JP6288091B2 - Thermosetting resin composition, cured film, substrate with cured film, and electronic component - Google Patents

Description

  The present invention relates to a thermosetting resin composition, a cured film, a substrate with a cured film, and an electronic component. More specifically, a thermosetting resin composition containing a specific compound, a cured film formed from the composition, a substrate with a cured film having the cured film, and an electronic component having the cured film or the substrate with a cured film About.

  In recent years, electronic devices have been rapidly reduced in size, weight and performance, and these developments have been achieved by making electronic components thinner and smaller. Particularly in the field of printed wiring boards, foldable flexible wiring boards have greatly contributed to the reduction in size and weight of electronic devices.

  Flexible wiring boards form a predetermined conductor circuit pattern by attaching a metal layer such as copper on one or both sides of a substrate made of a resin material such as epoxy resin or polyimide resin, and etching the metal layer. Further, it is manufactured by forming an insulating film that protects the conductor circuit.

The insulating film used here has electrical properties such as insulation, solder heat resistance, adhesion to the substrate, bending resistance, and resistance to chemicals that can be used in forming flexible wiring boards such as etching treatment. It is required that the substrate with an insulating film is excellent, and that warpage due to shrinkage during the formation of the insulating film hardly occurs. In recent years, a resin material having a relatively low heat resistant temperature such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) has been apt to be used as a substrate. It is required that the insulating film can be formed under a low temperature condition of a temperature or lower (for example, 150 ° C. or lower).
Various compositions have been studied for materials used for such insulating films.

Patent Document 1 discloses a thermosetting composition containing a specific carboxyl group-containing compound and an epoxy compound, and Patent Document 2 discloses a thermosetting ink composition containing a specific amide acid. ing. However, these patent documents do not describe an epoxy resin having a fluorene structure, and do not specifically examine an epoxy resin having a fluorene structure.
Patent Document 3 discloses a curable composition containing an epoxy compound having a fluorene skeleton and a curing agent.

  However, in any of the patent documents, specific physical property evaluation and the like for a film cured under a low temperature condition of 150 ° C. or less have not been studied.

JP 2012-25894 A JP 2013-32501 A JP 2012-102228 A

  The object of the present invention is to provide a cured film excellent in electrical characteristics such as insulation, solder heat resistance, adhesion to a substrate, flex resistance and resistance to chemicals such as acid and alkali even at low temperature conditions of 150 ° C. or lower, and It is an object of the present invention to provide a thermosetting resin composition capable of forming a substrate with a cured film that hardly warps due to shrinkage during film formation, and a use thereof.

The present inventors have intensively studied to solve the above problems.
For example, when the composition specifically described in the said patent document was examined, the cured film obtained on the low temperature conditions of 150 degrees C or less using this composition is electrical characteristics, such as insulation, solder heat resistance. It was not a cured film having excellent properties, adhesion to substrates, bending resistance, resistance to chemicals such as acids and alkalis, or warping resistance due to shrinkage during film formation.

As a result of various investigations based on the above findings, the present inventors have found that the above problems can be solved by a thermosetting resin composition having the following configuration, and have completed the present invention.
That is, the present invention relates to the following [1] to [13], for example.

[1] One or more carboxyl group-containing compounds (A) selected from the group consisting of compounds represented by formulas (i-1) to (i-2) and (ii-1) to (ii-4); ,
A thermosetting resin composition comprising an epoxy compound (B) having a fluorene skeleton.

［式中、Ｚは独立に、炭素数８以上の炭化水素、または、−（ＣＨ₂ＣＨ₂−Ｏ）_n−ＣＨ₂ＣＨ₂−で表される基（ｎは０〜１０の整数）であり、Ｘは独立に、炭素数１〜５０の２価の有機基である。］

[In the formula, Z is independently a hydrocarbon having 8 or more carbon atoms or a group represented by — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ — (n is an integer of 0 to 10). And X is independently a divalent organic group having 1 to 50 carbon atoms. ]

  [2] The thermosetting resin composition according to [1], wherein the epoxy compound (B) includes an epoxy compound having a fluorene skeleton having an epoxy equivalent of 400 g / eq or more.

[3] X in formulas (i-1) to (i-2) and (ii-1) to (ii-4) is independently any group in the following group (a): [1 ] Or the thermosetting resin composition according to [2].

[4] Z in formulas (i-1) to (i-2) and (ii-1) to (ii-4) is independently a dimer acid-derived group obtained from an unsaturated fatty acid, or-( _{CH 2 CH 2 -O) n -CH} 2 CH 2 - is a group represented by (n is an integer of 0), [1] to the thermosetting resin composition according to any one of [3] .

  [5] The unsaturated fatty acid is myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, stearolic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, brassic acid, nervonic acid, linoleic acid, eicosadiene Acid, docosadienoic acid, α-linolenic acid, γ-linolenic acid, pinolenic acid, eleostearic acid, medeic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, [4], which is one or more compounds selected from the group consisting of cetoleic acid, adrenic acid, boseopentaenoic acid, eicosapentaenoic acid, ozbond acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid and nisinic acid Thermosetting resin composition.

  [6] The thermosetting resin composition according to any one of [1] to [5], further including an epoxy compound (C) different from the epoxy compound (B).

［式（Ｃ１）中、ｐは１〜５０の整数である。］[7] The epoxy compound (C) is alkylene glycol diglycidyl ether, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A. Type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, formulas (C1) to ( C4) Things, a polymer and one or more compounds selected from the group consisting of a copolymer of a monomer with other monomers having an oxirane monomer having oxirane, thermosetting resin composition according to [6].

[In formula (C1), p is an integer of 1-50. ]

  [8] The thermosetting resin composition according to any one of [1] to [7], further containing a solvent (D).

[9] The thermosetting resin composition according to any one of [1] to [8], further including an epoxy curing agent (E) other than the carboxyl group-containing compound (A).
[10] The epoxy curing agent (E) is selected from the group consisting of acid anhydride curing agents, phenol resin curing agents, amine adducts, polycarboxylic acid curing agents, polyamine curing agents and catalytic curing agents. The thermosetting resin composition according to [9], which is a compound of at least one species.

[11] A cured film obtained from the thermosetting resin composition according to any one of [1] to [10].
[12] A substrate with a cured film, comprising the cured film according to [11].
[13] An electronic component having the cured film according to [11] or the substrate with the cured film according to [12].

  According to the present invention, a cured film having excellent electrical characteristics such as insulation, solder heat resistance, adhesion to a substrate, particularly a substrate made of copper, polyimide, etc., bending resistance, and resistance to chemicals such as acid and alkali, and In addition, a substrate with a cured film that is less likely to warp due to shrinkage during film formation can be obtained even under a low temperature condition of 150 ° C. or lower. Moreover, since the thermosetting resin composition of this invention can form the cured film which has these effects with sufficient balance, it is a composition with very high practicality, and can be applied to various uses.

Hereinafter, the thermosetting resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”), a method for preparing the composition, a method for forming a cured film, a substrate with a cured film, and an electronic component will be described in detail. .
In the present invention, compounds having different symbols indicate different compounds. For example, compound (B) is a compound other than compound (A).

