JPH11124436A - Resin composition and its production and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in heat resistance, heat cycle resistance, corrosion resistance, etc., by treating a composition containing a polycarbosilane and an epoxy compound with heat and/or light-irradiation. SOLUTION: This resin composition is obtained by blending preferably 0.01-100 pts.wt. of (A) a polycarbosilane, e.g., having a repeating unit of the formula [R<1> is H, etc.; R<2> is an alkyl, etc.; X is an alkylene; (n) is 1-0000] with 1 pt.wt. of (B) an epoxy compound (e.g.; 1, 2, 3, 4-diepoxy butane, etc.), and heat-treating the mixture at preferably 40-450 deg.C for 1 minute - 48 hours or irradiating with preferably 220-700 nm wave length for 5 seconds to 120 minutes, e.g. using a high-voltage mercury vapor lamp as a light source.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition obtained by subjecting a mixture containing polycarbosilane and an epoxy compound to at least one of a heat treatment and a 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 heat resistance at high temperatures have been demanded. R & D is underway.

As the high-temperature heat-resistant resin, a heat-resistant polymer such as a fluorine resin, a silicone resin, polyimide, polyphenylene sulfide, and polyether sulfone is used.

[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 drawback that the durability is not sufficient and the heat cycle resistance is particularly poor. ing. Further, when a coating film is formed on the surface of the substrate with these heat-resistant polymers, there is also a problem that the adhesion between the substrate and the coating film is generally insufficient.

[0005]

Accordingly, the present invention provides a resin composition having excellent corrosion resistance and durability, and particularly excellent heat cycle resistance, even under high temperature conditions in the air (or in an oxidizing atmosphere). And a molded product.

[0006]

Means for Solving the Problems The present inventor has conducted researches in consideration of the above-mentioned state of the art, and as a result, a resin composition containing polycarbosilane 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 article, and a method for producing the same.

[0008] 1. A resin composition obtained by subjecting a mixture containing polycarbosilane and an epoxy compound to at least one kind of heat treatment and light irradiation treatment.

[0009] 2. A mixture containing polycarbosilane and an epoxy compound is obtained by irradiating light and / or heating in an inert gas atmosphere, contains a polycarbosilane-derived Si-C bond, and contains a polycarbosilane component and an epoxy compound. Item 2. The resin composition according to the above item 1, wherein the parts modified with the components are bonded via a Si-C bond and / or a Si-O bond.

[0010] 3. A mixture containing polycarbosilane and an epoxy compound is obtained by irradiating light and / or heating in an oxygen-containing gas atmosphere, contains a Si-C bond derived from polycarbosilane, and contains a polycarbosilane component and an epoxy compound. The parts where the components have been modified are Si-C
Item 2. The resin composition according to item 1, wherein the resin composition is bonded via a bond and / or a Si—O bond and / or a Si—OC bond into which oxygen in the atmosphere is inserted.

4. Item 4. The resin composition according to any one of Items 1, 2 and 3, wherein the polycarbosilane is a carbosilane having a Si—H bond in a side chain.

5. A method for producing a resin composition, comprising mixing an epoxy compound and polycarbosilane, and subjecting the resulting mixture to at least one kind of heat treatment and light irradiation treatment.

6. Item 5. A molded article of a resin composition comprising the polycarbosilane according to any one of Items 1 to 4 and an epoxy compound.

7. Item 6 wherein the form of the molded article is a coating film.
The molded article according to the above.

[8] A product or article wherein a mixture containing polycarbosilane and an epoxy compound is applied to a substrate surface, and then at least one of heat treatment and light irradiation treatment is performed to cure the coating film. Manufacturing method.

9. Item 9. A product or article having a cured coating film obtained by the method according to Item 8.

10. Item 10. The product or article according to Item 9, wherein the cured coating film is a heat-resistant, corrosion-resistant, and flame-retardant surface protective film.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As used herein, "alkyl group", "alkenyl group", "aryl group", "alkylene 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.

"Aryl group" refers to an aromatic hydrocarbon group having at least one substituent or no substituent.

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

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

The polycarbosilane 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—C bond.
Carbopolysilane has Si-O bond, Si-N bond, Si
It may contain at least one of an -OM bond (M = Ti, Zr) and a Si-B bond.

As such a polycarbosilane, for example, a linear, branched or cyclic compound having a repeating unit represented by the following general formula (1) can be exemplified.

