JP3384922B2 - Resin composition for film and film molded article using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a coating which has excellent surface hardness and the like and is suitable for forming a coating, and a molded coating formed by using the resin composition.

[0002]

2. Description of the Related Art Generally, the surface of resin or metal is soft, easily scratched, and easily contaminated, and it is apt to be corroded by chemical substances. Therefore, it needs to be protected. However, in addition, in order to impart heat resistance, oxidation resistance, electrical insulation, corrosion resistance, light resistance, etc., and for the purpose of coloring the surface, a method of forming a coating layer on the surface is adopted. Has been done. As a means for forming this coating layer, a thin film is formed on the surface of a resin or metal by coating a resin composition containing an inorganic or organic pigment, a filler or the like, a plating method, a sputtering method or a chemical vapor deposition method. A method for forming the layer is known. Of these, the method of forming a film using a resin composition is simple and
Moreover, it is widely used because it can be implemented at low cost. The pigment or filler to be mixed in such a resin composition for coating film can be selected from a very wide range of inorganic and organic substances, and the resin binder used for fixing these pigments and fillers can also be used. A wide variety of resins are widely used, from thermosetting resins to thermoplastic resins.

As described above, the material used for the coating resin composition can be selected from a wide range of substances, but a combination of pigments or fillers with a resin binder having excellent affinity and coating characteristics is used. The choice is extremely limited. In particular, since the inorganic pigment or the inorganic filler and the resin binder are poor in chemical bondability, the resin composition for coating film, which is used by combining them, usually contains a surfactant and the like. However, this surfactant not only promotes deterioration of heat resistance and chemical resistance of the coating film, but also often causes migration problems in the resin composition, and is a material which should not be used as much as possible.

[0004]

In the resin composition for a coating film containing the above-mentioned inorganic pigment or inorganic filler and the resin binder, when silica-based fine particles are used as the inorganic filler, the silica-based fine particles have heat resistance, It has excellent properties such as chemical resistance, abrasion resistance, stain resistance, light resistance, electrical insulation, and hardness of the surface, and has an advantage of low manufacturing cost.

On the other hand, the resin binder used in combination with the silica-based fine particles has the property of sufficiently exhibiting the excellent properties of the silica-based fine particles described above, and is also excellent in the affinity or bonding with the silica-based fine particles. is necessary. Further, the resin binder is required not only to have excellent adhesiveness to the surface of the substrate on which the film is to be formed, but also to have workability for forming a film by applying the resin composition for a film containing the resin binder to the surface of the substrate. . Very few resin binders satisfy such characteristics, and polyvinyl alcohol resins are usually used as this type of resin binder.
However, although the polyvinyl alcohol resin is a water-soluble resin and is excellent in handleability, it has a problem in that it is insufficient in heat resistance, chemical resistance, abrasion resistance, electric insulation, hardness and the like.

The present invention has been made in view of the above-mentioned actual situation in the prior art. That is, an object of the present invention is to have a resin binder that has excellent affinity with silica-based fine particles, and has excellent heat resistance and chemical resistance as well as adhesiveness with a substrate and that can easily form a film-forming body. It is intended to provide a resin composition for a film and a film molded product formed by using the resin composition.

[0007]

Means for Solving the Problems The present inventors have found that the resin composition for coating using the silica-based fine particles exhibits the excellent characteristics of the silica-based fine particles and has good affinity with the silica-based fine particles. There, as a result of diligent studies on a resin binder having excellent film forming ability, as a resin binder, by using a polyamide resin having a specific phenolic hydroxyl group, not only excellent dispersibility of silica-based fine particles can be obtained, The inventors have found that a resin composition for a coating capable of forming a coating layer excellent in heat resistance, chemical resistance, abrasion resistance, electric insulation, hardness, workability, etc. can be obtained, and completed the present invention.

That is, the coating resin composition of the present invention comprises:
At least, in the coating resin composition containing an aromatic polyamide resin having a phenolic hydroxyl group in the main chain, silica-based fine particles and an organic solvent, the polyamide resin has a hydroxyl equivalent of 200 to 1500, and To 100 parts by weight of this polyamide resin, silica-based fine particles 50
˜400 parts by weight and 50 to 20,000 parts by weight of an organic solvent are blended. Further, the coated film molded article of the present invention is characterized in that it is formed by applying the coating resin composition onto a substrate and drying it. This substrate is preferably a polyimide resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. In the coating resin composition of the present invention, the aromatic polyamide resin having a phenolic hydroxyl group in the main chain used (hereinafter, also simply referred to as "polyamide having a hydroxyl group") is used for synthesis of a polyamide resin. At least one of the dicarboxylic acid component and the diamine component to be produced, by using a monomer containing a dicarboxylic acid having a phenolic hydroxyl group or a diamine having a phenolic hydroxyl group as a raw material, a known amidation polycondensation reaction You can