1. Thermosetting resin composition The composition of the present invention contains a specific carboxyl group-containing compound (A) and an epoxy compound (B) having a fluorene skeleton. In addition to the above components, the composition of the present invention comprises an epoxy compound (C) different from the epoxy compound (B) (hereinafter sometimes referred to as “other epoxy compound (C)”), a solvent (D), and a carboxyl group. An additive such as an epoxy curing agent (E) other than the containing compound (A) (hereinafter sometimes referred to as “epoxy curing agent (E)”) may be contained, and may be colored or colorless. .
According to such a composition of the present invention, electrical characteristics such as insulation, solder heat resistance, adhesion to a substrate, bending resistance, and chemicals such as acid and alkali (specifically, etching the metal layer) In addition, a cured film having excellent resistance to chemicals used in the process and a substrate with a cured film that does not easily warp due to shrinkage during film formation can be obtained even under a low temperature condition of 150 ° C. or lower.

1.1. Carboxyl group-containing compound (A)
The carboxyl group-containing compound (A) (hereinafter sometimes referred to as “compound (A)”) is represented by the formulas (i-1) to (i-2) and (ii-1) to (ii-4). One or more compounds selected from the group consisting of:
Since the compound (A) has a carboxyl group, it acts as an epoxy curing agent. That is, by the heat treatment, the carboxyl group of the compound (A) reacts with the oxirane ring or the oxetane ring of the epoxy compound (B) to cure and form a cured film. This cured film exhibits good adhesion to the substrate and is less likely to warp due to shrinkage during film formation.
Only when such a compound (A) is used in combination with a specific epoxy compound (B), a composition having the above-described effect is obtained.
Only 1 type may be used for a compound (A), and 2 or more types may be mixed and used for it.

  The concentration of the compound (A) in the composition of the present invention is preferably 1 to 80% by weight, and more preferably 5 to 60% by weight. Within this concentration range, the cured film obtained from the composition of the present invention has good adhesion to the substrate, flex resistance and resistance to acid and alkali, and is less likely to warp due to shrinkage during film formation. , These will be balanced.

［式中、Ｚは独立に、炭素数８以上の炭化水素、または、−（ＣＨ₂ＣＨ₂−Ｏ）_n−ＣＨ₂ＣＨ₂−で表される基（ｎは０〜１０の整数）であり、Ｘは独立に、炭素数１〜５０の２価の有機基である。］

[In the formula, Z is independently a hydrocarbon having 8 or more carbon atoms or a group represented by — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ — (n is an integer of 0 to 10). And X is independently a divalent organic group having 1 to 50 carbon atoms. ]

  The hydrocarbon having 8 or more carbon atoms in Z is preferably a hydrocarbon having 12 or more carbon atoms, more preferably a hydrocarbon having 18 or more carbon atoms, still more preferably a hydrocarbon having 26 or more carbon atoms, particularly preferably carbon. It is a hydrocarbon of several 28 or more. The upper limit of the carbon number of the hydrocarbon in Z is not particularly limited, but is preferably 60, more preferably 48, and further preferably 40.

As _{n in the} group represented by — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ — in Z, a compound having excellent compatibility with other components contained in the composition of the present invention is obtained. The integer of 0-5 is preferable, the integer of 0-3 is more preferable, and the integer of 1-3 is still more preferable from the point that the cured film which is excellent in the adhesiveness with respect to a board | substrate, especially a metal is obtained.

Z is independently a dimer acid-derived group obtained from an unsaturated fatty acid, or a group represented by — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ — (n is an integer of 0 to 10). Yes, preferably in the above-mentioned range.) From the viewpoint of adhesion to a substrate of a cured film formed from the composition containing the compound (A) to be obtained, particularly adhesion to copper and bending resistance.
Examples of the dimer acid-derived group obtained from the unsaturated fatty acid include a group obtained by removing the amino group from a diamine obtained by subjecting the dimer acid obtained from the unsaturated fatty acid to a reductive amination reaction.

Dimer acid is a dibasic acid obtained by dimerization of unsaturated fatty acids by an intermolecular polymerization reaction or the like. The dimer acid can be obtained, for example, by dimerizing an unsaturated fatty acid using a Lewis acid or a Bronsted acid as a catalyst. A dimer acid can be manufactured by a well-known method (for example, Unexamined-Japanese-Patent No. 9-12712).
A dimer acid usually has a double bond in the molecule. However, in the present invention, a dimer acid also has a dibasic acid that has been reduced to a saturated dibasic acid by reduction of the double bond present in the molecule. Shall be included.

Although dimer acid depends on the synthesis conditions and purification conditions, it usually contains a small amount of monomeric acid, trimer acid and the like in addition to dimer acid.
For example, when dimer acid is produced using linoleic acid, the resulting mixture generally contains dimer acid having 36 carbon atoms as a main component, but monomer acid having 18 carbon atoms and trimer acid having 54 carbon atoms are also minor components. As a general rule, a small amount is included, and various structures derived from raw materials are included.

Carbon number of unsaturated fatty acid is 4-24 normally, Preferably it is 14-20.
Examples of unsaturated fatty acids include myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, stearolic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, brassic acid, nervonic acid, linoleic acid, eicosadiene Acid, docosadienoic acid, α-linolenic acid, γ-linolenic acid, pinolenic acid, eleostearic acid, medeic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, Examples include cetoleic acid, adrenic acid, boseopentaenoic acid, eicosapentaenoic acid, ozbond acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid and nisic acid.

  The diamine obtained by the reductive amination reaction of the dimer acid obtained from the unsaturated fatty acid may be synthesized or may be a commercially available product. Examples of commercially available products include Versamine 551 (trade name, manufactured by BASF Japan Ltd.) and Priamine 1074 (trade name, manufactured by CRODA JAPAN CO., LTD.). The dimer acid type diamine also includes a compound obtained by hydrogenating a diamine obtained by the reductive amination reaction of dimer acid. As a commercially available product, for example, Versamine 552 (trade name, manufactured by BASF Japan Ltd.) Is mentioned.

X is independently preferably a divalent organic group having 1 to 40 carbon atoms from the viewpoint of compatibility with other components contained in the composition of the present invention and reactivity when synthesizing the compound (A). , More preferably a divalent organic group having 1 to 30 carbon atoms, —R ¹ — (R ¹ is a hydrocarbon having 2 to 4 carbon atoms) or —ph— (ph is a benzene ring) [ R ¹ and ph may be substituted with an organic group having 1 to 25 carbon atoms. It is more preferable that it is any group in the following group (a).

As the organic group, a hydrocarbon group or a part of the hydrocarbon group may be substituted with —C (CF ₃ ) ₂ —, —CO—, —COOH, —S— or —SO ₂ —. Groups. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In the case of an unsaturated hydrocarbon group, a group having a double bond is preferable.

The compound (A) is preferably at least one compound selected from the group consisting of the following amide acid (i) and the following compound (ii).
An amic acid obtained by reacting an amino compound (a1) represented by the formula (1) described below and an acid anhydride (a2) (hereinafter also referred to as “amidic acid (i)”).
A compound obtained by reacting amic acid (i) or a partially imidized product thereof (hereinafter also referred to as “imidized product (i)”) with an acid anhydride (a2 ′) (hereinafter also referred to as “compound (ii)”). Say.)
Compound (ii) obtained by reacting 1 mol of amino compound (a1) with 2 mol or more of acid anhydride (a2)

  Hereinafter, after explaining reaction raw materials such as amino compound (a1), acid anhydride (a2) and acid anhydride (a2 ′), and reaction solvent (a3) that may be used in the synthesis of compound (A), The synthesis conditions for compound (A) will be described.

1.1.1. Amino compound (a1)
The amino compound (a1) is represented by the formula (1): H ₂ N—Z—Y (Y is an amino group or a hydroxyl group, and Z is a formula (i-1) to (i-2) and (ii-1) It is synonymous with Z in-(ii-4), and a preferable example is also the same.
Only 1 type may be used for an amino compound (a1), and 2 or more types may be mixed and used for it.

