JPH11124435A - Resin composition and its production and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition capable of forming molded products excellent-in heat resistance, corrosion resistance, flame retardance, film forming ability, adhesiveness to base materials as coating films, especially in heat cycle resistance and provide its production and molded products from the said resin composition. SOLUTION: This resin composition is obtained by treating a mixture containing a Si-Si bond-containing silane compound and an epoxy compound with at least one of the following treatments: (1) a light irradiation treatment at a lower temperature at which carbon atoms in side chains of Si-Si bonds of the silane compound are inserted to Si-Si bonds of the main chain to form Si-C bonds and (2) a heat treatment at a higher temperature at which Si-Si bonds in the silane compound are cleaved or substituents in the side chains are eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition obtained by subjecting a mixture containing a silane compound and an epoxy compound to at least one of heat treatment and light irradiation treatment, a method for producing the same, and a resin composition. And a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the fields of electronic materials, electrical insulating materials, general industrial equipment, automobiles, energy conversion equipment, and aerospace equipment, heat-resistant resins having high-temperature heat resistance have been demanded. R & D is ongoing.

[0003] Heat-resistant polymers such as fluororesins, silicone resins, polyimides, polyphenylene sulfide, and polyether sulfone are used as high temperature heat-resistant resins.

[0004] However, these heat-resistant polymers are
In general, under high temperature conditions in air or in an oxidizing atmosphere, it is easily deformed by heat and easily oxidized, so that it has a defect that its durability is not sufficient and the heat cycle resistance is particularly poor. . Further, when a coating film is formed using these heat-resistant polymers, there is also a problem that the adhesion between the substrate and the coating film is generally not sufficient.

[0005]

Accordingly, the present invention is excellent in corrosion resistance, durability, adhesion to a substrate as a coating film, etc., even under high temperature conditions in air or oxidizing atmosphere.
In particular, it is an object of the present invention to provide a resin composition capable of forming a molded article having excellent heat cycle resistance, a method for producing the same, a molded article obtained from the resin composition, and a method for producing the same.

[0006]

Means for Solving the Problems The present inventor has conducted researches in consideration of the current state of the art as described above. As a result, a resin composition containing a silane compound and an epoxy compound has solved the above-mentioned problems. The inventors have found that the present invention can be performed, and have completed the present invention.

That is, the present invention provides the following resin composition, a method for producing the same, a molded product, and a method for producing the same.

[0008] 1. For a mixture containing a Si-Si bond-containing silane compound and an epoxy compound,
The carbon in the side chain of the -Si bond is inserted into the Si-Si bond of the main chain to form Si-C
At a temperature lower than the temperature at which a bond is formed, at least one of (1) a process of irradiating light, and (2) a process of heating at a temperature or higher at which a Si-Si bond of the silane compound is cleaved or a side chain substituent is eliminated. The resin composition obtained by performing the process of.

[0009] 2. A mixture containing a silane compound and an epoxy compound is obtained by irradiating and / or heating light in an inert gas atmosphere, and the portions where the silane compound component and the epoxy compound component are respectively modified have Si-C bonds and / or Or the resin composition according to item 1, which is bonded via a Si-O bond.

[0010] 3. A mixture containing a silane compound and an epoxy compound is irradiated with light in an oxygen-containing gas atmosphere and / or
Or obtained by heating, at least a part of the Si-Si bond of the main chain of the silane compound component has a Si-O-Si bond into which oxygen in the atmosphere is inserted, and the silane compound component and the epoxy compound The parts where the components are denatured respectively,
Item 2. The resin composition according to item 1, wherein the resin composition is bonded via a Si-C bond and / or a Si-O bond and / or an oxygen-inserted Si-OC bond.

4. Item 4. The resin composition according to any one of Items 1 to 3, wherein the silane compound is a polysilane.

5. 5. The resin composition according to the above 4, wherein the polysilane is a polysilane having a network structure.

6. Item 6. The resin composition according to any one of Items 1 to 5, which is obtained by performing a heat treatment at 150 to 200 ° C.

7. The epoxy compound and the Si-Si bond-containing silane compound are mixed, and the resulting mixture is subjected to Si-C bond by inserting the side chain carbon of the Si-Si bond of the silane compound into the main chain Si-Si bond. At a temperature lower than the temperature at which the silane compound is formed, (1) light irradiation treatment and (2) heat treatment at a temperature not lower than the temperature at which the Si-Si bond of the silane compound is cleaved or the side-chain substituent is eliminated. A method for producing a resin composition.

[8] Item 7. A molded article of a resin composition comprising the epoxy compound according to any one of Items 1 to 6 and a silane compound having a Si—Si bond.

9. Item 8 wherein the form of the molded article is a coating film
The molded article according to the above.

10. After applying a mixture of an epoxy compound and a Si-Si bond-containing silane compound to the substrate surface to form a coating film, the carbon in the side chain of the Si-Si bond of the silane compound becomes a Si-Si bond in the main chain. At a temperature lower than the temperature at which an Si-C bond is formed by insertion, the coating film is subjected to (1) light irradiation and
(2) A product or article having a cured coating film, wherein at least one of a treatment of heating at a temperature or higher at which a Si-Si bond of a silane compound is cleaved or a side chain substituent is eliminated is performed. Manufacturing method.

11. Item 11. The method for producing a product or article according to Item 10, wherein the silane compound is a polysilane having a network structure.

[12] Item or article having a cured coating film obtained by the method according to Item 10 or 11.

13. Item 13. The product or article according to Item 12, wherein the cured coating film is a heat-resistant, corrosion-resistant, and flame-retardant surface protective film.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION As used herein, "alkyl group", "alkenyl group", "aryl group" and "composition" have the meanings defined below.

