JPWO2018159674A1 - Thermosetting resin composition, cured film, substrate with cured film, electronic component, and ink composition for inkjet - Google Patents

Abstract

The thermosetting resin composition comprises a polyester amic acid (A), an epoxy compound having a weight-average molecular weight of less than 10,000 in order to improve adhesion to a substrate, flux resistance, solder resistance and solvent resistance. B) and a copolymer (C) having oxiranyl or oxetanyl and having a weight average molecular weight of 10,000 or more.

Description

  The present invention relates to a thermosetting resin composition, a cured film obtained from the thermosetting resin composition, a substrate with the cured film having the cured film, an electronic component having the cured film or the substrate with the cured film, and an ink jet ink. Composition.

  2. Description of the Related Art In a manufacturing process of a semiconductor package, a printed wiring board, and the like, a protective layer called a coverlay or a solder resist is coated on a circuit pattern in order to protect a circuit pattern formed on the substrate.

  The specific role of the protective layer is to protect the electronic circuit from heat and moisture, to prevent oxidation and corrosion of copper forming the circuit, to insulate and protect the circuit to prevent a short circuit, and in the soldering process. And to protect the solder from being attached to unnecessary portions.

  To fulfill such a role, the protective layer is required to have properties such as heat resistance, moisture resistance, insulation, adhesion to substrates and circuits, flux resistance, solder resistance, and solvent resistance. .

  Furthermore, in recent years, as electronic devices such as smartphones and tablet terminals have become more sophisticated and smaller and thinner, there has been a demand for higher density and smaller and thinner semiconductor packages and printed wiring boards. In particular, wafer level packaging (WLP) technology has attracted attention as a technology for realizing higher density, smaller size, and thinner semiconductor packages, and their adoption is accelerating. In such a WLP, lead-free solder balls are often used as interconnections from a die to a printed circuit board, and it is necessary to arrange solder balls having a diameter of 100 to 300 μm accurately at a pitch of 500 μm or less. Therefore, in addition to the above-mentioned characteristics, a protective layer called a solder resist is required to have a fine pattern shape, pattern positional accuracy, heat resistance and insulating property in a thin film, and the like.

  Patent Literature 1 describes a screen printing resist ink containing a filler and a hydrophobic vehicle as main components. The ink has a small fluctuation in ink viscosity even when repeatedly printed by screen printing, and maintains good printability. I have. However, in screen printing, it is difficult to accurately arrange hole shapes having a diameter of 100 to 300 μm at a pitch of 500 μm or less.

  In addition, since it is difficult to visually confirm the fine pattern shape, the positional accuracy of the pattern, and the film thickness, an inspection device for confirming the covering of the protective layer is used. Generally, an optical device is used for the inspection device, and it is necessary to color the protective layer in order to inspect the coating of the protective layer. In order to perform accurate inspection with an optical inspection device, it is necessary to darken the color of the protective layer so that the underlying circuit such as copper is not transparent, and when the film thickness becomes thin such as 20 μm or less, In addition, black is required to enhance the shielding property.

  Patent Document 2 discloses a composition containing an active energy ray-curable resin having a specific structure, a photopolymerization initiator, an organic solvent, and the like as a photocurable developable liquid solder resist ink composition. Such an ink composition for a liquid solder resist capable of forming a pattern in the photolithography process can form a fine pattern and increase the positional accuracy of the pattern, but because of its high transparency, it can be accurately measured by an inspection device. Inspection is difficult.

  Patent Document 3 discloses a photocurable developable black solder resist composition, which includes a carboxyl group-containing resin, a photopolymerization initiator, a diluent, a polyfunctional epoxy compound having a specific structure, a black colorant, and a black colorant other than black. Compositions containing colorants and the like have been proposed. However, because of the black color, light absorption at the time of exposure increases, and it is particularly difficult for light to reach the deep part of the solder resist coating film. Therefore, the photocuring in the deep part of the solder resist coating film is not sufficient, and the size of the deep part of the solder resist coating film after development is too small, and the cured coating film is peeled off from the printed wiring board, and the resolution and the line remaining are poor. There was a problem.

  Furthermore, in recent years, as a method for forming a fine pattern of a protective layer called a coverlay or a solder resist, a method of directly applying a necessary amount of a composition for a protective layer to a necessary portion by an inkjet method has been proposed, Recruitment is increasing. The inkjet system does not require equipment for exposure and development, and does not need to produce a screen mesh, a photomask, or the like. Further, the number of steps can be reduced as compared with the screen printing and photolithography steps. As described above, the ink-jet method has attracted attention because of its great merits in cost reduction and tact time reduction.