In the present invention, examples of the dicarboxylic acid having a phenolic hydroxyl group include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 3-hydroxyphthalic acid, 2-hydroxyphthalic acid and 2-hydroxyterephthalic acid. Examples of the diamine used and having a phenolic hydroxyl group include, for example, 3,3'-dihydroxy-4,4'-diaminobiphenyl and 3,3'-bis (4-hydroxy-3-aminophenyl) hexafluoropropane. Etc. are used, and these can be used alone or as a mixture.

Examples of the dicarboxylic acid having no phenolic hydroxyl group used for producing a polyamide having a hydroxyl group include isophthalic acid, terephthalic acid, 4,
4'-biphenyldicarboxylic acid, 3,3'-methylenedibenzoic acid, 4,4'-methylenedibenzoic acid, 4,4'-
Oxydibenzoic acid, 3,4'-oxydibenzoic acid, 4,
4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, ethylenediamine bisphthalimide-4,4'-dicarboxylic acid, 3,3'-
Bis (4-carboxylphenyl) propane, 3,3 '
-Bis (4-carboxylphenyl) hexafluoropropane, bis (4-carboxylphenyl) methane,
Examples thereof include carboxylic acids such as 3,3′-bis (4-carboxylphenyl) hexafluoropropane and derivatives thereof, but are not limited thereto.

Further, examples of the diamine having no phenolic hydroxyl group used for the production of the polyamide having a hydroxyl group include p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, metatolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3,
3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone,
3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylmethane, 3,3'-dimethoxy-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5'-tetraethyl-4,4'-diaminodiphenylmethane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane,
4,4'-diaminodiphenyl sulfoxide, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-
Xylylenediamine, m-xylylenediamine, bis (4-amino-3-methylphenyl) methane, bis (4
-Amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4
-Amino-3,5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane,
Examples thereof include bis (4-amino-3-isopropylphenyl) methane and bis (4-amino-3,5-diisopropylphenyl) methane, but are not limited thereto.

The hydroxyl group-containing polyamide used in the present invention is produced from the above-mentioned dicarboxylic acid component and diamine component, and the reaction system thereof contains a condensing agent such as phosphorous acid and its derivative and a pyridine derivative. It can be easily produced by a known method used. Examples of the phosphorous acid and its derivatives include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, and di-o phosphite.
-Tolyl, tri-m-tolyl phosphite, di-m-phosphite
-Tolyl, di-p-tolyl phosphite, tri-p phosphite
-Tolyl, di-p-chlorophenyl phosphite, tri-p-chlorophenyl phosphite and the like are used. Further, as the pyridine derivative, pyridine, 4-methylpyridine,
3-methylpyridine, 2,4-lutidine, 2,5-lutidine, 3,5-lutidine and the like are used, but not limited thereto.

Further, as a method for producing a polyamide having a hydroxyl group by using the above condensing agent, generally, the following publicly known method (1991, edited by Polymer Society of Japan, "Polymer Functional Material Series 2, Synthetic Syntax") is used. And "reaction"). That is, the polyamide having a hydroxyl group is obtained by using the above-mentioned monomers composed of a dicarboxylic acid component and a diamine component, a condensing agent composed of phosphorous acid or a derivative thereof and a pyridine derivative, and an amide solvent (N-methyl which dissolves a polyamide resin to be generated). 2-pyrrolidone, dimethylacetamide, pyridine, 1,3-dimethyl-2-imidazolidinone, etc.) so as to be contained in an amount of 5 to 30% by weight at a reaction temperature of room temperature to 160. It can be synthesized by carrying out a polymerization reaction at 30 ° C. for about 30 minutes to several hours. Lithium chloride, calcium chloride, or the like is added to this polymerization reaction system, if necessary.

The polyamide having a hydroxyl group used in the present invention is obtained by the above-mentioned method, has a glass transition temperature of usually 200 ° C. or higher, and exhibits not only high heat resistance but also various substrates. It is characterized by having excellent adhesiveness with. The polyamide having the above hydroxyl group has a phenolic hydroxyl group equivalent of 200 to
It must be in the 1500 range. When the hydroxyl equivalent is a polyamide within this range, excellent dispersibility of the silica-based fine particles used in combination can be obtained. The reason for this is not clear, but it is presumed that hydrogen bonds are formed between the hydroxyl groups possessed by the polyamide and the hydroxyl groups possessed on the surface of the silica fine particles. Further, the affinity with an organic solvent, particularly an alcohol solvent, is remarkably improved. When the hydroxyl equivalent is 150 or more, the concentration of hydroxyl groups contained in the polyamide is too low to weaken the interaction with the silica-based fine particles, and the dispersion stability of the silica-based fine particles cannot be sufficiently achieved. Solubility by a solvent also becomes low, and there is a high possibility that a problem of poor workability in forming a film will occur.

