JPS6246669B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silicone-coated cloth having improved surface properties and a method for manufacturing the same, and more specifically, the present invention relates to a silicone-coated cloth having improved surface properties and a method for manufacturing the same. The present invention relates to a silicone-coated fabric having a silicone resin layer present on at least one surface thereof in order to improve the tactile feel, and a method allowing its production. Woven or non-woven fabrics made mainly of glass fibers coated or impregnated with silicone elastic materials are used as firefighting uniforms by taking advantage of their excellent heat resistance, cold resistance, flame resistance, waterproofness, and water repellency. , flame-retardant clothing, flame-retardant curtains, gas station equipment covers,
It is used for tents, roofing materials, hot air blower hoses, emergency bags, etc. It is also used in metal smelting, iron industry,
It is widely used in shipbuilding, construction, and other industries that handle molten metal or perform welding. Furthermore, organic fibers such as cotton cloth coated with silicone elastic material are also widely used for waterproof purposes. but,
Cloths treated with these silicone elastomers have a silicone elastomer surface, and most of them are silicone elastomers of the type that harden at room temperature or with slight heating, so they have their own electrical insulation properties. Due to the ease of charging and stickiness of the base, it has the disadvantage that it tends to attract dust, and the attached dust cannot be easily removed. Another drawback was that if the silicone elastic bodies were folded or stacked and left for a long time, the surfaces of the silicone elastic bodies would tightly adhere to each other. Therefore, to solve these shortcomings,
It has been desired to improve the feel of cloth, that is, the texture. As a result of intensive research into methods to solve these drawbacks, the present inventors formed a silicone resin layer with a selected molecular structure on the surface of the silicone elastic body, which has excellent dust resistance, smoothness, and toughness. It has been found that these drawbacks can be overcome by using silicone resin, and that the thinner the silicone resin layer is, the less the texture of the base material is affected, and the more flexible the fabric is. Furthermore, in order to uniformly form such a silicone resin layer on the surface of the silicone elastomer, the silicone resin is applied to the surface of the silicone elastomer as a solution of a mixed solvent consisting of a volatile organosilicon compound and a hydrocarbon, and then dried. The present invention was achieved by discovering what was possible. That is, in the present invention, on at least one surface of a cloth coated or impregnated with a silicone elastomer, (A) R〓SiO〓 units per mole of SiO ₂ units,
(However, R ¹ represents substituted or unsubstituted monovalent hydrocarbon groups that are the same or different from each other.) 0.4 to
In a ratio of 1.0 mol, substantially SiO ₂ units and R〓
Composed of SiO〓 units, 0.0004 per silicon atom
Benzene-soluble polyorganosiloxane having a reactive group bonded to a silicon atom selected from the group consisting of ~1 hydroxyl group and an alkoxy group
(B) 20 to 200 parts by weight of a silanol-terminated polyorganosiloxane having a viscosity of 10,000 to 2,000,000 cSt at 25°C;
Regarding a silicone-coated cloth having a silicone resin layer formed by a condensation reaction with parts by weight, at least one surface of the cloth coated with or impregnated with a silicone elastomer contains (1)(A) SiO ₂ units. R〓SiO〓 unit per 1 mole (however, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group that is the same or different from each other)
Consisting essentially of SiO ₂ units and R〓SiO〓 units in a proportion of 0.4 to 1.0 mol, per silicon atom
100 parts by weight of a benzene-soluble polyorganosiloxane having a reactive group bonded to a silicon atom selected from the group consisting of 0.0004 to 1 hydroxyl group and an alkoxy group, and (B) a silanol having a viscosity of 10000 to 2000000 cSt at 25°C. Terminal polydiorganosiloxane 20
~200 parts by weight of the condensation reaction product, (2)(a) The molecular formula is R〓Si, R〓SiO〔R〓SiO〕 _n SiR
〓, R ⁵ Si (OSiR〓) ₃ , or [R〓
SiO〕 _o (However, R ² to ^{R 7} are the same or different hydrogen atoms or alkyl groups,
m is 0 or a positive number, n is a positive number), and the boiling point at normal pressure is 70 to 250