  In the ink jet system, the ink viscosity is required to be low to some extent in order to stably discharge the ink from the ink jet head. In particular, when a fine pattern shape is required, such as a solder resist for WLP, an ink jet head having a small nozzle size is used, so that the ink viscosity at the time of ejection needs to be 10 mPa · s or less. Ink jet devices capable of printing by heating the ink jet head have been developed, but printing troubles such as nozzle clogging are likely to occur due to ink drying near the nozzles due to the heating. By diluting the composition for inkjet ink with a high-boiling solvent, the ejection property with an inkjet head having a small nozzle size is improved, but when the ratio of the solvent increases, the film thickness after drying and curing becomes thinner. There is.

  Patent Document 4 contains a monomer having a (meth) acryloyl group and a thermosetting functional group in a molecule, a photoreactive diluent having a weight average molecular weight of 700 or less, and a photopolymerization initiator, and has a viscosity of 150 mPa at 25 degrees. The following curable composition for inkjet is disclosed. By heating the inkjet head to 50 degrees or more, the viscosity can be reduced to 20 mPa · s or less, but there is a problem that storage stability under an environment of 50 degrees or more is poor.

  Further, Patent Document 5 discloses that storage stability is good even in an environment in an inkjet apparatus heated to 50 ° C. or more, containing a photocurable compound, a thermosetting compound, a photopolymerization initiator, and a thermosetting agent. Curable compositions for inkjet have been proposed. However, the viscosity at 25 degrees is 160 mPa · s or more, and even when heated to 50 degrees or more, it becomes 10 mPa · s or more. Therefore, there is a problem that the ink jet head having a small nozzle size has poor print stability. Was. Further, there is also a problem that the photocurability is reduced when colored black.

  Patent Document 6 proposes a thermosetting black inkjet ink containing an epoxy resin, an oxetane compound, a copolymer having a specific structure, carbon black, a solvent, and the like. However, the flux resistance and the solder resistance when used as a solder resist have not been studied.

JP-A-60-188482 JP-A-61-000272 JP 2008-257045 A WO2004 / 099272A1 WO2016 / 129670A1 JP 2011-231247 A

  Solder resist used in high-density, small and thin semiconductor packages utilizing WLP technology etc. includes heat resistance, moisture resistance, insulation, adhesion to substrates and circuits, flux resistance, soldering In addition to properties such as resistance and solvent resistance, heat resistance and insulation properties of a thin film are required. Further, it is necessary to form a fine pattern shape with high positional accuracy. In order to inspect the pattern shape and the position of the pattern, it is required to have a dark black enough to shield the underlying circuit even with a thin film of 20 μm or less. However, a resin composition that can achieve both the above characteristics and a deep black color has not yet been realized.

  In the manufacturing process of a coverlay or a solder resist for a semiconductor package or a printed wiring board, application by an ink-jet method capable of reducing cost and tact time is attracting attention, and its use is increasing. However, high-density, stable printing can be performed with an ink jet head with a small nozzle size that can form a fine pattern shape of the level required for semiconductor packages that are small and thin, heat resistance required for solder resist, A resin composition having excellent moisture resistance, insulation properties, adhesion to substrates and circuits, flux resistance, solder resistance, solvent resistance, heat resistance in thin films, and insulation properties has not yet been realized.

  An object of the present invention is to provide a cured product having excellent adhesion to a substrate, flux resistance, solder resistance, and solvent resistance, and a thermosetting resin composition capable of forming the cured product.

  The present inventors have found that a cured product excellent in adhesion to a substrate, flux resistance, solder resistance and solvent resistance can be formed by using a polyester amide acid, an epoxy compound and a specific copolymer. Was completed. The present invention relates to the following [1] to [21].

[1] Polyester amic acid (A), epoxy compound (B) having a weight average molecular weight of less than 10,000, and copolymer (C) having oxiranyl or oxetanyl and having a weight average molecular weight of 10,000 or more. A thermosetting resin composition comprising:

[2] The copolymer (C) having oxiranyl or oxetanyl is a copolymer (C1) of a radical polymerizable monomer (c1) having an oxiranyl group and another radical polymerizable monomer (c3), and / or The thermosetting resin composition according to [1], which is a copolymer (C2) of a radical polymerizable monomer (c2) having an oxetanyl group and another radical polymerizable monomer (c3).