The term "alkyl group" refers to a monovalent linear, cyclic or branched aliphatic hydrocarbon group having 1 to 14 carbon atoms.

The term "alkenyl group" refers to a monovalent linear, cyclic or branched C1-C14 aliphatic hydrocarbon group having at least one carbon-carbon double bond.

The term "aryl group" refers to an aromatic hydrocarbon group having at least one substituent or no substituent.

The term "composition" refers to a substance or material in which a chemical bond exists partially or entirely between two or more compounds.

The silane compound used in the production of the resin composition of the present invention is not particularly limited as long as it is a linear, cyclic or branched compound having a Si—Si bond. Further, the silane compound further has a Si-C bond, a Si-O bond, a Si-N bond, a Si-OM bond (M = Ti, Zr) and
It may have at least one kind of Si-B bond. Examples of such a silane compound include polysilane.

Here, the polysilane is a compound represented by the following general formula (R ₂ Si) _m (1) (where R is the same or different and is an alkyl group, an alkenyl group, Represents an arylalkyl group, an aryl group, an alkoxy group or an amino group, m is 2 to 10000), a linear polysilane and a cyclic polysilane represented by the general formula (RSi) _n (2) Are the same or different and represent an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, and an amino group. N is 4 to 10,000.) And a general formula ( R ₂ Si) _x (RSi) _y Si _z (3) (wherein, R is the same or different and represents an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, and an amino group. May be the same, or two or more may be different. The sum of x, y and z is 5 to 10000.) The network polysilane having a Si—Si bond as a skeleton (reticulated polysilane) At least one polymer selected from the group consisting of

Among these polymers, polysilanes (2) and (3) having a network structure are more preferred.

These polymers can be produced by the following method using monomers having the respective structural units as raw materials. That is, a method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal ("Kipping method", J. Am. Chem. Soc., 110, 124 (1988), Macromolecule)
s, 23, 3423 (1990)), a method of dehalogenating polycondensation of halosilanes by electrode reduction (J. Chem. Soc., Chem. Commu).
n., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (199
2)), a method of dehydrocondensation polymerization of hydrosilanes in the presence of a metal catalyst (JP-A-4-33455), a method of anionic polymerization of disilene crosslinked with biphenyl or the like (Ma
cromolecules, 23, 4494 (1990)), ring-opening polymerization of cyclic silanes, and the like.

A silicon-based polymer containing a Si—Si bond obtained by heat-treating the above polysilane at 300 ° C. or higher in an atmosphere of an inert gas such as nitrogen or argon or in the air can also be used.

The epoxy compound used in the production of the resin composition according to the present invention has at least one compound in the chemical structure.
There is no particular limitation as long as it is a linear, cyclic or branched compound having two epoxy groups. Such compounds include, for example, 1,2,3,4-diepoxybutane, 1,4-cyclohexanedimethanol diglycidyl ether, N, N-diglycidyl-4-glycidyloxyaniline, 1,2,5, Examples thereof include 6-diepoxycyclooctane and the following epoxy compounds.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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In the production of the resin composition according to the present invention, the mixing ratio of the mixture of the silane compound and the epoxy compound (hereinafter sometimes simply referred to as “mixture”) is based on 1 part by weight of the epoxy compound. Silane compound 0.01
About 100 parts by weight, preferably about 0.05 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight.

In the production of the resin composition of the present invention, the heat treatment temperature of the above mixture is such that the carbon in the side chain of the Si—Si bond of the silane compound is inserted into the Si—Si bond of the main chain to form the Si—C bond. There is no particular limitation as long as the temperature is lower than the temperature at which the silane compound is formed and the temperature at which the Si—Si bond of the silane compound is cleaved or the side chain substituent (R) is eliminated. Heat treatment temperature is usually
The temperature is about 100 to 220 ° C, preferably about 150 to 220 ° C, and more preferably about 150 to 200 ° C. The heat treatment time is about 1 minute to 48 hours, preferably about 3 minutes to 24 hours, and more preferably about 5 minutes to 18 hours. The heating rate to the above temperature is not particularly limited, but 0.1 to 10
C./minute is preferred.

The heating can be performed in an atmosphere of an inert gas such as nitrogen or argon, or in an atmosphere of an oxygen-containing gas such as air.

Alternatively, in the present invention, the mixture can be irradiated with light instead of, together with, or before or after the heat treatment. As a light source for light irradiation of the mixture, a fluorescent lamp,
Low-pressure mercury lamp, high-pressure mercury lamp, hydrogen lamp, deuterium lamp, halogen lamp, helium-neon laser,
An argon laser, a nitrogen laser, a helium-cadmium laser, a dye laser and the like are used. The light irradiation wavelength is usually in the range of about 220 to 700 nm, and more preferably in the range of about 220 to 400 nm. Light irradiation time is usually 5
The time is about 120 seconds to 120 minutes, more preferably about 20 seconds to 30 minutes. Light irradiation is also performed in an inert gas atmosphere such as nitrogen or argon or an oxygen-containing gas atmosphere such as air.

Further, prior to heating and / or light irradiation of the mixture, preliminary heating is performed at a temperature of less than 100 ° C.
Volatile components may be distilled off or the curing reaction may be partially advanced.

By subjecting the mixture of the silane compound and the epoxy compound to a heat treatment and / or a light irradiation treatment,
Under an inert gas atmosphere, the silane compound component
Part or all of the Si-Si bond is cleaved, and as shown in the following reaction formula, at least one silicon of the silane compound,
A bond with at least one carbon of the modified epoxy group (Si-C bond) and / or a bond with at least one oxygen (Si-O bond) is formed by ring opening of the epoxy compound.