Next, in the resin composition for coating film of the present invention, the silica-based fine particles used by being dispersed in the above-mentioned polyamide having a hydroxyl group may be crystalline silica or fused silica, and its shape is It may be spherical or amorphous, and is not limited by its manufacturing method or shape. The silica-based fine particles may have a glass balloon shape,
Further, it may have a functional group such as a silicate or a hydroxyl group on its surface.

The silica-based fine particles used in the present invention preferably have a particle diameter of 20 μm or less. When the particle diameter is 20 μm or more, the formed coating layer has poor smoothness, and it becomes difficult to maintain abrasion resistance, which is not preferable. Specific examples of the silica-based fine particles used include organosilica sols (trade name: MA-ST-
M, manufactured by Nissan Chemical Co., Ltd., silicates (trade name: MKC silicate, manufactured by Mitsubishi Chemical Co., Ltd.), ultrafine silica particles (trade name: Nipseal, manufactured by Nippon Silica Co., Ltd.), superhydrophobicized silica powder (trade name: trefill, Toray Dow Corning Silicone), silicas (trade name: Hugh Rex, Tatsumori Co., Ltd.), glass beads (trade name: glass beads, Toshiba Ballotene Co., Ltd.) and silicas (trade name: Aerosil, Japan) Aerosil Co., Ltd., etc., but the invention is not limited thereto.

Next, the coating resin composition of the present invention contains an organic solvent. The organic solvent is not particularly limited as long as it dissolves the above-mentioned polyamide having a hydroxyl group, and examples thereof include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, pyridine and 1,3-dimethyl-2. An amide solvent represented by imidazolidinone, a ketone solvent represented by cyclohexanone, an alcohol solvent represented by methanol, ethanol, propanol, etc., and an aromatic hydrocarbon solvent represented by benzene, toluene, etc. , Acetone, ketone solvents typified by methyl ethyl ketone, chloroform, halogen solvents typified by chlorobenzene, ester solvents typified by ethyl acetate, nitro solvents typified by nitrobenzene, nitromethane, acetonitrile, etc. Represented by benzonitrile Triyl solvents, amine solvents typified by triethylamine and piperidine, ether solvents typified by diethyl ether and tetrahydrofuran, and the like, may be used alone or as a mixed solvent, and may be appropriately selected and used from these solvents. it can. In the present invention, it is particularly preferable to use alcohol or a mixed solvent containing alcohol. When alcohol is used, the toxicity is low and the cost is low, and not only the viscosity of the resin composition can be reduced, but also excellent dispersion stability of the silica-based fine particles can be obtained. Further, these solvents are preferably used because they have high solubility in the polyamide having a hydroxyl group in the present invention.

As described above, the coating resin composition of the present invention contains a polyamide having at least a hydroxyl group, silica-based fine particles and an organic solvent. The content of the polyamide in the resin composition is the polyamide. By adjusting the amount of the silica-based fine particles to 50 to 400 parts by weight and the organic solvent to 50 to 20,000 parts by weight in 100 parts by weight,
A composition capable of forming a coating layer having excellent workability and having heat resistance, chemical resistance, abrasion resistance, electric insulation, high hardness and the like can be obtained.

When the amount of the silica-based fine particles in the resin composition is 50 parts by weight or less, the abrasion resistance of the coating film is insufficient, and when it is 400 parts by weight or more, it is used as a binder. Since the amount of the polyamide is relatively small, the silica-based fine particles cannot be firmly held in the coating, which is not suitable. Also, the amount of organic solvent is 50
When the amount is less than or equal to parts by weight, the viscosity of the resin composition becomes high, which makes it difficult to apply the composition to a substrate and causes a film with poor smoothness, which is not preferable. It is not suitable because the viscosity of the resin composition becomes too low, it becomes difficult to apply the resin composition to the substrate, and an unnecessary solvent is used in a large amount, so that the efficiency is reduced in drying after the application.

The coating resin composition of the present invention may further contain a bifunctional or higher functional epoxy compound for the purpose of improving chemical resistance and adhesiveness. The epoxy compound used may be any bifunctional or higher functional compound, for example, glycidyl ethers, glycidyl esters, glycidyl amines, chain aliphatic epoxides, alicyclic epoxides, hydantoin type compounds. Resins such as epoxies may be mentioned.