[0026]

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Wherein R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, a hydroxyl group, a phenolic hydroxyl group, an amino group or a silyl group, and R ² is an alkyl group, an alkenyl group. Group, arylalkyl group, aryl group, alkoxy group, hydroxyl group, phenolic hydroxyl group, amino group or silyl group, x
Is an alkylene group, n is 1 to 10000, and R ¹ , R ² and x may be the same or different in all the repeating units. As the polycarbosilane compound, a compound having a reactive group such as Si-H in a side chain is preferable.

The polycarbosilane used in the present invention may be a polycarbosilane having a heat transition (functional material, 14, 1981 (1981)) of the corresponding polysilane.
It can be prepared by a ring-opening polymerization method (J. Org. Chem., 30, 2618 (1965)), a dechlorination method (J. Org. Chem., 29, 1601 (1964)), or the like. Examples of the polysilane used for the heat transfer include a linear polysilane and a cyclic polysilane represented by the following general formula (1-A).

(R ₂ Si) m (1-A) (wherein R is the same or different and is a hydrogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, a hydroxyl group, a phenyl group Or an amino group, and at least one of R is an alkyl group, an alkenyl group, an arylalkyl group, an aryl group or a phenyl group, m is 2 to 1000.) In the production of the resin composition according to the present invention, The epoxy compound to be used is not particularly limited as long as it is a linear, cyclic or branched compound having at least one epoxy group in the chemical structure. 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.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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

The heat treatment temperature of the mixture in the production of the resin composition of the present invention is usually about 40 to 450 ° C., preferably about 100 to 400 ° C., and more preferably about 150 to 4 ° C.
The temperature is about 00 ° C, particularly preferably about 220 to 400 ° 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 up to the above temperature is not particularly limited, but is preferably about 0.1 to 10 ° C / min. The heating is 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.

Light irradiation can be performed instead of, together with, or before or after the heat treatment. Light sources for light irradiation of the mixture include fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, hydrogen lamps, deuterium lamps, halogen lamps, helium-neon lasers, argon lasers, nitrogen lasers, helium-cadmium lasers, dye lasers, and the like. Used. The light irradiation wavelength is usually about 220 to 700 nm, more preferably about 220 to 400 nm. Light irradiation time is usually
It is about 5 seconds to 120 minutes, 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 may be performed at a temperature of less than 100 ° C. to distill off volatile components or partially advance the curing reaction.

By subjecting the mixture of the polycarbosilane compound and the epoxy compound to a heat treatment and / or a light irradiation treatment, at least one silicon of the polycarbosilane is reacted in an inert gas atmosphere as shown in the following reaction formula. Forming a bond between at least one carbon of the epoxy group modified by ring opening of the epoxy compound (Si-C bond) and / or a bond between at least one oxygen (Si-O bond) .

[0040]

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When the mixture is subjected to a heat treatment and / or a light irradiation treatment in an oxygen-containing gas atmosphere under the above-defined temperature conditions, the above-described silicon-carbon and In addition to the silicon-oxygen bond, the polycarbosilane component is bonded to the modified epoxy compound component via a Si-O bond that incorporates oxygen in the atmosphere.
(Si-OC bond) in some cases.

[0042]

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In the present invention, a curing accelerator for the mixture may be added. As the curing accelerator to be added,
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, tert-butyl peroxide, azoiso Compounds which generate radicals such as butyronitrile; organic aluminum compounds such as trismethoxyaluminum and trisphenoxyaluminum; triethylamine, pyridine, diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, tris (dimethylaminomethyl) phenol,
Amine compounds such as 2-ethyl-4-methylimidazole;
Amide compounds such as dimer acid polyamide; acid anhydrides such as phthalic anhydride, tetrahydromethyl phthalic anhydride, 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; halides such as chloroform, dichloromethane, and trichloromethane; and basic compounds such as sodium ethoxide.

The amount of the curing accelerator is 100 parts of polycarbosilane.
Parts by weight, usually about 0.01 to 50 parts by weight, preferably
It is about 0.1 to 20 parts by weight.