[0043]

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When the mixture is subjected to heat treatment and / or light irradiation treatment in an oxygen-containing gas atmosphere under the above-defined temperature conditions, the mixture is formed in the same manner as in the above-described inert gas atmosphere. Silicon-carbon bond
In addition to (Si-C bond) and silicon-oxygen bond (Si-O bond), for example, as shown in the following reaction formula, further atmosphere between the modified component of the silane compound and the modified component of the epoxy component The modified silane compound component and the modified epoxy compound component are bonded via the Si-OC bond incorporating oxygen in the
iOC bonding). Further, although not shown, an Si-OC bond in which oxygen in the atmosphere is taken in some or all of the Si-Si bond of the silane compound may be formed.

[0045]

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In the present invention, a curing agent for the mixture may be added. Examples of the curing accelerator include silicon compounds such as polyalkoxysilanes such as 1,2-disilylethane, ethylsilicate and methylsilicate; titanium compounds such as tetraalkoxytitanium; boron compounds such as phenyldichloroborane; benzoyl peroxide; Compounds that generate radicals such as -butyl peroxide and azoisobutyronitrile; organic aluminum compounds such as trismethoxyaluminum and trisphenoxyaluminum; triethylamine, pyridine,
Amine compounds such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, tris (dimethylaminomethyl) phenol and 2-ethyl-4-methylimidazole; amide compounds such as dimer acid polyamide; phthalic anhydride, tetrahydromethyl phthalic anhydride Acid anhydrides such as acid, hexahydrophthalic anhydride, trimellitic anhydride, and methylnadic anhydride; phenols such as phenol novolak; mercaptan compounds such as polysulfide; Lewis acid complex compounds such as boron trifluoride / ethylamine complex; chloroform , Dichloromethane, trichloromethane and the like; basic compounds such as sodium ethoxide and the like.

The amount of the curing agent used is about 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the silane compound.
It is about parts by weight.

When light irradiation is performed, a photoacid generator can be blended. Examples of the photoacid generator include pyridinium salts (such as N-ethoxy-2-methylpyridinium-hexafluorophosphate and N-ethoxy-4-phenylpyridinium-hexafluorophosphate), and sulfonium salts (for example, “San-Aid SI -60L "," San-Aid SI-80L "," San-Aid SI-100L ", and the like, which are commercially available from Sanshin Chemical Industry Co., Ltd., and ferrocene-based (for example," Irgacure 261 "). Commercially available from Ciba Specialty Chemicals, Inc., triazines (e.g., commercially available from Nihon SiberHegner, Inc. under trade names such as "Triazine A" and "Triazine B"), iodonium salts (e.g., “BB
Midori Chemical Co., Ltd. by brand names such as "I-101" and "BBI-102"
Commercially available from Co., Ltd.).
Furthermore, benzophenone and its derivatives, o-benzoyl benzoate and its derivatives, acetophenone and its derivatives, benzoin, benzoin ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatives, disulfide compounds, quinone compounds, halogenated carbonized Photosensitizers such as hydrogen group-containing compounds, amines and dyes may be added.

In the resin composition of the present invention, if necessary,
One or more inorganic fillers can be blended. Specific examples of inorganic fillers include silica-based materials such as silica sand, quartz, novaculite, diatomaceous earth, and synthetic amorphous silica; kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, and aluminum silicate. Glass bodies such as glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres; boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, nitride Non-oxide inorganic substances such as titanium and titanium carbide; calcium carbonate; metal oxides such as zinc oxide, alumina, magnesia, zirconia, titanium oxide, beryllium oxide; barium sulfate, molybdenum disulfide, tungsten disulfide;
Inorganic substances such as fluorocarbon; aluminum, bronze, lead,
Metal powders such as stainless steel and zinc; and carbon bodies such as carbon black, coke, graphite, pyrolytic carbon and hollow carbon spheres.

These fillers may be of various shapes such as fibrous, needle-like (including whisker), granular, and scaly, or may be used alone or in combination of two or more.

The resin composition of the present invention may further comprise, if necessary, a flame retardant aid such as antimony trioxide; natural waxes, synthetic waxes, straight-chain fatty acids and metal salts thereof,
Release agents such as acid amides, esters and paraffins;
Pigments such as carbon black and titanium dioxide; plasticizers such as esters, polyols, polysulfides and urethane prepolymers; liquid rubbers such as carboxyl group-terminated butadiene-acrylonitrile copolymer rubber and ethylene-vinyl acetate copolymer; silane coupling agents , Titanium-based coupling agents and other surface modifiers; silicone oils,
Low stress agents such as silicone rubber, various plastic powders, various engineering plastic powders, ABS resin powder, MBS resin powder and the like can be added.

Further, if necessary, known resin additives such as a flow regulator, a leveling agent, an antifoaming agent, an antistatic agent, an ultraviolet absorber, and a dispersant are added to the resin composition of the present invention. be able to.

When the above-mentioned additives such as a curing agent, a photoacid generator, a photosensitizer, and a filler are used, a silane compound and / or an epoxy compound before mixing or a mixture of both before the heat treatment are used. May be added.

The molded article made of the resin composition of the present invention is not particularly limited, and may be in any shape or form such as a sheet, a film, a pellet, a coating, a lump, and a powder.

According to the present invention, a mixture containing a silane compound and an epoxy compound is spray-coated on a substrate surface,
It is applied by a known method such as a bar coating method, a flow coating method, a dipping method, a casting method, or compression molding, casting molding, transfer molding, or a porous substrate (ceramic fiber body, glass fiber body, carbon fiber body). , Etc.) and then heat-treated to obtain a desired molded product.