  Examples of the amino compound (a1) in which Z is a hydrocarbon having 8 or more carbon atoms and Y is an amino group include the dimer acid diamine described above and hydrogenated products thereof.

Examples of the amino compound (a1) in which Z is a group represented by — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ — include 2-aminoethanol, 1,2-bis (2-aminoethoxy) ethane. 2- (2-aminoethoxy) ethanol and bis [2- (2-aminoethoxy) ethyl] ether. Among these, 2- (2-aminoethoxy) is obtained in that a compound having excellent compatibility with other components contained in the composition of the present invention is obtained, and a cured film having excellent adhesion to metal is obtained. ) Ethanol and bis [2- (2-aminoethoxy) ethyl] ether are preferred.

1.1.2. Acid anhydride (a2)
The acid anhydride (a2) is not particularly limited as long as it is a compound having an acid anhydride group, but is preferably a compound having one acid anhydride group (monoanhydride).
As the acid anhydride (a2), only one type may be used, or two or more types may be mixed and used.

  As monoanhydrides, compounds represented by formula (2), tetrapropenyl succinic anhydride, tetradecenyl succinic anhydride, octadecenyl succinic anhydride, 2-dodecen-1-yl succinic anhydride 4-methylphthalic anhydride, 4-t-butylphthalic anhydride, 4-fluorophthalic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 1,3-cyclohexanedicarboxylic anhydride Products, glutaric anhydride and the like.

［式（２）中、Ｘ'は、前記群（ａ）のうちの何れかの基である。］

[In the formula (2), X ′ is any group in the group (a). ]

  Among these, the compound represented by the formula (2), that is, succinic acid, can be prepared in that a composition having a high concentration of the compound (A) (the composition can be suitably used as an inkjet ink). Acid anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride and cis-1,2-cyclohexanedicarboxylic anhydride Maleic acid anhydride, citraconic acid anhydride, succinic acid anhydride, phthalic acid anhydride, and trimellitic acid anhydride are particularly preferable.

1.1.3. Acid anhydride (a2 ′)
The acid anhydride (a2 ′) to be reacted with the amic acid (i) or imidized product (i) is preferably a compound having one acid anhydride group, and the same compound as the acid anhydride (a2) is used. The preferred compounds are also the same as the acid anhydride (a2).
The acid anhydride (a2 ′) may be the same as or different from the acid anhydride (a2).
As the acid anhydride (a2 ′), only one type may be used, or two or more types may be mixed and used.

1.1.4. Reaction solvent (a3)
When synthesizing compound (A), reaction solvent (a3) is usually used.
As the reaction solvent (a3), ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol Mo Methyl ether, ethylene glycol monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether , Triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethyle Glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2 -Pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1 , 3-dimethyl-2-imidazolidinone, γ-butyrolactone, α-acetyl-γ-butyrolactone, ε-caprolactone, γ-hexanolactone, δ-hexanolactone, methyl ethyl sulfoxide, dimethyl sulfoxide and methyl sulfoxide Can be mentioned.
In addition, solvents other than these solvents can be further mixed and used.
As the reaction solvent (a3), only one type may be used, or two or more types may be mixed and used.

  When the reaction solvent (a3) remains when the synthesis of the compound (A) is completed, the reaction solvent (a3) can also be used as the solvent (D). Among the reaction solvents (a3), N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and the like from the viewpoint of good compatibility with other components in the composition of the present invention. Triethylene glycol dimethyl ether, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyrolactone are preferred.

<Synthesis conditions of carboxyl group-containing compound (A)>
-Amic acid (i) or imidized product (i)-
Amic acid (i) can be synthesized under mild reaction conditions by mixing amino compound (a1) and acid anhydride (a2). The mild reaction conditions are, for example, a normal pressure, a temperature of 5 to 60 ° C., a reaction time of 0.2 to 20 hours, preferably a temperature of 5 to 30 ° C. and a reaction time of 0.2 to 10 hours. The condition is that the acid anhydride group of the acid anhydride (a2) is allowed to react without activating the carboxyl group formed by ring opening by the reaction. The activation of the carboxyl group is, for example, conversion to acid chloride.
Under the mild reaction conditions, the amino group or hydroxyl group of the amino compound (a1) reacts with the acid anhydride group of the acid anhydride (a2) to react with the amine of the amino compound (a1). Therefore, the amide acid (i) having a carboxyl group can be obtained.

The partial imidation of the amic acid (i) can be carried out by a thermal method or a chemical method using a dehydration catalyst and a dehydrating agent. However, the composition of the present invention is not subjected to purification treatment on the synthesized mixture. It is preferable to carry out by a thermal method from the viewpoint that it can be used as a preparation material.
In the present invention, partial imidation means that in (i), a compound in which both ends are amino groups is used as the amino compound (a1), and both ends of the compound are reacted with an acid anhydride (a2). In this case, only one of them is imidized.

  Partial imidation is, for example, under normal pressure, a temperature of usually 50 to 200 ° C., preferably 60 to 180 ° C., a reaction time of usually 0.2 to 20 hours, preferably 0.5 to 10 hours, and no catalyst is used. It can be performed by a heating process. By this heating step, imidized product (i) can be obtained.

  Further, instead of the mild reaction conditions, the synthesis of amic acid (i) and its imidization may be performed by the heating step. That is, the imido compound (i) may be synthesized by mixing the amino compound (a1) and the acid anhydride (a2) and proceeding the reaction under the heating step.

  The preparation amount of the amino compound (a1) is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, per 1 mol of the acid anhydride group of the acid anhydride (a2).

—Compound (ii) —
When synthesizing the amic acid (i) or imidized product (i) thereof, the amount of the amino compound (a1) charged was set to more than 1 mol per 1 mol of the acid anhydride group of the acid anhydride (a2). In some cases, an unreacted hydroxyl group or amino group derived from the amino compound (a1) is present. In this case, the amic acid (i) or imidized product (i) thereof may be further reacted with an acid anhydride (a2 ′). In this way, compound (ii) containing a carboxyl group can be synthesized.
The amic acid (i) or imidized product (i) obtained as described above may be reacted with an acid anhydride (a2 ′) after being isolated by purification treatment, as described above. An acid anhydride (a2 ′) may be reacted by adding an acid anhydride (a2 ′) to the resulting solution containing the amic acid (i) or imidized product (i).

  Compound (ii) can also be obtained by reacting 1 mol of amino compound (a1) with 2 mol or more, preferably 2 to 4 mol of acid anhydride (a2).

  These reactions can be performed, for example, under normal pressure and at a temperature of usually 10 to 200 ° C., preferably 20 to 180 ° C., and a reaction time of usually 0.2 to 20 hours, preferably 0.5 to 10 hours. it can.

The charging amount of the acid anhydride (a2 ′) is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, per 1 mol of the amic acid (i) or imidized product (i).
From the standpoint of total charge, in the synthesis of compound (A), the number of moles of amino compound (a1) is _na1 , and the total number of moles of acid anhydrides (a2) and (a2 ') is _na2 . The molar ratio (n _a1 / n _a2 ) is usually 0.1 to 5.0, preferably 0.1 to 4.0, more preferably 0.1 to 3.0.
The molar ratio is preferable from the standpoint that a compound excellent in compatibility with other components in the composition of the present invention is obtained and a cured film excellent in adhesion to a substrate, particularly a metal, is obtained.

