JP2002129101A - Polyamide resin-containing varnish and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin varnish which is easy to remove a solvent on forming films and can obtain films and adhesive layers reduced in the remaining solvent. SOLUTION: The polyamide resin-containing varnish comprises (A) a phenolic hydroxyl group-containing aromatic polyamide resin, and (B) a solvent to be represented by the formula: R1O(R2O)nR3 (wherein R1 and R3 are each a 1-4C alkyl group; R2 is a 2C or 3C alkylene group; and (n) is 2, 3 or 4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide varnish excellent in processability applicable to spin coating, screen printing, adhesive films and the like.

[0002]

2. Description of the Related Art Aromatic polyamide resins are widely used as functional engineering plastics because of their excellent properties in heat resistance, film forming properties and toughness.

[0003]

However, since aromatic polyamide resins have poor solvent solubility, they are difficult to process when used as coatings or adhesive layers. Some amide solvents dissolve an aromatic polyamide resin, but generally have a problem that it is difficult to remove the solvent during film formation because of its high boiling point and low evaporation rate.
For this reason, a residual solvent is likely to remain in a film or an adhesive layer made of a conventional aromatic polyamide resin using the resin, and if the solvent remains, it greatly affects physical properties such as adhesive strength to a substrate and heat resistance. I do. Further, when a film or an adhesive layer made of a conventional aromatic polyamide resin dissolved in an amide-based solvent is formed on an organic-based substrate, the amide-based solvent having a high solubility is added to the organic-based substrate. There was also a problem of attacking the surface. There is a need for a polyamide resin varnish that does not cause these problems, can easily remove the solvent during film formation, and can provide a film or an adhesive layer with little residual solvent.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polyamide varnish excellent in processability which can solve the above-mentioned problems can be obtained. That is, the present invention provides a varnish containing a polyamide resin, comprising: (1) a phenolic hydroxyl group-containing aromatic polyamide resin (A) and a solvent (B) represented by the formula (1):

[0005]

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(R1, R3 are alkyl groups having 1 to 4 carbon atoms; R2 is an alkylene group having 2 or 3 carbon atoms; n is 2, 3 or 4) (2) Aromatic polyamide resin containing a phenolic hydroxyl group (A) is a block copolymer formed from a phenolic hydroxyl group-containing aromatic polyamide resin having aminoaryl groups at both terminals and a polybutadiene / acrylonitrile copolymer having a carboxyl group at both terminal groups (1) (3) The polyamide resin-containing varnish according to (2), wherein the phenolic hydroxyl group-containing aromatic polyamide resin (A) is a block copolymer represented by (Formula 2).

[0007]

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(Where x, y, z, l, m and n are average degrees of polymerization, respectively; x = 3-7, y = 1-4,
z = 5 to 15, l + m = integer of 2 to 200, m /
(M + 1) ≧ 0.04) (4) The solvent (B) is a trialkylene glycol dialkyl ether (1)
To (3), the varnish containing polyamide resin according to any one of (3), (5) the varnish containing polyamide resin according to (4), wherein the solvent (B) is triethylene glycol dialkyl ether, and (6) the solvent (B). Is a polyamide resin-containing varnish according to (5), wherein the varnish is triethylene glycol dimethyl ether; (7) a polyamide resin-containing varnish according to any one of (1) to (6), which contains a curable resin (C) (8) The polyamide resin-containing varnish according to (7), wherein the curable resin (C) is an epoxy resin.
(9) The curable resin (C) is a radiation curable resin (7)
(10) An adhesive film and / or an adhesive layer obtained by removing a solvent of the polyamide resin-containing varnish according to any one of (1) to (9). The present invention relates to a cured product obtained by removing the solvent of the polyamide resin varnish according to any one of (1) to (9) and curing the varnish.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide resin-containing varnish of the present invention contains a phenolic hydroxyl group-containing aromatic polyamide resin (A) and a solvent (B) represented by the formula (1).

The phenolic hydroxyl group-containing aromatic polyamide resin (A) used in the present invention is not particularly limited as long as it is an aromatic polyamide resin having a phenolic hydroxyl group in the polymer structure. A method for synthesizing a phenolic hydroxyl group-containing aromatic polyamide resin is described in, for example, JP-A-8-143661, by mixing an aromatic diamine having a hydroxyl group and / or an aromatic dicarboxylic acid to form an aromatic diamine. It can be produced by performing polycondensation of the component and an aromatic dicarboxylic acid component.