The mixture can be applied to the substrate surface in the form of an organic solvent solution. Examples of such an organic solvent include, but are not particularly limited to, tetrahydrofuran, xylene, toluene, benzene, ethanol, butanol, dimethoxyethane, dimethylacetamide, dimethylformamide, methyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. , Dimethylsulfoxide, phenols and the like. The concentration of the mixture in the solution is not particularly limited, but is usually about 1 to 60 w / v%, and more preferably about 10 to 40 w / v%.

The substrate is not particularly limited as long as it can withstand a predetermined heat treatment and / or light irradiation treatment.
Ceramics, glass, plastics, and the like can be used.

[0058]

The resin composition and the molded article according to the present invention have heat resistance, heat cycle resistance, acid resistance, alkali resistance, organic solvent resistance, water resistance, moisture resistance, flame retardancy, water repellency,
It has excellent insulation properties, film-forming properties, adhesion to a substrate in the state of a coating film, workability, moldability, and the like.

Articles or products in which the substrate is coated with the resin composition of the present invention have excellent properties of the resin composition itself. Such an article or product has heat resistance, heat cycle resistance, even under various severe environmental conditions.
It exhibits excellent properties such as acid resistance, alkali resistance, organic solvent resistance, water resistance, moisture resistance, flame retardancy, water repellency, insulation properties and coating film adhesion.

The resin composition and the molded article of the present invention can be used as a coating material, an insulating material for electric equipment, a covering material for electric wires, a sealing material for electronic equipment, an insulating film for a printed wiring board, a wiring insulating film, a protective film, and a liquid crystal alignment. In the form of films, sliding members, automotive parts materials, aviation / space materials, inks, adhesives, adhesives, and the like, they are particularly suitable for heat-resistant applications, corrosion-resistant applications, flame-retardant applications, and the like.

The resin composition of the present invention is excellent in heat resistance, heat cycle resistance, acid resistance, water resistance, moisture resistance, flame retardancy, water repellency, etc. as compared with a material obtained by curing only an epoxy resin. I have. Further, as compared with a material obtained by curing only a silane compound, it is excellent in workability, moldability, film formability, and the like.

In particular, when a polysilane having a network structure is used as the silane compound, heat resistance, acid resistance, organic solvent resistance, water resistance, moisture resistance, water repellency, flame retardancy and the like are remarkably improved. It exhibits extremely excellent properties as heat-resistant coating materials, corrosion-resistant coating materials, and flame-retardant coating materials for protecting the surface of various substrates.

[0063]

EXAMPLES Examples are shown below to further clarify the features of the present invention.

Example 1 0.2 g of methylphenylpolysilane (average degree of polymerization: 40) synthesized by an electrode reaction as a silane compound, and bisphenol A type epoxy resin (Asahi Chiba Co., Ltd.) as an epoxy compound
0.8 g of Araldite AER260) and photoacid generator
0.035 g of N-ethoxy-2-methylpyridinium-hexafluorophosphate (NEMH) was dissolved and mixed in 10 ml of tetrahydrofuran at room temperature. The resulting mixture was previously polished with sandpaper (# 500) to a stainless steel plate (SUS
-304).

A sample was obtained by placing a high-pressure mercury lamp of 100 W in an argon atmosphere at a position 15 cm from the coating film and irradiating the coating with light for 5 minutes while maintaining the obtained coating film-forming stainless steel plate at 50 ° C. . The thickness of the obtained cured coating film is 20 μm
Met.

Regarding the structure of the cured coating film of the obtained sample,
NMR analysis was performed. ²⁹ Si-NMR analysis showed peaks at -40 ppm and -20 ppm. From the result of ¹³ C-NMR analysis, a new peak was observed at 0 ppm.

Further, a heat resistance test, an acid resistance test, an alkali resistance test, a heat cycle resistance test, and a flammability test of the cured coating film were performed using the obtained sample.

The heat resistance test was performed by leaving the sample in an air furnace at 350 ° C. in an air atmosphere for one hour. When the surface state of the coating film was visually observed and observed with an electron microscope (SEM), no crack was observed, and the heat resistance was good.

In the acid resistance test, the sample was immersed in a 5% nitric acid aqueous solution for 2 hours, and the surface condition of the coating film was visually observed. Even in this case, no crack was observed,
The acid resistance was good.

In the alkali resistance test, the sample was immersed in a 5% aqueous NaOH solution for 2 hours, and the surface condition of the coating film was visually observed. Also in this case, no cracks were found,
The alkali resistance was good.

In the heat cycle resistance test, the cycle of “holding the sample at the set temperature (250 ° C.) for 2 hours and then holding at room temperature for 2 hours” was repeated 10 times to give a thermal shock to the coating film. After the test, the surface state of the coating film was visually observed. As a result, no crack was observed, and the heat cycle resistance was good.

In the flammability test, the pellets were left in the flame of a Bunsen burner for 1 minute, and the presence or absence of burning of the pellets was visually observed. As a result, no burning was observed, and it was confirmed that the resin composition according to the present invention was a highly flame-retardant material.

Example 2 0.2 g of methylphenylpolysilane (average degree of polymerization 40) synthesized by an electrode reaction as a silane compound and a bisphenol A type epoxy resin (Asahi Ciba Co., Ltd.) as an epoxy compound
0.8 g of Araldite AER260) in tetrahydrofuran
It was dissolved and mixed in 10 ml at room temperature. The obtained mixture was flow-coated on a stainless steel plate (SUS-304) polished with sandpaper (# 500) in advance.

The coated stainless steel plate was heated at a rate of 5 ° C./min from room temperature to 200 ° C. in an argon atmosphere, and when it reached 200 ° C., it was taken out into room temperature to obtain a sample with a cured coating film. The film thickness of the obtained cured coating film was 20 μm.

