JP2002088307A - Coating composition for fibrous base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition capable of forming a silicone cured coating film highly adhesive to a fibrous base material, and to provide a fibrous base material with such a cured coating film formed thereon. SOLUTION: This coating composition for fibrous base materials comprises (A) 100 pts.wt. of an organopolysiloxane having in one molecule at least two alkenyl groups bound to silicon atom, (B) 2-100 pts.wt. of a silica filler, (C) 0.1-20 pt(s).wt. of an alkoxysilane of the formula: R1nSt(OR2)4-n, (D) >=0.1 pt(s). wt. of water and (E) a curing agent. Air bags and seat belts each coated with the composition are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition capable of forming a cured silicone film having excellent adhesion to a fiber substrate, and a fiber substrate having a cured film of the coating composition formed thereon. In particular, it shows excellent adhesiveness to airbags and seatbelt base fabrics made of synthetic fiber woven fabric such as nylon 66, and is folded and stored (flexibility), extensibility and aging. The present invention relates to a coating composition that can provide an airbag and a seatbelt that are less deteriorated by the airbag.

[0002]

2. Description of the Related Art Conventionally, a silicone rubber is coated on a base fabric or a sewn product thereof and cured to obtain a flexible coating base material having excellent waterproofness and water repellency. Substrates are used in many fields such as waterproof sheets, tents, airbags, seat belts, and the like. Of these, coating materials for airbags and seatbelts are becoming increasingly important as materials for safety devices such as automobiles, and instead of the conventional chloroprene rubber coating, they have flame retardancy, heat resistance, and weather resistance. Silicone rubber excellent in properties and the like is widely used at present.

[0003] In the conventional coating of silicone rubber on a base fabric for airbags and seat belts, it has been common practice to dilute the silicone rubber composition in a solvent and adjust its viscosity before use. Solvents are problematic in terms of environment and work safety, and it is desired to eliminate the solvent or emulsify the solvent. Also, in such a solvent-free or emulsified silicone rubber composition, it is necessary that these compositions have sufficient adhesiveness to a substrate, and such a sufficient adhesiveness is required. It has been proposed to use a silane coupling agent in order to impart the following.

For example, JP-A-5-25435 discloses a method for adding an organosilicon compound containing an epoxy group.
Japanese Patent Application Laid-Open No. 9-124947 proposes a method in which a silicone resin is added in addition to a silane coupling agent for imparting adhesiveness. However, these prior arts do not yet have sufficient adhesiveness, and further improvements are desired. If the adhesion between the silicone rubber composition and the substrate is insufficient, the high temperature gas generated from the inside of the inflator when the air bag is activated, and the rubber layer peels off or burns out due to intense rubbing of the coating surfaces during expansion. This is a serious problem of doing so. Further, when a conventional adhesiveness-imparting agent is used, there has been a problem in that the tackiness of the surface of the cured silicone material is increased and the surface tack performance is deteriorated.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a coating composition capable of forming a cured silicone film having excellent adhesion to a substrate, which is desired in the art. It is another object of the present invention to provide a fibrous base material on which a cured film of the coating composition is formed. In particular, a composition having excellent adhesiveness to an airbag and a seatbelt base cloth made of synthetic fiber woven fabric such as nylon 66, and a fold-storability (flexibility) formed by forming a cured film of the composition. The purpose of the present invention is to provide an airbag and a seatbelt which are hardly deteriorated due to aging, extensibility and aging.

[0006]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have determined that a silicone composition capable of forming a cured film having excellent rubber elasticity has a specific alkoxysilane compound. It has been found that this problem can be solved by the addition of, and the present invention has been completed.

That is, the present invention relates to (A) an organopolysiloxane containing two or more alkenyl groups bonded to a silicon atom in one molecule: 100 parts by weight, (B) a silica filler: 2 to 100 parts by weight, _{^{C) R 1 n Si (oR}} 2) 4-n in the general formula alkoxysilane (wherein R ¹ represented by is a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, R ² is the same or different Represents a hydrocarbon group having 1 to 12 carbon atoms, where n is a positive number of 0 to 3): 0.1 to 20 parts by weight,
(D) water: 0.1 parts by weight or more; (E) curing agent: a coating composition for a fiber base material comprising an amount sufficient to cure the composition of the present invention, and a fiber on which a cured film of the composition is formed. A substrate is provided.