Further, when the purpose is to provide flexibility, flexibility, adhesiveness, etc., the phenolic hydroxyl group-containing aromatic polyamide resin (A) may be a phenolic hydroxyl group-containing aromatic compound having aminoaryl groups at both terminals. It is preferable to use a block copolymer obtained by reacting a polyamide resin with a polybutadiene / acrylonitrile copolymer having carboxyl groups at both terminal groups. In order to make both terminal groups of the polyamide resin an aminoaryl group, it can be easily achieved by subjecting an aromatic diamine component to a polycondensation reaction in excess of an aromatic dicarboxylic acid component. This polycondensation can be performed by a conventionally known method described in, for example, JP-A-6-299133. Among these, a block copolymer represented by the structure of the formula (2) is more preferred.

[0012]

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(Where x, y, z, l, m and n are the respective average degrees of polymerization, x = 3-7, y = 1-4,
z = 5 to 15, l + m = integer of 2 to 200, m /
(M + 1) ≧ 0.04. As the aromatic diamine used for producing the phenolic hydroxyl group-containing aromatic polyamide resin of the present invention, for example, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenylether, 3,4′-diaminodiphenylether, 4,4′-diaminodiphenylthioether, 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'-diaminodiphenylthioether, 2,
2′-bis (3-aminophenyl) propane, 2,2 ′
-Bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine ,
3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2'-bis (3-aminophenoxyphenyl)
Propane, 2,2'-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxyphenyl) benzene, 1,3'-bis (3-aminophenoxyf) propane, 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) Examples include, but are not limited to, methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane. These may be used alone or in combination of two or more. As the dicarboxylic acids used for producing the phenolic hydroxyl group-containing aromatic polyamide resin of the present invention, for example, phthalic acid, isophthalic acid, terephthalic acid,
4,4'-oxydibenzoic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-, methylene dibenzoic acid, 4,
4′-methylene dibenzoic acid, 4,4′-thiodibenzoic acid, 3,3′-carbonyl dibenzoic acid, 4,4′-carbonyl dibenzoic acid, 4,4′-sulfonyl dibenzoic acid, 1, 5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
Examples include, but are not limited to, 1,2-naphthalenedicarboxylic acid.

The hydroxyl-containing aromatic dicarboxylic acid or hydroxyl-containing aromatic diamine used to introduce a phenolic hydroxyl group into the aromatic polyamide resin of the present invention includes 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, and the like. 2-hydroxyisophthalic acid, 3-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3,
3'-dihydroxy-4,4'-dianiline, 2,2-
Bis (3'-amino-4-hydroxyphenyl) propane, 2,4-dihydroxy-1,5-diaminobenzene, 5-hydroxy-1,3-diaminobenzene and the like can be used. However, the present invention is not limited to these. The solvent (B) used in the present invention has a structure represented by the formula (1).

[0015]

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(R1 and R3 are an alkyl group having 1 to 4 carbon atoms; R2 is an alkylene group having 2 or 3 carbon atoms; n is 2, 3 or 4) Specific examples thereof include diethylene glycol dimethyl ether and triethylene glycol. Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol diethyl ether, Dipropylene glycol dibutyl ether, dipropylene glycol isopropyl methyl Ether, dipropylene glycol isopropyl ethyl ether and the like, preferably trialkylene glycol dialkyl ether, more preferably triethylene glycol dialkyl ether, and most preferably triethylene glycol dimethyl ether, It is not limited to these. It is also possible to use a mixed solvent with another solvent as long as the solubility of the polyamide resin is not hindered. The solvent to be mixed is not particularly limited, but for the purpose of improving the volatility of the solvent, a ketone-based solvent, an ether-based solvent, an aromatic solvent, or the like is preferable. The mixing ratio (weight ratio) of the phenolic hydroxyl group-containing aromatic polyamide resin (A) and the solvent (B) largely depends on the application and is not particularly limited, but is generally (A) / (B) = 0.01 to 2, preferably Is (A) /
(B) = 0.1-1. In the present invention, it is preferable to use the curable resin (C) as a component. By blending the curable resin, heat resistance, moisture resistance and solvent resistance can be imparted to the cured film and adhesive layer. The curable resin is not particularly limited, but a resin having reactivity with a phenolic hydroxyl group is preferable. The curing means is not particularly limited, but a method such as heat curing or radiation curing is used. Specific examples include, but are not limited to, epoxy resins, isocyanate resins, cyanate resins, maleimide resins, acrylate resins, methacrylate resins, unsaturated polyester resins, oxetane resins, vinyl ether resins, and the like. The mixing ratio of the curing agent (C) largely depends on the application and is not particularly limited, but is generally 5 to 95% by weight, preferably 20 to 80% by weight of the total composition excluding the solvent component.