The total amount of the reaction solvent (a3) used is usually based on 100 parts by weight of the total of the amino compound (a1), the acid anhydride (a2) and the acid anhydride (a2 ′) from the viewpoint of smoothly proceeding the reaction. 100 parts by weight or more, preferably 100 to 500 parts by weight.
The reaction solution or mixed solution obtained as described above contains the compound (A), the reaction solvent (a3) and the like. The reaction solution or mixed solution containing the compound (A) may be used as it is as a preparation material for the composition of the present invention, or the compound (A) may be isolated and used as a preparation material for the composition of the present invention. .

<Order of addition of reaction raw materials to reaction system>
The order of adding the reaction raw materials to the reaction system is not particularly limited.
In the synthesis of amic acid (i), for example, amino compound (a1) and acid anhydride (a2) are added simultaneously to reaction solvent (a3), and acid anhydride (a2) is dissolved in reaction solvent (a3). Any method can be used, such as a method of adding the amino compound (a1) after the reaction, and a method of adding the acid anhydride (a2) after dissolving the amino compound (a1) in the reaction solvent (a3).
In the synthesis of the compound (ii), for example, the amino compound (a1) and the acid anhydride (a2) are reacted as described above, and then the obtained amic acid (i) or imidized product (i) is simply used. And separating the isolated product, the acid anhydride (a2 ′), and the reaction solvent (a3). After reacting the amino compound (a1) and the acid anhydride (a2) as described above, Any method such as a method of adding an acid anhydride (a2 ′) can be used. In addition, the amino compound (a1), the acid anhydride (a2) (a part of which corresponds to the acid anhydride (a2 ′)) and the reaction solvent (a3) are mixed to obtain the compound (ii). You may synthesize.

<Specific examples of amic acid (i) and compound (ii)>
Specific examples of the amic acid (i) include compounds represented by formulas (i-1) to (i-2) and (ii-1) to (ii-2).
Specific examples of compound (ii) include compounds represented by formulas (ii-1) to (ii-4), but are not limited thereto.

1.2. Epoxy compound having a fluorene skeleton (B)
The epoxy compound (B) having a fluorene skeleton used in the present invention (hereinafter sometimes referred to as “epoxy compound (B)”) is not particularly limited as long as it is an epoxy compound having a fluorene skeleton.
Since such an epoxy compound (B) has a high decomposition temperature and excellent heat stability, a cured film having these effects in addition to the above effects can be obtained.
The epoxy compound (B) may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy compound (B) is preferably 200 to 550 g / eq, more preferably from the viewpoints of compatibility with other components in the composition of the present invention, flexibility of the resulting cured film, and the like. It is 220-530 g / eq, More preferably, it is 230-510 g / eq.
In addition, the composition of the present invention provides an epoxy film from the viewpoint that a cured film with good adhesion to the substrate and bending resistance can be obtained, and that a substrate with a cured film that does not easily warp due to shrinkage during film formation can be obtained. It is preferable to include an epoxy compound having a fluorene skeleton having an equivalent weight of 400 g / eq or more, and more preferably including an epoxy compound having a fluorene skeleton having an epoxy equivalent of 450 g / eq or more.
The epoxy equivalent of the epoxy compound (B) can be measured, for example, by the method described in JIS K7236.

The refractive index of the epoxy compound (B) is preferably 1.50 to 1.75, more preferably 1.52 to 1.73, from the viewpoint of obtaining a cured film having excellent chemical resistance. More preferably, it is 1.54-1.71.
The refractive index of the epoxy compound (B) can be measured by, for example, the method described in JIS K7105 or JIS K7142.

The epoxy compound (B) may be obtained by synthesis or may be a commercially available product.
Examples of commercially available products of the epoxy compound (B) include OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.64, epoxy equivalent 259 g / eq), OGSOL CG-500 (trade name, Osaka Gas Chemical Co., Ltd., refractive index 1.70, epoxy equivalent 311 g / eq), OGSOL EG-200 (trade name, Osaka Gas Chemical Co., Ltd., refractive index 1.62, epoxy equivalent 292 g / eq), OGSOL EG-250 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.58, epoxy equivalent 417 g / eq), OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.56) , Epoxy equivalent 467 g / eq), OGSOL CG-400 (refractive index 1.53, epoxy equivalent 540 g / eq).

  When the epoxy compound (B) is a compound having an epoxy equivalent of 400 g / eq or more and a refractive index of 1.57 or less, for example, OGSOL EG-280, a cured film having particularly good adhesion and flex resistance to the substrate. And a substrate with a cured film is obtained which is less likely to warp due to shrinkage during film formation. On the other hand, since the cured film obtained tends to have low resistance to acid and aqueous alkali solutions, these characteristics can be achieved by using an epoxy compound having an epoxy equivalent of less than 400 g / eq and a refractive index of 1.57 or more in combination. A cured film with excellent balance can be obtained.

  For example, when OGSOL EG-280 and OGSOL EG-200 or OGSOL CG-500 are used in combination as the epoxy compound (B), the blending amount of OGSOL EG-280 is 40 to 90% by weight in the total epoxy compound (B). In this case, it is preferable because a cured film having excellent resistance and bending resistance to an acid or alkaline aqueous solution and a balance between these can be obtained, and more preferably 50 to 80% by weight.

  Further, for example, when OGSOL EG-280 and “TECHMORE VG3101L” (manufactured by Printec Co., Ltd.) are used in combination as compound (C), OGSOL in all epoxy compounds (compound (B) + compound (C)) When the blending amount of EG-280 is 5 to 40% by weight, it is preferable because a cured film having excellent resistance to acid and alkali aqueous solution and bending resistance and a balance between these can be obtained, more preferably 10 to 35. % By weight.

  The content of the epoxy compound (B) is preferably 1 to 50% by weight, more preferably 100% by weight with respect to 100% by weight of the composition of the present invention from the viewpoint of obtaining a cured film having excellent chemical resistance and solder heat resistance. Is 2 to 45% by weight, more preferably 3 to 40% by weight, and preferably 10 to 400 parts by weight, more preferably 30 to 380 parts by weight, and still more preferably 50 to 50 parts by weight with respect to 100 parts by weight of the compound (A). 350 parts by weight.

1.3. Other epoxy compounds (C)
The composition of the present invention preferably further contains another epoxy compound (C) (hereinafter sometimes simply referred to as “epoxy compound (C)”). In the present invention, a compound having at least one oxirane ring or oxetane ring is referred to as an epoxy compound. In the present invention, the epoxy compound (C) refers to an epoxy compound other than the epoxy compound (B). As the epoxy compound (C), a compound having two or more oxirane rings is preferably used.
As for an epoxy compound (C), only 1 type may be used and 2 or more types may be mixed and used for it.

  Examples of the epoxy compound (C) include alkylene glycol diglycidyl ether, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and hydrogenated bisphenol A. Type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, formulas (C1) to ( Table in C4) Compound, a polymer of a monomer having oxirane, copolymers of monomers with other monomers having an oxirane and the like.

［式（Ｃ１）中、ｐは１〜５０の整数である。］

[In formula (C1), p is an integer of 1-50. ]

Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.
In the present invention, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acryl refers to acryl and / or methacryl.

  Other monomers that copolymerize with monomers having an oxirane ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene , (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide and the like.

  Preferable specific examples of a polymer of a monomer having an oxirane ring and a copolymer of a monomer having an oxirane ring and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer Polymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate copolymer Is mentioned. When the composition of this invention contains these epoxy compounds, since the solder heat resistance of the cured film formed from this composition becomes favorable, it is preferable.