Hereinafter, the present invention will be described in detail. The organopolysiloxane that is the component (A) of the present invention is a main component of a silicone rubber composition having excellent rubber elasticity after curing, and is an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule. Polysiloxane. Such an organopolysiloxane has a structural unit represented by the formula (1): RaSiO _{(4-a) / 2} (R in the formula (1) represents a substituted or unsubstituted monovalent hydrocarbon group, and a is 1.9. ~
2.1 is a positive number. ) Can be used.

In the polyorganosiloxane of the above formula (1), at least two of R's are a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group, a cyclohexenyl group or the like. Selected from alkenyl groups, the other groups are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl Group, tert-butyl group, pentyl group, neopentyl group, hexyl group, 2-
Ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, alkyl groups such as dodecyl group,

Cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group and naphthyl group, benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl Chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl in which part or all of the hydrogen atoms in these hydrocarbon groups are substituted by halogen atoms, cyano groups, etc. Group, 3-chloropropyl group, halogen-substituted alkyl group such as cyanoethyl group, cyano-substituted alkyl group and the like.

In selecting R, a vinyl group is preferable as the alkenyl group necessary for two or more, and a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are preferable as the other groups. Further, it is preferable that 70 mol% or more of all Rs is a methyl group from the viewpoint of physical properties and economy of the cured product, and usually, a methyl group having 90 mol% or more is used.

In the formula (1), a is from 1.9 to 2.1, and this polyorganosiloxane may be linear or branched, but usually, it is linear. Polydiorganosiloxane is used. These polyorganosiloxanes are prepared by methods known to those skilled in the art.

The polyorganosiloxane comprising the unit represented by the formula (1) is a low-viscosity liquid or a high-viscosity paste-like substance having a viscosity of 100 centipoise or more at 25 ° C. is preferably used. In consideration of strength, compounding workability, and the like, those having 1,000 centipoise or more are more preferable. Further, the above polyorganosiloxanes may be used as a mixture of two or more kinds.

Use in the present invention to reinforce silicone rubber
As the silica filler of the component (B), the
Known used as a reinforcing filler for silicone rubber
Can be used, and the type is not particularly limited. this
Examples of such silica fillers are hydrophilic or hydrophobic
Fumed silica, silica fume, sediment
Lica, calcined silica, colloidal silica, crushed quartz, silica
Algae soil, etc., especially those of fine powder are preferred
With a particle size of 100 μm or less and a specific surface area of 50 m ^Two/ G
The above ultrafine powder is more preferable. Also, organo
Silane, organosilazane, organocyclopolysiloxy
It is also preferable to use silica that has been previously surface-treated with sun, etc.
Can be. The amount of the silica filler added is usually
(A) 2 to 100 parts by weight with respect to 100 parts by weight of the component.
It is used in a range, preferably in the range of 4 to 50 parts by weight.

The alkoxysilane of the component (C) used in the present invention is a component necessary for the present invention composition has an excellent adhesion after curing, general formula (2): R ¹ _n Si
(OR ² ) An alkoxysilane represented by _4-n is used. R ¹ in the formula (2) is a substituted or unsubstituted C ¹ -C 1
And R ² is the same or different and has 1 to 12 carbon atoms. Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,
Pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, alkyl group such as dodecyl group,

A cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group,
Alkenyl groups such as isobutenyl group, hexenyl group, cyclohexenyl group, phenyl group, tolyl group, xylyl group,
And aryl groups such as biphenyl group and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group.

Further, a chloromethyl group, a 2-bromoethyl group, a 3,3,3 group in which part or all of the hydrogen atoms in these hydrocarbon groups are substituted by a halogen atom, a cyano group or the like.
3-trifluoropropyl group, 3-chloropropyl group,
Examples thereof include a halogen-substituted alkyl group such as a cyanoethyl group, a cyano-substituted alkyl group, and the like. Note that n is a positive number from 0 to 3.