Examples of the epoxy resin used in the present invention include a polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound, a polyfunctional epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, and a heterocyclic epoxy resin. Epoxy resins, glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like are included. Here, the polyfunctional epoxy resin is an epoxy resin having two or more glycidyl groups. Examples of the polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound include bisphenol A, bisphenol F, bisphenol S,
4,4′-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S,
Tetramethyl-4,4'-biphenol, dimethyl-
4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,
2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-
Methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenol And polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds such as polybutadiene. Examples of the polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins include various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols as raw materials. Glycidyl ether compounds of various novolak resins such as a novolak resin, a phenol novolak resin having a xylylene skeleton, a phenol novolak resin having a dicyclopentadiene skeleton, a phenol novolak resin having a biphenyl skeleton, and a phenol novolak resin having a fluorene skeleton. Examples of the alicyclic epoxy resin include an alicyclic epoxy resin having an aliphatic skeleton such as cyclohexane, and examples of the aliphatic epoxy resin include 1,4-butanediol and 1,4-butanediol.
Glycidyl ethers of polyhydric alcohols such as 6-hexanediol, polyethylene glycol, pentaerythritol and the like can be mentioned. As a heterocyclic epoxy resin,
For example, a heterocyclic epoxy resin having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring can be mentioned, and as the glycidyl ester-based epoxy resin, for example, an epoxy resin composed of a carboxylic acid such as hexahydrophthalic acid diglycidyl ester can be mentioned, and glycidyl can be mentioned. Examples of the amine-based epoxy resin include epoxy resins obtained by glycidylation of amines such as aniline and toluidine.

Epoxy resins obtained by glycidylation of halogenated phenols include, for example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol. An epoxy resin obtained by glycidylation of a halogenated phenol such as A is exemplified.

Among these epoxy resins, which epoxy resin is used is appropriately selected depending on required characteristics, and a curing agent is used as needed. As a curing agent,
Examples include acid anhydrides, amines, phenols, hydrazides, and imidazoles.

Examples of amines used as curing agents include, for example, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, and m-xylylenediene. Aromatic amines such as amines, ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane,
Examples thereof include aliphatic amines such as polyetherdiamine, dicyanamide, and guanidines such as 1- (o-tolyl) biguanide.

Examples of phenols used as a curing agent include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, and tetramethylbisphenol F. Methyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1-
(4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6
tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-diphenol Various phenols such as phenols having a fluorene skeleton such as -4-hydroxyphenylfluorene, phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc. Novolak resin as raw material, phenol novolak resin containing xylylene skeleton, phenol novolak resin containing dicyclopentadiene skeleton, phenol novola containing biphenyl skeleton Various novolak resins such as lac resin, phenol novolak resin containing a fluorene skeleton,
Halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol A are exemplified.

Examples of the hydrazides used as the curing agent include adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, and maleic dihydrazide.

Examples of the imidazole used as the curing agent include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2 -Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-
Undecyl imidazole, 2,4-diamino-6 (2 ′
-Methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'- Ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s
-Triazine / isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-
3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole,
Various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and those imidazoles and phthalic acid, isophthalic acid,
Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid and the like can be mentioned.

[0024] Among these curing agents, which curing agent is used is appropriately selected depending on the required properties of the curing system, but is preferably phenols, dicyandiamide, or phenol.
Guanidines such as-(o-tolyl) biguanide;
The amount of these curing agents used is in the range of 0.3 to 2.0 in an equivalent ratio of the curing agent to the epoxy group of the epoxy resin,
Preferably it is used in the range of 0.4 to 1.6, more preferably in the range of 0.5 to 1.3. The curing agents may be used as a mixture of two or more, and the imidazoles are also used as a curing accelerator.

