JPH01215818A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant resin composition excellent in adhesion, especially, adhesion to an iron material, by adding a specified diepoxysilicone compound to a polyamide-imide resin. CONSTITUTION:A polyamide-imide resin (A) is mixed with a diepoxysilicone compound (B) of formula I (wherein R1 and R2 are each a bivalent hydrocarbon group, R3 and R4 are each a monovalent hydrocarbon group, and n is an integer >=1), e.g., a compound of formula II, and an organic liquid (C) (e.g., N- methylpyrrolidone) in a B to (A+B) ratio of 0.001-0.3wt. A polyamide-imide resin is disadvantageous in that it is poor in adhesion to an iron material not primed with a primer, though it is excellent in adhesion to an aluminum material without priming. By using the resin composition, a polyamide-imide resin can be adhered to also an iron material without priming.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a heat-resistant resin composition.

(Prior Art) Conventionally, polyimide resins with excellent heat resistance, such as polyamide-imide resin, polyimide resin, and polyamino bismaleimide resin, have been used as heat-resistant paints and heat-resistant adhesives for various metal substrates. Among them, polyamide-imide resin has an excellent balance of heat resistance, adhesion to substrates, solvent solubility, and price, and is highly evaluated as a heat-resistant material.

(Problems to be Solved by the Invention) However, when the base material is aluminum, polyamide-imide resin exhibits excellent adhesion to aluminum even without surface treatment with an undercoat.

When the base material is iron, there is a problem in that adhesion is poor unless surface treatment is performed with an undercoat paint. especially.

Without surface treatment, there is a problem in that the adhesion between the polyamide-imide resin and the metal base material is significantly poor in applications that require baking at high temperatures and for long periods of time, or applications that are used in hot water for long periods of time. but.

Surface treatment using an undercoat paint is not preferred because it requires a complicated work process and increases the number of prints, resulting in a significant cost disadvantage. Further, since iron base materials have a major advantage in use that they are cheaper than aluminum base materials, there is a strong desire to develop polyamide-imide resins that do not require surface treatment.

In the present invention, a specific gepoxy silicone compound was added to the polyamideimide resin. In particular, the present invention provides a heat-resistant resin composition that has excellent adhesion to iron base materials.

(Means for Solving the Problems) The present invention provides a heat-resistant resin composition containing a polyamideimide resin (A) and a jepoxy silicone compound (Bl and organic amount ratio) of the following general formula (1). Regarding.

(In the formula, FLI and FL2 are divalent hydrocarbon groups.

Rs and R4 are monovalent hydrocarbon groups, and R1 and R1゜R3 and R4 may be the same or different, respectively.
(n is O or an integer of 1 or more) as the polyamide-imide resin in the present invention.

Although there are no particular limitations, those obtained from trimellitic acid or a reactive derivative of trimellitic acid and diamines or diisocyanates are preferably used.

Examples of reactive derivatives of trimellitic acid include 1.

Trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-N,N-dimethylcarbamoylbenzene, 1,4-dicarboxy-3-carbophenoxybenzene, 1,4-dicarboxylic anhydride Ammonium salts consisting of methoxy-3-carboxybenzene, trimellitic acid and ammonia, dimethylamine, triethylamine, etc. are used. Particularly preferred are trimellitic anhydride and trimellitic anhydride monochloride.

Examples of diamines include aliphatic and alicyclic diamines.

Diamines of heterocyclic type, aromatic type, silicon type, etc. can be used. Among them, 4.4'-diaminodiphenyl nityl, 3.4'-') aminodiphenyl ether, 4.4'-diaminodiphenylmethane, 4.4'-
Methylene-bis-(2,6-dimethylaniline), 4°4'-methylene-bis-(slo-diethylaniline).

4.4'-methy1/un-bis(2-methyl-6-nitylaniline), 4.4'-diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, 4.4'-
Benzophenone diamine, 3.3'-benzophenone diamine, metaphenylene diamine, paraphenylene diamine, 44'-di(4-aminophenoxy) phenyl sulfone, 4.4'-di (3-aminophenoxy) phenyl sulfone, 4.4 '-di(4-aminophenoxy)benzene, formula 3'-di(4-aminophenoxy)benzene, 44'-di(3-aminophenoxy)benzene, 2+
4-diaminotoluene, 2゜6-diaminotoluene, 4
．． 4'-diaminodiphenylpropane, 4.4'-diaminophenyl, 2I2-bis(4-(4-aminophenoxy)phenyl)propane, 2-bis(4-(3-aminophenoxy)phenyl)propene, 1. 1.1
．． 3.3.3-hexafluoro-2,2-bis[4-(
Aromatic diamines such as 4-aminophenoxy)phenyl]propane.