  Among epoxy compounds (C), alkylene glycol diglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F Type epoxy resin, bisphenol S type epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and compounds represented by formulas (C1) to (C4) are preferred.

  Commercially available products of the epoxy compound (C) include trade names “jER807”, “jER815”, “jER825”, “jER825”, “jER828”, “jER828EL”, “jER871”, “jER872”, “jER190P”, “ “jER191P”, “jER1001”, “jER1004”, “jER1004AF”, “jER1007”, “jER1032H60”, “jER1256”, “jER157S70” (above, manufactured by Mitsubishi Chemical Corporation), trade names “Araldite CY177”, “Araldite” CY184 ”(above, manufactured by BASF), trade names“ Celoxide 2021P ”,“ Celoxide 3000 ”,“ Celoxide 8000 ”,“ EHPE-3150 ”(above, manufactured by Daicel Corporation), trade name“ TECHMORE VG31 ” 1L "(manufactured by Printec Co., Ltd.)," HP7200 "," HP7200H "," HP7200HH "(trade name, manufactured by DIC Corporation)," NC-3000 "," NC-3000H "," EPPN-501H " ”,“ EOCN-102S ”,“ EOCN-103S ”,“ EOCN-104S ”,“ EPPN-501H ”,“ EPPN-501HY ”,“ EPPN-502H ”,“ EPPN-201-L ” Nippon Kayaku Co., Ltd.), "TEP-G" (trade name, manufactured by Asahi Organic Materials Co., Ltd.), "MA-DGIC", "Me-DGIC", "TG-G" Shikoku Kasei Kogyo Co., Ltd.), “TEPIC-VL” (trade name, manufactured by Nissan Chemical Industries, Ltd.), “FLEP-10”, “FLEP-50”, “FLEP-60”, “FLEP-80” (Below The above-mentioned trade name, manufactured by Toray Rethiokor Co., Ltd.). Among these, in view of obtaining a cured film having particularly good solder heat resistance and adhesion to the substrate, the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “TECHMORE VG3101L”, the trade name “JER828” and trade name “jER828EL” are preferable.

  Although the density | concentration of the epoxy compound (C) in the composition of this invention is not specifically limited, 10 to 80 weight% is preferable and 15 to 70 weight% is further more preferable. This concentration range is preferred because the cured film formed from the composition of the present invention has good heat resistance and resistance to acids and alkalis.

1.4. Solvent (D)
The composition of the present invention preferably further contains a solvent (D). The solvent (D) is preferably a solvent that can dissolve the compound (A) and the epoxy compound (B). Moreover, even if it is a solvent which does not melt | dissolve a compound (A) or an epoxy compound (B) independently, it may become possible to use as a solvent (D) by mixing with another solvent.
Only 1 type may be used for a solvent (D), and 2 or more types may be mixed and used for it.

The boiling point of the solvent (D) is usually 150 to 300 ° C, preferably 150 to 250 ° C.
As the solvent (D), ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Mechi Ether, ethylene glycol monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene Glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propano) ), Triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2 -Pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone and the like can be mentioned.

  Among the solvents (D), N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, triethylene glycol are good in compatibility with other components in the composition of the present invention. Dimethyl ether, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyrolactone are preferred.

  The solvent (D) is preferably used in such a proportion that the solid content concentration (concentration of components other than the solvent) in the composition of the present invention is 20 to 80% by weight, particularly 20 to 70% by weight. . In addition, solid content means all components other than the solvent in a composition. When the reaction solution or mixture obtained at the time of synthesizing the compound (A) is mixed with other components as it is, the solvent includes the reaction solvent (a3) used at the time of synthesizing the compound (A).

1.5. Epoxy curing agent (E)
The composition of the present invention may further contain an epoxy curing agent (E) other than the compound (A) in order to further improve the solder heat resistance of the obtained cured film and the resistance to acid or alkaline aqueous solution. Examples of the epoxy curing agent (E) include an acid anhydride curing agent, a phenol resin curing agent, an amine adduct, a polycarboxylic acid curing agent, a polyamine curing agent, and a catalyst curing agent.
As the epoxy curing agent (E), only one kind may be used, or two or more kinds may be mixed and used.

When the epoxy curing agent (E) is used, the epoxy curing agent (E) in the composition of the present invention is usually more than 0 parts by weight and preferably 100 parts by weight or less, preferably 100 parts by weight with respect to 100 parts by weight of the compound (A). More than 0 parts by weight and 80 parts by weight or less, more preferably more than 0 parts by weight and 70 parts by weight or less.
In addition, the total of the compound (A) and the epoxy curing agent (E) is obtained from the point that an excellent thermosetting composition is obtained and a cured film having excellent chemical resistance is obtained. Preferably it is 25-75 weight part with respect to 100 weight part of total of a compound (C), More preferably, it is 30-70 weight part, More preferably, it is contained in 35-65 weight part.

  Acid anhydride curing agents include maleic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride , Hexahydrotrimellitic anhydride, styrene-maleic anhydride copolymer, and the like.

  Examples of the phenol resin-based curing agent include novolak-type phenol resins such as phenol novolak resin and cresol novolak resin; modified novolak resins such as paraxylylene-modified novolak resin, metaxylylene-modified novolak resin and orthoxylylene-modified novolak resin; rosin-modified phenol resin; bisphenol Bisphenol type resins such as A and bisphenol F; phenolic resins such as biphenyl type phenolic resin, resol type phenolic resin, phenol aralkyl resin, triphenolalkane type resin and polymers thereof; naphthalene ring-containing phenolic resin, dicyclopentadiene modified phenolic resin , Alicyclic phenol resin, heterocyclic phenol resin and the like.

Examples of the amine adduct include, but are not limited to, a reaction product of an amine and an epoxy compound and a reaction product of a diamine, an acid anhydride, and an epoxy compound.
Specific examples of reactive organisms of amines and epoxy compounds include reaction products of S510 (trade name, manufactured by JNC Corporation) and 4-benzylpiperidine, S510 (manufactured by JNC Corporation), and 3,5- Reaction product of dimethylpiperidine, reaction product of jER828EL (trade name, manufactured by Mitsubishi Chemical) and 3,5-dimethylpiperidine, reaction of jER828EL (manufactured by Mitsubishi Chemical) and 4-hydroxypiperidine Products.

  Specific examples of a reaction product of a diamine, an acid anhydride, and an epoxy compound include a reaction product of 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of maleic anhydride, and S510. (Product of JNC Co., Ltd.) reaction product with 2 mol, 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of 3- (triethoxysilyl) propyl succinic anhydride A reaction product of the reaction product with 2 mol of S510 (manufactured by JNC), a reaction product of 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of maleic anhydride, Reaction product of 2 moles of N-glycidylphthalimide, 1 mole of Polea SL-100A (trade name, manufactured by Ihara Chemical Industry Co., Ltd.) and 1 mole of maleic anhydride If, like S510 (manufactured by JNC (Ltd.)) the reaction product of 2 moles.

  Examples of the polycarboxylic acid curing agent include a reaction product of 1 mol of oxydiphthalic anhydride and 2 mol of isoleucine, a reaction product of 1 mol of oxydiphthalic anhydride and 2 mol of leucine, and 1 mol of biphenyltetracarboxylic anhydride. A reaction product of 2 moles of leucine, a reaction product of 1 mole of biphenyltetracarboxylic anhydride and 2 moles of isoleucine, and the like can be mentioned.

