JP2008045032A - Thermosetting resin composition, overcoating agent and protective film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a protective film having high long-term reliability of electric insulation, flexibility, slight warpage by curing shrinkage and especially low tackiness, an overcoating agent for obtaining the protective film and a thermosetting resin composition for providing the overcoating agent. <P>SOLUTION: The thermosetting resin composition comprises a carboxy group-containing urethane resin (A) obtained by reacting a raw material containing (a) a polyisocyanate compound, (b) a polyol compound, (c) a carboxy group-containing dihydroxy compound and (d) an N-hydroxyethylacrylamide. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, an overcoat agent and a protective film, and more specifically, from a thermosetting resin composition containing a carboxyl group-containing urethane resin, an overcoat agent comprising the resin composition, and the overcoat agent. It relates to the obtained protective film.

  Conventionally, surface protection films for flexible wiring circuits are made by punching a die that matches the pattern of a polyimide film called a coverlay film, and then pasting it with an adhesive, or UV curing with flexibility. A type or a thermosetting type overcoat agent is applied by a screen printing method, and the latter is particularly useful in terms of workability. As these curing type overcoat agents, resin compositions mainly composed of epoxy resin, acrylic resin, or composites thereof are known. These are often mainly composed of resins that have been modified, such as the introduction of a butadiene skeleton, a siloxane skeleton, a polycarbonate diol skeleton, a long-chain aliphatic skeleton, and the like. In addition, while suppressing the deterioration of chemical resistance and electrical insulation as much as possible, the improvement of flexibility and the occurrence of warpage due to curing shrinkage have been suppressed.

  However, in recent years, flexible substrates have become lighter and thinner as electronic devices become lighter and smaller, and accordingly, the effects of flexibility and curing shrinkage of the resin composition to be overcoated are becoming more prominent. . For this reason, in the present situation, the curing type overcoat agent cannot satisfy the required performance in terms of warpage due to flexibility and curing shrinkage.

  For example, Japanese Patent Application Laid-Open No. 2004-137370 (Patent Document 1) includes both end diisocyanate polyurethane and trimellitic acid obtained by reacting a polycarbonate diol using a diol having 6 or less carbon atoms as a raw material with a diisocyanate compound. Although a reacted polyamideimide resin is disclosed, there is a drawback that the long-term reliability of the electrical properties of the cured product is not sufficient.

Moreover, if the tackiness before thermosetting is high, the film cannot be wound and stored as a roll-to-roll film, and there is a problem that restrictions during production become very large.
Further, the curing of the epoxy resin and the polyimide resin used here has a problem that a high temperature is required and a curing time is very long.

In order to accelerate the curing, it is also conceivable to introduce acrylic radical polymerization. Japanese Patent Application Laid-Open No. 11-035657 discloses a dihydroxyalkanoic polycarboxylic acid as a raw material for urethane acrylate. A technique for attaching a hydroxyalkyl acrylate such as hydroxyethyl acrylate to the surface is disclosed. The hydroxyethyl acrylate used here has a very high skin irritation (PII value 8.0), not only need to be used with caution, but also if it remains unreacted after the reaction, The skin irritation of objects is also a problem. On the other hand, in order not to leave hydroxyethyl acrylate, it is necessary to reduce the amount of hydroxyethyl acrylate used relative to the isocyanate group, but the isocyanate group itself is still highly skin irritating and the isocyanate group remains. Then, there existed a fault that the storage stability of the liquid mixture using such a reaction liquid worsened. In general, when acrylate polymerization is used, particularly when used as a protective film for an electric wiring board, there is a disadvantage that adhesion to copper wiring or a substrate is poor compared to epoxy resin or polyimide resin. there were.
JP 2004-137370 A Japanese Patent Laid-Open No. 11-035657

An object of the present invention is to provide a protective film with high long-term reliability of electrical insulation, flexibility, small warpage due to curing shrinkage, and particularly low tackiness, an overcoat agent for obtaining the protective film, and thermosetting that provides the same It aims at providing a conductive resin composition.
Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have
The protective film obtained from the overcoat agent made of a thermosetting resin composition containing a specific carboxyl group-containing urethane resin has low tack before curing, fast curing, and good adhesion to the substrate. As a result, the inventors have found that the long-term reliability of electrical insulation is improved, and have completed the present invention.

That is, the present invention relates to the following [1] to [17].
[1]
A thermosetting resin composition containing a carboxyl group-containing urethane resin (A) obtained by reacting raw materials containing the following (a) to (d);
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
(D) N-hydroxyethylacrylamide.

[2]
The polyisocyanate compound (a) is
At least one compound selected from the group consisting of 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated 1,3-xylylene diisocyanate, and hydrogenated 1,4-xylylene diisocyanate The thermosetting resin composition according to [1], which is characterized in that it exists.

[3]
The polyol compound (b) is
Selected from the group consisting of polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polybutadiene polyols, hydroxylated polysilicons at both ends, and polyol compounds other than hydroxyl groups and containing 18 to 72 carbon atoms and containing no oxygen The thermosetting resin composition according to [1] or [2], which is at least one kind of compound.

[4]
The heat according to any one of [1] to [3], wherein the dihydroxy compound (c) having a carboxyl group is 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid. Curable resin composition.

[5]
The carboxyl group-containing urethane resin (A) has a number average molecular weight of 1,000 to 100,000 and an acid value of 5 to 150 mg-KOH / g [1] to
[4] The thermosetting resin composition according to any one of the above.

[6]
The number average molecular weight of the carboxyl group-containing urethane resin (A) is 2,000 to 20,000, and the acid value is 10 to 60 mg-KOH / g [1] to [4]
] The thermosetting resin composition in any one of.

[7]
The thermosetting resin composition according to any one of [1] to [6], further comprising a curing agent (B).

[8]
The thermosetting resin composition according to [7], wherein the curing agent (B) is an epoxy resin.

[9]
The curing agent (B) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, The thermosetting resin composition according to [7] or [8], which is at least one epoxy resin selected from the group consisting of a dicyclopentadiene type epoxy resin and an alicyclic epoxy resin.

[10]
Furthermore, a solvent (C) is contained, The thermosetting resin composition in any one of [1]-[9] characterized by the above-mentioned.

[11]
The solvent (C) is toluene, xylene, ethylbenzene, nitrobenzene, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methoxy Methyl propionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, n-butyl acetate, isoamyl acetate, ethyl lactate, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone , Γ-butyrolactone and dimethyl sulfoxide. The characterized thermosetting resin composition according to [10].

[12]
The thermosetting resin composition according to any one of [1] to [11], further containing inorganic and / or organic fine particles (D).

[13]
Furthermore, the antifoamer (E) is contained, The thermosetting resin composition in any one of [1]-[12] characterized by the above-mentioned.

[14]
The thermosetting resin composition according to any one of [1] to [13], further comprising a radical polymerization initiator (F).