In the following general formula [I[1 (R5, R4 are divalent hydrocarbon groups, &, FLs are monovalent hydrocarbon groups, !l), R5 and R4, R7 and Toshi are respectively the same or different; Silicon diamine represented by Moyo (m is an integer of 1 or more) is preferably used.

Considering heat resistance and solvent solubility, 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylmethane, and 4.4'-benzophenone diamine.

4.4'-diaminodiphenylsulfone, 2.2-bis(4-(4-aminophenoxy)phenyl)propane,
4.4'-methylene-bis-(2+6-dimethylaniline), 4.4'-methylene-bis-(2,6-dinitylaniline), 4.4'-methylene-bis-(2-methyl-6 Aromatic diamines such as -nitylaniline) are particularly preferred.

In particular, in order to improve the adhesion with the base material, - general formula (I
It is preferable to use 0.01 to 0.3 mol of silicon diamine in combination with 0.99 to 0.7 mol of the above-mentioned aromatic diamine. Too much silicon diamine tends to reduce heat resistance, and too little silicon diamine tends to reduce adhesion.

Moreover, a crosslinkable polyamide-imide resin can be obtained by using a trifunctional or higher-functional polyamine as part of the diamines described above. Examples of such polyamines include aromatic triamines such as 1,2,4-1 liaminobenzene, 1,2,4,5-tetraaminobenzene, 3.
Aromatic tetraamines such as 3'-diaminobenzidine, aromatic polyamines represented by the following general formula (1) (l is an integer of 0 to 10), and the like are used.

As the diisocyanate, for example, a diisocyanate obtained by reacting the above diamine with phosgene or thionyl chloride is used. Also used are polyisocyanates obtained by treating polyamines in the same manner or polyisocyanates containing isocyanurate rings obtained by trimerizing diisocyanates. Considering heat resistance and cost, 4,4'-diphenylmethane diisocyanate, 4゜4'-diphenyl ether diisocyanate, 3
．． 3'-dimethyldiphenyl-4,4'-diisocyanate.

Aromatic diisocyanates such as tolylene diisocyanate, carbodiimide group-containing aromatic diisocyanates obtained by condensation reaction of these aromatic diisocyanates, and incyanurate ring-containing polyisocyanates are preferably used.

Other polyamide-imide resins include tetrabasic acid dianhydrides, dicarboxylic acids, and the diamines described above.

Of course, those obtained by reacting with polyamines, diisocyanates, or polyisocyanates can also be used. As a tetrabasic acid dianhydride.

For example, aliphatic and alicyclic systems in which two carbonyl groups of an acid anhydride group are bonded to adjacent carbon atoms.

Tetracarboxylic dianhydrides such as heterocyclic, aromatic, and silicon-based dianhydrides can be used. Among them, 1,2°3.4-
Butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid.

Bicyclo-[λsu2]-octo-(carene-2:3.
5: 6-tetracarboxylic acid, pyromellitic acid.

3, 3; 4.4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 2
゜3,6.7-naphthalenetetracarboxylic acid, 1,2,
5.6-naphthalenetetracarboxylic acid, ethylene glycol bistrimelitate, 2-bis(3,4-dicarboxyphenyl)propane, 2. a'3.3'-also haa, :54.4'-biphenyltetracarboxylic acid,
Berylene-3.4.9.10-tetracarboxylic acid, bis-3,4-dicarboxyphenylsulfone, 2,2-bis(4-(2,3- or 3,4-dicarboxyphenoxy)phenyl)propane, 1, 1, 1, 3, 3.3
-hexafluoro-2,2-bis[4-(su3- or 3
．． 4-dicarboxyphenoxy)phenyl]propane.

Dianhydrides of tetrabasic acids such as thiophene-2,3,4,5-tetracarboxylic acid and pyrazinetetracarboxylic acid.

The following general formula Oka (horse and R1° represent a -valent hydrocarbon group, R1 and a
tO may be the same or different.

X is an integer of 1 or more), preferably a tetrabasic acid dianhydride in which & and RIO are methyl groups, and used.

-10= Considering heat resistance and cost, pyromellitic dianhydride, 3.3H4,4'-benzophenonetetracarboxylic dianhydride, and 3,1,4'-biphenyltetracarboxylic dianhydride are particularly recommended. preferable.

Examples of dicarboxylic acids include terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as phthalic acid or acid chloride compounds thereof are preferably used.