[3] The radical polymerizable monomer (c1) having an oxiranyl group is selected from the group consisting of glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. The thermosetting resin composition according to [1] or [2], which is one or more types.

[4] The radical polymerizable monomer (c2) having an oxetanyl group is 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane The thermosetting resin composition according to [1] or [2], which is one or more types selected.

[5] The copolymer according to [1], wherein the copolymer (C) is obtained by copolymerizing a monomer composition containing three types of an N-substituted maleimide compound, a compound having oxiranyl or oxetanyl, and a methacrylate compound. Thermosetting resin composition.

[6] The thermosetting resin composition according to [5], wherein the methacrylate compound is a monofunctional methacrylate compound.

[7] The monomer composition of the copolymer (C) is such that glycidyl methacrylate is 15 to 50 parts by weight and n-butyl methacrylate is 2 to 10 parts by weight with respect to 10 parts by weight of phenylmaleimide. The thermosetting resin composition according to [5].

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

[9] The thermosetting resin composition according to [8], wherein 100 parts by weight of the solvent (D) contains 50 parts by weight or more of a high boiling point solvent having a boiling point of 200 ° C. or more.

[10] The thermosetting resin composition according to [8], wherein the solvent (D) is γ-butyrolactone.

[11] The thermosetting resin composition according to any one of [1] to [10], further comprising a coloring agent (E).

[12] The thermosetting resin composition according to [11], wherein the colorant (E) contains titanium compound particles and / or carbon black particles.

[13] The thermosetting resin composition according to [11], wherein the content of the coloring agent (E) is 2 to 15 parts by weight based on 100 parts by weight of the resin solid content in the thermosetting resin composition. object.

[14] The thermosetting resin composition according to any one of [1] to [13], wherein the copolymer (C) has a weight average molecular weight of 10,000 or more and 100,000 or less.

[15] The thermosetting resin according to any one of [1] to [13], wherein the polyester amic acid (A) is a compound having a structural unit represented by Formulas (1) and (2). Composition.


(Wherein, R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is independently a divalent organic group having 1 to 40 carbon atoms, and R ³ is independently a carbon atom having 1 carbon atom. ~ 20 divalent organic groups.)

[16] The thermosetting resin composition according to any one of [1] to [15], further comprising an epoxy curing agent (F).

[17] The thermosetting resin composition according to [16], wherein the epoxy curing agent (F) is an acid anhydride curing agent.

[18] A cured film obtained from the thermosetting resin composition according to any one of [1] to [17].

[19] A substrate with a cured film having the cured film according to [18].

[20] An electronic component having the cured film according to [18] or the substrate with a cured film according to [19].

[21] An inkjet ink composition comprising the thermosetting resin composition according to any one of [1] to [17].

  The thermosetting resin composition of the present invention contains a specific copolymer (C) in addition to the polyesteramic acid (A) and the epoxy compound (B) having a weight average molecular weight of less than 10,000. Accordingly, it is possible to form a cured film having good adhesion to the substrate and good flux resistance, solder resistance and solvent resistance.

  Hereinafter, the thermosetting resin composition (hereinafter, also referred to as “composition” as appropriate) according to one embodiment of the present invention will be described in detail.

  The composition according to one embodiment of the present invention has a polyesteramic acid (A), an epoxy compound (B) having a weight average molecular weight of less than 10,000, and an oxiranyl or oxetanyl having a weight average molecular weight of 10,000 or more. It contains a copolymer (C), a solvent (D) and a colorant (E). The composition according to one embodiment of the present invention may contain additives in addition to the above components.

1.1. Polyester amic acid (A)
The polyester amide acid (A) used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond and a carboxyl group, and more specifically, represented by the formulas (1) and (2). More preferably, the compound has a structural unit represented by the formula:

For the first time, the use of such a polyester amic acid (A) in combination with a specific epoxy compound (B) and a specific copolymer (C) results in hardness, heat resistance, water resistance, flux resistance, solder resistance, and solder resistance. A composition capable of forming a cured product that is excellent in solvent properties and chemical resistance in a well-balanced manner and that has excellent adhesion to substrates and circuits is obtained. A specific example of the shape of a cured product formed from the composition according to one embodiment of the present invention includes a film-like material. Also called.
As the polyesteramic acid (A), only one type may be used, or two or more types may be used.