Examples of the glycidyl ethers include biphenyl glycidyl ether, bisphenol glycidyl ether, phenol novolac polyglycidyl ether, alkylene glycol or polyalkylene glycol glycidyl ether, and naphthalene diglycidyl ether. As the glycidyl ether of bisphenol, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, tetramethylbisphenol A type,
Examples thereof include diglycidyl ethers of divalent phenols such as tetramethylbisphenol F type, tetramethylbisphenol AD type, tetramethylbisphenol S type, tetrachlorobisphenol A type and tetrabromobisphenol A type. Examples of the polyglycidyl ether of phenol novolac include polyglycidyl ethers of novolac resins such as phenol novolac, cresol novolac, brominated phenol novolac and orthocresol novolac.

Examples of the polyphenylol type glycidyl ether, diglycidyl ether of alkylene glycol or polyalkylene glycol include diglycidyl ether of glycols such as polyethylene glycol, polypropylene glycol and butanediol. The glycidyl esters include, for example, glycidyl ester of hexahydrophthalic acid and glycidyl ester of dimer acid, and the glycidyl amines include, for example, triglycidylaminodiphenylmethane, triglycidylaminophenol, triglycidyl isocyanate. Etc.

Further, as the chain aliphatic epoxides,
For example, epoxidized polybutadiene, epoxidized soybean oil and the like, and examples of alicyclic epoxides include:
Examples thereof include 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxycyclohexylmethylcarboxylate, and hydrogenated bisphenol epoxy. As the hydantoin-type epoxides, cyglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and a tris (hydroxyphenyl) methane-based polyfunctional epoxy compound,
Examples thereof include, but are not limited to, tetraglycidyloxyphenyl sulfone and biphenyl novolac type glycidyl ether.

By using the epoxy compound in an amount of 2 to 50 parts by weight based on 100 parts by weight of the polyamide having a hydroxyl group, a resin composition having excellent chemical resistance and adhesion to a substrate can be obtained. . It is presumed that these are improved by the crosslinking reaction carried out via the hydroxyl group in the polyamide. If the amount of the epoxy compound used is 50 parts by weight or more, the crosslink density increases and the resin binder becomes brittle, which is not preferable. On the other hand, if it is less than 2 parts by weight, the crosslink density is low and sufficient chemical resistance and adhesiveness cannot be improved, which is not preferable.

A reaction accelerator may also be used in the resin composition for coating film of the present invention. This reaction accelerator is added as needed in order to accelerate the reaction between the polyamide having a hydroxyl group and the epoxy compound. Examples of such a reaction accelerator include phosphorus compounds such as triphenylphosphine and / or tertiary amine compounds such as
Triethylamine, triethanolamine, 1,8-diaza-bicyclo [5,4,0] -7-undecene (DB
U), N, N-dimethylbenzylamine, 1,1,3,
Boron compounds such as 3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-methylpiperazine, etc., for example, 1,8-diazabicyclo [5,4,0]-
7-undecenium tetraphenyl borate or the like is used. The resin composition for a film and the film molded product formed by using the resin composition include those before and after the reaction between the hydroxyl group of the polyamide having a hydroxyl group and the epoxy group of the epoxy compound within the scope of the present invention. Be done. This reaction is
Generally, it is carried out by heating at 250 ° C. or lower for several hours or standing at room temperature, but the present invention is not limited to those obtained by these reaction methods.

The coating resin composition of the present invention is used as a composition for coating a substrate and drying it to form a coating layer, but the substrate is not limited at all, and examples thereof include: Copper, stainless steel, aluminum,
Inorganic bases such as iron, ceramics, glass and silicone, and organic bases such as polyester, polyimide, epoxy resin, polyethylene, polypropylene, silicone resin and vinyl chloride resin are used. In particular, a film molded article formed by using a polyimide resin having excellent heat resistance as a base material not only has excellent adhesion to the base material, but also has excellent hardness, heat resistance, chemical resistance, and abrasion resistance. It is useful as a material for electronic parts, electric parts and the like.

The polyimide resin used as the substrate is KAPTON (manufactured by du Pont), AP
IKAL (Kanebuchi Chemical Co., Ltd.), NOVAL (Mitsubishi Chemical Co., Ltd.), UPILEX (Ube Industries Co., Ltd.), 2080 (Up
jion), XU216 (Ciba-Geigy), ARC-TPI (Mitsui Toatsu), ULTEM.
Films such as (manufactured by GE), TI (manufactured by Toray), PAIFRON (manufactured by Hitachi Chemical Co., Ltd.), and TORLON (manufactured by Amoco) may be mentioned, but the invention is not limited thereto.