In the present invention, the component (C) is a particularly important component. Conventionally, so-called silane coupling agents having a functional group such as an amino group or an epoxy group have been used as a component for imparting adhesiveness as described above, but they have a functional group such as an amino group or an epoxy group. Thereby, the affinity between the silicone rubber and the base material is improved. On the other hand, since the alkoxysilane of the present invention does not have a functional group such as the silane coupling agent described above, it has not been used at all as an adhesive imparting agent for a silicone rubber composition. Nevertheless, it has surprisingly been found by the present inventors that the adhesion is very effective.

The inventor of the present invention has argued that alkoxysilanes, especially tetraalkoxysilanes, have an effect of imparting adhesiveness only when the silicone rubber composition undergoes hydrolysis and condensation under the conditions of application and curing. It is presumed that the substance contributes to the adhesion between the base material and the silicone rubber to be coated.

That is, in general, the alkoxy group of alkoxysilane has a lower hydrolysis energy with water than other hydrolyzable groups, for example, chloro, acetoxy, isopropenoxy and amino groups. It is easy to generate silanol groups that are highly reactive with the material, but these silanol groups partially condense,
It is considered that the oligomer is oligomerized, then adsorbed on the surface of the inorganic material by hydrogen bonding, and dehydrated and condensed promptly by heat treatment, thereby forming a strong chemical bond with the inorganic material.

The degree of the dehydration condensation by hydrolysis, that is, the degree of the condensation varies depending on the conditions.
It is presumed that under the conditions of applying and curing the silicone rubber composition to the fiber base material, an appropriate condensate having an affinity for both the rubber component and the base material is generated, and the adhesiveness is improved.

The alkoxysilane used in the present invention includes tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane,
Dimethyldiethoxysilane, dimethyldimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-chloropropylmethyldimethoxysilane and the like, and mixtures thereof It may be. Preferably tetraethoxysilane,
Methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, and dimethyldimethoxysilane.

The component (C) of the present invention comprises the component (A) 100
It is used in the range of 0.1 to 20 parts by weight, particularly preferably in the range of 0.5 to 10 parts by weight, based on the weight%. 0.1
If the amount is less than 20 parts by weight, the effect of improving the adhesiveness is not sufficient.
If the amount is more than the weight part, the hardness of the cured coating film is undesirably increased. In the present invention, a complex composed of a metal component and / or fine particles of a metal hydroxide can be added as the component (F) to the alkoxysilane (C) in order to further improve its effect. It has been found for the first time by the present inventors that the mixing of an alkoxysilane with these components is very effective in imparting adhesion to silicone rubber.

The reason why the effect of imparting adhesiveness is improved by the addition of the component (F) is that the metal complex or the hydrolyzate of the metal complex and the metal hydroxide have an OH group. This contributes to hydrolysis, and under the conditions of application and curing of the silicone rubber composition, the added component greatly affects the change in the surface properties of the inorganic material side, so that the adhesive effect of the alkoxysilane is sufficiently exhibited. As a result, it is presumed that it contributes to adhesion to silicone rubber.

The complex of component (F) used in the present invention includes acetylacetonato complex, bipiperidine complex, bipyrazine complex, tetraazacyclotetradecane complex, ethylenebis (guanide) complex, tetraethyleneglycol complex, glycine complex, Triglycine complexes, naphthyridine complexes, phenanthroline complexes, pyridine complexes, salicylaldehyde complexes, porphyrin complexes, thiouric acid complexes, and the like can be preferably used, and acetylacetonato complexes are particularly preferred.

The center metal of the complex of the component (F) used in the present invention is Al, Ba, Be, Ca, Cd, C
e, Co, Cr, Cu, Fe, Ga, In, Mg, M
n, Mo, Ni, Pb, Pd, Pt, Rh, Ru, S
c, Si, Sn, Sr, Th, Ti, V, Y, Zn, Z
r, particularly preferably Al, Ba, Be, C
a, Cd, Co, Fe, Mg, Mn, Pb, Pt, N
i, Si, Ti, V, Zn, and Zr.