Regarding the structure of the cured coating film of the obtained sample,
NMR analysis was performed. ²⁹ Si-NMR analysis showed peaks at -40 ppm and -20 ppm. From the result of ¹³ C-NMR analysis, a new peak was observed at 0 ppm after the heat treatment.

Using this sample, the coating film was subjected to a heat resistance test, an acid resistance test, an alkali resistance test, a heat cycle resistance test, and a flammability test.

The heat resistance test was performed by leaving the coating film-formed sample in an electric furnace at 350 ° C. in an air atmosphere for one hour. Visual observation of the surface condition of the coating film and electron microscope (SEM)
As a result, no generation of cracks or the like was observed, and the heat resistance was good.

In the acid resistance test, the cured coating film-forming sample was immersed in a 5% aqueous nitric acid solution for 2 hours, and the surface condition of the coating film was visually observed. Also in this case, no cracks or the like were observed in the coating film, and the acid resistance was good.

In the alkali resistance test, the cured coating film form sample was immersed in a 5% NaOH aqueous solution for 2 hours, and then the surface condition of the coating film was visually observed. Also in this case, generation of cracks or the like was not observed, and the alkali resistance was good.

In the heat cycle resistance test, the same heat cycle as in Example 1 (except that the high temperature side was 300 ° C.)
Was repeated 10 times to give a thermal shock to the coating film. After the test, the surface state of the coating film was visually observed. No occurrence of cracks or the like was observed, and the heat cycle resistance was good.

In the flammability test, the coating film portion of the obtained sample was allowed to stand in a Bunsen burner flame for 1 minute, and the presence or absence of burning of the coating film was visually observed. As a result, no burning was observed, and it was confirmed that the resin composition according to the present invention was a material excellent in flame retardancy.

Example 3 0.5 g of methylphenylpolysilane having an average degree of polymerization of 40 as a silane compound and 0.5 g of a bisphenol A type epoxy resin (Araldite AER260 manufactured by Asahi Ciba Co., Ltd.) as an epoxy compound
A cured coating film was formed on a stainless steel plate in the same manner as in Example 1 except that a mixture with the above was used. Using the obtained sample, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance were performed. After performing the property test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 4 0.8 g of methylphenylpolysilane having an average degree of polymerization of 40 as a silane compound and 0.2 g of a bisphenol A type epoxy resin (Araldite AER260 manufactured by Asahi Ciba Co., Ltd.) as an epoxy compound
A cured coating film was formed on a stainless steel plate in the same manner as in Example 1 except that a mixture with the above was used. Using the obtained sample, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance were performed. After performing the property test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

Further, in the flammability test performed in the same manner as in Example 2, no burning of the sample coating film was recognized, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 5 A cured coating film was formed on a stainless steel plate in the same manner as in Example 2 except that the heat treatment temperature was changed to 175 ° C., and a heat resistance test, an acid resistance test, After performing the alkali resistance test and the heat cycle resistance test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In the flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and the resin composition according to the present invention was found to be a material having high flame retardancy. confirmed.

Example 6 A cured coating was formed on a stainless steel plate in the same manner as in Example 2 except that 0.02 g of benzoyl peroxide was further added to the mixture, and the heat treatment temperature was changed to 150 ° C. After performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the sample, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 7 Example 1 was repeated except that 0.2 g of novolak type epoxy resin (EPN1180 manufactured by Asahi Chiba KK) was used as an epoxy compound and 0.8 g of methylphenylpolysilane having an average degree of polymerization of 40 was used as a silane compound. In the same manner as above, a cured coating film was formed on a stainless steel plate, and a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed using the obtained sample. Observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test performed in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 8 Same as Example 1 except that 0.5 g of methylphenylpolysilane having an average degree of polymerization of 40 was used as a silane compound and 0.5 g of a novolak type epoxy resin (EPN1180, manufactured by Asahi Ciba Co., Ltd.) was used as an epoxy compound. Then, a cured coating film was formed on a stainless steel plate, and after performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the obtained sample, the coating film was visually observed. . In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 9 Same as Example 1 except that 0.2 g of methylphenylpolysilane having an average degree of polymerization of 40 was used as a silane compound and 0.8 g of a novolak-type epoxy resin (EPN1180 manufactured by Asahi Ciba Co., Ltd.) was used as an epoxy compound. Then, a cured coating film was formed on a stainless steel plate, and after performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the obtained sample, the coating film was visually observed. . In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition of the present invention was a flame-retardant material.

Example 10 The procedure of Example 1 was repeated except that 0.2 g of methylphenylpolysilane having an average degree of polymerization of 200 was used as the silane compound.
A cured coating film was formed on a stainless steel plate, and after performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the obtained sample, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

Further, in the flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 11 A cured film was formed on a stainless steel plate in the same manner as in Example 1 except that 0.2 g of methylphenylpolysilane having an average degree of polymerization of 5 was used as a silane compound. After performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 12 The same procedure as in Example 1 was carried out except that 0.2 g of cyclic methylphenylpolysilane having an average degree of polymerization of 6 was used instead of methylphenylpolysilane having an average degree of polymerization of 40 as the silane compound. After forming a film and performing a heat resistance test, an acid resistance test, an alkali resistance test and a heat cycle resistance test using the obtained sample, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 13 A stainless steel plate was prepared in the same manner as in Example 1 except that 0.2 g of methyl-n-hexylpolysilane having an average polymerization degree of 40 was used instead of methylphenylpolysilane having an average polymerization degree of 40 as the silane compound. A cured coating film was formed, and after performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the obtained sample, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 14 A silane compound was replaced with methylphenylpolysilane having an average degree of polymerization of 40, except that 0.2 g of a copolymer of methylphenylsilane and dimethylsilane (average degree of polymerization: 40, polymerization ratio: 6/4) was used. A cured coating was formed on a stainless steel plate in the same manner as in Example 1, and a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed on the obtained sample. The membrane was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In the flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 15 0.2 g of phenyl network polysilane having an average degree of polymerization of 40 was used in place of methylphenylpolysilane having an average degree of polymerization of 40 as the silane compound, and the heat resistance test temperature was set to 50.
A cured coating film is formed on a stainless steel plate in the same manner as in Example 1 except that the temperature is set to 0 ° C., and a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test are performed using the obtained samples. After that, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In the flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition of the present invention was a flame-retardant material.