Further, the coating resin composition of the present invention comprises
If necessary, other additives may be added. For example, natural waxes, synthetic waxes, release agents such as long-chain fatty acids or metal salts thereof, acid amides, esters and paraffins, stress relief agents such as silicone rubber, nitrile rubber, butadiene rubber and polysiloxane, chlorine Paraffin, bromotoluene, hexabromobenzene,
Flame retardants such as antimony trioxide, silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, Boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, zinc, lead, iron powder, iron oxide, metal powder such as iron oxide, graphite, inorganic filler such as carbon or conductive fine particles, dye or pigment, etc. The colorant, the oxidation stabilizer, the light stabilizer, the moisture resistance improver, the thixotropy imparting agent, the diluent, the defoaming agent, and other resins can be appropriately mixed.

The resin composition for coating film of the present invention can be easily produced by the above-mentioned method. That is, 100 parts by weight of a polyamide having a hydroxyl group is dissolved in a solvent of 50 to 20,000 parts by weight in an organic solvent, if necessary, to which 50 parts by weight or more of silica-based fine particles are added to obtain a silica-based solution. A dispersion of fine particles is formed, or a dispersion of fine silica particles is mixed with the polyamide, and if necessary, a solvent containing an organic solvent is added so that the content of fine silica particles is 50 to 50%. The resin composition for a coating film can be produced by forming a dispersion of silica-based fine particles in an amount of 400 parts by weight and the total amount of solvent in the range of 50 to 20,000 parts by weight.

Further, if necessary, it is preferable to add 2 to 50 parts by weight of a bifunctional or higher epoxy compound to 100 parts by weight of a polyamide having a hydroxyl group in the dispersion liquid of the silica type fine particles. The resin composition for a coating film thus obtained is applied onto a metal or resin substrate, preferably a polyimide resin substrate, and dried at room temperature, heating or vacuum to obtain a coated film molded article.
After forming this film, an epoxy compound may be added to the polyamide to carry out a crosslinking reaction, if necessary. The resin composition for a coating film and the molded film product according to the present invention are not limited to those obtained by the method for producing the composition or the method for forming a coating film.

The coating resin composition of the present invention produced in this way, excellent heat resistance, has chemical resistance, wear resistance and high hardness and the like, a surface protective agent, coating agent and lightfastness It is useful as a material that can be used not only as a coating film but also as an electric insulating film, a sealant, an adhesive, and the like.

The present invention will be specifically described below with reference to Examples.
The present invention is not limited to these. Synthesis example 1
5 is an example of producing a hydroxyl group-containing polyamide used in the present invention, while Synthesis Example 6 is an example of producing a hydroxyl group-containing polyamide used for comparison with the present invention.

Synthesis Example 1 In a 200 ml three-neck round bottom flask equipped with a mechanical stirrer, a cooling tube, a calcium chloride tube and a nitrogen introducing tube, 3.642 g (20 m) of 5-hydroxyisophthalic acid was added.
mol) and 3,3 ', 5,5'-tetraethyl-
6,4'-Diaminodiphenylmethane 6.209 g (2
0 mmol), calcium chloride 2.0
2 g, lithium chloride 0.66 g, N-methyl-2-pyrrolidone 120 ml, pyridine 6 ml and triphenyl phosphite 12.41 g (40 mmol) were added, and the mixture was stirred at 120 ° C. for 4 hours under a nitrogen atmosphere to synthesize polyamide. I went. The resulting reaction solution was introduced into a mixed solution of water and methanol (weight ratio 8: 2) to precipitate a polymer. Further, the obtained polymer was repeatedly washed twice with this mixed solution and dried to obtain a polyamide resin having a phenolic hydroxyl group. The hydroxyl group equivalent of the obtained polyamide resin is about 475.
And the intrinsic viscosity value of this resin is 0.60 dl / g
(Viscosity was measured in a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C.). Moreover, this polyamide resin was soluble in ethanol. The intrinsic viscosity value (η) in this case is a value obtained by an Ostwald viscometer, and is obtained by the following formula. η = (1 / c) × ln (T ₁ / T ₀ ), where T ₁ is the resin solution drop time (seconds), T ₀ is the solvent drop time (seconds), and c is the solution concentration (g / Dl).)