The radiation-curable resin of the present invention refers to a resin curable by radiation such as infrared rays, visible rays, ultraviolet rays, electron beams, and X-rays. Examples of the radiation-curable resin include a (meth) acrylate compound, an epoxy compound, a vinyl ether compound, an oxetane compound, an azide compound, a diazo compound, and a nitro compound, and a (meth) acrylate compound is particularly preferable. Examples of the (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, acryloyl monophorin, isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and nonanediol di. (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol poly (meth) And acrylates such as acrylate. These can be used alone or in combination.

The polyamide resin varnish of the present invention may contain a filler. As fillers, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, and the like, preferably fused silica, crystalline silica, silicon nitride, and boron nitride , Calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide. The particle size of these fillers is 80% by weight with an average particle size of 20 μm or less
Or more, preferably 85% by weight or more, more preferably 90% by weight or more.
% By weight or more. If it is less than 80% by weight, there is a problem in smoothness. These fillers may be used alone or in a combination of two or more.

To the polyamide resin varnish of the present invention, a flame retardant, a coloring agent, a coupling agent, a leveling agent and the like can be appropriately added according to the purpose. Examples of the flame retardant include halogenated epoxy resins, antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, and calcium aluminate. Phosphoric acid-based flame retardants such as inorganic flame retardants and tris (tribromophenyl) phosphate. Further, the colorant is not particularly limited, phthalocyanine, azo, disazo, quinacridone,
Anthraquinone, flavanthrone, perinone, perylene, dioxazine, condensed azo, various azomethine organic dyes, titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermillion, valve shell, cobalt purple, navy blue,
Examples include inorganic pigments such as ultramarine, carbon black, chrome green, chromium oxide, and cobalt green.

As coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- (2-
(Aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N Silane-based cups such as-(2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane Ring agent, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphate) Site) titanate, neoalkoxy tri (p-N- (β- aminoethyl) aminophenyl)
Titanium-based coupling agents such as titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy Tris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, zirconium such as Al-propionate, or an aluminum-based coupling agent. Preferred is a silicon-based coupling agent. By using a coupling agent, a cured product having excellent moisture resistance reliability and a small decrease in adhesive strength after moisture absorption can be obtained.

As the leveling agent, acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate having a molecular weight of 4000 to 12 are used.
000 oligomers, epoxidized soybean fatty acid, epoxidized aviethyl alcohol, hydrogenated castor oil, titanium-based coupling agent, modified silicone, anionic / nonionic surfactant, and the like. The polyamide resin-containing varnish of the present invention contains the polyamide resin (A), solvent (B), curable resin (C), curing agent, filler, flame retardant, colorant, coupling agent, leveling agent, and the like. It can be obtained by mixing uniformly. The solid content concentration of the obtained varnish is usually 10
８０80% by weight, preferably 30-70% by weight.

In order to obtain the adhesive film or the adhesive layer of the present invention, a polyamide resin is applied on a substrate by a roll coater, a comma coater, a die coater, a spin coater or the like, and then dried in a heating oven. . The drying conditions largely depend on the solvent used and the film thickness, but are generally selected in the range of 80 ° C. to 180 ° C. for 30 seconds to 60 minutes. The above-mentioned curing may be carried out by a usual method according to the curable resin, curing agent, accelerator and initiator to be used.

[0031]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” means parts by weight.

Synthesis Example 1 Phenolic hydroxyl group-containing aromatic polyamide resin (hereinafter referred to as R
Synthesis of PAM) 13.29 g (80 mmol) of isophthalic acid, bis (4
-Amino-3,5-diethylphenyl) methane 31.0
5 g (10 mmol), 3.64 g (20 mmol) of 5-hydroxyisophthalic acid, 2.50 lithium chloride
g, 7.55 g of calcium chloride, 200 ml of N, N dimethylacetamide and 30 ml of pyridine in 1 liter of 4
The mixture was placed in a one-necked round-bottomed flask, and dissolved by stirring. Then, 62.05 g (20 mmol) of triphenyl phosphite was added, and the mixture was reacted at 100 ° C. for 3 hours under a stream of dry nitrogen. This was allowed to cool to room temperature, diluted with 400 ml of N, N-dimethylacetamide, and then poured into an 8 l methanol precipitation bath with stirring to obtain a crude polymer. This crude polymer was purified by a conventional method. The yield was 43.9 g (yield 9
9%).