Example 16 The procedure was carried out except that as the silane compound, 0.1 g of methylphenylpolysilane having an average degree of polymerization of 40 and 0.1 g of phenyl network polysilane having an average degree of polymerization of 40 were used instead of 0.5 g of methylphenylpolysilane having an average degree of polymerization of 40. As in Example 1,
A cured coating film was formed on a stainless steel plate, and after performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the obtained sample, the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

In the flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition of the present invention was a flame-retardant material.

Example 17 A cresol novolak type epoxy resin (Asahi Chiba) was used in place of the bisphenol A type epoxy resin as the epoxy compound.
0.2 g of methylphenylpolysilane having an average degree of polymerization of 40 as a silane compound.
A cured coating film was formed on a stainless steel plate in the same manner as in Example 1 except that 8 g was used, and a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed using the obtained samples. After that, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition of the present invention was a flame-retardant material.

Example 18 An epoxy-modified silicone resin (Toshiba Silicone) was used in place of bisphenol A type epoxy resin as the epoxy compound.
XF42-B2249) 0.5 g of methylphenylpolysilane having an average degree of polymerization of 40 as a silane compound
A cured coating was formed on a stainless steel plate in the same manner as in Example 1 except that 0.5 g was used, and a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance were performed using the obtained sample. After performing the test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 19 A sample having a cured coating film on a stainless steel plate was obtained in the same manner as in Example 1 except that the atmosphere during the irradiation of the mixture was air, instead of argon.

Regarding the structure of the cured coating film of the obtained sample,
IR and NMR analyzes were performed.

According to the IR analysis, 11
A large absorption of 00 cm ^-1 was observed.

From the result of the ²⁹ Si-NMR analysis, it was found that -40 ppm and -2
A peak was observed at 0 ppm. From the result of ¹³ C-NMR analysis, a new peak was observed at 0 ppm after the heat treatment.

Using the obtained sample, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed, and the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no combustion of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 20 A sample having a cured coating film on a stainless steel plate was obtained in the same manner as in Example 2 except that the atmosphere during the heat treatment of the mixture was changed to air instead of argon.

Regarding the structure of the cured coating film of the obtained sample,
IR and NMR analyzes were performed.

According to the IR analysis, 11
A large absorption of 00 cm ^-1 was observed.

From the results of the ²⁹ Si-NMR analysis, it was found that -40 ppm and -2
A peak was observed at 0 ppm. From the result of ¹³ C-NMR analysis, a new peak was observed at 0 ppm after the heat treatment.

Using the obtained sample, a heat resistance test, an acid resistance test, an alkali resistance test and a heat cycle resistance test were performed, and the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 21 The procedure of Example 2 was repeated except that 0.5 g of a novolak type epoxy resin (EPN1180, manufactured by Asahi Chiba KK) was used as the epoxy compound, and 0.5 g of phenyl network polysilane having an average degree of polymerization of 40 was used as the polysilane compound. A cured film was formed on a stainless steel plate in the same manner as in Example 19, and a heat resistance test (the test temperature was set to 500 ° C.), an acid resistance test, an alkali resistance test, and a heat resistance test were performed using the obtained sample. After performing the cycle test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test performed in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 22 The same procedure as in Example 19 was carried out except that 0.5 g of a novolak type epoxy resin (EPN1180, manufactured by Asahi Chiba KK) was used as the epoxy compound and 0.5 g of phenyl network polysilane having an average degree of polymerization of 10 was used as the polysilane compound. Then, a cured coating film is formed on a stainless steel plate, and a heat resistance test (the test temperature is 500 ° C.), an acid resistance test, an alkali resistance test, and a heat cycle resistance test are performed using the obtained sample. After that, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

Further, in the flammability test performed in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 23 The procedure of Example 23 was repeated except that 0.2 g of a novolak type epoxy resin (EPN1180 manufactured by Asahi Chiba KK) was used as the epoxy compound and 0.8 g of phenyl network polysilane having an average degree of polymerization of 10 was used as the silane compound. In the same way as 19,
A cured coating was formed on a stainless steel plate, and a heat resistance test (the test temperature was set to 500 ° C.), an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed using the obtained sample. Thereafter, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