Synthesis Example 2 5-hydroxyisophthalic acid used in Synthesis Example 1 3.64
2 g (20 mmol) of 5-hydroxyisophthalic acid 2.732 g (15 mmol) and isophthalic acid 0.8
An aromatic polyamide having a phenolic hydroxyl group was obtained in the same manner as in Synthesis Example 1 except that 31 g (5 mmol) was used. The hydroxyl equivalent of the obtained polyamide resin is about 627, and the intrinsic viscosity value of this resin is 0.63 dl.
/ G (viscosity measurement in a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C.). The polyamide resin was soluble in a mixed solvent of ethanol and toluene.

Synthesis Example 3 5-hydroxyisophthalic acid 3.64 used in Synthesis Example 1
2 g (20 mmol) of 5-hydroxyphthalic acid 1.
821 g (10 mmol) and isophthalic acid 1.661
An aromatic polyamide having a phenolic hydroxyl group was obtained in exactly the same manner as in Synthesis Example 1 except that g (10 mmol) was used instead. The hydroxyl equivalent of the obtained polyamide resin is about 9
33, and the intrinsic viscosity value of this resin is 0.63 dl /
g (viscosity measurement in a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C.). The polyamide resin was soluble in dimethylformamide.

Synthesis Example 4 3,3 ', 5,5'-tetraethyl-used in Synthesis Example 1
6,4'-Diaminodiphenylmethane 6.209 g (2
0 mmol) to 3,4'-oxydianiline 4.00
An aromatic polyamide having a phenolic hydroxyl group was obtained in exactly the same manner as in Synthesis Example 1 except that 5 g (20 mmol) was used. The hydroxyl equivalent of the obtained polyamide resin is about 364, and the intrinsic viscosity value of this resin is 0.73 dl.
/ G (30 ° C, viscosity: measured in a dimethylacetamide solution having a concentration of 0.5 g / dl). The polyamide resin was soluble in dimethylformamide.

Synthesis Example 5 3,3 ', 5,5'-tetraethyl-used in Synthesis Example 2
6.209 g of 4,4'-diaminophenylmethane (20
Aromatic polyamide having a phenolic hydroxyl group was obtained in exactly the same manner as in Synthesis Example 2, except that 4.996 g (20 mmol) of bis (4-aminophenyl) sulfonic acid was used instead of (mmol). The hydroxyl equivalent of the obtained polyamide resin is about 678, and the intrinsic viscosity value of this resin is 0.1.
It was 73 dl / g (at 30 ° C., viscosity was measured in a dimethylacetamide solution having a concentration of 0.5 g / dl). The polyamide resin was soluble in dimethylformamide.

Synthesis Example 6 The monomer in Synthesis Example 1 was prepared by using 0.911 g (5 mmol) of 5-hydroxyisophthalic acid and 2.4 of isophthalic acid.
An aromatic polyamide having a phenolic hydroxyl group was obtained in exactly the same manner as in Synthesis Example 1 except that the monomer composition was changed to 92 g (15 mmol) and bis (4-aminophenyl) sulfonic acid 4.996 g (20 mmol). . The hydroxyl equivalent of the obtained polyamide resin is about 160.
2 and the intrinsic viscosity value of this resin is 0.73 dl / g
(30 ° C., viscosity measured in a dimethylacetamide solution with a concentration of 0.5 g / dl). The polyamide resin was soluble in diacetamide.

Example 1 4.00 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 1
Was dissolved in 16 g of ethanol, and 10 g of hollow glass beads having an average particle diameter of 8 to 12 μm (glass beads SHC-110, manufactured by Toshiba Ballotini Co., Ltd.) were dispersed in this solution to obtain a resin composition solution. The obtained solution was a resin composition containing 100 parts by weight of polyamide, 250 parts by weight of glass beads, and 400 parts by weight of ethanol solvent. This resin composition solution is formed to a thickness of 100 μm.
Was coated on the polyimide film (Upilex S, manufactured by Ube Industries, Ltd.) and dried by heating to form a coating layer having a thickness of about 20 μm on the film. The pencil hardness of this coating layer was 4H, and the obtained molded coating product had a hardness of 250
Heating to ° C did not show any change.

Example 2 1.00 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 1
Was dissolved in 9 g of ethanol, and then 11.6 g of a silica solution having an average particle size of 10 Å (MKC silicate MS51SG1, manufactured by Mitsubishi Chemical Corporation) was further dissolved in this solution to obtain a resin composition solution. The obtained solution was a resin composition containing 100 parts by weight of polyamide, 186 parts by weight of silica fine particles and 1886 parts by weight of an ethanol solvent. A 100 μm thick polyimide film (Upilex S,
Ube Kosan Co., Ltd.) was applied using a dip coating method, and this was heated and dried to form a coating layer having a thickness of about 3 μm on the film. The pencil hardness of this coating layer was 5H, and the obtained coating film molding did not show any change even when heated to 250 ° C.