Synthesis Example 2 Phenolic hydroxyl group-containing aromatic polyamide-polybutadiene / acrylonitrile block copolymer (hereinafter referred to as BPA
M, synthesis of 14 mol% of phenolic hydroxyl groups contained in the aromatic polyamide part, an example of a copolymer represented by the formula (2)) 19.93 g (120 mmol) of isophthalic acid, 3,
30.63 g of 4'-diaminodiphenyl ether (15
3 mmol), 3.64 g of 5-hydroxyisophthalic acid
(20 mmol), 3.9 g of lithium chloride, 12.1 g of calcium chloride, 240 m of N-methyl-2-pyrrolidone
l, 54 ml of pyridine was placed in a 1 liter four-necked round-bottomed flask, stirred and dissolved, 74 g of triphenyl phosphite was added, and the mixture was reacted at 90 ° C. for 4 hours to give a phenolic hydroxyl group-containing aromatic compound. A polyamide oligomer was produced. A polybutadiene / acrylonitrile copolymer having carboxyl groups at both ends (Hycar CTBN, BF G
Made by oodrich. A solution in which 48 g of an acrylonitrile component contained in the polybutadiene acrylonitrile portion having 17 mol% and a molecular weight of about 3600) was dissolved in 240 ml of N-methyl-2-pyrrolidone was added, and the mixture was further reacted for 4 hours. This reaction solution is poured into 20 liters of methanol, and an aromatic polyamide-polybutadiene / acrylonitrile block containing about 14 mol% of a phenolic hydroxyl group having a polybutadiene / acrylonitrile copolymer part content of 50 wt% is used in the present invention. The polymer was precipitated. The precipitated polymer was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer is 0.85 dl / g (dimethylacetamide, 30
° C). When the infrared spectrum of the polymer powder was measured by the diffuse reflection method, the absorption was based on the amide carbonyl group at 1,674 cm -1, the absorption based on the CH bond of the butadiene portion at 2,856-2975 cm -1, and the absorption based on the nitrile group at 2,245 cm -1. Absorption was observed.

[0034]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” means parts by weight.

Example 1 Epomic R-302 (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals, Inc., epoxy equivalent: 630 g / e)
q) 100.0 parts, PN-80 (phenol novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 100 g / e
q) 160 parts of triethylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point: 216 ° C.) in 0.3 part of 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole) as a curing accelerator; The mixture was stirred at room temperature and completely dissolved. Synthesis Example 1
50.0 parts by weight of the RPAM obtained in the above was added, and the mixture was stirred and completely dissolved at room temperature to obtain a polyamide resin varnish of Example 1.
The obtained polyamide resin varnish was applied on a PET film using an applicator, and dried with a hot air circulating drier at 140 ° C. for 4 minutes to obtain an adhesive film having a thickness of 30 μm. The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results.

Example 2 Epomic R-302 (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals, Inc., epoxy equivalent: 630 g / e)
q) 100.0 parts, PN-80 (phenol novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 100 g / e
q) 160 parts by weight of diethylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point: 162 ° C.) in 16.2 parts of 0.3 part of 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole) as a curing accelerator Was added and stirred at room temperature to complete dissolution. To this, 50.0 parts by weight of RPAM obtained in Synthesis Example 1 was added, and the mixture was stirred at room temperature.
It was completely dissolved to obtain a polyamide resin varnish of Example 2. The obtained polyamide resin varnish is subjected to PE using an applicator.
Coated on T film, 4 with hot air circulation dryer at 140 ℃
After drying for 30 minutes, an adhesive film having a thickness of 30 μm was obtained.
The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results.