When performing the light irradiation treatment, a photoacid generator can be blended with the mixture. 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-100
L ”or the like, commercially available from Sanshin Chemical Industry Co., Ltd.), ferrocene-based (for example,“ Irgacure 26 ”).
1 ", commercially available from Ciba Specialty Chemicals, Inc., triazines (e.g.,
Commercially available from Nihon SiberHegner under the trade names such as “Triazine A” and “Triazine A”, iodonium salts (eg, “BBI-101” and “BBI-101” under the trade names Midori Chemical ( (Commercially available from Co., Ltd.)
Etc. can be used. 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-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 the inorganic filler include silica sand, quartz,
Silicas such as novacurite and diatomaceous earth; silicas such as synthetic amorphous silica; silicates such as kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate; glass powder, glass spheres , Hollow glass spheres, glass flakes, foamed glass spheres, and other glass bodies; non-oxide inorganic substances such as boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride, and titanium carbide Calcium oxide; metal oxides such as zinc oxide, alumina, magnesia, zirconia, titanium oxide, beryllium oxide; other inorganic substances such as barium sulfate, molybdenum disulfide, tungsten disulfide, and carbon fluoride; aluminum, bronze, lead, Metal powders such as stainless steel and zinc; carbon Rack, coke, graphite, pyrolytic carbon, and the like carbon material such as a hollow carbon spheres.

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

Further, the resin composition of the present invention may contain, if necessary, a flame retardant auxiliary such as antimony trioxide; natural waxes, synthetic waxes, linear fatty acids and metal salts thereof, acid amides, esters. Release agents such as alcohols and paraffins; pigments such as carbon black and titanium dioxide; esters;
Plasticizers such as polyols, polysulfides and urethane prepolymers; liquid rubbers such as carboxyl-terminated butadiene-acrylonitrile copolymer rubbers and ethylene-vinyl acetate copolymers; surface modifiers such as silane coupling agents and titanium coupling agents Low-stress agents such as silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, and ABS resin and MBS resin powders can be appropriately added.

Further, the resin composition of the present invention may contain a flow regulator, a leveling agent, an antifoaming agent, an antistatic agent, an ultraviolet absorber, a dispersant, and the like, if necessary.

When additives such as the above-mentioned curing accelerators, photoacid generators, photosensitizers and fillers are used, polycarbosilane and / or epoxy compounds before mixing or heat treatment and / or What is necessary is just to add to the mixture of both before irradiation treatment.

The molded article made of the resin composition of the present invention can 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 polycarbosilane and an epoxy compound is applied to a substrate surface by a known method such as a spray coating method, a bar coating method, a flow coating method, a dipping method, a casting method, or the like. Or compression molding, casting molding, transfer molding, porous substrate
(Ceramic fiber, glass fiber, carbon fiber, etc.), and then heat treatment and / or light irradiation treatment can obtain a desired molded product.

The application of the mixture to the surface of the substrate can be carried out in the form of an organic solvent solution. Such organic solvents are not particularly limited, but include tetrahydrofuran, xylene, toluene, benzene, ethanol, butanol, dimethoxysilane, dimethylacetamide, dimethylformamide, methylcellosolve, butylcellosolve, diethylene glycol monoethyl ether, diethylene glycol mono Examples thereof include butyl ether, dimethyl sulfoxide, and phenols. 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.
Ceramics, glass, plastics, and the like can be used.

[0055]

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.

In addition, an article or product in which a substrate is coated with the resin composition of the present invention is formed with a coating film having excellent physical properties of the resin composition itself. Such articles or products have high heat resistance, heat cycle resistance, acid resistance, alkali resistance, organic solvent resistance, water resistance, moisture resistance, flame retardancy, water repellency, even under various severe environmental conditions. Insulation,
Demonstrates excellent properties such as film formability and coating film adhesion.

The resin composition and the molded article of the present invention can be used as a paint, 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 or a protective film, a liquid crystal alignment. Suitable for heat-resistant applications such as films, sliding members, automotive parts materials, aerospace materials, inks, adhesives, adhesives, etc., corrosion-resistant applications, and flame-retardant applications.

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

[0059]

The following examples are provided to further clarify the features of the present invention.

Example 1 0.2 g of polycarbosilane obtained by thermal rearrangement (at 450 ° C. in an argon atmosphere) of methylphenylpolysilane (average degree of polymerization: 40) synthesized by an electrode reaction as polycarbosilane.
A mixture of 0.8 g of a bisphenol A-type epoxy resin (manufactured by Asahi Ciba Co., Ltd .: Araldite AER260) as an epoxy compound was placed in a stainless steel cylindrical container, and placed under an argon atmosphere.
The temperature was raised from room temperature to 300 ° C. at a rate of 10 ° C./min. After reaching 300 ° C., the mixture was cooled to room temperature to obtain a pellet.