Example 3 4.00 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 1
Was dissolved in 36 g of ethanol, and then an organosilica sol (MA-ST-M, manufactured by Nissan Chemical Co., Ltd.) containing 40% by weight of silica having an average particle size of 20 to 25 nm was dissolved in this solution.
A resin composition solution was obtained by dissolving 40 g.
The obtained solution was a resin composition containing 100 parts by weight of polyamide, 400 parts by weight of silica fine particles and 1500 parts by weight of an ethanol solvent. This resin composition solution,
It was applied on a polyimide film (Upilex S, manufactured by Ube Industries, Ltd.) having a thickness of 100 μm and dried by heating to form a coating layer having a thickness of about 1 μm on the film. The pencil hardness of this coating layer was 6H, and the obtained coated molded article did not show any change even when heated to 250 ° C.

Example 4 4.00 g of hydroxyl group-containing polyamide obtained in Synthesis Example 2
Was dissolved in 36 g of a mixed solvent of ethanol and toluene, and then an organosilica sol (MA-ST) containing 40% by weight of silica having an average particle size of 20 to 25 nm was added to this solution.
-M, manufactured by Nissan Kagaku Co., Ltd.) to obtain a resin composition solution. The resulting solution is polyamide 10
The resin composition contained 200 parts by weight of silica fine particles and 520 parts by weight of the mixed solvent in 0 parts by weight. This resin composition solution was applied on a polyimide film (Upilex S, manufactured by Ube Industries, Ltd.) having a thickness of 100 μm and dried by heating to form a coating layer having a thickness of about 1 μm on the film. The pencil hardness of this coating layer is 6H,
The coated film obtained did not show any change even when heated to 250 ° C.

Example 5 4.00 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 3
Was dissolved in 16 g of diacetamide and then added to this solution,
True spherical silica with an average particle size of 1.6 μm (FUSELEX
SO-3C, manufactured by Tatsumori Co., Ltd.) to obtain a resin composition solution. The resulting solution is polyamide 1
The resin composition contained 250 parts by weight of silica fine particles and 400 parts by weight of a diacetamide solvent in 100 parts by weight. This resin composition solution was applied onto a polyimide resin film (Upilex S, manufactured by Ube Industries, Ltd.) having a thickness of 100 μm and dried by heating to form a coating layer having a thickness of about 20 μm on the film. The pencil hardness of this coating layer was 4H, and the obtained coated molded article did not show any change even when heated to 250 ° C.

Example 6 4.00 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 4
Was dissolved in 36 g of dimethylacetamide, and then bisphenol A type epoxy resin (Epicoat 82
(8, manufactured by Yuka Shell Co., Ltd.) and 0.01 g of triphenylphosphine as a curing accelerator were dissolved in a solution obtained,
A resin composition solution was obtained by dispersing 10 g of hollow glass beads having an average particle diameter of 8 to 12 μm (glass beads SHC-110, manufactured by Toshiba Ballotini). The obtained solution is 100 parts by weight of polyamide and 250 beads of glass.
It was a resin composition containing parts by weight, 900 parts by weight of a dimethylacetamide solvent, and 25 parts by weight of an epoxy resin.
This resin composition solution was applied onto a polyimide film (Upilex S, Ube Industries, Ltd.) having a thickness of 100 μm, which was heated and dried to give a film thickness of about 2 on the film.
After forming a 0 μm coating layer, the coating layer was further heated at 150 ° C. for 3 hours to cure the coating layer. The pencil hardness of this coating layer was 6H, and the obtained coated molded article did not show any change even when heated to 250 ° C. Further, when this formed film article was impregnated with a dimethylacetamide solvent, no change was observed in the formed layer.

Example 7 The hydroxyl group-containing polyamide used in Example 6 was
A resin composition solution was obtained in exactly the same manner as in Example 6 except that the polyamide having a hydroxyl group obtained in Synthesis Example 5 was used instead. The obtained solution was a resin composition containing 100 parts by weight of polyamide, 250 parts by weight of glass beads, 900 parts by weight of a solvent, and 25 parts by weight of an epoxy resin. This resin composition solution was applied onto a copper foil having a thickness of 25 μm, dried by heating to form a coating layer having a thickness of about 20 μm on the copper foil, and then further heated at 150 ° C. for 3 hours to form a coating layer. Was cured. The pencil hardness of this coating layer was 6H, and the obtained coated molded article showed no change even when heated to 250 ° C., and showed strong adhesiveness and heat resistance. Further, when this formed film article was impregnated with a dimethylacetamide solvent, no change was observed in the formed layer.