(R ¹ is independently a C 1-30 tetravalent organic group, R ² is independently a C 1-40 divalent organic group, and R ³ is independently a C 1-20 carbon group. It is a divalent organic group.)

From the viewpoint that a compound having good compatibility with other components in the composition is obtained, R ¹ is preferably independently a tetravalent organic group having 2 to 25 carbon atoms, and preferably has 2 to 20 carbon atoms. Is more preferable, and more preferably a group represented by the formula (5).

(In the formula (5), R ⁴ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁵ —, or —COO—R ⁵ —OCO— (R ⁵ Independently, it is an alkylene having 1 to 4 carbon atoms.)

R ² is preferably a divalent organic group having 2 to 35 carbon atoms, for example, from the viewpoint that a compound having good compatibility with other components in the composition is obtained. It is more preferably a valence organic group, and further preferably a group represented by the formula (6).

(In the formula (6), R ⁶ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ —, or —O-ph-R ⁸ -ph-O— (a ph is a benzene ring, R ⁸ is, -O -, - CO -, - SO 2 -, - C (CF 3) 2 - or -R ⁷ -. a a) in which. Incidentally, R ⁷ is Independently, it is an alkylene having 1 to 4 carbon atoms.)

R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, and a group represented by the formula (7): —R ¹⁰ —NR ¹¹ —R ¹² — (R ¹⁰ and R ¹² are independently R ¹¹ is hydrogen or alkyl having 1 to 8 carbons in which at least one hydrogen may be substituted with hydroxyl.), Alkylene having 2 to 15 carbons, Alternatively, at least one hydrogen of alkylene having 2 to 15 carbon atoms may be substituted with hydroxyl, and a group which may have -O- is more preferable, and divalent having 2 to 6 carbon atoms is preferable. More preferably, it is alkylene.

(In the formula (7), R ⁹ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ — or —ph—R ⁸ —ph— a benzene ring, R ⁸ is, -O is -, - CO -, - SO 2 -, - C (CF 3) 2 - or -R ⁷ -.. a is) Incidentally, R ⁷ is independently carbon It is an alkylene of Formulas 1 to 4.)

  The polyester amic acid (A) is a compound obtained by reacting a component containing a tetracarboxylic dianhydride (a1), a component containing a diamine (a2), and a component containing a polyvalent hydroxy compound (a3). Are preferable, by reacting a component containing a tetracarboxylic dianhydride (a1), a component containing a diamine (a2), a component containing a polyhydric hydroxy compound (a3), and a component containing a monohydric alcohol (a4). Is also preferred.

That is, in the formulas (1) and (2), R ¹ is independently a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue. Is preferred.
In this reaction, a reaction solvent (a5), an acid anhydride (a6), or the like may be used.

The component containing the tetracarboxylic dianhydride (a1) may contain another compound having three or more acid anhydride groups other than this compound. This is the same for the component containing the diamine (a2), and the component may contain another compound having three or more amino groups.
These (a1) to (a6) may be used alone or in combination of two or more.

  When the polyester amide acid (A) has an acid anhydride group at the molecular terminal, it is preferably a compound reacted with a monohydric alcohol (a4) as necessary. Polyester amic acid (A) obtained by using monohydric alcohol (a4) is a compound having excellent compatibility with epoxy compound (B) having a weight average molecular weight of less than 10,000 and specific copolymer (C). And a composition having excellent coatability tends to be obtained.

1.1.1. Tetracarboxylic dianhydride (a1)
The tetracarboxylic dianhydride (a1) is not particularly limited, but specific examples include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 2,2 ′, 3,3′-benzophenonetetraanhydride. Carboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3 3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, , 2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3', 4'-diphenylethertetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl) Heki Aromatic tetracarboxylic dianhydrides such as fluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name: TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.); cyclobutanetetracarboxylic dianhydride Alicyclic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride and butanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydride;

  Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, from the viewpoint that a compound having good adhesion to a glass substrate can be obtained when used in combination with an epoxy compound. , 4,4'-diphenylethertetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (Trade name: TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.), preferably 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfonetetra Carboxylic dianhydrides are particularly preferred.

1.1.2. Diamine (a2)
The diamine (a2) is not particularly limited, but specific examples include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, and bis [4- (4-amino). Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4 -Aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferred in that a compound having good adhesion to a glass substrate can be obtained when used in combination with an epoxy compound. Preferably, 3,3′-diaminodiphenyl sulfone is particularly preferred.