Example 3 Epomic R-302 (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals, Inc., epoxy equivalent: 630 g / e)
q) 100.0 parts, PN-80 (phenol novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 100 g / e
q) 160 parts by weight, tripropylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point: 220 ° C.) 160 parts by 0.3 parts of 2E4MZ (2-ethyl-4-methylimidazole manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator
The mixture was stirred at room temperature and completely dissolved. To this, 50.0 parts by weight of RPAM obtained in Synthesis Example 1 was added, and the mixture was stirred and completely dissolved at room temperature to obtain a polyamide resin varnish of Example 3.
The obtained polyamide resin varnish was applied on a PET film using an applicator, and dried with a hot air circulating drier at 140 ° C. for 4 minutes to obtain an adhesive film having a thickness of 30 μm. The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results.

Example 4 Epomic R-302 (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals, Inc., epoxy equivalent 630 g / e)
q) 100.0 parts, PN-80 (phenol novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 100 g / e
q) 160 parts of triethylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point: 216 ° C.) in 0.3 part of 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole) as a curing accelerator; The mixture was stirred at room temperature and completely dissolved. Synthesis example 2
Was added and stirred and completely dissolved at room temperature to obtain a polyamide resin varnish of Example 4.
The obtained polyamide resin varnish was applied on a PET film using an applicator, and dried with a hot air circulating drier at 140 ° C. for 4 minutes to obtain an adhesive film having a thickness of 30 μm. The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results. Example 5 Epomic R-302 (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals, Inc., epoxy equivalent 630 g / e)
q) 100.0 parts, PN-80 (phenol novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 100 g / e
q) 160 parts by weight of diethylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point: 162 ° C.) in 16.2 parts of 0.3 part of 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole) as a curing accelerator Was added and stirred at room temperature to complete dissolution. To this was added 50.0 parts by weight of BPAM obtained in Synthesis Example 2, and the mixture was stirred at room temperature.
It was completely dissolved to obtain a polyamide resin varnish of Example 5. The obtained polyamide resin varnish is subjected to PE using an applicator.
Coated on T film, 4 with hot air circulation dryer at 140 ℃
After drying for 30 minutes, an adhesive film having a thickness of 30 μm was obtained.
The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results.

Example 6 Epomic R-302 (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals, Inc., epoxy equivalent: 630 g / e)
q) 100.0 parts, PN-80 (phenol novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 100 g / e
q) 160 parts by weight, tripropylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point: 220 ° C.) 160 parts by 0.3 parts of 2E4MZ (2-ethyl-4-methylimidazole manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator
The mixture was stirred at room temperature and completely dissolved. 50.0 parts by weight of the BPAM obtained in Synthesis Example 2 was added thereto, and the mixture was stirred and completely dissolved at room temperature to obtain a polyamide resin varnish of Example 6.
The obtained polyamide resin varnish was applied on a PET film using an applicator, and dried with a hot air circulating drier at 140 ° C. for 4 minutes to obtain an adhesive film having a thickness of 30 μm. The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results.

Example 7 100 parts of Kayarad R-115 (bisphenol A type epoxy acrylate, manufactured by Nippon Kayaku Co., Ltd.), Irgacure 907 (2-methyl- (4
5 parts of-(methylthio) phenyl) -2-morpholino-1-propane (manufactured by Ciba Geigy), 100 parts by weight of tripropylene glycol dimethyl ether (manufactured by Toho Chemical Industry Co., Ltd., boiling point 220 ° C) was added, and the mixture was stirred at room temperature and completely dissolved I let it. To this, 30.0 parts by weight of the BPAM obtained in Synthesis Example 2 was added, and the mixture was stirred and completely dissolved at room temperature to obtain a polyamide resin varnish of Example 7. The obtained polyamide resin varnish was applied on a PET film using an applicator, and dried with a hot air circulating drier at 80 ° C. for 30 minutes to obtain an adhesive film having a thickness of 20 μm. The adhesive film was peeled off from the PET film to obtain a sample for measuring the residual solvent amount. Table 1 shows the residual solvent amount measurement results.