Further, in the flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 24 The procedure of Example 24 was repeated except that 0.8 g of a novolak type epoxy resin (EPN1180 manufactured by Asahi Chiba KK) was used as the epoxy compound and 0.2 g of phenyl network polysilane having an average degree of polymerization of 10 was used as the silane compound. In the same way as 19,
A cured coating was formed on a stainless steel plate, and a heat resistance test (the test temperature was set to 500 ° C.), an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed using the obtained sample. Thereafter, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 25 0.8 g of novolak type epoxy resin (EPN1180 manufactured by Asahi Chiba KK) was used as an epoxy compound, and methylphenylpolysilane having an average degree of polymerization of 40 was used as a silane compound.
Phenyl network polysilane with 0.1g and average degree of polymerization of 10
Except for using 0.1 g, a cured film was formed on a stainless steel plate in the same manner as in Example 19, and a heat resistance test was performed using the obtained sample (provided that the test temperature was 500 ° C.), After performing the acid resistance test, the alkali resistance test, and the heat cycle resistance test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test performed in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 26 0.8 g of novolak type epoxy resin (EPN1180, manufactured by Asahi Chiba KK) was used as an epoxy compound, and a copolymer of methylphenylpolysilane and phenyl network polysilane (average degree of polymerization: 40) was used as a silane compound. A cured coating was formed on a stainless steel plate in the same manner as in Example 19, except that 0.2 g of the polymerization ratio 1/1) was used. Was 500 ° C.), an acid resistance test, an alkali resistance test, and a heat cycle resistance test, and the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 27 To a mixture of 0.2 g of a phenyl network polysilane having an average degree of polymerization of 40 as a silane compound and 0.8 g of a novolak type epoxy resin (EPN1180 manufactured by Asahi Ciba Co., Ltd.) as an epoxy compound was further added 0.02 g of benzoyl peroxide. A cured coating film was formed on a stainless steel plate in the same manner as in Example 2 except that it was added (however, the heat treatment of the coating film was performed at 150 ° C.), and a heat resistance test (however, , The test temperature was 500 ° C.), an acid resistance test, an alkali resistance test, and a heat cycle resistance test, and the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 28 To a mixture of 0.5 g of phenyl network polysilane having an average degree of polymerization of 40 as a silane compound and 0.5 g of a novolak type epoxy resin (EPN1180 manufactured by Asahi Ciba Co., Ltd.) as an epoxy compound was further added 0.02 g of benzoyl peroxide. Except for the addition, the same as in Example 2 (however,
° C), a cured coating was formed on a stainless steel plate, and a heat resistance test (the test temperature was 500 ° C), an acid resistance test, an alkali resistance test, and a heat resistance test were performed using the obtained sample. After performing the cycle test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 29 A cured coating film was formed on a stainless steel plate in the same manner as in Example 2 except that a phenyl network polysilane having an average degree of polymerization of 10 was used as a silane compound. Test (however, the test temperature was 500 ° C),
After performing the acid resistance test, the alkali resistance test, and the heat cycle resistance test, the coating film was visually observed. In any of the tests, cracks, voids,
No occurrence of peeling or the like was observed, and good results were obtained.

In a flammability test performed in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 30 0.02 g of benzoyl peroxide was further added to a mixture of 0.2 g of phenyl network polysilane having an average degree of polymerization of 10 as a silane compound and 0.8 g of a novolak type epoxy resin (EPN1180, manufactured by Asahi Ciba Co., Ltd.) as an epoxy compound. A hardened coating film was formed on a stainless steel plate in the same manner as in Example 2 except that the heat treatment temperature was set to 150 ° C., and a heat resistance test was performed using the obtained sample (provided that the test temperature was 500 ° C.). ° C), an acid resistance test, an alkali resistance test, and a heat cycle resistance test, and the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test performed in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 31 A mixture of 0.5 g of phenyl network polysilane having an average degree of polymerization of 10 as a silane compound and 0.5 g of a novolak type epoxy resin (EPN1180 manufactured by Asahi Ciba Co., Ltd.) as an epoxy compound was further added with 0.1 g of benzoyl peroxide. A hardened coating film was formed on a stainless steel plate in the same manner as in Example 2 except that 02 g was added and the heat treatment temperature was changed to 150 ° C., and a heat resistance test was performed using the obtained sample (excluding the test temperature). Was 500 ° C.), an acid resistance test, an alkali resistance test, and a heat cycle resistance test, and the coating film was visually observed. In any of the tests, cracks, voids, peeling, etc. were not observed in the surface state of the coating film,
Good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 32 0.1 g of methylphenylpolysilane having an average degree of polymerization of 40 and 0.1 g of phenyl network polysilane having an average degree of polymerization of 10 were used as silane compounds, and 0.02 g of benzoyl peroxide was further added. A cured coating film was formed on a stainless steel plate in the same manner as in Example 2 except that the heat resistance test (however, the test temperature was 500 ° C.), an acid resistance test, After performing the alkali resistance test and the heat cycle resistance test, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 33 As a silane compound, a copolymer of methylphenyl polysilane and phenyl network polysilane (average degree of polymerization 40,
(Polymerization ratio 1/1) 0.2 g was used, and 0.02 g of benzoyl peroxide was further added to the mixture.
A cured coating was formed on a stainless steel plate in the same manner as in Example 2 except that the temperature was set to 0 ° C, and a heat resistance test (the test temperature was set to 500 ° C) and an acid resistance test were performed using the obtained samples. ,
After performing the alkali resistance test and the heat cycle resistance test, the coating film was visually observed. In both tests,
No cracks, voids, peeling, etc. were observed in the surface state of the coating film, and good results were obtained.

In a flammability test conducted in the same manner as in Example 2, no burning of the sample coating film was observed, and it was confirmed that the resin composition according to the present invention was a flame-retardant material.

Example 34 0.3 g of methylphenylpolysilane having an average degree of polymerization of 40 as a silane compound and an alicyclic epoxy resin as an epoxy compound
(Daicel Chemical Industries, Ltd .; Celloxide 2021p) A cured film was formed on a stainless steel plate in the same manner as in Example 19 except that 0.7 g and 10 ml of dimethoxyethane were used as a solvent. Heat resistance test,
After performing the acid resistance test, the alkali resistance test, and the heat cycle resistance test, the coating film was visually observed. In any of the tests, cracks, voids,
No occurrence of peeling or the like was observed, and good results were obtained.