1.1.3. Polyvalent hydroxy compound (a3)
The polyvalent hydroxy compound (a3) is not particularly limited as long as it is a compound having two or more hydroxy groups. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol having a molecular weight of 1,000 or less. , Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2- Pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2 , 6- Xanthritol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2 , 8-Octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decane Examples include triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.

  Among them, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferred, and 1,4-octanediol is preferred. Butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred from the viewpoint of good solubility in the reaction solvent (a5).

1.1.4. Monohydric alcohol (a4)
The monohydric alcohol (a4) is not particularly limited as long as it is a compound having one hydroxy group. Specific examples include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and propylene glycol. Monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol (in the present invention, phenols Is also a monohydric alcohol), borneol, maltol, linalool , Terpineol, dimethyl benzyl carbinol and 3-ethyl-3-hydroxymethyl oxetane and the like.

  Among them, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are preferred. Considering the compatibility between the obtained polyesteramic acid (A), the epoxy compound (B) having a weight average molecular weight of less than 10,000 and the epoxy curing agent (F), the monohydric alcohol (a4) Benzyl alcohol is more preferred.

1.1.5. Reaction solvent (a5)
The reaction solvent (a5) is not particularly limited, but specific examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether. Examples include acetate, dipropylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

  Among these, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, methyl 3-methoxypropionate and N-methyl-2-pyrrolidone are preferred from the viewpoint of solubility.

  Specific examples of the reaction solvent (a5) include these solvents. However, if the proportion of these solvents is 30% by weight or less based on the total amount of the solvents used in the reaction, other solvents may be used. A mixed solvent obtained by mixing other solvents can also be used.

1.1.6. Acid anhydride (a6)
The acid anhydride is not particularly limited, but specific examples include carboxylic anhydrides such as 3- (triethoxysilyl) propyl succinic anhydride and maleic anhydride. Further, a polyvalent anhydride such as a copolymer containing a carboxylic acid anhydride can also be used. Commercially available polyanhydrides include SMA (trade name, manufactured by Kawahara Yuka Co., Ltd.), which is a styrene-maleic anhydride copolymer.

<< Synthesis of polyester amic acid (A) >>
The method for synthesizing the polyester amic acid (A) is not particularly limited, but the tetracarboxylic dianhydride (a1), the diamine (a2), the polyhydric hydroxy compound (a3), and if necessary, the monohydric alcohol (a4) are used. The reaction is preferably performed as an essential component, and this reaction is more preferably performed in a reaction solvent (a5).

The order of addition of each component in this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3) may be simultaneously added to the reaction solvent (a5) and reacted, or the diamine (a2) and the polyvalent hydroxy compound may be used. After dissolving (a3) in the reaction solvent (a5), tetracarboxylic dianhydride (a1) may be added and reacted, or tetracarboxylic dianhydride (a1) and diamine ( After pre-reacting with a2), a polyvalent hydroxy compound (a3) may be added to the reaction product to cause a reaction, and any method can be used.
The monohydric alcohol (a4) may be added at any time during the reaction.

  In the above reaction, in order to increase the weight average molecular weight of the obtained polyester amide acid (A), a compound having three or more acid anhydride groups may be added to carry out a synthesis reaction. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer.

  The polyester amide acid synthesized in this manner contains the structural units represented by the above formulas (1) and (2), and its terminal is derived from the starting material, tetracarboxylic dianhydride, diamine or polyhydroxy compound, respectively. An acid anhydride group, an amino group or a hydroxy group, or a group derived from a component other than these compounds (for example, a monohydric alcohol residue).

When the amounts of the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyhydroxy compound (a3) used in the reaction are X mol, Y mol and Z mol, respectively, X, Y and It is preferable that the relationship between Expressions (3) and (4) be established between Z. By using each component in such an amount, a polyesteramic acid (A) having high solubility in the following solvent (E) can be obtained, a composition having excellent coatability can be obtained, and a cured film having excellent flatness can be obtained. Obtainable.
0.2 ≦ Z / Y ≦ 8.0 (3)
0.2 ≦ (Y + Z) /X≦1.5 (4)

  The relationship of the expression (3) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. Further, the relationship of the expression (4) is preferably 0.3 ≦ (Y + Z) /X≦1.2, and more preferably 0.4 ≦ (Y + Z) /X≦1.0.

  When the amount of the monohydric alcohol (a4) used in the reaction is Z ′ mol, the amount is not particularly limited, but preferably 0.1 ≦ Z ′ / X ≦ 5.0, more preferably Is 0.2 ≦ Z ′ / X ≦ 4.0.