[15]
Furthermore, the hardening accelerator (G) is contained, The thermosetting resin composition in any one of [1]-[14] characterized by the above-mentioned.

[16]
The overcoat agent which consists of a thermosetting resin composition in any one of [1]-[15].
[17]
[16] A protective film obtained from the overcoat agent according to [16].

The protective film obtained from the overcoat agent comprising the thermosetting resin composition of the present invention provides a film-forming material that is very fast and excellent in adhesion to the substrate and long-term reliability of electrical insulation.

Next, the thermosetting resin composition, overcoat agent and protective film of the present invention will be specifically described.
The thermosetting resin composition of the present invention contains a carboxyl group-containing urethane resin (A) obtained by reacting raw materials including the following (a) to (d), and usually contains a curing agent (B). Contains;
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
(D) N-hydroxyethylacrylamide.

<Carboxyl group-containing urethane resin (A)>
The carboxyl group-containing polyurethane resin (A) used in the present invention is obtained by reacting the following raw materials (a) to (d);
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
(D) N-hydroxyethylacrylamide.

Hereinafter, (a) to (d) used as raw materials for the carboxyl group-containing polyurethane resin (A) will be described.
Specific examples of the polyisocyanate compound (a) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate Methylene bis (4-cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4 , 4'-diisocyanate, 4,4'-
Examples include diisocyanates such as diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, and hydrogenated 1,4-xylylene diisocyanate. These diisocyanates can be used alone or in combination of two or more.

The polyisocyanate compound (a) usually has two isocyanate groups per molecule. However, the polyisocyanate compound (a) has a polyisocyanate group having three or more isocyanate groups such as triphenylmethane triisocyanate as long as the polyurethane of the present invention does not gel. A small amount of isocyanate can also be used.

  Among these, particularly when an alicyclic compound having 6 to 30 carbon atoms other than an isocyanate group (NCO group) is used, the cured product of the present invention is particularly excellent in long-term insulation reliability at high temperature and high humidity. Express performance. These alicyclic compounds are desirably contained in an amount of 10 mol% or more, preferably 20 mol%, more preferably 30 mol% or more based on the total amount (100 mol%) of the polyisocyanate compound (a). These alicyclic compounds include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate.

As the polyol compound (b), polycarbonate polyol, polyether polyol, polyester polyol, polylactone polyol, polybutadiene polyol, both-end hydroxylated poly-silicone, other than hydroxyl groups and containing no oxygen and having 18 to 72 carbon atoms A polyol compound is mentioned.
The polycarbonate polyol is represented by the following structural formula (1), and the starting diol component is 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5. -Pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1 , 9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol or 1,2-tetradecanediol.

  The polycarbonate diol may be a polycarbonate diol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate diol), and the use of the copolymerized polycarbonate diol is advantageous from the viewpoint of preventing crystallization of the produced polyurethane. There are many. In view of solubility in a solvent, it is preferable to partially use a polycarbonate diol having a branched skeleton.

  The polyether polyol is obtained by dehydration condensation of a diol having 2 to 12 carbon atoms or ring-opening polymerization of an oxirane compound, oxetane compound or tetrahydrofuran compound having 2 to 12 carbon atoms. It is represented by the structural formula (2).

  Specific examples include polyethylene glycol, polypropylene glycol, poly-1,2-butylene glycol, polytetremethylene glycol, poly-3-methyltetramethylene glycol, and the like. These copolymers can also be used for the purpose of improving compatibility and hydrophobicity.

  The polyester polyol is obtained by dehydration condensation of a dicarboxylic acid and a diol or an ester exchange reaction between an esterified product of a lower alcohol of a dicarboxylic acid and a diol. Specifically, the polyester polyol is represented by the following structural formula (3). The

Specific diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol or 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, 1,3-cyclohexanedi Methanol, 3-xylylene glycol, 1,4-xylylene glycol, diethylene glycol Examples include coal, triethylene glycol, dipropylene glycol and the like. Dicarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, brassic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, Examples thereof include methyl endomethylenetetrahydrophthalic acid, chlorendic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.

  The polylactone polyol is obtained by ring-opening polymerization of a diol and a lactone compound or a condensation reaction of a diol and a hydroxyalkanoic acid, and is represented by the following structural formula (4).

Specifically, 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, 5-hydroxyhexanoic acid (ε-caprolactone) and the like are listed.
The polybutadiene polyol diol is a diol obtained by polymerizing butadiene or isoprene by anionic polymerization and introducing hydroxyl groups at both ends by terminal treatment, and hydrogen reduction of those double bonds.

Specifically, hydroxylated polybutadiene mainly having 1,4-repeating units (for example, Poly bd R-45HT, Poly bd R-15HT (produced by Idemitsu Kosan Co., Ltd.)), hydroxylated hydrogenated polybutadiene (for example, Polytail H, Polytail HA (manufactured by Mitsubishi Chemical Corporation)), hydroxylated polybutadiene mainly having 1,2-repeat units (for example, G-1000, G-2000, G-3000 (manufactured by Nippon Soda Co., Ltd.)) ), Hydroxylated hydrogenated polybutadiene (for example, GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxyl-terminated polyisoprene (for example, Poly IP (produced by Idemitsu Kosan Co., Ltd.)), Hydrogenated polyisoprene (for example, Epol (made by Idemitsu Kosan Co., Ltd.)) can be mentioned.

  The both-terminal hydroxylated polysilicone is represented by the following structural formula (5).

As a commercial item, Shin-Etsu Chemical Co., Ltd. product "X-22-160AS, KF6001, KF6002, KF6003" etc. are mentioned, for example.
The polyol compound containing no oxygen other than the hydroxyl group and having 18 to 72 carbon atoms as a constituent component is specifically a diol compound having a skeleton obtained by hydrogenating dimer acid, and commercially available products include, for example, Cognis “Sovermol 908” manufactured by the company can be mentioned.

In addition, a diol having a molecular weight of 300 or less can be used as long as the physical properties are not impaired.
Specific examples of such low molecular weight diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,
2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, 1,3-cyclohexanedimethanol, 1,3-xylylene glycol, 1,4-xylylene glycol, diethylene glycol, triethylene glycol Ethylene glycol or dipropylene glycol can be raised.

  Specific examples of the dihydroxy compound (c) having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, and N, N-bishydroxyethyl. Examples include alanine, and among them, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferable from the viewpoint of solubility in a solvent. These dihydroxy compounds containing a carboxyl group can be used singly or in combination of two or more.

The carboxyl group-containing polyurethane resin (A) used in the present invention is reacted with N-hydroxyethylacrylamide (hereinafter also referred to as HEAA) (d) in order to impart radical polymerization by heat or light.