°C range, and (b) a hydrocarbon solvent, obtained by dissolving it in a mixed solvent in which the amount of (a) is 5% by weight or more of the total amount of (b). The present invention relates to a method for producing a silicone-coated fabric, which comprises applying a composition and drying it. The cloth used in the present invention may be either woven or nonwoven. Cloth materials include inorganic fibers such as glass fiber and carbon fiber, natural fibers such as cotton, silk, and hemp, recycled fibers such as rayon, semi-synthetic fibers such as cellulose acetate, polyamide, and polyester. Although any synthetic fibers may be used, inorganic fibers are particularly preferred in order to take advantage of the heat resistance and flame resistance that are important features of silicone-coated fabrics. Among these, glass fibers are preferable because they are easily available and have an affinity with silicone elastomers. is preferred. Silicone elastomers are easy to handle and process, and do not require heating conditions that can damage fabrics. Therefore, they are fluid or paste-like in their uncured state, and harden at room temperature or with slight heating to form a rubber material. A type that exhibits elasticity is suitable. Such silicone elastomers include polyorganosiloxanes that have at least two vinyl groups bonded to silicon atoms in one molecule, and polyorganosiloxanes that have an average of more than two hydrogen atoms bonded to silicon atoms in one molecule. condensation reaction between a silanol-terminated polydiorganosiloxane and an organosilicon compound in which an average of more than two hydrolyzable groups bonded to a silicon atom exist in one molecule. The following is an example. In the latter case, the hydrolyzable groups bonded to the silicon atom include hydrogen atoms, lower alkoxy groups such as methoxy, ethoxy, and propoxy groups, substituted alkoxy groups such as methoxyethoxy and ethoxyethoxy groups, and isopropenyl. an enoxy group such as an oxy group, an acyloxy group such as an acetoxy group, a substituted oxime group such as an acetone oxime group, a methyl ethyl ketoxime group, a substituted amino group such as a diethylamino group, a substituted aminoxy group such as a diethylaminoxy group, Examples include substituted amide groups such as N-methylacetamide groups, and organosilicon compounds containing such groups include, but are not limited to, silanes, siloxanes obtained by partial hydrolysis thereof, and the aforementioned silanes. Examples include linear, branched, or cyclic polysiloxanes composed of siloxane units containing hydrolyzable groups and other siloxane units. Most of these siloxane elastomers are obtained by curing in the presence of a catalyst, but some do not require a catalyst, such as when a substituted aminoxy group is used as a hydrolyzable group. In addition, in order to provide mechanical strength and hardness, inorganic fillers such as fumed silica, precipitated silica, silica aerogel, calcined silica, crushed silica, diatomaceous earth, and calcium carbonate, as well as heat-resistant Heat resistance improvers such as iron oxide, cerium oxide, and organic acid salts of iron and cerium are used to improve heat resistance, and flame retardants such as platinum compounds and carbon black are used to impart flame retardancy, as well as adhesives. Known additives such as property improvers and colorants may be used depending on the purpose. Such siloxane elastomers are supplied in an uncured state with all components uniformly mixed and housed in the same container, and cured by contact with moisture in the air. , those that cure by heating, those that are supplied with at least one component essential for curing housed in a separate container, and those that cure at room temperature by mixing, and those that are supplied in the same way and after mixing There are those that harden by heating, and any of them can be used in the present invention. When using heat-resistant and oxidation-resistant inorganic fibers such as glass fibers as the cloth material, in addition to the above, polydiorganosiloxane with a degree of polymerization of 1000 or more is used as the silicone elastomer, and organic peroxides are used. It is also possible to use a type that can be blended and cured by heating to a temperature of 150° C. or higher to obtain a rubber-like elastic body. Most of the organic groups bonded to silicon atoms are methyl groups, and some phenyl groups are used as needed for heat resistance, cold resistance, radiation resistance, etc., but 0.02 of these organic groups
~5% and at least two vinyl groups in one molecule are preferable because the organic peroxide to be used can be selected from a wide range and its amount can be small. There is no effect when the amount of vinyl groups is less than 0.02%,
Moreover, when it exceeds 5%, heat resistance decreases. In this case as well, the same additives as those of the type that harden at room temperature or with slight heating mentioned above can be used. The silicone elastomer is left in its uncured state.