The metal hydroxide of the component (F) used in the present invention is a hydroxide of the central metal of the above-mentioned complex, and particularly preferably Al (OH) ₃ , Ba (OH) ₂ , B
e (OH) ₂ , Ca (OH) ₂ , Cd (OH) ₂ , Co
(OH) ₂ , Fe (OH) ₂ , Mg (OH) ₂ , Mn (O
H) ₂ , Pb (OH) ₂ , Pt (OH) ₂ , Pt (OH) ₄
2H ₂ O, Ni (OH) ₂ , Si (OH) ₄ , Ti (O
H) ₄ , V (OH) _2-5 , Zn (OH) ₂ , Zr (OH)
₄ , and their precursors.

The component (F) is composed of the component (A) 100
0.1 to 15 parts by weight per weight%,
(C) The effect of imparting adhesiveness of the component can be enhanced. The component (F) is preferably added as appropriate depending on the type of the substrate to be coated, its surface properties, and the like.

The water of the component (D) used in the present invention is:
It is an essential component for accelerating the hydrolysis of the component (C), and when the composition of the present invention is used as a solvent-type or non-solvent-type composition, based on 100% by weight of the component (A) 0.1 part by weight or more and 10 parts by weight or less. In the present invention, water is added alone or mixed with other components of the present invention. However, when the composition of the present invention is used as an emulsion, 100 to 2000 parts by weight per 100 parts by weight of component (A). Since part by weight of water is present, no further addition is necessary.

The water used in the present invention includes tap water, tap water, industrial water, distilled water, ion-exchanged water, alkaline ionized water, water subjected to ultrasonic treatment, water subjected to electromagnetic wave treatment, and once frozen. Water, ultrapure water for semiconductor production, etc. are exemplified, and the pH is in the range of 3 to 9, preferably in the range of 4 to 8.

The curing agent (E) used in the present invention is a catalyst or a mixture of a catalyst and a crosslinking agent for curing the composition of the present invention. What is used for hardening can be used.

As a method of curing the organopolysiloxane, a composition utilizing a dehydration condensation reaction, a composition utilizing an addition reaction between a hydrogen atom bonded to a Si atom and an ethylenically unsaturated group bonded to a Si atom, There are known compositions and the like in which an ethylenically unsaturated group bonded to a Si atom is crosslinked with an organic peroxide. The composition of the present invention can be used as long as moisture or volatile components are removed during the drying process, and at the same time, any silicone composition having the ability to form a cured silicone film on a substrate by curing.
From the viewpoint of reaction rate and economic reasons, a composition utilizing an addition reaction or a composition utilizing a crosslinking reaction with an organic peroxide is preferable, and it is particularly preferable to use an addition reaction type silicone composition having a high reaction rate.

Examples of the curing agent used in the addition-reaction type silicone composition include a platinum compound catalyst and an organohydrogen polysiloxane containing a hydrogen atom bonded to at least two silicon atoms in one molecule. Examples thereof include those using siloxane in combination, and examples of the curing agent used in the composition cured by peroxide include organic peroxides.

Among the curing agents used in the former composition utilizing the addition reaction, platinum compound catalysts include, for example, platinum fine powder, platinum black, chloroplatinic acid, platinum tetrachloride, olefin complexes of chloroplatinic acid, A complex of chloroplatinic acid and methylvinylsiloxane, a rhodium compound, and a palladium compound are used. The amount of the platinum compound catalyst added is usually
(A) The platinum-based metal is used in an amount of 0.1 to 500 parts by weight based on 1 million parts by weight of the component.

Examples of the organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule include methylhydrogenpolysiloxane, dimethylsiloxane / methylhydrogensiloxane copolymer, methylphenylsiloxane / methyl Hydrogensiloxane copolymers, cyclic methylhydrogenpolysiloxanes, and copolymers composed of dimethylhydrogensiloxy units and SiO _4/2 units are used. The proportion of the organohydrogenpolysiloxane is such that the ratio of the number of moles of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane to the number of moles of alkenyl groups in component (A) is (0.5: 1) to (20:
The amount which becomes 1) is preferable.

As the latter organic peroxide, for example, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide and o-chlorobenzoyl peroxide are used. These organic peroxides are used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the component (A).