  Examples of polyamine curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, and 1,3-bis (amino). Methyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane and diaminodiphenylsulfone.

  Examples of the catalyst type curing agent include tertiary amine compounds and imidazole compounds.

1.6. Other Additives The composition of the present invention contains additives other than the compound (A), the epoxy compounds (B) and (C), the solvent (D), and the epoxy curing agent (E) depending on the intended properties. You may contain. Examples of the additive include a polymerizable monomer, an antistatic agent, a coupling agent, a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, a surfactant, a reduction inhibitor, an evaporation accelerator, Examples include chelating agents and water-soluble polymers. Moreover, the composition of this invention may contain a pigment or dye.
Only one type of additive may be used, or two or more types may be mixed and used.

1.6.1. Polymerizable monomer Examples of the polymerizable monomer include monofunctional polymerizable monomers, bifunctional (meth) acrylates, and trifunctional or higher polyfunctional (meth) acrylates.
As the polymerizable monomer, only one type may be used, or two or more types may be mixed and used.

  Although the density | concentration of the polymerizable monomer in the composition of this invention is not specifically limited, 0.1-20 weight% is preferable and 1-10 weight% is further more preferable. Within this concentration range, the chemical resistance and flatness of the cured film formed from the composition of the present invention will be good.

The monofunctional polymerizable monomer is a compound having one polymerizable unsaturated double bond, and specific examples thereof are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , Tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate, glycerol mono (meth) acrylate, 5-tetrahydrofurfuryl-oxy-carbonyl pentyl (meth) acrylate, ethylene oxide adduct of lauryl alcohol (meth) Acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryl Roxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl -3- (meta ) Acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (3-ethyl-3-oxetanyl) methyl (meth) ) Acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide, N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethylmethacrylate macromonomer, (meth) acrylic acid , Crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) a Acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] maleate, and mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate.

  Examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanedio Distearate (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate.

  Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and epichlorohydrin modified tri Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified tri (meth) acrylate phosphate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.

1.6.2. The antistatic agent can be used to prevent the composition of the present invention from being charged, and is preferably contained in an amount of 0.01 to 1% by weight in the composition of the present invention.
A known antistatic agent can be used as the antistatic agent. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; quaternary ammonium salts, and the like.
Only one type of antistatic agent may be used, or a mixture of two or more types may be used.

1.6.3. The coupling agent is not particularly limited, and a known coupling agent such as a silane coupling agent can be used. The coupling agent is preferably used by adding it to 10% by weight or less with respect to 100% by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition).
In the present invention, the coupling agent refers to a compound having a reactive functional group such as an epoxy group and a hydrolyzable group such as an alkoxy group, having an oxirane ring or an oxetane ring, and having an alkoxysilane structure. The compound having is a coupling agent.
A coupling agent may use only 1 type and may mix and use 2 or more types.

  Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyl Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-amino Propyltrimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Methyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyana DOO propyl methyl diethoxy silane, include γ- isocyanato propyl triethoxysilane.

  Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are particularly preferable.

1.6.4. Antioxidant When the composition of the present invention contains an antioxidant, it is possible to prevent deterioration when a cured film obtained from the composition is exposed to high temperature or light.
It is preferable to add 0.1 to 3 parts by weight of the antioxidant to 100 parts by weight of the solid content of the composition excluding the antioxidant (residue obtained by removing the solvent from the composition).
Only 1 type may be used for antioxidant and 2 or more types may be mixed and used for it.

  Examples of the antioxidant include hindered amine compounds and hindered phenol compounds. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (above trade names, manufactured by BASF) and the like can be mentioned.

1.6.5. Surfactant When the composition of the present invention contains a surfactant, it is possible to obtain a composition having improved wettability, leveling property or coating property to the base substrate.
The surfactant is preferably used in an amount of 0.01 to 1% by weight based on 100% by weight of the composition of the present invention.
Only one surfactant may be used, or two or more surfactants may be mixed and used.

  As the surfactant, for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-310”, from the viewpoint that the coating property of the composition of the present invention can be improved. “BYK-341”, “BYK-344”, “BYK-370” (manufactured by Big Chemie Japan), “KP-112”, “KP-326”, “KP-341” (above, Shin-Etsu Chemical Co., Ltd.) Silicone surfactants such as “BYK-354”, “BYK-358”, “BYK-361” (manufactured by BYK Japan Japan), etc .; Fluorosurfactants such as names “DFX-18”, “Factent 250”, and “Factent 251” (manufactured by Neos Co., Ltd.) can be mentioned.

1.6.6. Examples of the pigment or dye pigment include one or more compounds selected from the group consisting of silicon carbide, alumina, magnesia, silica, zinc oxide, and graphite.
Examples of the dye include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Examples of azo dyes include “VALIFAST BLACK 3810”, “VALIFAST BLACK 3820”, “VALIFAST RED 3304”, “VALIFAST RED 3320”, and “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industry Co., Ltd.). It is done.
Each of the pigment and the dye may be used alone or in combination of two or more.

2. Preparation method of thermosetting resin composition The composition of the present invention comprises a compound (A) and an epoxy compound (B), and, if necessary, an epoxy compound (C), a solvent (D), an epoxy curing agent (E) and It can be prepared by mixing with other additives.

  Further, the composition of the present invention is prepared by using the reaction solution or mixed solution obtained at the time of synthesis of the compound (A) as it is, the epoxy compound (B), the epoxy compound (C) used as necessary, and the solvent (D). It can also be prepared by mixing with an epoxy curing agent (E) or other additives.

3. Forming method of cured film The cured film of the present invention is not particularly limited as long as it is a film obtained from the composition of the present invention. The cured film of the present invention can be obtained, for example, by applying the composition of the present invention on a substrate and heating.
Hereinafter, the coating method and the curing method of the composition of the present invention will be described.

3.1. Application Method of Thermosetting Resin Composition Application of the composition of the present invention on a substrate can be performed by spray coating, spin coating, roll coating, dipping, slit coating, bar coating, gravure printing, flexographic printing. It can be performed by a conventionally known method such as a printing method, an offset printing method, a dispenser method, a screen printing method and an ink jet printing method.

  For example, in the case of forming an insulating film for protecting a patterned conductor circuit from the composition of the present invention, the gravure printing method, the flexographic printing method, the offset printing method, the dispenser method, the screen in that the pattern formation is easy. Printing methods such as printing methods and inkjet printing methods are preferred.

  The substrate is not particularly limited, and a known substrate can be used. For example, glass that conforms to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668. Epoxy substrate, glass composite substrate, paper phenol substrate, paper epoxy substrate, green epoxy substrate, BT (bismaleimide triazine) resin substrate; copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or A substrate made of metal such as stainless steel (may be a substrate having a layer made of these metals on the surface); indium tin oxide (ITO), aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium Silicate (zircon), magnesium oxide (magnesia), titanium Aluminum, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia) ), Silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spojumen Substrates made of inorganic substances (may be substrates having a layer containing these inorganic substances on the surface); PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene) Terephthalate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, polyphenylene ether, polyimide, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), heat A substrate made of a resin such as a plastic elastomer or a liquid crystal polymer (may be a substrate having a layer containing these resins on its surface); a semiconductor substrate such as silicon, germanium or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO Or a substrate on which an electrode material (wiring) such as ATO (antimony tin oxide) is formed; αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel) or γGEL (gamma gel) Above, the gel sheet of the registered trademark), etc., Ltd. Tayca; it includes.