Alternatively, if necessary, in the presence of a solvent, the surface of the cloth is coated or impregnated to the inside by methods such as roll coating, knife coating, or dipping, and then cured using a bar according to the respective curing mechanism. A cloth coated or impregnated with a silicone elastomer is thus obtained. The first feature of the present invention is a silicone-coated cloth in which a silicone resin layer formed by a condensation reaction of (A) and (B) is present on at least one surface of the silicone elastic body of such cloth. It is in. The thinner the silicone resin layer is, the less it will impair the texture of the base material, and even if it is thin, it can exhibit excellent dustproofing properties, anti-sticking properties, and surface texture modification effects. Less silicone resin is also required. The formation of such a thin layer of silicone resin also allows the formation of (1), i.e., the condensation reaction product of (A) and (B), to (2)
That is, this is possible by a method in which a composition obtained by dissolving in a mixed solvent of (a) and (b) is applied and dried, and this is where the second invention lies. Depending on the purpose, such a silicone resin layer may be formed on only one surface of the silicone elastic body;
Sometimes it's done on both sides. (1) used in the present invention is a co-condensation of the benzene-soluble polyorganosiloxane (A) and the silanol-terminated polyorganosiloxane (B). The amount of (1) is preferably in the range of 5 to 80% by weight, more preferably in the range of 10 to 50% by weight, based on the total amount of (1) and (2). If the amount of (1) is too small, the thickness of the film obtained in one coating will be small, requiring multiple coatings, which will greatly reduce work efficiency, which is not preferable. Furthermore, if the amount of (1) is too large, the viscosity will be high, making handling inconvenient and making it impossible to obtain a smooth film. The benzene-soluble polyorganosiloxane (A) is composed of SiO ₂ units and R〓SiO〓 units (where R ¹ is as described above), and has a relatively low molecular weight. R ¹ is a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group, alkenyl groups such as vinyl group, aralkyl groups such as β-phenylethyl group, aryl groups such as phenyl group, and Examples include those in which some of the hydrogen atoms of are substituted with chlorine atoms, fluorine atoms, nitrile groups, etc., but they are easily synthesized, have good weather resistance, and are highly reactive with (B). Therefore, it is preferable that 90 mol% or more of R ¹ is a methyl group, and it is particularly preferable that all of R ¹ is a methyl group. The amount of R〓SiO〓 units is between 0.4 and 1.0 mol per 1 mol of SiO ₂ units, and R〓SiO〓
If the number of units is small, it is difficult to stably obtain a benzene-soluble, low-molecular-weight polymer, and it tends to gel during synthesis or storage, resulting in an insoluble and infusible polymer. Also R〓
If there are too many SiO units, the reactivity during condensation with the silanol-terminated polydiorganosiloxane (B) will be low, making it difficult to obtain a composition capable of forming a film with sufficient dustproofing effect and toughness. Such polysiloxane is produced by adding a tetrafunctional silicon-containing compound selected from alkyl silicates such as ethyl silicate and propyl silicate, partial condensates thereof, silicon tetrachloride, and water glass to trimethylchlorosilane, trimethylchlorosilane, and water glass in the presence of a solvent. It can be obtained by cohydrolyzing with a triorganochlorosilane such as dimethylvinylchlorosilane or dimethylphenylchlorosilane and removing by-products by conventional means. As a solvent,
Benzene, toluene, xylene, gasoline, n-
Hydrocarbons such as hexane and n-heptane are commonly used. As the silanol-terminated polydiorganosiloxane (B), one having a viscosity of 10,000 to 2,000,000 cSt at 25°C is used. If the viscosity is less than 10,000 cSt, the resulting film will have poor toughness and flexibility, and if it exceeds 2,000,000 cSt, the viscosity of the composition will increase, impeding workability. The organic group bonded to the silicon atom is exemplified by the same one as R ¹ in (A), and the balance between the viscosity of the composition and the necessary physical properties, the reactivity of condensation with the polysiloxane in (A), It is preferable that all of the intermediates be methyl groups because they can be easily obtained industrially and have UV resistance, but depending on the use and required properties, phenyl groups may be added within a range of up to 20 mol%. ,Ten
It is also possible to introduce vinyl groups within a range of up to mol %. The co-condensation of the polysiloxane (A) and the silanol-terminated polydiorganosiloxane (B) is carried out by mixing the two and heating them. The polysiloxane (A) is usually obtained as a hydrocarbon solution with a solid content of 30 to 60% by weight, but if necessary, a solvent is added, and then the silanol-terminated polydiorganosiloxane (B) is added. Heat the mixing system.