An NMR analysis was performed on the structure of the obtained pellet (hereinafter sometimes referred to as a sample). ^From the result of ²⁹ Si-NMR analysis, a peak was observed at 0 ppm. Also, ¹³ C-NM
From the result of the R analysis, a peak was observed at 0 ppm.

Using the obtained samples, a heat resistance test, an acid resistance test, an alkali resistance test, a heat cycle resistance test and a flammability test were performed.

In the heat resistance test, after the sample was left in an air atmosphere at 600 ° C. in an air atmosphere for 1 hour, the surface state 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 state was visually observed. As a result, no crack was observed and the acid resistance was good.

In the alkali resistance test, the sample was immersed in a 5% NaOH aqueous solution for 2 hours, and the surface state was visually observed. As a result, no crack was observed and the alkali resistance was good.

In the heat cycle resistance test, the cycle of “holding the sample at the set temperature (500 ° C.) for 2 hours and then holding at room temperature for 2 hours” was repeated 10 times, and the sample was subjected to thermal shock. After the test, when the surface state of the sample was visually observed, no crack was observed, and the heat cycle resistance was good.

In the flammability test, the sample was left in a Bunsen burner flame for 1 minute, and the presence or absence of burning of the sample 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 0.5 g of polycarbosilane obtained by thermal rearrangement (at 450 ° C. in an argon atmosphere) of methylphenylpolysilane (average degree of polymerization: 40) as polycarbosilane and bisphenol A type epoxy resin (Asahi Chiba) as an epoxy compound 0.5 g of Araldite AER260) 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).

After the coated stainless steel plate was heated from room temperature to 300 ° C. at a rate of 10 ° C./min under an argon atmosphere, when the temperature reached 300 ° C., the sample was taken out into room temperature and a sample having a cured coating film was removed. Obtained. The thickness of the obtained coating film is 20 μm
Met.

The obtained sample 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 were performed.

In the heat resistance test, the sample was allowed to stand in an air atmosphere at 600 ° C. in an air atmosphere for 1 hour, and then the surface state of the coating film was visually observed and observed with an electron microscope (SEM).
No cracks, voids, peeling, etc. were observed, and the heat resistance was good.

In the acid resistance test, after the sample was immersed in a 5% nitric acid aqueous solution for 2 hours, the surface state of the coating film was visually observed. As a result, no cracks, voids or peeling were observed.
The acid resistance was good.

In the alkali resistance test, after immersing the sample in a 5% NaOH aqueous solution for 2 hours, the surface state of the coating film was visually observed. As a result, no cracks, voids or peeling were observed, and the alkali resistance was good. Was.

In the heat cycle resistance test, a cycle of “holding the sample for 2 hours with the coating film temperature reaching the set temperature (500 ° C.) and then holding the sample at room temperature for 2 hours” is repeated 10 times. The coating film was subjected to a thermal shock. After the test was completed, the surface condition of the sample was visually observed.
No occurrence of voids or peeling was observed, and the heat cycle resistance was good.

In the flammability test, the coating film portion of the sample was left in a Bunsen burner flame for 1 minute, and the presence or absence of combustion 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 3 0.8 g of polycarbosilane obtained by thermal rearrangement (at 450 ° C. in an argon atmosphere) of methylphenylpolysilane (average degree of polymerization: 40) was used as the polycarbosilane, and bisphenol A type epoxy resin was used as the epoxy resin. (Asahi Ciba Co., Ltd.)
(Araldite AER260) Except for using 0.2 g, a sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 and then subjected to a heat resistance test, an acid resistance test, an alkali resistance test, and a heat resistance test. A cycle test was performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 4 As polycarbosilane, 0.2 g of polycarbosilane obtained by thermal rearrangement of methylphenyl polysilane (average degree of polymerization: 40) (at 450 ° C. in an argon atmosphere) was used, and bisphenol A type epoxy resin was used as an epoxy compound. (Asahi Ciba Co., Ltd.)
(Araldite AER260) was prepared in the same manner as in Example 2 except that 0.8 g of a hardened coating film was formed on stainless steel. Then, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat resistance test were performed. A cycle test was performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 5 The heat treatment temperature of the mixture coating film formed on the stainless steel plate was
A sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 except that the temperature was set to 250 ° C.
An acid resistance test, an alkali resistance test and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 6 As an epoxy resin, bisphenol A type epoxy resin 0.5
g in place of novolak epoxy resin (manufactured by Asahi Ciba Co .; E
Polycarbosilane using 0.2 g of PN1180) and obtained by thermal rearrangement (450 ° C under argon atmosphere) of methylphenyl polysilane (average degree of polymerization 40) as polycarbosilane
A heat resistant test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed after obtaining a sample having a cured coating film formed on stainless steel in the same manner as in Example 2 except that 0.8 g was used. Was.