The above materials may be used alone or in combination of two or more. Of course, polyamide-imide resins other than those mentioned above can also be used in the present invention as long as they can cover or bond the base material evenly and smoothly by baking.

Easy to synthesize as a polyamide-imide resin.

It is obtained by reacting trimellitic anhydride with polyvalent isocyanate and trimellitic anhydride and 4,4'-diphenylmethane diisocyanate in approximately equimolar ratios, which are superior in terms of cost such as versatility of materials. It is preferable to use one that can be used. The polyamideimide resin obtained in this way is usually

The terminal group is an isocyanate group or a carboxyl group, and it has excellent storage stability as a heat-resistant resin composition compared to a terminal amine group-containing polyamideimide resin obtained using a diamine.

Considering film-forming properties, the molecular weight of the polyamide-imide resin in the present invention is 0.3 to 2.0 in terms of reduced viscosity. , Odl! /g
It is preferable to use something of a certain degree.

Such polyamide-imide resins are obtained by using isocyanate groups or amino groups and carboxyl groups or acid anhydride groups, preferably in approximately equivalent proportions.

This reduced viscosity is a value measured at a temperature of 30° C. using dimethylformamide as a solvent and a sample concentration of 0.5 g/dj′.

The jepoxysilicon compound represented by the general formula (1) in the present invention is an alkylene group or phenylene group in which at and R2 have 1 to 5 carbon atoms.

Preferably it is an alkyl-substituted phenylene group.

It is preferable that R3 and R4 are an alkyl group having 1 to 5 carbon atoms, a phenyl group, a diphenyl group, or an alkyl-substituted phenyl group.

for example (n is an integer of 1 to 200).

These can be used alone or in combination of two or more.

What is the ratio of polyamide-imide resin (3) and jepoxy silicon compound used in the present invention?

Ru. If it is less than o, ooi, the blending effect of (B) will be insufficient, and if it exceeds 0.3, the heat resistance will be poor. Especially 0.01~0
．． It is preferable to use the range of 15.

As the organic liquid in the present invention, one that functions as a solvent or dispersion medium for the polyamideimide resin or the jepoxy silicon compound is preferably used. When an organic liquid that functions as a solvent is used, a heat-resistant resin composition in the form of a solution can be obtained.

When an organic liquid that functions as a dispersion medium is used, a heat-resistant resin composition in the form of a dispersion liquid can be obtained. The solubility of the organic liquid changes depending on the type of polyamideimide resin or jepoxy silicon compound, and whether the organic liquid is used as a solvent or a dispersion medium depends on the purpose.
Can be used arbitrarily. Specifically, examples of the organic liquid that normally functions as a solvent for polyamideimide resin include N-methylpyrrolidone and dimethylformamide.

Nitrogen-containing solvents such as dimethylacetamide, vinylpyrrolidone and pyridine, lactones such as γ-butyrolactone and ε-caprolactone, alicyclic ketones such as cyclohexanone and 4-methylcyclohexanone, tetrahydrofuran, dioxane, 1,2-simethoxy Ethers such as ethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, phenol, and cresol.

Phenols such as xylenol, chlorinated aromatic solvents such as m-chlorophenol and p-chlorophenol, dimethyl sulfoxide, sulfolane, and the like are preferably used.

Examples of organic liquids that normally function as a dispersion medium for polyamideimide resins include n-hexane.

Octane, Dodecane, l5OPAR-E, l80PAR
Aliphatic or alicyclic hydrocarbons such as -H, l5OPAR-K (trade name manufactured by Esso Standard Oil Co., Ltd.; petroleum-based saturated aliphatic or alicyclic hydrocarbons with a boiling point range of about 40 to 300°C) , benzene, toluene.

Xylene, Nl8SEKI'HISOL-100°N
Aromatic hydrocarbons such as 15SEKI HISOL-150 (trade name manufactured by Nippon Petrochemical Co., Ltd.; a petroleum-based aromatic hydrocarbon with a boiling point range of about 80 to 300°C).

Ketones such as acetone and methyl ethyl ketone, esters such as acetic acid ethyl ester, and methanol.

Alcohols such as ethanol, butanol, and octyl alcohol, water, and the like are preferably used.

These organic liquids may be used alone or in combination of two or more.

Examples of the organic liquid that functions as a solvent for the jepoxysilicon compound include the above-mentioned nitrogen-containing solvents, lactones, and aliphatic or alicyclic ketones.