Hydrocarbon solvents are suitable for the solvent used.
Particularly preferred are toluene or xylene. The heating temperature is preferably between 80 and 150°C, and it is particularly advantageous to use the reflux temperature of the added solvent in terms of temperature control. This condensation reaction does not need to be continued until completion, and may be stopped when components (A) and (B) form a homogeneous phase and become a transparent solution. In order to form a thick silicone resin layer of the present invention, the condensation reaction product of (A) and (B) is applied as it is or in the presence of a hydrocarbon solvent onto the silicone elastomer layer and cured. However, in order to form the resin layer thinly, the presence of (2) is essential. That is, (2) used in the second invention is
It consists of (a) a volatile organosilicon compound and (b) a hydrocarbon solvent, and is necessary to give the composition wettability to the surface of the silicone elastomer and to apply it thinly and uniformly. The volatile organosilicon compound in (a) is a silane or siloxane that does not contain unstable groups and has appropriate volatility, in other words, a boiling point of 70 to 250°C.
It is necessary to be within the range of . If the boiling point is lower than this, it will volatilize early during application and will not work effectively, whereas if it is too high, drying properties will be poor and the formation of a film will be delayed. Silanes such as triethylsilane, dimethyldiethylsilane, trimethylbutylsilane, linear siloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 3-trimethylsiloxy-1.
1,1,3,7,7,7-branched siloxanes such as heptamethyltrisiloxane, hexamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1-ethyl-3,3- 5.5.7.7-
Although cyclic siloxanes such as hexamethylcyclotetrasiloxane are exemplified, methyl-based siloxanes are preferred due to their ease of synthesis, and particularly octamethylcyclotetrasiloxane is preferred in view of appropriate volatility. The amount of (a) needs to be at least 5% by weight, preferably at least 10% by weight, based on the total amount of (a) and (b). This is because if the amount of (a) is less than this, good wettability to the surface of the silicone elastomer will not be obtained, causing repellency and uneven coating, and a uniform film will not be formed. The hydrocarbon solvent in (b) is benzene, toluene,
Examples include xylene, n-hexane, n-heptane, cyclohexane, and gasoline. Among these, toluene and/or
Or xylene is preferred. When the degree of condensation of the condensation reaction product in (1) is high, the obtained composition can be applied directly to the surface of a silicone elastomer to form a film having dustproof properties, toughness, and flexibility. be able to. (1) is used in the form of a partial condensate in which the hydroxyl group bonded to the silicon atom remains, and an organosilane containing a curing catalyst and/or at least two hydrolyzable groups bonded to the silicon atom in the molecule during coating. Alternatively, the condensation reaction may be completed by adding an organosiloxane, or the reaction may be accelerated by heating. Examples of the curing catalyst include organic acid salts of metals such as tin, alkyl titanates, titanium chelate compounds, nickel chelate compounds, cobalt chelate compounds, and amine compounds. Hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, and propoxy groups, acyloxy groups such as acetoxy, organoaminoxy groups such as diethylaminoxy, amino groups such as diethylamino, and acetone oxime groups. ,
An oxime group such as a methyl ethyl ketoxime group is exemplified. These hydrolyzable silanes or siloxanes can promote the condensation reaction when used in combination with the above-mentioned curing catalyst. In addition, γ-aminopropyltriethoxysilane is
This is an example of a hydrolyzable silane that also serves as a curing catalyst.