  When the reaction solvent (a5) is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3), the reaction proceeds smoothly. Therefore, it is preferable.

  The reaction is preferably performed at 40 to 200 ° C. for 0.2 to 20 hours.

<< Physical properties and amount of polyester amic acid (A) >>
The weight average molecular weight of the polyester amic acid (A) measured by gel permeation chromatography (GPC) is determined based on the solubility in the solvent (E) and particularly the epoxy compound (B) having a weight average molecular weight of less than 10,000 and the epoxy compound (B). When used in combination with the copolymer (C), from the viewpoint of obtaining a cured film having a good balance between adhesion to a substrate and a circuit, flux resistance, solder resistance, solvent resistance and chemical resistance, etc. It is preferably from 3,000 to 30,000, and more preferably from 3,000 to 30,000.
This weight average molecular weight can be specifically measured by the method described in the following examples.

  The viscosity of the polyester amic acid (A) is preferably from 5 to 200 mPa · s at 25 ° C., more preferably from the viewpoint of adjusting the handleability of the obtained polyester amic acid (A) and the weight average molecular weight to the above preferable ranges. Is 10 to 150 mPa · s, more preferably 15 to 100 mPa · s.

  The content of the polyester amic acid (A) is determined based on the solid content of the composition according to one embodiment of the present invention (for example, from the viewpoint of obtaining a cured film having excellent adhesion to metal and excellent chemical resistance). The amount is preferably 1 to 60 parts by weight, more preferably 5 to 55 parts by weight, and still more preferably 10 to 50 parts by weight, based on 100 parts by weight of the residue obtained by removing the solvent from the product.

1.2. Epoxy compound (B) having a weight average molecular weight of less than 10,000 (hereinafter, also referred to as “epoxy compound (B)” as appropriate).
The epoxy compound (B) used in the present invention is a compound containing two or more oxirane rings or oxetane rings in the molecule, and a compound having two or more oxirane rings is preferably used.

  Only one epoxy compound (B) may be used, or two or more epoxy compounds may be used. The epoxy compound (B) may be obtained by synthesis or may be a commercially available product.

  Examples of the epoxy compound (B) include bisphenol A type epoxy compounds, glycidyl ester type epoxy compounds, and alicyclic epoxy compounds.

  Specific examples of the compound containing two or more oxirane rings in the molecule include “807”, “815”, “825”, “827”, “828”, “828EL”, “871”, “872”, “872”, and “872”. 190P "," 191P "," 1001 "," 1004 "," 1004AF "," 1007 "," 1256 "," 157S70 "," 1032H60 "(trade names, manufactured by Mitsubishi Chemical Corporation)," Araldite CY177 " "," Araldite CY184 "(trade name, manufactured by Huntsman Japan KK)," Celoxide 2021P "," Celoxide 3000 "," Celoxide 8000 "," EHPE-3150 "(trade name, manufactured by Daicel Co., Ltd.) ), “TECHMORE VG3101L” (trade name, manufactured by PRINTEC CORPORATION), “HP7200”, “HP720” H "," 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 "(trade name, manufactured by Nippon Kayaku Co., Ltd.)," TEP-G "(product "MA-DGIC", "Me-DGIC", "TG-G" (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), "TEPIC-VL" (product) "FLEP-10", "FLEP-50", "FLEP-60", "FLEP-80" (trade name, manufactured by Toray Fine Chemical Co., Ltd.), OGSOL PG -10 0, OGSOL CG-500, OGSOL EG-200, OGSOL EG-250, OGSOL EG-280, OGSOL CG-400 (all trade names, manufactured by Osaka Gas Chemical Co., Ltd.), N, N, N ', N'- Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane. Among them, a composition containing the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “TECHMORE VG3101L”, the trade name “157S70”, the trade name “EHPE3150” is a sodium hydroxide aqueous solution or hydrochloric acid, and Preferred is that a cured film having good resistance to chemicals such as sulfuric acid can be obtained, and among them, more preferred are trade name “157S70” and trade name “EHPE3150”.

  Specific examples of the compound containing two or more oxetanyl rings in the molecule include “Alone oxetane OXT-121 (XDO)”, “Alon oxetane OXT-221 (DOX)”, “OX-SQ”, and “PNOX-1009”. , “NDMOX”, “TMPOX”, “HQOX”, “RSOX”, “2,2′-BPOX”, “4,4′-BPOX”, “BisFOX”, “OX-SC” (all trade names or developments) Product name, manufactured by Toagosei Co., Ltd.).