N-hydroxyethylacrylamide (d) used here has very low skin irritation (PII value of 0), and is not only easy to handle in use but also generally more functional than a polyfunctional acrylate used as a reactive diluent. Low irritation. Therefore, by using it excessively in the urethanization reaction, it is possible to increase the consumption rate of isocyanate groups that cause deterioration of the storage stability of the resin liquid by remaining high in skin irritation. .

  HEAA (d) is known to have higher polymerizability, lower hydrolyzability, and better adhesion to the substrate than 2-hydroxyethyl acrylate (hereinafter also referred to as HEA). .

  Therefore, not only for the purpose of crushing the isocyanate group, but also by actively using HEAA in excess and allowing it to remain after the reaction, radical polymerization can be improved and rapid curing can be achieved, or the amide group can be used for improving adhesiveness. It is possible to greatly contribute to improving the performance of the cured product after curing.

  The carboxyl group-containing polyurethane resin (A) used in the present invention can be used in combination with other monohydroxy compounds (e) other than (d) N-hydroxyethylacrylamide, as long as the polymerizability is not impaired. As such, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide of each of the above (meth) acrylates Adducts, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxy Ethanol, glycolic acid, hydroxypivalic acid, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butano Le, t-butanol, amyl alcohol, hexyl alcohol, octyl alcohol and the like.

Of course, when using those having high skin irritation such as hydroxy acrylate, it is necessary to take care not to leave them. For that purpose, it is only necessary to react hydroxyethyl acrylate when the isocyanate group concentration is high and confirm that it is sufficiently consumed, and then add hydroxyethyl acrylamide. They can be used in combination.

When the carboxyl group-containing polyurethane resin (A) used in the present invention is obtained by reacting only (a) to (d) as raw materials, when the total amount of (a) to (d) is 100% by mass, a) polyisocyanate 10-80% by mass, (b) 5-80% by mass of a polyol compound, (c) 5-40% by mass of a dihydroxy compound having a carboxyl group, (d) 5-80% by mass of N-hydroxyethylacrylamide. And (a) the total number of moles of isocyanate groups of the polyisocyanate> ((b) the total number of moles of hydroxyl groups of the polyol compound + (c) the total number of moles of hydroxyl groups of the dihydroxy compound having a carboxyl group) {((A) total number of moles of isocyanate groups of polyisocyanate compound-((b) total number of hydroxyl groups of polyol compound) The total number of moles of the dihydroxy compound having a number + (c) a carboxyl group)) <(d) the number of moles of N- hydroxyethyl acrylamide.

When the carboxyl group-containing polyurethane resin (A) used in the present invention is obtained by reacting (a) to (d) and (e) as raw materials, the total amount of (a) to (d) is 100 masses. %, (A) 10 to 80% by mass of polyisocyanate, (b) 5 to 80% by mass of polyol compound, (c) 5 to 40% by mass of dihydroxy compound having a carboxyl group, (d) N-hydroxyethylacrylamide 5 -80 mass%, (e) in the range of 5-40 mass% of other monohydroxy compounds, and (a) the total number of moles of isocyanate groups of the polyisocyanate> ((b) the total number of hydroxyl groups of the polyol compound Number of moles + (c) total number of moles of hydroxyl groups of the dihydroxy compound having a carboxyl group),
{((A) total number of moles of isocyanate group of polyisocyanate compound-((b) total number of moles of hydroxyl group of polyol compound + (c) total number of moles of dihydroxy compound having carboxyl group)) <(( d) moles of N-hydroxyethylacrylamide + (e) moles of other monohydroxy compounds)
(D) Number of moles of N-hydroxyethylacrylamide> (e) Number of moles of other monohydroxy compounds.

As the use ratio of (c), the use molar amount is determined so that the acid value of the carboxyl group-containing polyurethane resin (A) to be generated is 5 to 150 mg-KOH / g, more preferably 10 to 60 mg / KOH.

  The acid value is a measure of the concentration of the functional group that reacts with the epoxy resin of the curing agent. If it is too high, the cured product becomes brittle, and conversely if it is too low, it will hinder heat resistance and curing speed. The However, when it is desired to impart alkali developability as a photoresist, the acid value is desirably set to 60 mg / KOH or more from the viewpoint of solubility during development.

In the present specification, the acid value of the resin is a value measured by the following method.
About 0.2 g of a sample is precisely weighed in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / toluene = 1/2 (weight ratio) is added and dissolved therein. Further, 1 to 3 drops of phenolphthalein ethanol solution is added to this container as an indicator, and the mixture is sufficiently stirred until the sample becomes uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is taken when the indicator is slightly red for 30 seconds. The value obtained from the result using the following formula (Equation 1) is taken as the acid value of the resin.

  The number average molecular weight of the carboxyl group-containing polyurethane resin (A) used in the present invention is preferably 1,000 to 100,000, and more preferably 2,000 to 20,000. Here, the molecular weight is a value in terms of polystyrene measured by gel permeation chromatography. If the molecular weight is less than 1,000, the elongation, flexibility and strength of the cured film may be impaired. If the molecular weight exceeds 100,000, the solubility of the polyurethane in the solvent becomes low and the viscosity even if dissolved. Since it becomes too high, restrictions may be increased in terms of use.

In this specification, unless otherwise specified, the GPC measurement conditions are as follows.
Device name: JASCO Corporation HPLC unit HSS-2000
Column: Shodex column LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample amount: Sample loop 100 μl Sample concentration: prepared at around 0.1 wt% The carboxyl group-containing polyurethane resin (A) of the present invention is used in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate, Using an appropriate organic solvent, the polyisocyanate compound (a), polyol compound (b), dihydroxy compound having a carboxyl group (c), and N-hydroxyethylacrylamide (d), if necessary, other than (d) The other monohydroxy compound (e) can be synthesized by reacting, but when it is reacted without a catalyst, the physical property value in actual use as a cured film is finally improved.

  As a raw material charging method, all the raw materials may be charged all at once, but when the compounds of (a), (b), and (c) are reacted in advance and become a certain high molecular weight, ( It is better to prepare d) and (e) if necessary.

As the organic solvent, any solvent having low reactivity with isocyanate can be used, and a solvent containing no basic functional group such as amine is preferable. Examples of such solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether. Acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone γ- butyrolactone, dimethyl sulfoxide, can be mentioned chloroform and methylene chloride. Among them, a solvent having a boiling point of 110 ° C. or higher, preferably 200 ° C. or higher is preferable.

  In view of the fact that the organic solvent having low solubility of the resulting carboxyl group-containing polyurethane is not preferable, and considering that polyurethane is used as a raw material for ink in electronic material applications, among these, in particular, propylene glycol methyl ether acetate, propylene Glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, γ-butyrolactone and the like are preferable.

As the reaction temperature, after the raw materials are charged and dissolved in the solvent, the diisocyanate compound (a) is added dropwise at 20 to 150 ° C., more preferably 60 to 120 ° C.,
These are reacted at 30 to 160 ° C, more preferably at 50 to 130 ° C.