Ethers, phenols, alcohols, esters, aliphatic, alicyclic or aromatic hydrocarbons, sulfolane, dimethyl sulfoxide and the like are preferably used.

For example, water is preferably used as the organic liquid that functions as a dispersion medium for the jepoxy silicon compound. It is preferable to use the organic liquid in an amount of usually 20% by weight or more based on the total amount of the polyamideimide resin and the jepoxy silicone compound. If it is less than 20% by weight, the coating properties of the composition will be impaired.

The method for preparing the heat-resistant resin composition in the present invention includes:
Any method may be used depending on the purpose.

There are no particular restrictions. Considering the cost, it is possible to synthesize a polyamide-imide resin solution or a polyamide-imide resin dispersion in an organic liquid and add a jepoxy silicon compound to this solution or dispersion, or to add polyamide to the above-mentioned organic liquid that functions as a solvent. It is preferable to use a method in which a solution containing an imide resin and a jepoxy silicon compound is dispersed in the above-mentioned organic liquid (for example, water) that functions as a dispersion medium. A method for producing a polyamide-imide resin solution in an organic liquid is described in 2, for example, in Japanese Patent Publication No. 19274-1974.
Publication No. 2% Publication No. 49-4077.

JP-A-58-154728 and JP-A-58-4
It is disclosed in the No. 066 publication. Also.

Methods for producing polyamide-imide resin dispersions in organic liquids are disclosed in, for example, Japanese Patent Publication No. 48531/1982 and Japanese Patent Application Laid-open No. 51722/1982. The above-mentioned organic liquid that functions as a solvent for the polyamide-imide resin or the jepoxy silicon compound can be used in combination with the polyamide-imide resin dispersion as a film-forming aid, if necessary.

A heat-resistant resin composition using N-methylpyrrolidone as the organic liquid is preferably used.

In the heat-resistant resin composition of the present invention, the following substances may be used, if necessary, preferably in an amount of 0.1 to 200% by weight based on the polyamide-imide resin in the heat-resistant resin composition. One or more of these substances may be used. Specifically, for example, triethylamine 9, triethylenediamine, N.

Amines such as N-dimethylbenzylamine, N-trimethylmorpholine, dimethylaminoethanol, 2-methylimidazole, 1-cyanethyl-2-methylimidazole, quaternary such as benzyldimethyltetradecylammonium chloride, cetyltrimethylammonium chloride, etc. Catalysts such as ammonium salts that promote the reaction between polyamide-imide resins and jepoxy silicon compounds;
Metals, metal oxides, metal nitrides, metal carbides, metal silicides.

Boron, boron oxide, silicon nitride, silicon.

Other than inorganic fine particles such as silicon oxide, silicon nitride, and silicon carbide, silane coupling agents such as γ-aminopropyltriethoxysilane and glycidoxypropyltrimethoxysilane, melamine resin, phenol resin, and jepoxy silicone compounds Modifying materials such as epoxy resins and fluororesins, red iron.

Titanium dioxide, carbon black, barium sulfate.

Organic materials such as mica, Merck, yellow lead, and cyanine blue.

Inorganic or extender pigments, dispersants such as surfactants, leveling agents, antisettling agents, ultraviolet absorbers, and the like are used. In particular, non-adhesion and abrasion resistance can be imparted by using a fluororesin powder or aqueous dispersion having an average particle size of 0.1 to 10 μm. Examples of the fluororesin include polytetrafluoroethylene, a copolymer of tetrafluoroethylene and a fluorine-containing monoethylenically unsaturated monomer other than tetrafluoroethylene, and the like.

The heat-resistant resin composition of the present invention is preferably used as a coating material adhesive for various base materials. As the base material, for example, pure iron, steel, iron alloy, aluminum, copper, plated or surface-treated products of these metals, ceramics, glass, etc. are preferably used.

In particular, inexpensive irons are preferably used.

(Effects of the Invention) The heat-resistant resin composition of the present invention is excellent in both heat resistance and adhesion, and exhibits excellent adhesion to iron substrates at 1%, and is suitable for use as a heat-resistant overcoat. adhesive, heat-resistant adhesive,
It can be widely applied to heat-resistant paints, etc.

(Example) The two-pronged EiA will be explained below using a comparative example and an example.

Example 1 (1) Preparation components of polyamideimide resin solution
Durham malt trimellitic anhydride
347.5 1.81N-methylpyrrolidone 1
485.7 - the above ingredients with a thermometer, stirrer,!
Cord introduction tube.