Organosilanes and organosiloxanes having a diethylaminoxy group exhibit rapid and good curability without being used in combination with a curing catalyst. Furthermore, powders such as silica, titanium oxide, calcium carbonate, and carbon black may be added for the purpose of coloring, matting, and reinforcing the film. The silicone-coated cloth according to the first aspect of the present invention does not attract dust, so it does not lose its aesthetic appearance even when used for a long period of time, and it does not stick to each other even when it is folded or stacked and left for a long time. It also has many advantages over cloth simply treated with a silicone elastic material, such as a smooth surface. Also,
The second invention makes it possible to form a thin and uniform silicone resin layer on the surface of a cloth coated or impregnated with a silicone elastomer, making it easier to create a silicone-coated cloth that is more flexible and retains the texture of the base material. , and it has become possible to manufacture it industrially advantageously. The silicone-coated fabric according to the present invention is useful as firefighting clothing, flame-retardant clothing, flame-retardant curtains, various covering materials, hoses, and the like. Hereinafter, the present invention will be explained with reference to Examples. In Reference Examples, Synthesis Examples, and Examples, all parts represent parts by weight. Also, to simplify the description, the following abbreviations are used. Me: Methyl group Bu: Butyl group Et: Ethyl group Ph: Phenyl group M: Trimethylsiloxane unit (Me ₃ SiO〓) D: Dimethylsiloxane unit (Me ₂ SiO) T: Monomethylsiloxane unit (MeSiO〓) Q: SiO ₂ Unit D ^f : diphenylsiloxane unit (Ph ₂ SiO) Reference example 1 100 parts of dimethylvinylsilyl-terminated polydimethylsiloxane with a viscosity of 15000 cSt at 25°C,
24 parts of fumed silica was added and kneaded to obtain a base compound. A complex obtained by mixing and heating chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane is added to the above base compound.
10 ppm was added and kneaded uniformly to obtain sample E-1a. Separately 100 parts of the above polydimethylsiloxane, 25
60 parts of polymethylhydrodiene siloxane having a viscosity of 50 cSt at °C and 2-hydroxy-2
-Methyl-3-butyne (1.5 parts) was mixed to obtain a homogeneous sample E-1b. Reference Example 2 A base compound was obtained by uniformly kneading 7 parts of fumed silica surface-treated with polydimethylsiloxane and 5 parts of aluminum powder into 100 parts of silanol-terminated polydimethylsiloxane having a viscosity of 20,000 cSt at 25°C. Dibutyltin diacetate 0.5 to this
1 part and 5 parts of a partially hydrolyzed condensate of methyltriacetoxysilane were sequentially added and kneaded uniformly,
Sample E-2 was obtained. This was sealed and stored in a cartridge. Reference example 3 Reference example 2 except that the amount of fumed silica was 10 parts
A paste-like mixture obtained in the same manner as above was dissolved in an equal amount of toluene to obtain sample E-3. This was sealed and stored in a metal can with a gasket. Reference Example 4 100 parts of silanol-terminated polydimethylsiloxane with a viscosity of 3000 cSt at 25°C was added with fumed silica.
A base compound was obtained by uniformly kneading 15 parts of carbon black, 0.5 parts of carbon black, and 18 parts of trimethylsilyl-terminated polydimethylsiloxane. A mixture of 0.2 parts of dibutyltin dilaurate, 1.5 parts of γ-aminopropyltriethoxysilane, and 8 parts of methyltris(methylethylketoxime)silane was added and kneaded to obtain Sample E-4. This was filled into a cartridge, sealed and stored. Reference Example 5 45 parts of precipitated silica was blended in a kneader with 100 parts of polydiorganosiloxane having an average degree of polymerization of 7000, terminals blocked with trimethylsilyl groups, and consisting of 0.2 mol% methylvinylsiloxane units and the remainder dimethylsiloxane units. Sample E-5 was obtained by adding this to 338 parts of xylene and stirring until uniform. Synthesis Example 1 100 parts of a 50% toluene solution of a benzene-soluble polyorganosiloxane resin consisting of Q units and M units, the ratio of M units to 1 mole of Q units being 0.65 moles, and having hydroxyl groups and isopropoxy groups bonded to silicon atoms. And the viscosity at 25℃ is about 500000cSt
of silanol-terminated polydimethylsiloxane, 0.006 parts of caustic soda was added, and the viscosity of the system was increased under reflux of xylene while stirring.