The composition of the present invention comprises the above components (A) to (E)
(F)
Although components are added, an organopolysiloxane resin can be further blended as a component (G) in addition to these components. In particular, when a platinum catalyst and an organohydrogenpolysiloxane are used as the curing agent of the component (E), it is preferable that a silicone rubber coating film having a high strength can be obtained by blending the organopolysiloxane resin.

Examples of such an organopolysiloxane resin include, for example, (CH ₃ ) ₃ SiO _1/2 units and SiO 2
Resin consisting of _4/2 units, resin consisting of (CH ₃ ) ₃ SiO _1/2 units and (CH ₂ = CH) SiO _3/2 units and SiO _4/2 units, (CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 unit and S
Resin consisting of iO _4/2 units, (CH ₂ = CH) (CH ₃ )
₂ SiO _1/2 unit and (CH ₂ = CH) SiO _3/2 unit and Si
_Resins consisting of O _4/2 units are mentioned. Among these, a resin containing a vinyl group is particularly preferred.

In the coating composition of the present invention, if necessary, various additives conventionally known as silicone rubber additives can be added. These additives include pigments, curing inhibitors, heat-resistance additives, flame retardants, preservatives, stabilizers and the like.

Examples of the pigment include titanium oxide, alumina silicic acid, iron oxide, zinc oxide, calcium carbonate, carbon black, rare earth oxide, cerium silanolate, aluminum oxide, aluminum hydroxide, titanium yellow, carbon black, and the like. Are exemplified.

Examples of the curing inhibitor include acetylene compounds, hydrazines, triazoles, phosphines,
Mercaptans are exemplified. Further, examples of the heat resistance imparting agent include cerium hydroxide, cerium oxide, iron oxide, fume titanium dioxide, and the like, and a mixture thereof.

Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc carbonate, silica, carbon black, halogen compounds, phosphorus compounds, and the like, and mixtures thereof.

To produce the composition of the present invention, for example, the components (A) and (B) or (A), (B)
Mixing the component and the component (E) with a stirrer, or 2
This roll, kneader mixer, pressure kneader mixer,
After uniformly kneading with a mixer such as a loss mixer or a loss mixer to prepare a silicone rubber base, the (C)
A well-known method of adding and blending the component and the component (D) is used.

When an addition reaction type composition is used for the silicone composition of the present invention, it is preferable to store the composition in advance in the form of at least two different components so that curing does not proceed in a solution. One of the components contains an organopolysiloxane (A) having an unsaturated aliphatic group, and the other component contains an organohydrogenpolysiloxane having a Si-bonded hydrogen atom. And additives are preferably contained in one or both of the components.

The coating composition of the present invention can be used for paper, cloth,
It can be applied to a fiber base made of various fiber substances such as, for example, and is most preferably used for a cloth. As the fibrous base material, all kinds of woven fabric, knitted fabric, nonwoven fabric, film, paper and the like are used, and they can be used for coating or finishing them. As the material of the fiber, for example,
Hemp, cotton, glass, wool, silk, natural fibers and artificial fibers (eg, polyamide, polyester, acrylic, aramid, carbon, polyethylene, polypropylene, polystyrene, polyurethane, silk, viscose, cellulose, etc.). All fabrics using fibers,
Fleece, knit, sediment, knit, film, etc. are used.

In particular, as a base fabric for an air bag or a seat belt, a synthetic fiber woven fabric, for example, nylon 6,
Polyamide fiber fabrics such as nylon 66 and nylon 46, aramid fiber fabrics, polyester fiber fabrics represented by polyalkylene terephthalate, polyetherimide fiber fabrics, sulfone fiber fabrics, carbon fiber fabrics, and the like are used.

Among them, as the synthetic fiber woven fabric for the airbag or the seat belt, a plain woven fabric using a yarn of 420 denier or less is preferable, and 350 denier is more preferable from the viewpoint of easy processability and light weight. Base fabric using the following yarns, particularly preferably 210
It is a base fabric using denier or less yarn.