  The composition of the present invention is preferably applied on a glass substrate, an ITO substrate, a resin film substrate or a substrate in which a conductor circuit is formed on these substrates, and the effect of the present invention can be exhibited more. More preferably, it is applied on a polyimide substrate that is often used for flexible wiring boards or a polyimide substrate on which a circuit made of copper is formed.

3.2. Method for curing thermosetting resin composition After the coating step, a cured film can be obtained by heating the composition coated on the substrate. As a method for forming a cured film in this manner, it is preferable to remove the solvent by vaporization or the like by heating with a hot plate or an oven after the coating step (drying treatment), and then further heating ( Curing process) is used.

  The conditions for the drying treatment vary depending on the types and blending ratios of the components contained in the composition to be used, but the heating temperature is usually 70 to 120 ° C., and the heating time is 5 to 15 minutes for an oven and 1 for a hot plate. 10 minutes. By such a drying process, a coating film to the extent that the shape can be maintained can be formed on the substrate.

After the coating film is formed, a curing treatment is usually performed at 100 to 300 ° C, preferably 120 to 250 ° C. At this time, a final cured film can be obtained by heat treatment usually for 10 to 120 minutes when an oven is used, and usually 5 to 30 minutes when a hot plate is used.
Note that the curing process is not limited to the heat treatment, and may be a process such as ultraviolet ray, ion beam, electron beam, or gamma ray irradiation.

If the composition of this invention is used, even if it performs the said drying process and hardening process on low temperature conditions, the cured film which has the said effect can be obtained. For this reason, if the composition of this invention is used, it will not be influenced by the object (board | substrate etc.) which apply | coats this composition, but the cured film which has the outstanding physical property, Furthermore, an insulating film can be formed. Therefore, the composition of the present invention is a particularly effective composition when it is desired to form a cured film on a resin material having a relatively low heat resistant temperature.
Although it does not restrict | limit especially as said low temperature conditions, For example, it is the temperature of 150 degrees C or less, Preferably it is 120-150 degreeC.

4). Substrate with Cured Film The substrate with a cured film of the present invention is not particularly limited as long as it has the cured film of the present invention, but the substrate, in particular, a glass substrate, an ITO substrate, a resin film substrate such as polyimide, and these substrates It is preferable to have the above-mentioned cured film on at least one kind of substrate selected from the group consisting of substrates on which conductor circuits are formed.
Such a substrate with a cured film is, for example, a substrate made of glass, ITO, polyimide, PET, PEN, or the like, and a substrate on which a conductor circuit is formed on the substrate. It can be formed by applying to the entire surface or a predetermined pattern (such as a line) by, and then performing a drying process and a curing process as described above.

5. Electronic component An electronic component of the present invention is an electronic component having the above-described cured film or substrate with a cured film. In this case, a flexible electronic component can be obtained by using a flexible substrate as the substrate. Moreover, a semiconductor electronic component can be obtained by using a silicon wafer as a substrate.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.
Amino compound (a1), acid anhydride (a2), acid anhydride (a2 ′), reaction solvent (a3), epoxy compound (B) having a fluorene skeleton, and epoxy compound (C) used in Examples and Comparative Examples The names of the solvent (D) and the epoxy curing agent (E) and their abbreviations are shown. This abbreviation is used in the following description.

<Amino compound (a1)>
AEE: 2- (2-aminoethoxy) ethanol P-1074: Priamine 1074 (trade name, manufactured by CRODA JAPAN)
<Acid anhydride (a2)>
MA: maleic anhydride <acid anhydride (a2 ′)>
TMA: trimellitic anhydride <Reaction solvent (a3)>
EDM: Diethylene glycol methyl ethyl ether NMP: N-methyl-2-pyrrolidone

<Epoxy compound having a fluorene skeleton (B)>
CG-500: OGSOL CG-500 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
EG-200: OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
EG-280: OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)

<Epoxy compound (C)>
VG3101: TECHMORE VG3101L (trade name, manufactured by Printec Co., Ltd.)

<Solvent (D)>
EDM: Diethylene glycol methyl ethyl ether MTM: Triethylene glycol dimethyl ether

<Epoxy curing agent (E)>
TMA: trimellitic anhydride

  First, the carboxyl group-containing compound (A) solution was synthesized as shown below (Synthesis Examples 1 to 4). Table 1 summarizes Synthesis Examples 1 to 4.

[Synthesis Example 1]
A 1000 ml separable flask equipped with a thermometer, stirring blade, raw material charging inlet and nitrogen gas inlet was charged with 480.0 g of EDM and 111.7 g of AEE and stirred under ice-cooling with stirring and ice cooling. 104.2 g of MA was added as an anhydride (a2), and the mixture was stirred at room temperature for 1 hour. Thereafter, 104.2 g of MA is further added as an acid anhydride (a2 ′), and the mixture is stirred at room temperature for 10 minutes. The reaction solution in which MA is completely dissolved is stirred at 110 ° C. for 3 hours, and the formula (ii-1- A liquid mixture (A) -1 containing the compound represented by 1) and the compound represented by formula (ii-3-1) was obtained.

  The rotational viscosity of the liquid mixture (A) -1 measured at 25 ° C. using an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI, hereinafter the same) was 17.6 mPa · s. The solid content concentration was 40%. In addition, solid content concentration here is a density | concentration of the component except the reaction solvent in the obtained liquid mixture. The same description in the following synthesis examples has the same meaning.

[Synthesis Example 2]
A 1000 ml separable flask equipped with a thermometer, stirring blade, raw material charging inlet and nitrogen gas inlet is charged with 480.0 g of EDM and 85.1 g of AEE, and stirred under ice-cooling with stirring and ice cooling. 79.4 g of MA was added as an anhydride (a2), and the mixture was stirred at room temperature for 1 hour. Thereafter, 155.5 g of TMA was further added as an acid anhydride (a2 ′), and the mixture was stirred at room temperature for 30 minutes, and the reaction solution in which TMA was completely dissolved was stirred at 110 ° C. for 3 hours to obtain the formula (ii-1- A liquid mixture (A) -2 containing the compound represented by 2) and the compound represented by formula (ii-3-2) was obtained.

  The rotational viscosity of the liquid mixture (A) -2 measured at 25 ° C. using an E-type viscometer was 45.0 mPa · s. The solid content concentration was 40%.

[Synthesis Example 3]
A 1000 ml separable flask equipped with a thermometer, stirring blade, raw material charging inlet and nitrogen gas inlet is charged with 480.0 g of EDM and 234.5 g of P-1074, stirred under ice-cooled nitrogen flow, and ice-cooled. While adding 85.5 g of MA as an acid anhydride (a2) and stirring at room temperature for 3 hours, a mixed solution containing an amic acid generated by reacting the amine terminal of P-1074 with the acid anhydride group of MA (A) -3 was obtained.

  The rotational viscosity of the liquid mixture (A) -3 measured at 25 ° C. using an E-type viscometer was 16.5 mPa · s. The solid content concentration was 40%.

[Synthesis Example 4]
In Synthesis Example 4, synthesis was carried out in the same manner as in Synthesis Example 3 except that the type and amount of the reaction solvent were changed as shown in Table 1, and the amine terminal of P-1074 reacted with the acid anhydride group of MA. To obtain a mixed liquid (A) -4 containing the amic acid produced.

  The rotational viscosity of the liquid mixture (A) -4, measured at 25 ° C. using an E-type viscometer, was 14.8 mPa · s. The solid concentration was 37%.