Further, when N-hydroxyethyl acrylamide (d) is charged later, both of the polyurethanes are obtained when the reaction between the polycarbonate polyol (b) and the dihydroxy compound (c) and the diisocyanate (a) is almost completed. In order to react the isocyanate group remaining at the terminal with N-hydroxyethylacrylamide (d), N-hydroxyethylacrylamide (d) is added to the polyurethane solution at 20 to 150 ° C, more preferably 70 to 120 ° C. After that, the reaction is completed by holding at the same temperature.
For the purpose of preventing polymerization during the reaction, hydroquinone, p-methoxyphenol (methoquinone), t-butylhydroquinone (TBHQ), 2,6-di-t-butyl-4-methylphenol (BHT), 2- A polymerization inhibitor such as t-butyl-4-methoxyphenol (BHA) or 4-t-butylcatechol (TBC) may be added.

<Curing agent (B)>
The thermosetting resin composition of the present invention usually contains a curing agent (B). The curing agent (B) is not particularly limited as long as it can cure the carboxyl group-containing polyurethane, but an epoxy resin is preferable.

  Examples of the curing agent (B) include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, Chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, silicone modified epoxy resin, ε-ca Epoxy compounds having two or more epoxy groups in one molecule, such as Rorakuton modified epoxy resins. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin An alicyclic epoxy resin is preferred. As said hardening | curing agent (B), 1 type may be used individually or 2 or more types may be used.

  Further, in order to impart flame retardancy, a material in which an atom such as halogen such as chlorine or bromine or phosphorus is introduced into the structure may be used. Furthermore, bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylenoyl ethane resin, and the like may be used.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups. However, an epoxy resin monofunctional epoxy resin may be contained.
Moreover, when providing alkali developability after photocuring, the one where the molecular weight of the epoxy resin to be used is smaller is preferable.

  When an epoxy resin is blended as the curing agent (B), the epoxy group of the curing agent (B) should be used in the range of 0.5 to 2 equivalents relative to the carboxyl group of the carboxyl group-containing polyurethane resin (A). Is preferred.

<Solvent (C)>
The thermosetting resin composition of the present invention preferably further contains a solvent (C). More preferably, the carboxyl group-containing polyurethane resin (A) is preferably dissolved in a solvent, and the carboxyl group-containing polyurethane resin (A) is contained in the solvent used for the synthesis of the carboxyl group-containing polyurethane resin (A). It is particularly preferable that it is in a dissolved state.

  After the synthesis, when trying to obtain a thermosetting resin composition with the resin as a solid, it is difficult to disperse the thermosetting resin without using a solvent, and the step of dissolving the solid with a solvent after the synthesis Is necessary and economically undesirable.

The solvent is not particularly limited as long as it can dissolve the thermosetting resin, but preferably has a boiling point of 30 ° C to 400 ° C, more preferably a boiling point of 110 ° C to 300 ° C.
Toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methoxypropion Methyl acid, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N, N-dimethyl Acetamide, N-methylpyrrolidone, γ- Butyrolactone, dimethyl sulfoxide, and the like can be exemplified chloroform and methylene chloride.

  Among them, toluene, xylene, ethylbenzene, nitrobenzene, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, methoxypropion Ethyl acetate, methyl ethoxypropionate, ethyl ethoxypropionate, n-butyl acetate, isoamyl acetate, ethyl lactate, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone and dimethyl Sulfoxide is preferred.

  As a solvent amount, the carboxyl group-containing polyurethane concentration (solid content concentration) in the thermosetting resin composition is preferably 20 to 90% by weight, more preferably 30 to 70% by weight.

<Inorganic and / or organic fine particles (D)>
The thermosetting resin composition of the present invention may further contain inorganic and / or organic fine particles (D).

  Known inorganic and / or organic fine particles (D) can be used. Further, the blending ratio varies depending on the selection of the carboxyl group-containing polyurethane resin (A), and when it is added, it is preferably in the range of 5 to 40 wt% with respect to the entire thermosetting resin composition. Organic fine particles include epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, silicone powder, etc., and inorganic fine particles include silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, Mention may be made of inorganic fillers such as glass powder and quartz powder.

In the case of adding the inorganic and / or organic fine particles (D), if the total of (A) and (B) is 100 parts by mass, 5 to 200 parts by weight, more preferably 5 to 100 parts by weight are added.
<Defoamer (E)>
The thermosetting resin composition of the present invention may further contain an antifoaming agent (E). As the antifoaming agent (E), a silicone-based antifoaming agent or a non-silicone-based antifoaming agent is used, and in particular, it is used in consideration of bubble entrainment properties and bubble removal properties during screen printing. These may be used in combination. For example, as a silicone type antifoaming agent, KS-602A (made by Shin-Etsu Chemical Co., Ltd .: trade name), KS-603 (made by Shin-Etsu Chemical Co., Ltd .: trade name), KS-608 (made by Shin-Etsu Chemical Co., Ltd.) : Trade name), FA600 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), BYK-A506 (manufactured by BYK Japan, Inc .: trade name), BYK-A525 (manufactured by BYK Japan, Inc .: trade name), BYK- A530 (BIC Chemie Japan Co., Ltd .: trade name), as non-silicone antifoaming agents, BYK-A500 (BIC Chemie Japan Co., Ltd .: trade name), BYK-A500 (BIC Chemie Japan Co., Ltd .: trade name) ), BYK-A501 (BIC Chemie Japan Co., Ltd .: trade name), BYK-A515 (BIC Chemie JA Made emissions Co., Ltd. trade name), BYK-A555 (BYK Chemie Japan Co., Ltd .: trade name), etc., are preferably used. When adding an antifoamer (E), 0.1-5 weight part is added when the whole thermosetting resin composition is 100 weight part, Preferably 0.5-3 weight part is added.

<Radical polymerization initiator (F)>
The thermosetting resin composition of the present invention may further contain a radical polymerization initiator (F). As the radical polymerization initiator (F), any radical polymerization initiator can be used, and examples thereof include azo-based, organic peroxides, and photopolymerization initiators.

For example, 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, 2,2'-
Azo compounds such as azobis (2,4-dimethylvaleronitrile), methyl peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyryl peroxide, benzoyl peroxide, 2 Diacyl peroxides such as 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide Hydroperoxides such as oxide, cumene hydroperoxide, t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, tris (t-butylperoxy) triazi Dialkyl peroxides such like, 1,1-di -t-
Peroxyketals such as butylperoxycyclohexane and 2,2-di (t-butylperoxy) butane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylper Oxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, Alkyl peresters such as t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyisopropyl Parker carbonates such as carbonates are listed.

Examples of radical polymerization initiators that can be used for photopolymerization such as ultraviolet rays include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4′-isopropyl-2-hydroxy-2-methylprote. Piophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis (diethylamino) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o -Ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, Benzyl dimethyl ketal, benzyl diethyl ketal, Carbonyl compounds such as acetyl, methyl anthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methyl thioxanthone, anthraquinone or thioxanthone derivatives such as 2-isopropylthioxanthone, diphenyl disulfide, sulfur compounds such as dithiocarbamate and the like.