Both polysiloxanes were condensed by heating to 100,000 cSt. After neutralization and filtration in a conventional manner, toluene was added to obtain a toluene solution S-1 of the condensation reaction product with a solid content of 50%. Synthesis Example 2 50% toluene solution of benzene-soluble polyorganosiloxane resin consisting of Q units and M units, the ratio of M units to 1 mole of Q units being 0.53 moles, and having hydroxyl groups and ethoxy groups bonded to silicon atoms.
In the same manner as in Synthesis Example 1, a toluene solution S-2 of the condensation reaction product with a solid content of 50% was obtained from 100 parts of silanol-terminated polydimethylsiloxane having a viscosity of about 80,000 cSt at 25°C. Synthesis Example 3 100 parts of a benzene-soluble polyorganosiloxane resin solution similar to that used in Synthesis Example 2 was mixed with a silanol-terminated polyester having a viscosity of about 120,000 cSt at 25°C and consisting of 6 mol% of D ^f units and the remaining D units. A toluene solution S-3 of the condensation reaction product having a solid content of 50% was obtained from 37.5 parts of organosiloxane in the same manner as in Synthesis Example 1. Synthesis Example 4 100 parts of a 50% xylene solution of a benzene-soluble polyorganosiloxane consisting of Q units and M units, the ratio of M units to 1 mol of Q units being 0.55 mol, and having a hydroxyl group bonded to a silicon atom at 25°C. From 80 parts of silanol-terminated polydimethylsiloxane with a viscosity of approximately 1,000,000 CSt, 50% of the condensation reaction product with a solid content of 50% was prepared by heating under reflux of xylene in the same manner as in Synthesis Example 1.
A xylene solution S-4 was obtained. Synthesis Example 5 50% toluene solution of benzene-soluble polyorganosiloxane consisting of Q units and M units, the ratio of M units to 1 mole of Q units being 0.75 moles, and having hydroxyl groups and propoxy groups bonded to silicon atoms.
100 parts and 75 parts of silanol-terminated polydimethylsiloxane with a viscosity of approximately 1,200,000 cSt at 25°C.
In the same manner as in Synthesis Example 1, a 50% toluene solution S-5 of the condensation reaction product with a solid content of 50% was obtained. Example 1 Sample E-1a and Sample E-1b obtained in Reference Example 1
were mixed at a weight ratio of 10:1, stirred uniformly, and degassed by decompression treatment to obtain sample E-1. Roll this onto one side of glass cloth to 0.2mm.
The glass cloth was coated with a silicone elastomer and cured by heating at 120° C. for 1 hour to obtain a glass cloth coated with a silicone elastomer. On the surface of the silicone elastic body of this cloth, a first
Samples 11 to 19 prepared according to the formulations shown in the table were applied, dried and cured to form a silicone resin layer on the surface of the silicone elastomer, and this was applied to a 30cm x 10cm
It was cut into test pieces. However, Sample 11 is a comparative sample. In addition, for comparison, a test piece was prepared in which the surface of the silicone elastic body was not subjected to such silicone resin treatment. Note that samples 11 to 18 were applied using a paint brush, and sample 19 was applied using a knife because it had a high viscosity and a high solid content. The four corners of these test pieces were fixed on plywood and exposed outdoors to observe the state of staining. In addition, the friction coefficients of separately prepared specimens, untreated and treated with Samples 15 to 19, were measured. These results are shown in Table 1.

[Table] Example 2 Sample E-1 prepared in Example 1 was applied to a glass cloth with a roll to a thickness of 0.3 mm, heated at 120°C for 1 hour to cure it, and was coated with a silicone elastomer. Obtained glass cloth. Samples 21 to 23 prepared according to the formulations shown in Table 2 were applied to the surface of the silicone elastomer of this cloth, respectively, and dried and hardened to form a silicone resin layer. However, samples 21 and 22
Sample 23 was coated with a brush, but sample 23 had a high viscosity and high solids content, so knife coating was used. For comparison, a cloth without such treatment on the surface of the silicone elastomer was also prepared. These are each 10cm
Cut into pieces of 20cm x 20cm, divide the long side into two halves so that the silicone sides overlap, fold, sandwich it between two annealed copper plates, place a weight on it so that a load of 100g/ ^cm2 is applied, and leave it at room temperature. I left it for 30 days. No adhesion was observed in the products with a silicone resin layer formed thereon, but the surfaces of the products in contact with the silicone elastic material surface were stuck, so the force required to reach peeling was measured using a tensile tester. These results are shown in Table 2.