Comparative Example 1 The polyamide having a hydroxyl group obtained in Synthesis Example 6 was completely insoluble in alcohol solvents. Then, after dissolving 4 g of this polyamide in 36 g of N-methyl-2-pyrrolidone solvent, 4 g of hollow glass beads (glass beads SHC-110, manufactured by Toshiba Ballotini) having an average particle diameter of 8 to 12 μm are dispersed in this solution. By doing so, a resin composition solution was obtained. The obtained solution was a resin composition containing 100 parts by weight of polyamide, 100 parts by weight of silica fine particles and 900 parts by weight of a pyrrolidone solvent, but after several hours, the glass beads were precipitated and the resin composition for forming a film was formed. Could not be created.

Comparative Example 2 4 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 1 was dissolved in 36 g of a mixed solvent of ethanol and tetrahydrofuran (weight ratio 1: 1), and then bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Co., Ltd.) and 0.01 g of triphenylphosphine as a curing accelerator are dissolved in a solution of spherical silica (FUSELEXSO-3C, manufactured by Tatsumori Co., Ltd.) 1 having an average particle size of 1.6 μm.
A resin composition solution was obtained by dispersing 0 g. The resulting solution is 100 parts by weight of polyamide, 250 parts by weight of silica fine particles, 900 parts by weight of solvent and 3 parts of epoxy resin.
It was a resin composition containing 7.5 parts by weight. This resin composition solution was applied onto a polyimide film (Upilex S, Ube Industries, Ltd.) having a thickness of 100 μm and dried by heating to form a coating layer having a thickness of about 20 μm on the film, and then further. The coating layer was cured by heating at 150 ° C. for 3 hours. The coating thus obtained was very brittle and could not serve as a coating layer.

Comparative Example 3 Instead of the hydroxyl group-containing polyamide used in the present invention,
20 g of 20% aqueous solution of polyvinyl alcohol (Kuraray Poval PVA-117H, manufactured by Kuraray Co., Ltd.) was added to 20 g of true spherical silica (FUSELEX SO-3) having an average particle size of 1.6 μm.
C, manufactured by Tatsumori Co., Ltd.) to obtain a resin composition solution. The resulting solution was obtained by adding 100 parts by weight of polyvinyl alcohol, 250 parts by weight of silica fine particles and 40 parts of water.
It was a resin composition containing 0 parts by weight. This resin composition solution was applied onto a copper foil having a thickness of 40 μm and dried by heating to form a coating layer having a thickness of about 20 μm on the film. When this film-forming product was heated to 150 ° C., the film was deformed and peeled from the substrate, and had low heat resistance.

[0050]

EFFECT OF THE INVENTION Since the resin composition for coating film of the present invention uses a specific polyamide resin in combination with silica-based fine particles, it is a resin composition solution in which the dispersibility of silica-based fine particles is improved. Property, adhesiveness, chemical resistance, abrasion resistance, electrical insulation, hardness and processability can be formed, and by further containing a specific epoxy compound, further A coating layer having excellent chemical resistance and adhesiveness can be obtained. Further, in the present invention, coating molding product formed by coating the coating resin composition on the substrate, which is excellent in heat resistance, light resistance and hardness. In particular, the base polyimide resin The coated molded article is useful as an electronic component, an electrical component, or the like.

Claims (6)

(57) [Claims] 1. A coating resin composition containing at least an aromatic polyamide resin having a phenolic hydroxyl group in the main chain, silica-based fine particles and an organic solvent, wherein the polyamide resin has a hydroxyl equivalent in the range of 200 to 1500. And 100 parts by weight of this polyamide resin, 50 to 400 parts by weight of silica-based fine particles and 50 to 2 parts of an organic solvent.
A resin composition for a coating film, characterized in that it is mixed with 30,000 parts by weight. 2. The resin composition for a coating film according to claim 1, wherein the silica-based fine particles have a particle diameter of 20 μm or less. 3. The resin composition for coating according to claim 1, wherein 100 parts by weight of the aromatic polyamide resin is mixed with 2 to 50 parts by weight of a bifunctional or higher functional epoxy compound. 4. The resin composition for coating according to claim 1, wherein the organic solvent is alcohol or a mixed solvent containing alcohol. 5. A molded film product, which is formed by applying the resin composition for film according to any one of claims 1 to 3 onto a substrate and drying the composition. 6. The coated molded article according to claim 5 , wherein the substrate is a polyimide resin.