After completion of each test, the surface condition of the coating film was visually observed. In each case, 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 7 0.5 g of polycarbosilane obtained by thermal rearrangement (at 450 ° C. in an argon atmosphere) of methylphenylpolysilane (average degree of polymerization: 40) as polycarbosilane, and a novolak-type epoxy resin (Asahi Chiba (Asahi Chiba)) as an epoxy compound Co., Ltd .; EPN1180)
After obtaining a sample in which a cured coating film was formed on stainless steel in the same manner as in Example 2 except that 0.5 g was used, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed. went.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 8 0.2 g of polycarbosilane obtained by thermal rearrangement (at 450 ° C. in an argon atmosphere) of methylphenylpolysilane (average degree of polymerization: 40) as polycarbosilane, and a novolak-type epoxy resin (Asahi Ciba Co., Ltd .; EPN1180)
After obtaining a sample in which a cured coating film was formed on stainless steel in the same manner as in Example 2 except that 0.8 g was used, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed. went.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 A stainless steel was prepared in the same manner as in Example 2 except that polycarbosilane obtained by thermal rearrangement of methylphenyl polysilane (average degree of polymerization: 200) (at 450 ° C. in an argon atmosphere) was used as the polycarbosilane. After obtaining a sample in which a cured coating film was formed on steel, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 10 A stainless steel was obtained in the same manner as in Example 2 except that polycarbosilane obtained by thermal rearrangement of methylphenyl polysilane (average degree of polymerization: 5) (at 450 ° C. in an argon atmosphere) was used as the polycarbosilane. After obtaining a sample in which a cured coating film was formed on steel, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 11 As polycarbosilane, cyclic methylphenylpolysilane (average degree of polymerization: 6) was subjected to thermal rearrangement (450 under argon atmosphere).
C)), a sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 except that the polycarbosilane obtained by the above method was used. A heat cycle test was performed.

After the completion of each test, the surface condition of the coating film was visually observed. In each case, 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 12 As polycarbosilane, methyl-n-hexylpolysilane (average degree of polymerization: 40) was subjected to thermal rearrangement (450 under an argon atmosphere).
C), a sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 except that the polycarbosilane obtained in Example 1 was used, and then a heat resistance test, an acid resistance test, an alkali resistance test and a resistance test were performed. A heat cycle test was performed.

After the completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 13 A stainless steel was prepared in the same manner as in Example 2 except that polycarbosilane (average degree of polymerization: 40) obtained by thermal rearrangement of dimethylpolysilane (at 450 ° C. in an argon atmosphere) was used as polycarbosilane. After obtaining a sample in which a cured coating film was formed on steel, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 14 As polycarbosilane, a copolymer of methylphenylsilane and dimethylsilane (average degree of polymerization: 40, polymerization ratio: 1/1)
In the same manner as in Example 2 except that polycarbosilane obtained by thermal rearrangement (450 ° C. in an argon atmosphere) was used,
After obtaining a sample in which a cured coating film was formed on stainless steel, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 15 As polycarbosilane, thermal rearrangement of methyl network polysilane (average degree of polymerization: 40) (450 ° C. in an argon atmosphere)
C)), a sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 except that the polycarbosilane obtained by the above method was used. A heat cycle test was performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, 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 16 As a polycarbosilane, a mixture of methylphenyl polysilane (average degree of polymerization 40) and methyl network polysilane (average degree of polymerization 40) (weight ratio 1/1) was subjected to thermal rearrangement (450 ° C. in an argon atmosphere). )), A sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 except that the polycarbosilane obtained in (2) was used, and then a heat resistance test, an acid resistance test, an alkali resistance test, and a heat resistance test were performed. A cycle test was performed.