[Table] Example 3 Sample E-2 obtained in Reference Example 2 was applied to a cotton cloth with a roll to a thickness of 0.2 mm, left to harden at room temperature for 7 days, and the cotton cloth coated with silicone elastic material was coated. Obtained. Samples 11 and 15 prepared in Example 1 were applied to the surface of this silicone elastic body, dried and cured at room temperature, and then cut into 30 cm x 30 cm pieces to obtain test pieces. However, Sample 11 is a comparative sample. For comparison, a test piece was prepared in which the surface of the silicone elastomer was not subjected to such treatment. Regarding these test pieces, an outdoor exposure test and a friction coefficient measurement were performed in the same manner as in Example 1. These results are shown in Table 3.

[Table] Example 4 Sample E-2 obtained in Reference Example 2 was applied to a cotton cloth with a roll to a thickness of 0.3 mm, and left to harden at room temperature for 7 days to form a cotton cloth covered with a silicone elastic material. Obtained. Samples 21 to 23 prepared in Example 2 were applied onto the surface of this silicone elastic body, respectively, and dried and cured to form a silicone resin layer. However, the method for applying the sample was the same as in Example 2. For comparison, a cloth without such treatment on the surface of the silicone elastomer was also prepared. Regarding these, the presence or absence of adhesion and the force required for peeling were measured in the same manner as in Example 2. These results are shown in Table 4.

[Table] (Note) ** Adhesion was observed, but the adhesion was not strong enough to measure peeling force.
Example 5 A silicone-treated polyester nonwoven fabric in which a silicone elastic layer was formed on both sides by impregnating a 4 cm wide polyester nonwoven fabric with Sample E-3 obtained in Reference Example 3 and leaving it at room temperature for 3 days to cure. I got it. Samples 51 to 54 prepared according to the formulations shown in Table 5 were applied to both surfaces, respectively, and dried and cured to form silicone resin layers. However, Sample 51 is a comparative sample. Also,
For comparison, a nonwoven fabric without such treatment on the surface of the silicone elastomer was also prepared. These nonwoven fabrics were cut to a length of 20 cm, the top and bottom ends were fixed with metal fittings, and an outdoor exposure test was conducted. In addition, 10 similar samples prepared separately were cut to a length of 4 cm, stacked on top of each other, sandwiched between two mild steel plates, and left to stand for 30 days under a load of 100 g/cm ² to check for adhesion. These results are shown in Table 5.

[Table] Example 6 Sample E-4 obtained in Reference Example 4 was applied to a polyamide cloth and left to cure at room temperature for 7 days to obtain a silicone elastomer-coated polyamide cloth. Sample 22 prepared in Example 2 and sample 52 prepared in Example 5 were coated on the surface of this silicone elastomer.
was applied, and the presence or absence of adhesion under load was examined in the same manner as in Example 2, but no adhesion was observed. Example 7 0.8% by weight was added to sample E-5 obtained in Reference Example 5.
Add and dissolve 2,4-dichlorobenzoyl peroxide, apply this to a glass cloth, volatilize the xylene at room temperature, and then leave it in a heated air stream at 200°C for 5 minutes to coat the silicone on both sides. A silicone-impregnated glass cloth with an elastic surface was fabricated. This glass cloth is 10cm
Samples 71 to 73 prepared according to the formulations shown in Table 6 were cut into 10 cm pieces, coated with them, dried at room temperature, heated to 150°C for 1 hour to completely cure, and coated with silicone resin on both sides. A layer was formed.
However, sample 71 is a comparative sample. The results of an outdoor exposure test on these are shown in Table 6.