  The content of the epoxy compound (B) is excellent in flux resistance (resistance to flux and heat resistance when reflow baking is performed by applying flux), and curing excellent in resistance to chemicals such as sodium hydroxide aqueous solution, hydrochloric acid, and sulfuric acid. From the viewpoint of obtaining a film and the like, preferably 10 to 80 parts by weight, more preferably 10 to 80 parts by weight, based on 100 parts by weight of the solid content of the composition according to one embodiment of the present invention (the residue obtained by removing the solvent from the composition). Is 15 to 75 parts by weight, more preferably 20 to 70 parts by weight. From the same point, the content of the epoxy compound (B) is preferably 10 to 600 parts by weight, more preferably 20 to 500 parts by weight, and still more preferably 30 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A). Parts by weight.

  The epoxy equivalent of the epoxy compound (B) is preferably 100 to 280, and more preferably 120 to 280, from the viewpoint of improving the flux resistance of the cured product formed from the composition and the resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid. To 270 are more preferable, and 140 to 240 are still more preferable.

1.3. Copolymer (C) having oxiranyl or oxetanyl and having a weight average molecular weight of 10,000 or more (hereinafter, also appropriately referred to as “copolymer (C)”).

  The copolymer (C) used in the present invention is a copolymer obtained by copolymerizing a monomer containing at least one oxirane ring or oxetane ring in the molecule with another monomer, and forming a composition of the present invention. There is no particular limitation as long as the compatibility with the components is good.

  The copolymer (C) is obtained by, for example, radically copolymerizing a monomer having oxiranyl or oxetanyl with another monomer. The production method is not particularly limited, but the copolymer (C) can be produced by heating the above-mentioned radically polymerizable compounds in the presence of a radical initiator. As the radical initiator, an organic peroxide, an azo compound, or the like can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50 to 150 ° C. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours. In addition, the reaction can be performed under any of pressure, reduced pressure, or atmospheric pressure.

  Specific examples of the monomer having oxiranyl include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Among these, glycidyl methacrylate is preferred because it can provide a cured film having good resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid.

  Specific examples of the monomer having oxetanyl include 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, p-acetoxystyrene and 3-ethyl-3-hydroxy Examples include a compound of methyloxetane, and a compound of p- (1-ethoxyethoxy) styrene and 3-ethyl-3-hydroxymethyloxetane.

Specific examples of other monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, methyl (Meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate, glycerol model (Meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl ( (Meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-ethyl- 3- (meth) acryloxyethyloxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethylether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) Acryloxime Tyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide , N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethyl methacrylate 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, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] maleate , Chlohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl] and the like can be mentioned. Among them, methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, and methyl (meth) acrylate are preferable in that a copolymer (C) having excellent compatibility with the polyester amic acid (A) is obtained. -Hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and styrene are preferred. Among them, N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide are more preferred in that they can provide a cured film having flux resistance and solder heat resistance.

  The solvent used in the above radical copolymerization reaction is preferably a solvent in which the produced polymer is dissolved. Specific examples of the solvent include 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, dipropylene glycol methyl ether acetate, methyl 2-hydroxyisobutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolan, ethylene glycol dimethyl ether, 1,4- Dioxane, propylene glycol dimethyl Ether, propylene glycol monomethyl ether, ethylene glycol monomethyl 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 dibi Alkyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, tetramethylene glycol bal 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 Equamide (trade name) manufactured by Idemitsu Kosan Co., Ltd. The solvent may be one of these or a mixture of two or more of these.

  The copolymer (C) used in the present invention may be used as a copolymer solution in consideration of handling properties or the like by leaving the solvent used for polymerization as it is, or may be removed by removing this solvent and taking into consideration the transportability and the like. It may be a copolymer having a shape.

  The proportion of the copolymer of the oxiranyl-containing monomer and the other monomer is preferably 30% by mole or more because the monomer having oxiranyl has excellent resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid. More preferably, the amount of the monomer having oxiranyl is 50 mol% or more.