The above-described coating of the base cloth can be performed immediately during or after the cleaning step of the base cloth, and the post-coating curing is performed in one processing step simultaneously with the drying step and the shrinking step. Can be. And, in the case of fabrics that have to be washed and dried, the coating composition according to the present invention can be directly coated on the still wet fabric after the washing process, and the curing takes place simultaneously with the drying process be able to.
On the other hand, in the case of a fabric that does not need to be washed, the coating composition according to the present invention can be directly coated on the fabric at any time.

The coating of the coating composition of the present invention can be carried out by a generally used method, for example, dipping and padding, brushing, flow coating, spraying, roller coating, printing. , Knife coating, Meyer bar, airbrush, slop padding,
Roll coating or the like is used.

Drying and curing of the substrate after the coating is performed is usually performed in a heating device that can be heated by hot air, infrared rays, a gas burner, a heat exchanger or another energy source. In addition, for the drying and curing, in addition to a commonly used heating device, any device having a drying ability capable of achieving the desired drying and curing can be used. For example, a heating roll A calender, a heatable laminating press, a heatable step press or a high temperature contact roll, a hot air dryer, a microwave dryer, and the like can also be used.

At the time of curing, it is preferable to provide a heating device with a plurality of temperature zones having different temperatures in order to avoid formation of bubbles in the cured film.
Predrying is carried out at a temperature of 0 to 150 ° C, preferably 80 to 130 ° C, more preferably 90 to 120 ° C, and curing can be carried out at a temperature up to 300 ° C in a subsequent second temperature zone. However, since most fibers have heat resistance limitations in processing, the temperature is preferably set to a temperature range of 120 to 190 ° C.

Even if it is difficult to provide a plurality of temperature zones in the process, it is preferable that the substrate to be cured reaches a temperature of at least 170 ° C. at least once. Also, the residence time required for curing varies depending on the coating weight, the thermal conductivity of the fabric and the heat transfer to the coated fabric, and varies from 0.5 minutes to 3 minutes.
About 0 minute is preferable. The above-mentioned drying and curing may be carried out by leaving at room temperature for 10 minutes to several tens hours.

The substrate on which the cured film of the coating composition of the present invention is formed is used for all air bags and air back side curtains installed inside and outside the vehicle for the safety of drivers and passengers. And seat belts, as well as sportswear, sports equipment such as sails, boat covers or rucksacks and tent materials and their protective coverings, seat covers, conveyor belts, compensators, collapsible containers, raincoats,
Bulks, tents, tarpaulins, flags, wallpapers, stickers and labels, adhesive tapes, interior panels for passenger cars, furniture and office automation
Non-slip sheets of equipment and the like are exemplified.

[0054]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Further, parts in the examples indicate parts by weight, and% indicates% by weight.

(Preparation of rubber base) Commercially available viscosity of about 1,0
Vinyl group-containing dimethyl policy having 00 mPa · s
Has 55 parts of roxane and a viscosity of about 20,000 mPa · s
30 parts of a vinyl group-containing dimethylpolysiloxane,
Contains a silanol group having a viscosity of about 1000 mPa · s
0.5 parts of dimethylpolysiloxane and a viscosity of about 40 m
Methyl hydrogen polysiloxane having Pa · s
4.5 parts and a specific surface area of 200 m as a filler ^Two/ G
14 parts of fumed silica and platinum containing 1% by weight of platinum
-0.8 parts of divinyltetramethyldisiloxane complex,
0.3 part of ethynylcyclohexanol with a stirring mixer
A rubber base was prepared by mixing.

(Base cloth) A commercially available plain woven nylon base cloth composed of 350 denier yarns and having not been subjected to a surface washing step was used. (Coating method) Using a knife coater, drying and curing of the base fabric after coating were performed in temperature zone 1 (temperature 12).
The test was carried out under the curing conditions of 0 ° C., curing time of 1 minute, temperature zone 2 (temperature of 150 ° C., curing time of 1 minute) and temperature zone 3 (170 ° C., curing time of 1 minute).