【table】

Claims (1)

[Claims] 1. On at least one surface of a cloth coated or impregnated with a silicone elastomer, (A) R ¹ ₃ SiO _1/2 units per mol of SiO ₂ units (wherein R ¹ are mutually (represents the same or different substituted or unsubstituted monovalent hydrocarbon groups) 0.4 to 1.0
In molar proportions, substantially SiO ₂ units and R ¹ ₃ SiO _1/2
(B) 100 parts by weight of a benzene-soluble polyorganosiloxane having a reactive group selected from the group consisting of 0.0004 to 1 hydroxyl group and alkoxy group per silicon atom and bonded to the silicon atom; Silanol terminated polydiorganosiloxane 20~ with viscosity of ~2000000cSt
A silicone-coated fabric characterized by the presence of a silicone resin layer formed by a condensation reaction with 200 parts by weight. 2. Claim 1, in which R ¹ is a methyl group
Silicone-coated fabric as described in Section. 3. The silicone-coated fabric according to claim 1, wherein the organic group bonded to the silicon atom in (B) is a methyl group. 4 The silicone elastomer is a polyorganosiloxane in which there are at least two vinyl groups bonded to silicon atoms in one molecule, and a polyorganosiloxane in which an average number of hydrogen atoms bonded to silicon atoms is more than two in one molecule. A silicone-coated fabric according to claim 1, which is cured by an addition reaction with a hydrogen siloxane. 5 The silicone elastomer is cured by a condensation reaction between a silanol-terminated polydiorganosiloxane and an organosilicon compound in which each molecule has an average of more than two hydrolyzable groups bonded to silicon atoms. , a silicone-coated fabric according to claim 1. 6. The silicone-coated cloth according to claim 1, wherein the cloth is made of glass fiber. 7. The silicone-coated fabric according to claim 6, wherein the silicone elastomer is cured by heating polydiorganosiloxane having a degree of polymerization of 1000 or more in the presence of an organic peroxide. 8 Polydiorganosiloxane accounts for 0.02 to 5% of the organic groups bonded to silicon atoms and has at least two vinyl groups per molecule,
A silicone-coated fabric according to claim 7. 9 At least one surface of the cloth coated or impregnated with a silicone elastomer is coated with (1)(A) R ¹ ₃ SiO units per mole of SiO ₂ units (where R ¹ is the same or different substitution). or unsubstituted monovalent hydrocarbon group)
In a proportion of 0.4 to 1.0 mol, substantially SiO ₂ units and
Consisting of R ¹ ₃ SiO〓 units, per silicon atom
100 parts by weight of a benzene-soluble polyorganosiloxane having a reactive group bonded to a silicon atom selected from the group consisting of 0.0004 to 1 hydroxyl group and an alkoxy group, and (B) a silanol having a viscosity of 10000 to 2000000 cSt at 25°C. Terminal polydiorganosiloxane 20
~200 parts by weight of the condensation reaction product with (2)(a) Molecular formula is R ² ₄ Si, R ³ ₃ SiO [R ⁴ ₂ SiO] _n
SiR ³ ₃ , R ⁵ Si [OSiR ⁶ ₃ ] ₃ , or [R ⁷ ₂ SiO] _o
(However, R ² to ^{R 7} are the same or different hydrogen atoms or alkyl groups, m is 0
or a positive number, n indicates a positive number), and has a boiling point in the range of 70 to 250°C at normal pressure; (b) a hydrocarbon solvent; Dissolved in a mixed solvent in which the amount of (a) is 5% by weight or more of the total amount of (a) and (b),
A method for producing a silicone-coated fabric, which comprises applying and drying the resulting composition. 10. The manufacturing method according to claim 9, wherein R ¹ is a methyl group. 11. The manufacturing method according to claim 9, wherein the organic group bonded to the silicon atom in (B) is a methyl group. 12. The manufacturing method according to claim 9, wherein ^R2 to ^R7 in (a) are methyl groups. 13. The hydrocarbon solvent is an aromatic hydrocarbon selected from the group consisting of toluene and xylene.
A manufacturing method according to claim 9.