[Example 1]
A 300 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 20.8 g of the mixed liquid (A) -1 obtained in Synthesis Example 1 was added to the flask as an epoxy compound (B) having a fluorene skeleton. -280 15.6g, EG-200 11.0g, EDM 47.5g as solvent (D) and TMA 5.0g as epoxy curing agent (E) were charged and stirred for 1 hour at room temperature. It was dissolved uniformly. Then, it filtered with the membrane filter (0.2 micrometer), and obtained the filtrate (thermosetting resin composition).

[Examples 2-7 and Comparative Examples 1-4, 7-8]
A thermosetting resin composition was prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 2.

[Comparative Examples 5 and 6]
Comparative Examples 5 and 6 are the same as the mixed liquids (A) -3 and (A) -4 obtained in Synthesis Examples 3 and 4, respectively.

  The above Examples 1-7 and Comparative Examples 1-8 are summarized in Table 2.

After spin-coating the thermosetting resin composition obtained above on the following polyimide film and on the glossy surface of the copper foil so that the thickness of the cured film is as shown in Table 3, it is on the hot plate. And dried at 80 ° C. for 5 minutes to form a coating film.
Polyimide film: 60 × 60 mm, 25 μm thick polyimide film (Toray DuPont, Kapton 100H)
Copper foil: 40 × 40 mm, 35 μm thick rolled copper foil (manufactured by JX Nippon Mining & Metals, BHY-22B-T)

  Thereafter, the coating film was cured by heating at 150 ° C. for 30 minutes using an oven. The cured film thus obtained was evaluated for solder heat resistance, adhesion to the substrate, flex resistance, chemical resistance, and warpage. These evaluation results are shown in Table 3. In addition, the thickness of the cured film was measured using a stylus type film thickness meter XP-200 (manufactured by KLA Tencor).

[Evaluation method]
(I) Solder heat resistance About the obtained copper foil with a cured film, in order to evaluate solder heat resistance, a rosin-type flux (trade name: NS-829, manufactured by Nippon Superior Co., Ltd.) on the surface of the cured film of the copper foil. ) Was then immersed in a 260 ° C. solder bath for 30 seconds. Thereafter, the laminate was taken out of the solder bath, and it was visually examined whether peeling or swelling occurred between the substrate and the cured film. The case where no peeling or swelling occurred was indicated by “◯”, and the case where even peeling or swelling occurred was indicated by “X”.

(Ii) Adhesiveness with substrate After the obtained polyimide film with cured film and copper foil with cured film were immersed in ultrapure water at 60 ° C. for 60 minutes, a cross-cut test by tape peeling (JIS-K-5400) ) And the remaining number was counted to evaluate the adhesion between the polyimide film or copper foil and the cured film. The case where the remaining number / 100 was 100/100 was evaluated as ◯, and the case where it was 99/100 or less was evaluated as ×.

(Iii) Bending resistance About the obtained copper foil with a cured film, it bend | folds 180 degrees so that the surface of a cured film may come to an outer side, a load of 3 kg / cm < ² > is applied to a bending part, and a bending part is spread after that, A load of 3 kg / cm ² was applied. This was repeated three times, and it was observed with an optical microscope whether cracks or peeling occurred at the bent portion. A case where no crack or peeling occurred and no abnormality was observed was indicated as “◯”, and a case where a crack or peeling occurred was indicated as “X”.

(Iv) Chemical resistance The obtained cured film-coated polyimide film and cured film-coated copper foil were each immersed in 2N NaOH aqueous solution at room temperature for 15 minutes, washed with water, and then dried at 60 ° C. for 30 minutes. Thereafter, the chemical resistance was evaluated by an optical microscope according to the following evaluation criteria. The same evaluation was performed using a 2N aqueous HCl solution instead of the 2N aqueous NaOH solution.
○: Abnormalities such as infiltration and peeling are not observed at the interface between the cured film and the substrate. ×: Abnormalities such as infiltration and peeling are observed at the interface between the cured film and the substrate.

(V) Warpage Cut out so that the central part 40 × 40 mm of the obtained polyimide film with cured film remains, place it on a horizontal plane, measure the average height of the four corners from the flat surface, and the arithmetic mean value thereof Was the average warpage. As a result of the large warp, the cylindrical shape was called “curl”.

As is clear from the results shown in Table 3, the cured films formed from the thermosetting resin compositions obtained in Examples 1 to 7 are solder heat resistance, adhesion to copper and polyimide films, flex resistance, It was excellent in chemical resistance, and the obtained substrate with a cured film had a warp of 5 mm or less. On the other hand, the cured film formed from the thermosetting resin composition obtained in Comparative Examples 1 to 8 had poor bending resistance, and the obtained substrate with a cured film had large warpage.
As described above, only a cured film obtained from a composition containing a specific carboxyl group-containing compound and an epoxy resin having a fluorene skeleton could satisfy all desired properties.

  Since the composition of the present invention can form a cured film having the above effects, for example, as an insulating film for a flexible printed wiring board, a rigid wiring board, or a semiconductor, or a material for forming an electronic component including the insulating film It can be used suitably.

Claims (12)

One or more carboxyl group-containing compounds (A) selected from the group consisting of compounds represented by formulas (i-1) to (i-2) and (ii-1) to (ii-4);
A thermosetting resin composition comprising an epoxy compound (B) having a fluorene skeleton having an epoxy equivalent of 400 g / eq or more .

[In the formula, Z is independently a hydrocarbon having 8 or more carbon atoms or a group represented by — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ — (n is an integer of 0 to 10). And X is independently a divalent organic group having 1 to 50 carbon atoms. ] Formula (i-1) ~ (i -2) and (ii-1) ~ X is independently in (ii-4), is any group of the following groups (a), according to claim 1 Thermosetting resin composition.

Z in the formulas (i-1) to (i-2) and (ii-1) to (ii-4) is independently a group derived from a dimer acid obtained from an unsaturated fatty acid, or — (CH ₂ CH _The thermosetting resin composition according to any one of claims 1 and 2 , wherein the thermosetting resin composition is a group represented by ₂ -O) _n -CH ₂ CH _2- (n is an integer of 0 to 10). Unsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, stearolic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, brassic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadiene Acid, α-linolenic acid, γ-linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, cetreic acid, The thermosetting according to claim 3 , which is one or more compounds selected from the group consisting of adrenic acid, boseopentaenoic acid, eicosapentaenoic acid, ozbond acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid and nisinic acid. Resin composition. Furthermore, the thermosetting resin composition of any one of Claims 1-4 containing the epoxy compound (C) different from an epoxy compound (B). Epoxy compound (C) is alkylene glycol diglycidyl ether, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin , Hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m- Xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, in formulas (C1) to (C4) The compound represented, A polymer and one or more compounds selected from the group consisting of a copolymer of a monomer with other monomers having an oxirane monomer having a xylan, a thermosetting resin composition according to claim 5.

[In formula (C1), p is an integer of 1-50. ] Furthermore, the thermosetting resin composition of any one of Claims 1-6 containing a solvent (D). Further contains a carboxyl group-containing compound (A) other than the epoxy curing agent (E), the thermosetting resin composition according to any one of claims 1-7. The epoxy curing agent (E) is at least one selected from the group consisting of acid anhydride curing agents, phenol resin curing agents, amine adducts, polycarboxylic acid curing agents, polyamine curing agents and catalytic curing agents. The thermosetting resin composition according to claim 8 , which is a compound. Cured film obtained from the thermosetting resin composition according to any one of claims 1-9. The board | substrate with a cured film which has a cured film of Claim 10 . The electronic component which has a cured film of Claim 10 , or a board | substrate with a cured film of Claim 11 .