The mixture was placed in a four-bottle flask equipped with a moisture meter, and reacted at 100°C for 1 hour, 115°C for 2 hours, and 120°C for 2 hours while stirring in a nitrogen stream, and then the reaction was continued by raising the temperature to 135°C. (Resin content is 35% by weight). It was diluted by adding 381 g of xylene. The resin content (calculated value) of the obtained polyamide-imide resin solution was 30% by weight, and the reduced viscosity of the polyamide-imide resin (0.59/dl
! , dimethylformamide, 30℃, the same applies hereafter) is 0
．． It was 42 (ar/g).

(2) Preparation of heat-resistant resin composition Add 1.5 g of a jepoxy silicone compound represented by the formula below to the polyamide-imide resin solution (resin content: 30% by weight) 1009 obtained in (1) and stir thoroughly. A liquid heat-resistant resin composition was obtained by mixing.

CH, CH3 I Example 2 Example 1. (Polyamideimide resin solution obtained in step 11 (resin content: 30% by weight) xoog was added to Example 1, [21
2.19 of the jepoxy silicone compound described in 2.19 and 0.69 of Ebicor) 828 (manufactured by Shell Chemical Co., bisphenol type epoxy resin) were added and thoroughly stirred and mixed to obtain a liquid heat-resistant resin composition.

Example 3 (1) Preparation of powdered polyamide-imide resin Trimellitic anhydride 192.0 1.00 The above ingredients were mixed using a thermometer, a stirrer, and a nitrogen introduction tube.

The mixture was poured into a fourth flask equipped with a moisture meter while stirring, and the temperature was raised to 160° C. while passing nitrogen gas. While gradually raising the temperature and removing distilled water from the system,
℃, and the reaction was carried out in a temperature range of 205 to 210℃. The end point of the reaction is controlled by Gardner viscosity, and the reduced viscosity is 0.
43 (dl/9) of polyamideimide resin was obtained. The obtained polyamide-imide resin solution was diluted with N-methylpyrrolidone to a concentration of about 25% by weight, and this solution was poured into water that had been strongly stirred with a mixer, and the solid polyamide-imide resin was collected by filtering it. did. After thoroughly washing this with hot water, it was boiled and washed with a large amount of water. After taking the product in a furnace, it was dried in a hot air dryer at 150° C. for 6 hours to obtain a powdered polyamide-imide resin.

(2) Preparation of heat-resistant resin composition 100G of the powdered polyamide-imide resin obtained in (1).

Example 1. Jepoxy silicon compound 4 used in (1)
g, diethylene glycol dimethyl ether 2169,
A liquid heat-resistant resin composition was obtained by mixing and dissolving 200 g of dioxane.

Comparative Examples 1-3 Example 1. The polyamide-imide resin solution obtained in (1) (resin content: 30% by weight) and TGIC (trade name, heterocyclic epoxy resin manufactured by Ciba Geigi) or T
ETFLAD-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd., polyfunctional epoxy resin containing 7 tertiary amide groups) was mixed and dissolved in the formulation shown in Table 1 to obtain a liquid resin composition.

Adhesion was evaluated for the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3. The results are shown in Table 2.

The test pieces were prepared by the method shown below. Iron substrate (carbon steel material G4051-8IOC for machine structures.

JIS K 6850 polished product, thickness 1.6 inn
) A resin composition was applied onto the surface to a dry film thickness of about 10 μm.

80°C - 1 hour, 150°C - 0.5 hours, 250°C
It was dried and baked in -0.5 hours. This coated iron substrate is
Test pieces were prepared by heat treating at 808C for 4 hours and at 380°C for 4 hours, which were then further treated in hot water for 100 hours.

Adhesion was measured using a cross-cut test method according to JISD0202. Reaching iron substrates with a single-edged razor III
100 squares (IOXIO) of [II] were prepared and evaluated based on the number of squares remaining that could not be completely peeled off after a peel test using cello adhesive tape.

As is clear from the results in Table 2 and above, the resin composition of the present invention has superior adhesion compared to the comparative compositions using other polyepoxy compounds, and is extremely useful industrially.

Procedural amendment (voluntary)

Claims (1)

[Scope of Claims] 1. Polyamideimide resin (A), having the following general formula (
I) diepoxy silicon compound (B) and organic liquid (
C), B is (B)/[(A)+(B)]=0.0
A heat-resistant resin composition containing 0.01 to 0.3 (weight ratio). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 and R_2 are divalent hydrocarbon groups, R_3 and R_4 are monovalent hydrocarbon groups, and R_1, R_2, R_3 and R_4 may be the same or different, and n is an integer of 0 or 1 or more)