Example 35 A cured coating film was formed on a stainless steel plate in the same manner as in Example 1 except that a ferrocene-based photoacid generator (Circa Specialty Chemicals; Irgacure 261) was used as the photoacid generator. After performing a heat resistance test, an acid resistance test, an alkali resistance test and a heat cycle resistance test using the obtained sample, the coating film was visually observed. In any of the tests, the surface condition of the coating film includes cracks,
No occurrence of voids or peeling was observed, and good results were obtained.

Example 36 The same procedure as in Example 1 was carried out except that a sulfonium-based photoacid generator (manufactured by Sanshin Chemical Industry Co., Ltd .; Sun-Aid SI-60L) was used as the photoacid generator to cure on a stainless steel plate. A coating film was formed, and after performing a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test using the obtained sample, the coating film was visually observed. In any of the tests, cracks, voids, peeling, and the like were not observed in the surface state of the coating film, and good results were obtained.

Comparative Example 1 Only 0.2 g of bisphenol A type epoxy resin (manufactured by Asahi Ciba Co., Ltd .; Araldite AER260) and 0.035 g of NEMH were dissolved in 5 ml of tetrahydrofuran at room temperature, and the obtained solution was previously sanded. Flow coating was performed on a stainless steel plate (SUS-304) polished with paper (# 500).

A sample was obtained by placing a high-pressure mercury lamp of 100 W under an argon atmosphere at a position 15 cm from the coating film and irradiating with light for 5 minutes while maintaining the obtained coating film-forming stainless steel plate at 50 ° C. . The thickness of the obtained cured coating film is 20 μm
Met.

When the obtained sample was left for 1 hour in an air atmosphere at 350 ° C. in an electric furnace, cracks were observed on the surface of the coating film.

Comparative Example 2 0.5 g of bisphenol A type epoxy resin (manufactured by Asahi Ciba Co., Ltd .; Araldite AER260) and 0.14 of diethylenetriamine
g was dissolved in 5 ml of tetrahydrofuran at room temperature,
The obtained solution was flow-coated on a stainless steel plate (SUS-304) polished with sandpaper (# 500) in advance.

Next, the coated stainless steel plate was heat-treated in air at 100 ° C. for 30 minutes to form a cured film having a thickness of 20 μm.

When the obtained sample was allowed to stand for 1 hour in an air atmosphere at 350 ° C. in an air atmosphere, cracks occurred in the coating film, and peeling occurred between the coating film and the stainless steel plate. I was

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Ryoichi Nishida, Inventor Osaka Gas Co., Ltd. 4-1-2 Hirano-cho, Chuo-ku, Osaka-shi Inside Kansai New Technology Research Institute Co., Ltd.

Claims (13)

[Claims] 1. A mixture containing a silane compound containing an Si—Si bond and an epoxy compound, and a silane compound containing Si—Si
At a temperature lower than the temperature at which the carbon in the side chain of the bond is inserted into the Si-Si bond of the main chain to form a Si-C bond, (1) light irradiation treatment,
And (2) a resin composition obtained by performing at least one treatment of heating at a temperature not lower than the temperature at which the Si-Si bond of the silane compound is cleaved or the side chain substituent is eliminated. 2. A mixture containing a silane compound and an epoxy compound, which is obtained by irradiating light and / or heating in an atmosphere of an inert gas, wherein portions where the silane compound component and the epoxy compound component are respectively modified are Si The resin composition according to claim 1, wherein the resin composition is bonded via a -C bond and / or a Si-O bond. 3. A mixture containing a silane compound and an epoxy compound, which is obtained by irradiating light and / or heating in an oxygen-containing gas atmosphere, wherein at least a part of Si-Si bonds in the main chain of the silane compound component is obtained. Oxygen in the atmosphere has a Si-O-Si bond inserted, and the parts where the silane compound component and the epoxy compound component are respectively modified are Si-C
The resin composition according to claim 1, wherein the resin composition is bonded via a bond and / or a Si-O bond and / or an oxygen-containing Si-OC bond. 4. The method according to claim 1, wherein the silane compound is polysilane.
4. The resin composition according to any one of items 1 to 3. 5. The resin composition according to claim 4, wherein the polysilane is a polysilane having a network structure. 6. The resin composition according to claim 1, which is obtained by performing a heat treatment at 150 to 200 ° C. 7. An epoxy compound and a Si-Si bond-containing silane compound are mixed, and in the resulting mixture, carbon in the side chain of the Si-Si bond of the silane compound is inserted into the Si-Si bond of the main chain. hand
At a temperature lower than the temperature at which the Si-C bond is formed, (1) light irradiation treatment and (2) heat treatment at a temperature higher than the temperature at which the Si-Si bond of the silane compound is cleaved or the side chain substituent is eliminated A method for producing a resin composition, comprising performing at least one treatment. 8. A molded article of a resin composition comprising the epoxy compound according to claim 1 and a silane compound having a Si—Si bond. 9. The molded article according to claim 8, wherein the form of the molded article is a coating film. 10. A coating comprising a mixture of an epoxy compound and a Si-Si bond-containing silane compound applied to the surface of a substrate to form a coating film. At a temperature lower than the temperature at which the Si-Si bond is formed by insertion into the Si-Si bond, the coating film is subjected to (1) light irradiation treatment and (2) the Si-Si bond of the silane compound is cleaved or the side chain A method for producing a product or an article having a cured coating film, wherein at least one of a treatment of heating at a temperature higher than a temperature at which a substituent is eliminated is performed. 11. The method according to claim 10, wherein the silane compound is a polysilane having a network structure. 12. A product or article having a cured coating film obtained by the method according to claim 10. 13. The product or article according to claim 12, wherein the cured coating film is a heat-resistant, corrosion-resistant and flame-retardant surface protective film.