When using a radical polymerization initiator (F), it is preferable to add 0.1-5 weight part, when a carboxyl group-containing urethane resin (A) is 100 weight part.
<Curing accelerator (G)>
The thermosetting resin composition of the present invention may further contain a curing accelerator (G). Examples of the curing accelerator (G) include imidazole derivatives (for example, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, manufactured by Shikoku Chemical Industry Co., Ltd.) 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, etc.); Polyamines such as diphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide; these organic acid salts and / or epoxy adducts; Boron amine complexes; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N -Amines such as dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak; organic phosphines such as tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine; tri-n-butyl Phosphonium salts such as (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the polybasic acid anhydride; diphenyliodonium tetrafluoroboroate , Triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, manufactured by Ciba Geigy, Irgacure 261, manufactured by Asahi Denka Co., Ltd., Optoma-SP-170, etc. Polymerization catalyst; styrene-maleic anhydride resin; equimolar reaction product of phenyl isocyanate and dimethylamine, presence of tolylene diisocyanate, isophorone diisocyanate, etc. Polyisocyanate and the curing agents or curing accelerators such known conventional such equimolar reaction product of dimethyl amine.

When using a hardening accelerator (G), it is preferable to add 0.1-5 weight part, when a carboxyl group-containing urethane resin (A) is 100 weight part.
<Copolymerizable monomer (H)>
Further, curing may be carried out in the presence of a copolymerizable monomer (H) having good polymerizability with acrylamide in the carboxyl group-containing polyurethane of the present invention.

As the copolymerizable monomer (H), any monomer capable of radical copolymerization with an acrylamide double bond can be used. For example, acrylamide and its derivatives, (meth) acrylic acid ester and its derivatives, styrene And derivatives thereof, vinyl acetate and derivatives thereof, (meth) acrylonitrile and derivatives thereof, vinyl esters and derivatives of organic carboxylic acids, allyl esters and derivatives of organic carboxylic acids, dialkyl esters and derivatives of fumaric acid, maleic acid Examples thereof include dialkyl esters and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinylamide derivatives of organic carboxylic acids, maleimides and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof, and the like.
Acrylamide and its derivatives include acrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, acryloylmorpholine, N, N-diethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide and the like.

As (meth) acrylic acid esters and derivatives thereof, monofunctional or use amount is limited, but polyfunctional (meth) acrylate can also be used, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, (
(Meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-
sec-butyl, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic 2-hydroxybutyl acid, 2-hydroxyphenylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, triethyle Glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta ) Acrylamide, N-acryloylmorpholine and the like.

Examples of styrene and derivatives thereof include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2 , 6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethyl Styrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy Styrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxys Len, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyl Toluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl -Α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene and the like.

Examples of (meth) acrylonitrile and derivatives thereof include acrylonitrile and methacrylonitrile.
Examples of vinyl esters of organic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate.

  Examples of allyl esters of organic carboxylic acids and derivatives thereof include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

Dialkyl esters of fumaric acid and derivatives thereof include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate And dibenzyl fumarate.

Dialkyl esters of maleic acid and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate And dibenzyl maleate.

Dialkyl esters of itaconic acid and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate And dibenzyl itaconate.

Examples of N-vinylamide derivatives of organic carboxylic acids include N-methyl-N-vinylacetamide.
Examples of maleimide and derivatives thereof include N-phenylmaleimide and N-cyclohexylmaleimide.

Examples of terminal unsaturated hydrocarbons and derivatives thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and allyl alcohol.
<Additive (I)>
The thermosetting resin composition of the present invention may further contain an additive (I). As the additive (I), various known additives, for example, fiber reinforcing materials such as glass fiber, carbon fiber and boron nitride fiber, colorants such as titanium oxide, zinc oxide, carbon black, iron black, organic pigment, organic dye, etc. Antioxidants such as hindered phenol compounds, phosphorus compounds and hindered amine compounds, and UV absorbers such as benzotriazole compounds and benzophenone compounds can be blended.

Moreover, a viscosity modifier, a flame retardant, an antibacterial agent, an antifungal agent, an anti-aging agent, an antistatic agent, a plasticizer, a lubricant, a foaming agent, and the like can be added and mixed according to the application.
<Thermosetting resin composition, overcoat agent, and protective film>
The thermosetting resin composition of the present invention contains a carboxyl group-containing urethane resin (A) as described above, usually further contains a curing agent (B), and optionally contains a solvent (C), inorganic and / or Or it contains organic fine particles (D), antifoaming agent (E), radical polymerization initiator (F), curing accelerator (G), copolymerizable monomer (H), and additive (I), and these are kneaded. Can be obtained. As a kneading method, a mixer such as a disper, a kneader, a three-roll mill, a bead mill, or a homogenizer can be used.

The overcoat agent of this invention consists of the said thermosetting resin composition.
The overcoat agent of the present invention can be obtained by curing using a curing method such as drying, light irradiation, and heating after coating by screen printing or the like.

The protective film of the present invention thus obtained is excellent in high temperature tackiness, adhesion to a substrate, low warpage, flexibility, plating resistance, solder heat resistance, and long-term reliability of electrical insulation. .
In addition, since the carboxyl group-containing urethane resin (A) has an acrylamide group and a carboxyl group, when the carboxyl group-containing urethane resin (A) has a relatively low molecular weight and a high acid value, it is a polyfunctional acrylate. By combining with the above, patterning can also be performed by a photolithography method using ordinary alkali development, and the utility as a solder resist is high.

The overcoat agent of the present invention can be simply cured by heating after coating by screen printing or the like, and in the case of a carboxyl group-containing urethane resin (A) having a high acid value, a mask as a so-called photopatterning resin. It is also possible to irradiate with light, dissolve the unexposed portion with an alkali developer, and then cure with heat.
[Example]
Examples The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Production Example 1]
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 37.11 g of T-4691 (polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation) as the polyol compound (b), and 2,2 as the dihydroxy compound (c) having a carboxyl group -28.77 g of dimethylolpropionic acid (manufactured by Nippon Kasei Co., Ltd.) and 129.68 g of diethylene glycol ethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.) as a solvent were dissolved in 2,2-dimethylolpropionic acid at 90 ° C ( Some insolubles). The temperature of the reaction solution was lowered to 70 ° C., and 55.49 g of Takenate 600 (manufactured by Mitsui Takeda Chemical Co., Ltd.) was added dropwise as a polyisocyanate compound (a) over 30 minutes with a dropping funnel. After completion of the dropping, the reaction was carried out at 80 ° C. for 6 hours, and after confirming that the isocyanate had almost disappeared, 8.47 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 1.5 hours.