After the completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 17 A sample having a cured coating film formed on stainless steel was obtained in the same manner as in Example 2 except that a cresol novolak type epoxy resin (ECN1299, manufactured by Asahi Ciba Co., Ltd.) was used as the epoxy compound. After that, a heat resistance test, an acid resistance test, an alkali resistance test and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 18 A cured coating film was formed on stainless steel in the same manner as in Example 2, except that 0.5 g of an epoxy-modified silicone resin (XF42-B2249, manufactured by Toshiba Silicone Co., Ltd.) was used as the epoxy compound. After obtaining the sample, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, and good results were obtained.

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 of the present invention was a flame-retardant material.

Example 19 Pellets were obtained in the same manner as in Example 1 except that the mixture of polycarbosilane and bisphenol A type epoxy resin was subjected to heat treatment, except that the atmosphere was air. , IR analysis and NMR analysis were performed.

As a result of IR analysis, a large absorption at 1100 cm ^-1 attributed to Si-O was observed after the heat treatment.

From the result of ²⁹ Si-NMR analysis, 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.

The obtained pellets were prepared in Example 1
A heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed in the same manner as described above.

After the completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 20 After a mixture of polycarbosilane and bisphenol A type epoxy resin was applied to a stainless steel plate, the coating film formed was subjected to a heat treatment, except that the atmosphere was air. After similarly obtaining a sample, the structure of the cured coating film was subjected to IR analysis and NMR analysis.

As a result of IR analysis, a large absorption at 1100 cm ^-1 attributed to Si-O was observed in the cured coating film.

From the result of ²⁹ Si-NMR analysis, 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 in the same manner as in Example 1.

After completion of each test, the surface condition of the coating film was visually observed. In each case, 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.

Examples 21 to 32 Samples having a cured coating film on a stainless steel plate were obtained in the same manner as in Example 2 except that the atmosphere during heating the mixture in Examples 7 to 18 was air. A heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test were performed.

After completion of each test, the surface condition of the coating film was visually observed. In each case, cracks, voids,
No occurrence of peeling or the like was observed, 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 33 As polycarbosilane, a thermal rearrangement (450 g under an argon atmosphere) of a copolymer of methylphenyl polysilane and methyl network polysilane (average degree of polymerization: 40, polymerization ratio: 1/1)
° C) using the obtained polycarbosilane,
Example 2 except that the atmosphere during heating of the mixture was air.
After obtaining a sample having a cured coating on a stainless steel plate in the same manner as in Example 2, a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test of the cured coating were performed in the same manner as in Example 2. Was.

After the test was completed, the surface condition of the coating film was visually observed. In each case, no cracks, voids, peeling, etc. were observed, 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 34 As a polycarbosilane, 0.5 g of polycarbosilane obtained by thermal rearrangement (at 450 ° C. in an argon atmosphere) of methylphenyl polysilane (average degree of polymerization: 40) and a bisphenol A type epoxy resin (Asahi Chiba) as an epoxy compound (Araldite AER260) 0.5 g of a mixture of benzoyl peroxide, and a stainless steel sheet in the same manner as in Example 2 except that the heating temperature of the steel sheet coated with the mixture was 200 ° C. After obtaining a sample having a cured coating film thereon, the cured coating film was subjected to a heat resistance test, an acid resistance test, an alkali resistance test, and a heat cycle resistance test in the same manner as in Example 2.

After completion of the test, the surface condition of the coating film was visually observed. In each case, no cracks, voids, peeling, etc. were observed, and good results were obtained.

Also, 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 35 As a polycarbosilane, 0.5 g of polycarbosilane obtained by thermal transition (450 ° C. in an argon atmosphere) of methylphenyl polysilane (average degree of polymerization: 40) and a bisphenol A type epoxy resin (Asahi Chiba) as an epoxy compound 0.5 g of N-ethoxy-2-methylpyridinium-hexafluorophosphate (0.035 g of Araldite AER260, manufactured by K.K.) was dissolved and mixed in 10 ml of tetrahydrofuran at room temperature.