(Test Method) The adhesion state of the cured film of the obtained coating cloth was confirmed by a scratch test and a kneading test. In the scratch test, the cured surface was scratched about 20 times with a nail back and forth, and the peeling state of the cured film was visually observed. In the rubbing test, two samples were prepared by cutting the coating cloth of each example into 10 cm (length) × 5 cm (width) to confirm the storage property (flexibility) at the time of folding and the adhesiveness at the time of expansion. After the cured film forming surfaces of the above were bonded to each other, they were rubbed and reciprocated 1,000 times in a fixed direction at a constant speed by a rubbing tester manufactured by SNE JPS, and then the surface condition was visually observed.

The flame retardancy properties of the coated fabrics are described in US Federal Motor Vehicle Safety Standard: FMVSS No. 302. Further, an inflation test was conducted to confirm the foldability (flexibility), extensibility and adhesiveness at high temperatures. Hot air at a temperature of 160 to 180 ° C. is blown into the air bag made from the coating cloth under the condition of a pressure of 6 to 8 kg / m ² to instantaneously inflate, and the spreadability, the presence or absence of peeling of the cured film, and the airtightness are visually observed. Was observed.

[0059]

Example 1 0.15 parts of ion-exchanged water was added as an additive to the rubber base obtained by the above-mentioned preparation method, and the mixture was sufficiently kneaded again. After adding 2 parts of tetraethoxysilane, 18 μm of the mixture was added. And dried and cured to produce a coated cloth. As a result of the scratch test, no peeling of the cured film was observed even when the cured surface was reciprocated about 20 times with a nail. Also, the obtained coating cloth is flexible,
As a result of the rubbing test, no pinholes and peeling were found in the cured film after 700 roundtrips of rubbing, and the
Pinholes and peeling were observed in the cured film after 50 times of rubbing. In the flame retardancy test, the flame during combustion was small and the amount of smoke generated was small. The speed at which the flame propagated through the base cloth was constant after the base cloth was ignited, and the base cloth passed during combustion without melting dripping. As a result of the inflation test, peeling of the cured film was not confirmed. Table 1 shows the above results.

Example 2 As an additive, 0.15 parts of ion-exchanged water was added to the same rubber base as in Example 1, and the mixture was sufficiently kneaded again. Then, 0.8 parts of tetraethoxysilane and aluminum acetylacetonate were added to 2 parts. Coated with a thickness of 18 μm,
The coated cloth was dried and cured. As a result of the scratch test, no peeling of the cured film was observed even when the cured surface was reciprocated about 20 times with a nail. Also,
The obtained coating cloth was flexible, and as a result of performing a rubbing test, no pinholes and peeling were observed in the cured film after 850 roundtrips of rubbing, and no pinholes and no peeling in the cured film after 900 roundtrips of rubbing. Peeling was observed.
In the flame retardancy test, the flame during combustion was small and the amount of smoke generated was small. The speed at which the flame propagated through the base cloth was constant after the base cloth was ignited, and the base cloth passed during combustion without melting dripping. As a result of the inflation test,
No peeling of the cured film was observed. Table 1 shows the above results.
Shown in

Example 3 0.15 parts of ion-exchanged water was added as an additive to the same rubber base as in Example 1, and the mixture was sufficiently kneaded again. Then, 2 parts of tetraethoxysilane and 2 parts of aluminum acetylacetonate were added. The addition was applied to a thickness of 17 μm, dried and cured to prepare a coating cloth. As a result of the scratch test, no peeling of the cured film was observed even when the cured surface was reciprocated about 20 times with a nail. In addition, the obtained coating cloth was soft, and as a result of conducting a rubbing test, no pinholes and peeling were observed in the cured film after 900 rounds of rubbing, and the cured film was still formed after 1000 rounds of rubbing. No pinholes and peeling were seen. In the flame retardancy test, the flame during combustion was small and the amount of smoke generated was small. The speed at which the flame propagated through the base cloth was constant even after the base cloth was ignited, and no melting and dripping of the base cloth during combustion was observed. As a result of the inflation test, peeling of the cured film was not confirmed. Table 1 shows the above results.