The obtained carboxyl group-containing urethane resin (A-1) had a number average molecular weight of 3490 and a solid acid value of 92.7 mgKOH / g.
[Production Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 42.93 g of T-4691 (polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation) as the polyol compound (b) and 2,2 as the dihydroxy compound (c) having a carboxyl group -26.83 g of dimethylolpropionic acid (manufactured by Nippon Kasei Co., Ltd.) and 126.38 g of diethylene glycol ethyl ether acetate (manufactured by Daicel Chemical Co., Ltd.) as a solvent were prepared, and 2,2-dimethylolpropionic acid was dissolved at 90 ° C ( Some insolubles). The temperature of the reaction solution was lowered to 70 ° C., and 48.43 g of T-65 / 35 (manufactured by Mitsui Takeda Chemical Co., Ltd.) was added dropwise over 30 minutes as a polyisocyanate compound (a) using a dropping funnel. After completion of dropping, the reaction was carried out at 80 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 7.94 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 2 hours.

The obtained carboxyl group-containing urethane resin (A-2) had a number average molecular weight of 2000 and a solid acid value of 89.0 mgKOH / g.
[Production Example 3]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 35.33 g of T-4691 (polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation) as the polyol compound (b) and 2,2 as the dihydroxy compound (c) having a carboxyl group -58.95 g of dimethylol butanoic acid (manufactured by Nippon Kasei Chemical Co., Ltd.) and 205.78 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as a solvent were dissolved in 2,2-dimethylol butanoic acid at 70 ° C. Then, 97.12 g of Takenate 600 (manufactured by Mitsui Takeda Chemical Co., Ltd.) was dropped as the polyisocyanate compound (a) over 30 minutes. After completion of the dropping, the reaction was carried out at 80 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 14.39 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 2 hours.

The obtained carboxyl group-containing urethane resin (A-3) had a number average molecular weight of 3300 and a solid acid value of 108.3 mgKOH / g.
[Production Example 4]
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 52.41 g of P-530 (polyester diol manufactured by Kuraray Co., Ltd .: isophthalic acid + 3-methyl-1,5-pentanediol) as a polyol compound (b), carboxyl 37.12 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as the dihydroxy compound (c) having a group, 203.68 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as the solvent, 2-dimethylolbutanoic acid was dissolved, and 104.94 g of Dismodule-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise over 30 minutes as a polyisocyanate compound (a) with a dropping funnel. After completion of the dropwise addition, the reaction was carried out at 90 ° C. for 4 hours. After confirming that the isocyanate had almost disappeared, 9.21 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 2 hours.

The obtained carboxyl group-containing urethane resin (A-4) had a number average molecular weight of 5100 and a solid acid value of 68.9 mgKOH / g.
[Production Example 5]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 91.85 g of UM-CRAB90 (3/1) (polycarbonate diol manufactured by Ube Industries, Ltd.) as a polyol compound (b), a dihydroxy compound having a carboxyl group (c) ), 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Chemical Co., Ltd.) 32.18 g, and diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) 205.92 g as a solvent, and 2,2-dimethylolbutanoic acid at 70 ° C. It melt | dissolved and 73.66g of NBDI (made by Mitsui Takeda Chemical Co., Ltd.) was dripped over 30 minutes as a polyisocyanate compound (a) with the dropping funnel. After completion of the dropwise addition, the reaction was carried out at 90 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 8.22 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was dropped, and further 90 ° C. For 2 hours.

The obtained carboxyl group-containing urethane resin (A-5) had a number average molecular weight of 5770 and an acid value of solid content of 59.1 mgKOH / g.
[Production Example 6]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 91.09 g of C-1015N (polycarbonate diol manufactured by Kuraray Co., Ltd.) as a polyol compound (b) and 2,2- as a dihydroxy compound (c) having a carboxyl group. 31.6 g of dimethylolbutanoic acid (manufactured by Nippon Kasei Chemical Co., Ltd.) and 205.92 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as a solvent are charged, and 2,2-dimethylolbutanoic acid is dissolved at 70 ° C. Then, 71.12 g of NBDI (Mitsui Takeda Chemical Co., Ltd.) was added dropwise as the polyisocyanate compound (a) over 30 minutes. After completion of the dropwise addition, the reaction was carried out at 90 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, N-hydroxyethylacrylamide (d) (Kojin Co., Ltd.)
7.94 g) was added dropwise, and the reaction was further carried out at 90 ° C. for 2 hours.

The obtained carboxyl group-containing urethane resin (A-6) had a number average molecular weight of 5850 and a solid content acid value of 58.7 mgKOH / g.
[Production Example 7]
In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 82.39 g of P-530 (polyester diol manufactured by Kuraray Co., Ltd .: isophthalic acid + 3-methyl-1,5-pentanediol) as a polyol compound (b), carboxyl 12.18 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as the dihydroxy compound (c) having a group, and 201.21 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as the solvent, 2-dimethylolbutanoic acid was dissolved, and 87.45 g of Dismodule-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate compound (a) over 30 minutes using a dropping funnel. After completion of the dropping, the reaction was carried out at 90 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 19.19 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 2 hours.

The obtained carboxyl group-containing urethane resin (A-7) had a number average molecular weight of 2410 and a solid content acid value of 22.9 mgKOH / g.
[Production Example 8]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 48.0 g of P-530 (polyester diol manufactured by Kuraray Co., Ltd .: isophthalic acid + 3-methyl-1,5-pentanediol) as a polyol compound (b), carboxyl 28.38 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as the dihydroxy compound (c) having a group, and 20.64 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as the solvent, 2-dimethylolbutanoic acid was dissolved, and 101.88 g of Dismodule-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate compound (a) over 30 minutes using a dropping funnel. After completion of the dropwise addition, the reaction was carried out at 90 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 22.36 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 2 hours.

The obtained carboxyl group-containing urethane resin (A-8) had a number average molecular weight of 2070 and an acid value of solid content of 53.5 mgKOH / g.
[Reference Example 1]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 48.0 g of P-530 (polyester diol manufactured by Kuraray Co., Ltd .: isophthalic acid + 3-methyl-1,5-pentanediol) as a polyol compound (b), carboxyl 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Chemical Co., Ltd.) 23.4 g as a dihydroxy compound (c) having a group, and 20.64 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as a solvent, 2-dimethylolbutanoic acid was dissolved, and 101.88 g of Dismodule-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate compound (a) over 30 minutes using a dropping funnel. After completion of the dropwise addition, the reaction was carried out at 90 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 22.5 g of N-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added dropwise, and the temperature was further increased to 90 ° C. For 2 hours.