The measurement of the amount of residual solvent in the examples is carried out by the following method. (1) The temperature of the hot-air circulation dryer is increased to 220 ° C. in advance. (2) Measure the weight of the aluminum foil dish and set it to W0. (3) Approximately 0.2 g of a sample is put in an aluminum foil dish and weighed to obtain W1. (4) Place the aluminum foil dish in the dryer at 220 ° C.
Dry for minutes. (5) The weight of the aluminum foil dish after drying is weighed and set as W2. (6) The residual solvent amount is calculated by the following equation. Residual solvent amount (wt%) = (W1-W2) / (W1-W
0) × 100

The measurement of the adhesion in the examples is carried out by the following method. (1) Transfer the adhesive film with a release film to a glass substrate using a laminator, peel off the release film,
What was cured under predetermined curing conditions was used as a sample. (2) According to JIS K5400, 100 test pieces having a diameter of 1 mm were formed on a test piece and a peeling test was performed using Cellotape (registered trademark). The state of peeling was evaluated by the following criteria. 〇: No peeling ×: Peeling Curing conditions: Examples 1 to 6 Thermal curing: 150 ° C. × 1 hour Example 7 UV curing: Integrated light amount 200 mJ / cm
Exposure to UV irradiation 2

Table 1 Example 1 2 3 4 5 6 7 Remaining solvent amount / wt% 0.6 0.4 0.6 0.5 0.40. 6 0.5 Adhesion ○ ○ ○ ○ ○ ○ ○

[0044]

According to the present invention, as apparent from the results in Table 1, a polyamide resin varnish is obtained in which the solvent can be easily removed at the time of film formation, and a film or an adhesive layer with less residual solvent can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 163/00 C09D 163/00 201/00 201/00 C09J 7/00 C09J 7/00 153/00 153 / 00 163/00 163/00 177/00 177/00 201/00 201/00 F term (reference) 4J002 AC071 CD022 CD032 CD052 CD062 CD072 CD112 CD122 CD132 CD142 CL071 ED036 FD206 GH00 GJ01 HA05 4J004 AA05 AA10 AA16 AB05 BA02 FA05 4J038 CE052 CG142 CQ001 DB062 DB072 DB132 DB292 DD182 DG012 DG022 DH001 GA03 GA06 GA10 JA26 KA03 MA06 MA09 NA11 NA14 NA24 PA19 PB09 4J040 DD052 DF042 DM001 EC072 EC101 EC142 ED122 EF012 EH032 GA01 GA05 GA19 GA20 HB15 KA16 MA20

Claims (11)

[Claims] 1. A polyamide resin-containing varnish comprising a phenolic hydroxyl group-containing aromatic polyamide resin (A) and a solvent (B) represented by the formula (1). Embedded image (Wherein R ₁ and R ₃ are alkyl groups having 1 to 4 carbon atoms.
₂ is an alkylene group having 2 or 3 carbon atoms. n represents 2, 3 or 4) 2. A phenolic hydroxyl group-containing aromatic polyamide resin (A) comprising a phenolic hydroxyl group-containing aromatic polyamide resin having aminoaryl groups at both terminals and a polybutadiene / acrylonitrile copolymer having carboxyl groups at both terminals. The polyamide resin-containing varnish according to claim 1, which is a block copolymer formed from: 3. The polyamide resin-containing varnish according to claim 2, wherein the phenolic hydroxyl group-containing aromatic polyamide resin (A) is a block copolymer represented by the following formula (2). Embedded image (Where x, y, z, l, m, and n are average polymerization degrees, respectively; x = 3-7, y = 1-4, z = 5-1)
5, 1 + m = integer of 2 to 200, m / (m + 1)
≧ 0.04) 4. The polyamide resin-containing varnish according to claim 1, wherein the solvent (B) is a trialkylene glycol dialkyl ether. 5. The polyamide resin-containing varnish according to claim 4, wherein the solvent (B) is a triethylene glycol dialkyl ether. 6. The varnish containing a polyamide resin according to claim 5, wherein the solvent (B) is triethylene glycol dimethyl ether. 7. The polyamide resin-containing varnish according to claim 1, further comprising a curable resin (C). 8. The polyamide resin-containing varnish according to claim 7, wherein the curable resin (C) is an epoxy resin. 9. The polyamide resin-containing varnish according to claim 7, wherein the curable resin (C) is a radiation curable resin. 10. An adhesive film and / or adhesive layer obtained by removing the solvent of the polyamide resin-containing varnish according to any one of claims 1 to 9. 11. A cured product obtained by removing the solvent of the polyamide resin varnish according to any one of claims 1 to 9, followed by curing.