Next, the obtained mixture was applied to a steel plate (SUS-304).
And then irradiating it with a high-pressure mercury lamp of 100 W at 50 ° C. for 5 minutes in an argon atmosphere to obtain a sample having a cured coating on a stainless steel plate. Were subjected to a heat resistance test, an acid resistance test, an alkali resistance test and a heat cycle resistance test.

After completion of the test, the surface state of the coating film was visually observed. In each case, no cracks, voids, peeling, etc. were observed, 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 36 A sample having a cured coating on a stainless steel plate was obtained in the same manner as in Example 35 except that the atmosphere during light irradiation was air. Heat resistance test of membrane,
An acid resistance test, an alkali resistance test and a heat cycle resistance test were performed.

After completion of the test, the surface condition of the coating film was visually observed. In each case, no cracks, voids, peeling, etc. were observed, 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.

Comparative Example 1 Only 0.2 g of a bisphenol A type epoxy resin (manufactured by Asahi Ciba Co., Ltd .; Araldite AER260) was dissolved in 5 ml of tetrahydrofuran at room temperature, and sandpaper (# 50) was previously prepared.
This solution was flow coated on a stainless steel plate (SUS-304) polished according to 0).

Next, the coated stainless steel plate was heated from room temperature to 300 ° C. at a rate of 10 ° C./min.
When the temperature reached ° C, the film was taken out into room temperature, and no coating film was formed.

Comparative Example 2 Thermal transition of dimethylpolysilane (450 under argon atmosphere)
C)), only 1.0 g of the polycarbosilane obtained in the above method is dissolved in 5 ml of tetrahydrofuran at room temperature, and then this solution is flow-coated on a stainless steel plate (SUS-304) that has been polished in advance with sandpaper (# 500). did.

Next, the temperature of the coated stainless steel plate was increased from room temperature to 300 ° C. at a rate of 10 ° C./min.
When the temperature reached ° C, the film was taken out into room temperature. As a result, cracks were generated in the coating film, and peeling was observed in a part of the coating film.

Comparative Example 3 0.5 g of bisphenol A epoxy resin (manufactured by Asahi Ciba Co., Ltd .; Araldite AER260) and 0.14 g of diethylenetriamine were dissolved in 5 ml of tetrahydrofuran at room temperature.
This solution was flow coated on a stainless steel plate (SUS-304) that had been polished with sandpaper (# 500) in advance.

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

After leaving the obtained sample in an electric furnace at 450 ° C. for 1 hour in an air atmosphere, the surface state of the coating film was observed visually and by SEM. Further, a part of the coating film was peeled off from the stainless steel plate.

 ──────────────────────────────────────────────────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 (10)

[Claims] 1. A resin composition obtained by subjecting a mixture containing polycarbosilane and an epoxy compound to at least one kind of heat treatment and light irradiation treatment. 2. A mixture containing a polycarbosilane and an epoxy compound, which is obtained by irradiating light and / or heating in an inert gas atmosphere to contain a polycarbosilane-derived Si--C bond, and The resin composition according to claim 1, wherein the modified portions of the silane component and the epoxy compound component are bonded via a Si-C bond and / or a Si-O bond. 3. A method comprising irradiating a mixture containing polycarbosilane and an epoxy compound with light in an oxygen-containing gas atmosphere and / or
Or a portion obtained by heating and containing a Si-C bond derived from polycarbosilane, and in which the polycarbosilane component and the epoxy compound component are respectively modified, the Si-C bond and / or the Si-O bond and / or 2. The resin composition according to claim 1, wherein oxygen in the atmosphere is bonded via an inserted Si-OC bond. 4. The resin composition according to claim 1, wherein the polycarbosilane is a carbosilane having a Si—H bond in a side chain. 5. A method for producing a resin composition, comprising mixing an epoxy compound and polycarbosilane, and subjecting the resulting mixture to at least one kind of heat treatment and light irradiation treatment. 6. A molded article of a resin composition comprising the polycarbosilane according to claim 1 and an epoxy compound. 7. The molded article according to claim 6, wherein the form of the molded article is a coating film. 8. A method comprising applying a mixture containing polycarbosilane and an epoxy compound to the surface of a substrate, and performing at least one kind of heat treatment and light irradiation treatment.
A method for producing a product or article, comprising curing a coating film. 9. A product or article having a cured coating film obtained by the method according to claim 8. 10. The product or article according to claim 9, wherein the cured coating film is a heat-resistant, corrosion-resistant and flame-retardant surface protective film.