The obtained polyurethane (S-1) had a number average molecular weight of 2070 and an acid value of solid content of 54.3 mgKOH / g.
[Reference Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 48.0 g of P-530 (polyester diol manufactured by Kuraray Co., Ltd .: isophthalic acid + 3-methyl-1,5-pentanediol) as a polyol compound (b), carboxyl 28.38 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) as the dihydroxy compound (c) having a group, and 20.64 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) as the solvent, 2-dimethylolbutanoic acid was dissolved, and 101.88 g of Dismodule-W (manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as a polyisocyanate compound (a) over 30 minutes using a dropping funnel. After completion of the dropwise addition, the reaction was carried out at 90 ° C. for 4 hours. After confirming that the isocyanate had almost disappeared, 14.5 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the reaction was further carried out at 90 ° C. for 2 hours. Went.

The obtained polyurethane (S-2) had a number average molecular weight of 2060 and an acid value of solid content of 55.7 mgKOH / g.
[Reference Example 3]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 107.5 g of P-530 (polyester diol manufactured by Kuraray Co., Ltd .: isophthalic acid + 3-methyl-1,5-pentanediol) as a polyol compound (b), solvent 200 g of diglyme (manufactured by Maruzen Petrochemical Co., Ltd.) is charged, and 76.4 g of Dismodule-W (manufactured by Sumika Bayer Urethane Co., Ltd.) is added as a polyisocyanate compound (a) for 30 minutes using a dropping funnel at 70 ° C. It was dripped over. After completion of the dropwise addition, the reaction was performed at 90 ° C. for 4 hours, and after confirming that the isocyanate had almost disappeared, 16.7 g of N-hydroxyethylacrylamide (d) (manufactured by Kojin Co., Ltd.) was added dropwise, and further 90 ° C. For 2 hours.

The number average molecular weight of the obtained polyurethane (S-3) was 2020.
<Evaluation of thermosetting resin composition>
Various physical properties in Examples and Comparative Examples were measured and evaluated by the following methods.

  The thermosetting resin composition was applied to the substrate by screen printing using a # 100 mesh polyester plate as an overcoat agent. Table 2 shows the results of evaluation of high temperature tackiness, adhesion, warpage, flexibility, plating resistance, solder heat resistance and long-term reliability under the following conditions.

[Adhesion]
A 75 μm-thick polyimide film [Kapton (registered trademark) 300H, manufactured by Toray DuPont Co., Ltd.] was used as the substrate, and the printed film was dried at 80 ° C. for 30 minutes, and then thermally cured at 150 ° C. for 1 hour. The film after thermosetting was subjected to a cross cut test according to JISK5600-5-6.

[Low warpage]
A 25 μm-thick polyimide film [Kapton (registered trademark) 300H, manufactured by Toray DuPont Co., Ltd.] was used as the substrate, and the printed film was dried at 80 ° C. for 30 minutes, and then thermally cured at 150 ° C. for 1 hour. The film after thermosetting was cut into a circle with a diameter of 50 mm, placed with the printed surface facing upward, and evaluated according to the following criteria.

○: The maximum warp height is less than 5 mm. X: The maximum warp height is 5 mm or more.
[Flexibility]
A 25 μm-thick polyimide film [Kapton (registered trademark) 100H, manufactured by Toray DuPont Co., Ltd.] was used as the substrate, and the printed film was dried at 80 ° C. for 30 minutes, and then thermally cured at 150 ° C. for 1 hour. The polyimide film on which the solder resist ink was applied and heat-cured was bent 180 ° outward so that the cured film was whitened. The flexibility was evaluated according to the following criteria.

○: No whitening of the cured film ×: Whitening or cracking of the cured film occurs.
[Plating resistance]
A printed circuit board made of copper foil (thickness: 35 μm), single area layer polyimide film (thickness: 50 μm) is washed with an acidic degreasing agent AC-401, and washed with water. Then, what was dried at 70 degreeC for 3 minutes was used. After printing, drying at 80 ° C. for 30 minutes, thermosetting at 150 ° C. for 1 hour, washing with water, and then immersed in an aqueous solution (40 ° C.) of 200 ml / l IPC Clean S135 (Okuno Pharmaceutical Co., Ltd.) for 4 minutes. . Then, it was immersed in an aqueous solution (23 ° C.) of 100 g / l (NH ₄ ) ₂ S ₂ O ₈ +10 ml / l H ₂ SO ₄ for 1 minute, and then immersed in an aqueous 10 mass% H ₂ SO ₄ solution (23 ° C.) for 1 minute. Then, it was immersed in an aqueous 3.5 mass% HCl solution (23 ° C.) for 1 minute, and then in an aqueous solution (23 ° C.) of 200 ml / l IPC Axela (Okuno Pharmaceutical Co., Ltd.) for 1 minute. The substrate washed in this manner was subjected to an electroless Ni plating solution at 80 ° C. (IPC Nicolon GM-SD Ni concentration 5.0 g / l, pH 4.6, manufactured by Okuno Pharmaceutical Co., Ltd.) for 20 minutes, 3.5% by mass. Immerse in an aqueous HCl solution (23 ° C.) for 1 minute, and then in an electroless Au plating solution (IM-GOLD IB Au concentration 2.0 g / l, pH 4.8, manufactured by Nippon Kojun Chemical Co., Ltd.) at 85 ° C. for 20 minutes Soaked. Thereafter, the sample was immersed in ion exchange water at 80 ° C. for 10 minutes, and then the test piece was dried at 80 ° C. for 3 minutes using a hot air circulation dryer.

Using the optical microscope, the chemical | medical solution used by the plating process observed the sample obtained here sunk into the interface of a resist surface and copper, and evaluated visually the discoloration of the resist film.
○: Neither discoloration of the cured film nor retraction of the plating Δ: Although there was penetration of the plating, no discoloration of the cured film ×: Discoloration of the cured film or retraction of the plating.

[Solder heat resistance]
In accordance with JIS C-6481 test method, printed circuit board made of copper foil (thickness 35 μm) and single area layer polyimide film (thickness 50 μm) as the base material [Iupicel (registered trademark) N, manufactured by Ube Industries, Ltd.] Was washed with a 1% aqueous sulfuric acid solution, washed with water, and dried with an air stream. After printing, the film was dried at 80 ° C. for 30 minutes and then thermally cured at 150 ° C. for 1 hour. The substrate on which the thermosetting resin composition was applied and thermoset was floated in a 260 ° C. solder bath for 10 seconds, the cured film was visually observed, and solder heat resistance was evaluated according to the following criteria.
○: No swelling or soldering of the cured film ×: There is swelling or soldering of the cured film.

[Long-term reliability of electrical insulation (long-term insulation characteristics)]
A flexible copper-clad laminate (trade name: UPISEL-N BE1310 (trade name: UPISEL-N BE1310) using a 200-mesh stainless steel screen plate with a mixture of the main agent and the curing agent so as to have a thickness of 16 μm (after drying). Grade name), applied to a comb-shaped substrate (copper wiring width / copper wiring width = 50 μm / 50 μm) manufactured by etching Ube Industries, Ltd.) (excluding wiring connection portion), and at 75 ° C. for 30 minutes. It dried using the hot air circulation type dryer.

