined polyester cloth at 36 g / m 2} to prepare a coated cloth in the same manner as in Example 1. After leaving for 24 hours, no pinholes or peeling were observed up to 200 times, but peeling was observed after 400 times, so the test was discontinued. In addition, those stored at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours were discontinued because peeling was observed 100 times after the start. The judgment of adhesiveness was unacceptable.

<Comparative example 3>
In the blocked polyisocyanate composition which is the component (B) of the formulation of Example 1, the number of moles of methyl ethyl ketooxime as a heat dissociative blocking agent was adjusted to be 2 with respect to the number of moles of isocyanate groups. , The molar ratio was adjusted to 0.6, and this was designated as Comparative Example 3. This was left at room temperature for 5 hours ^{and then coated on a refined polyester cloth at 36 g / m 2} to prepare a coated cloth in the same manner as in Example 1. After leaving for 24 hours, pinholes were observed at 1,800 times, but there were no pinholes or peeling up to 1,600 times, showing good adhesiveness. However, those stored at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours had no pinholes or peeling up to 900 times, but peeling was observed after 1000 times, so the test was stopped. The judgment of adhesiveness was unacceptable.

<Comparative example 4>
The formulation prepared in Comparative Example 3 left at room temperature for 5 hours ^{was coated on an unrefined polyester cloth at 36 g / m 2} to prepare a coated cloth in the same manner as in Example 1. After leaving for 24 hours, pinholes were observed at 1,400 times, but there were no pinholes or peeling up to 1,200 times, showing good adhesiveness. However, those stored at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours had no pinholes or peeling up to 500 times, but peeling was observed at 600 times, so the test was stopped. The judgment of adhesiveness was unacceptable.

According to the present invention, the silicone rubber composition containing the block polyisocyanate composition and the curable silicone rubber composition is an unrefined or refined hydrolyzable woven fabric, and the amount of oil is 5% by mass or less based on the weight of the woven fabric. It coats the woven fabric, which adheres strongly even when cured, and maintains the adhesiveness even after the obtained coated material is stored for a long period of time under high temperature and high humidity, so that the workload of the scouring process is greatly increased. It can be reduced and the durability of the coated material can be greatly improved.

Claims (11)

(A) an organopolysiloxane 100 parts by weight having 1.8 or more on silicic per molecule on average bonded alkenyl groups atom,
(B) A polyisocyanate obtained from at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate, and a heat-dissociable blocking agent are contained, and the heat-dissociable blocking agent is an isocyanate in the polyisocyanate. 0.01 to 5 parts by mass of a blocked polyisocyanate composition containing 1 mol or more per 1 mol of a group, substantially free of organic solvents, and having a viscosity at 60 ° C. of 100,000 mPa · s or less.
(C) Effective amount of addition curing catalyst,
(D) The number of hydrogen atoms bonded to silicon atoms is 0.5 to 0.5 to the alkenyl group of the organohydrogenpolysiloxane component (A), which has two or more hydrogen atoms bonded to silicon atoms on average in one molecule. features and to Resid silicone rubbers composition that contains an amount <br/> to be 20 mol. At least one diisocyanate compound selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates in the blocked polyisocyanate composition is hexamethylene diisocyanate, and the heat dissociable blocking agent is an oxime-based or acid amide-based compound. The silicone rubber composition according to claim 1 , wherein the silicone rubber composition is at least one selected from an amine-based compound, an active methylene-based compound, and a pyrazole-based compound. The claimed component (E) contains 0.5 to 50 parts by mass of fine powdered silica having a specific surface area of 50 m ^{2 / g or more according to the BET method with respect to 100 parts by mass of the component (A).} Item 2. The silicone rubber composition according to any one of Items 1 or 2. As component (F), a siloxane unit having a vinyl group in the molecule and a Tsiloxane unit represented by the formula R ¹ SiO _3/2 (however, in the formula, R ¹ has the same or different carbon numbers 1 to 18). An organopolysiloxane resin containing a siloxane unit having a Qsiloxane unit represented by _{the formula SiO 4/2} , and / or an organopolysiloxane resin (A). The silicone rubber composition according to any one of claims 1 to 3 , wherein the silicone rubber composition is contained in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass. The silicone rubber composition according to any one of claims 1 to 4 , wherein the component (G) contains an organosilicon compound having an epoxy group and a silicon atom-bonded alkoxy group in one molecule. The component (H) is characterized by containing one or more compounds selected from the group consisting of metal alkoxides, metal acid salts and metal chelates, which have elements selected from B, Al, Ti, and Zr as metal atoms. , The silicone rubber composition according to any one of claims 1 to 5. ^{As the component (I), the density is 2.0 g / cm 3} or more, the oil absorption amount is 15 ml / 100 g or more, and the average particle size is 100 μm or less, which has a function of improving the dispersion of the blocked polyisocyanate composition of the component (B). The silicone rubber composition according to any one of claims 1 to 6, which comprises the powder of the above. The silicone rubber composition according to any one of claims 1 to 7 is coated on an unrefined or refined woven fabric having a hydrolyzable amount of an oil agent of 5% by mass or less based on the woven fabric mass. By curing, a cured product layer of the silicone rubber composition is formed on at least one surface of the woven fabric, and then by thermal dissociation of the heat dissociable blocking agent, moisture absorption and hydrolysis to the woven fabric are prevented. A method of maintaining adhesion between a cured product of a silicone composition and a fabric. The silicone rubber composition according to any one of claims 1 to 7 is coated on an unrefined or refined hydrolyzable woven fabric having an oil content of 5% by mass or less based on the woven fabric mass. by curing, thereby forming a cured layer of a silicone rubber composition on at least one surface of said textile, manufacturing how the coatings. A coated product obtained by the method for producing a coated product according to claim 9. An airbag using the coating according to claim 10.