Comparative Example 1 A composition was prepared without adding any additives to the rubber base used in Example 1, coated on the same cloth as in Example 1, and further formed a cured film to prepare a coated cloth. did.
As a result of performing a scratch test in the same manner as in Example 1,
A slight peeling of the cured film was observed with the naked eye by scratching the cured surface about 20 times with a nail. Moreover, although the obtained coating cloth was soft, as a result of the rubbing test, pinholes and peeling were observed in the cured film after the rubbing was performed 400 times back and forth. In the flame retardancy test, the combustion was fast, the flame during combustion was relatively large, and a lot of smoke was generated. The speed at which the flame propagated through the base fabric accelerated after the base fabric was ignited, was not constant, and the burning base fabric was dripping while melting, and the result was rejected. As a result of the inflation test, slight exfoliation was confirmed in the cured film. Table 1 shows the above results.

COMPARATIVE EXAMPLE 2 The same rubber base as in Example 1 was replaced by an epoxy silane coupling agent, 3- (2,3-epoxypropoxy) propyltriethoxysilane 2.0, instead of the alkoxysilane (C). Parts were added. As a result of performing a scratch test in the same manner as in Example 1, slight peeling of the cured film was visually observed by scratching the cured surface about 20 times with a nail. In addition, although the obtained coating cloth was soft, as a result of conducting a kneading test, although the situation was improved from that of Comparative Example 1, pinholes and peeling were observed in the cured film after performing 550 reciprocations of kneading. . The results of the flame retardancy test show almost the same combustion conditions as in Comparative Example 1,
The result was rejected. As a result of the inflation test, slight peeling was confirmed in the cured film. Table 1 shows the above results.

[0064]

[Table 1]

[0065]

The composition of the present invention has the effect of forming a cured silicone film having excellent adhesion to a fiber substrate. In particular, the composition of the present invention is made of nylon 66
Coating cloth coated with a base fabric for airbags and seat belts made of synthetic fiber woven fabrics and formed with a cured film has excellent adhesion of the film. By using this, it can be folded and stored (flexible). ), Extensibility and an airbag and a seatbelt with little deterioration due to aging can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 13/513 D06M 15/643 15/643 11/12 F term (Reference) 3D018 BA01 BA03 3D054 CC45 FF02 FF16 FF18 4J038 DL021 DL031 DL101 GA01 GA12 HA186 HA216 HA446 HA456 HA486 JA66 JC38 KA04 KA20 MA07 MA10 NA11 NA12 PA19 PB07 PC10 4L031 AB32 BA20 DA16 DA17 DA18 DA21 4L033 AB05 AC05 AC11 CA59

Claims (7)

[Claims] 1. (A) 100 parts by weight of an organopolysiloxane containing two or more alkenyl groups bonded to a silicon atom in one molecule: (B) silica filler: 2 to 100 parts by weight, (C) R Alkoxysilane represented by the general formula ¹ _n Si (OR ² ) _4-n (wherein R ¹ is a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and R ² may be the same or different Represents a hydrocarbon group having 1 to 12 carbon atoms, wherein n is 0
To 3): 0.1 to 20 parts by weight, (D) water: 0.1
(E) curing agent: a coating composition for a fibrous base material, comprising a part by weight or more and (E) a curing agent in an amount sufficient to cure the composition of the present invention. 2. (F) Al, Ba, Be, Ca, Cd,
Ce, Co, Cr, Cu, Fe, Ga, In, Mg, M
n, Mo, Ni, Pb, Pd, Pt, Rh, Ru, S
c, Si, Sn, Sr, Th, Ti, V, Y, Zn, Z
The fine particles of a complex and / or metal hydroxide composed of a metal component selected from the group consisting of 0.1 and 0.5 parts per 100 parts by weight of component (A).
2. The composition according to claim 1, wherein 1 to 15 parts by weight are added. 3. The method of claim 1, wherein the alkoxysilane of (C) is Si (O)
R ² ) ₄ Tetraalkoxysilane represented by the general formula (wherein R ² may be the same or different and has 1 to 12 carbon atoms)
Represents a hydrocarbon group. The composition according to claim 1 or 2, wherein 4. The composition according to claim 2, wherein the complex is an acetylacetonate complex. 5. A fibrous base material on which a cured film of the composition according to claim 1 is formed. 6. An air bag using the base material according to claim 5. 7. A seat belt using the base material according to claim 5.