  Next, the whole surface exposure of the irradiation amount of 500 mJ / cm <2> was performed using the ultraviolet-ray exposure apparatus (model | form: EXP-2807-B-02 Co., Ltd. product made from Oak Manufacturing Co., Ltd.). Thereafter, with a 1% by mass sodium carbonate aqueous solution at 30 ° C., 1.5 times the shortest development time obtained in the developability test (however, when the shortest development time is 15 seconds or less, the development time is 23 seconds) ), Spray-washed at a pressure of 110 kPa, and then spray-washed with ion-exchanged water at 30 ° C. at a pressure of 60 kPa for the same time as the development time, and then heated at 150 ° C. for 1 hour to prepare test pieces.

Using this test piece, a bias voltage of 100 V was applied, and a temperature and humidity steady test under conditions of a temperature of 85 ° C. and a humidity of 85% RH was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV Co., Ltd.). .
○: Neither migration nor decrease in insulation resistance value ×: Migration or decrease in insulation resistance value occurred in 1000 hours or less.

[Example 1]
Carboxy group-containing urethane resin (A-1) obtained in Example 1 (solid content concentration 50% by mass, acid value 92.7 mg-KOH / g) 100 g, Epicoat 834 (Epoxy equivalent 245 manufactured by Japan Epoxy Resin Co., Ltd.) 44.5 g, 1 g of melamine, Perhexa TMH (manufactured by Nippon Oil & Fats Co., Ltd.) 1.0 g, Aerosil R-974 (manufactured by Nippon Aerosil Co., Ltd.) 5.0 g, BYK-051 (manufactured by Big Chemie Japan Co., Ltd.) as an antifoaming agent ) The thermosetting resin composition 1 was prepared by mixing at a rate of 0.8 g and kneading with a three roll mill (model, RIII-1RM-2 manufactured by Kodaira Seisakusho Co., Ltd.).

Adhesion, low warpage, flexibility, plating resistance, solder heat resistance, and long-term reliability of electrical insulation were measured. The results are shown in Table 2.
[Examples 2 to 9]
In the same manner as in Example 1, thermosetting resin compositions 2 to 9 having the compositions shown in Table 1 were prepared.

Adhesion, low warpage, flexibility, plating resistance, solder heat resistance, and long-term reliability of electrical insulation were measured. The results are shown in Table 2.
[Comparative Examples 1-3]
Thermosetting resin compositions 10-12 were prepared with the composition shown in Table 1 in the same manner as in Example 1.

  Adhesion, low warpage, flexibility, plating resistance, solder heat resistance, and long-term reliability of electrical insulation were measured. The results are shown in Table 2.

  As described above, according to the present invention, the protective film having excellent adhesion to the base material, low warpage, flexibility, plating resistance, solder heat resistance, and long-term reliability at high temperature and high humidity, the protection An overcoat agent providing a film and a thermosetting resin composition can be provided. Further, the thermosetting resin composition of the present invention includes a thermosetting flexible circuit overcoat resin excellent in flexibility, an electrically insulating material such as a thermosetting solder resist and an interlayer insulating film excellent in insulation characteristics, and an IC. And can be used in fields such as VLSI sealing materials and laminated plates.

When the thermosetting resin composition of the present invention is used as an overcoat agent, it can be produced at a lower cost than a liquid polyimide ink used conventionally. Furthermore, the conventional protective film is
It was difficult to satisfy both adhesion strength and long-term reliability of electrical insulation at the same time, but in the present invention, good adhesion strength and long-term reliability of electrical insulation were achieved without causing trouble in the mounting process. It is possible to provide an overcoat agent that provides a protective film.
In addition, since the carboxyl group-containing urethane resin (A) has an acrylamide group and a carboxyl group, a system having a relatively low molecular weight and a high acid value can be combined with a polyfunctional acrylate to obtain a normal alkali. Patterning can also be performed by a photolithography method by development, and the utility as a solder resist is high.

Claims (17)

A thermosetting resin composition containing a carboxyl group-containing urethane resin (A) obtained by reacting raw materials containing the following (a) to (d);
(A) a polyisocyanate compound,
(B) a polyol compound,
(C) a dihydroxy compound having a carboxyl group,
(D) N-hydroxyethylacrylamide. The polyisocyanate compound (a) is
At least one compound selected from the group consisting of 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated 1,3-xylylene diisocyanate, and hydrogenated 1,4-xylylene diisocyanate The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is present. The polyol compound (b) is
Selected from the group consisting of polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polybutadiene polyols, hydroxylated polysilicons at both ends, and polyol compounds other than hydroxyl groups and containing no oxygen and having 18 to 72 carbon atoms The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is at least one compound.   The thermosetting according to any one of claims 1 to 3, wherein the dihydroxy compound (c) having a carboxyl group is 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid. Resin composition. The number average molecular weight of the carboxyl group-containing urethane resin (A) is 1,000 to 100,000, and the acid value is 5 to 150 mg-KOH / g.
The thermosetting resin composition in any one of -4. The number average molecular weight of the carboxyl group-containing urethane resin (A) is 2,000 to 20,000, and the acid value is 10 to 60 mg-KOH / g.
The thermosetting resin composition according to any one of the above.   Furthermore, a hardening | curing agent (B) is contained, The thermosetting resin composition in any one of Claims 1-6 characterized by the above-mentioned.   The thermosetting resin composition according to claim 7, wherein the curing agent (B) is an epoxy resin.   The curing agent (B) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, The thermosetting resin composition according to claim 7 or 8, which is at least one epoxy resin selected from the group consisting of a dicyclopentadiene type epoxy resin and an alicyclic epoxy resin.   Furthermore, a solvent (C) is contained, The thermosetting resin composition in any one of Claims 1-9 characterized by the above-mentioned.   The solvent (C) is toluene, xylene, ethylbenzene, nitrobenzene, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methoxy Methyl propionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, n-butyl acetate, isoamyl acetate, ethyl lactate, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone , Γ-butyrolactone and dimethyl sulfoxide. The thermosetting resin composition according to claim 10, wherein.   Furthermore, inorganic and / or organic fine particles (D) are contained, The thermosetting resin composition in any one of Claims 1-11 characterized by the above-mentioned.   Furthermore, the antifoamer (E) is contained, The thermosetting resin composition in any one of Claims 1-12 characterized by the above-mentioned.   Furthermore, the radical polymerization initiator (F) is contained, The thermosetting resin composition in any one of Claims 1-13 characterized by the above-mentioned.   Furthermore, the hardening accelerator (G) is contained, The thermosetting resin composition in any one of Claims 1-14 characterized by the above-mentioned.   The overcoat agent which consists of a thermosetting resin composition in any one of Claims 1-15. A protective film obtained from the overcoat agent according to claim 16.