  For example, when N-phenylmaleimide and butyl methacrylate are used as other monomers, the proportion of the monomer used as a raw material of the copolymer (C) is such that the monomer having oxiranyl is 30 mol% or more and 80 mol% or less. It is preferable that the content of -phenylmaleimide is 10 mol% or more and 30 mol% or less, and the content of butyl methacrylate is 5 mol% or more and 20 mol% or less. By copolymerizing using the monomer in this ratio, a copolymer (C) having excellent compatibility with the polyester amic acid (A) can be obtained, and further, a chemical such as an aqueous sodium hydroxide solution, hydrochloric acid, and sulfuric acid can be obtained. This is preferred in that a well-balanced cured film that achieves both resistance to flux and flux resistance can be obtained.

  When the composition is supplied onto a substrate by an ink jet method, the molecular weight of the copolymer (C) depends on the jetting property of the composition, the compatibility with the polyester amic acid (A), and the solvent (D). From the viewpoint of improving the solubility, the weight average molecular weight is preferably from 10,000 to 100,000, more preferably from 20,000 to 80,000. In this specification, discharging ink by an inkjet method is also referred to as jetting, and its characteristic is also referred to as discharging property or jetting property.

  The content of the copolymer (C) according to the present invention is such that the stress due to curing shrinkage is alleviated, and excellent adhesion to the substrate can be obtained, and a well-balanced cured film having excellent flux resistance can be obtained. 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, even more preferably 3 parts by weight, based on 100 parts by weight of the solid content of the composition according to one embodiment (the residue obtained by removing the solvent from the composition). -20 parts by weight.

1.4. Solvent (D)
The solvent (D) used in the present invention is preferably a solvent capable of dissolving the polyesteramic acid (A), the epoxy compound (B) and the copolymer (C). Further, even a solvent which does not dissolve the polyesteramide acid (A), the epoxy compound (B) and the copolymer (C) alone can be used as the solvent (D) by mixing with another solvent. In some cases.
As the solvent (D), only one type may be used, or two or more types may be used.

  Examples of the solvent (D) include ethyl lactate, ethanol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, methyl 2-hydroxyisobutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Cyclohexanone, 1,3-di Oxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl 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 Recohol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, -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-a Chill -γ- butyrolactone, .epsilon.-caprolactone, .gamma. hexa gluconolactone, .delta. hexa gluconolactone, methyl ethyl sulfoxide, dimethyl sulfoxide and Idemitsu Kosan Co. Ekuamido (trade name).

  Among these, in view of solubility in the polyester amic acid (A), the epoxy compound (B) and the copolymer (C), the composition of the present invention comprises ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether. , Diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, methyl 3-methoxypropionate, γ-butyrolactone, dimethyl sulfoxide, and Edemide manufactured by Idemitsu Kosan Co., Ltd. It is preferable that at least one selected from the group consisting of (trade names) is included as the solvent (D).

  The content of the solvent (D) is not limited, but when the composition is supplied onto a substrate by an ink-jet method, the jetting property of the composition is improved, so that the content in 100 parts by weight of the composition is The content is preferably 45 to 90 parts by weight, and more preferably 50 to 80 parts by weight. From the same viewpoint, it is preferable to adjust the solvent (D) so that the content of the solvent having a boiling point of 200 ° C. or higher in 100 parts by weight of all the solvents contained in the composition is 50 parts by weight or more, It is more preferable to adjust the solvent (D) so as to be 55 parts by weight or more.

1.5. Colorant (E)
The composition according to one embodiment of the present invention contains a coloring agent (E).
Examples of the coloring agent (E) include inorganic and organic dyes and pigments. For example, for insulating films that protect metal wiring, the concealment of wiring patterns and light-shielding properties are required so that inspection equipment can recognize them, and resistance to chemicals such as aqueous sodium hydroxide, hydrochloric acid, and sulfuric acid, and solder heat resistance are required. Therefore, it is preferable to use inorganic pigments having excellent performance. A commercially available product may be used as the colorant (E).

  Examples of the inorganic pigment used as the coloring agent (E) include particles of silicon carbide, alumina, magnesia, silica, titanium compounds such as zinc oxide, titanium oxide and titanium nitride, graphite, and carbon black. One type of inorganic pigment may be used alone, or two or more types may be mixed and used.

Examples of the organic pigment used as the colorant (E) include C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 202, C.I. I. Pigment Red 209, C.I. I. Pigment red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Violet 23, C.I. I. Pigment Orange 43, C.I. I. Pigment Black 1, C.I. I. Pigment Black 7 and other color index numbers.
The organic pigment may be used alone or in combination of two or more.

Examples of the dye include an azo dye, an azomethine dye, a xanthene dye, and a quinone dye. Examples of azo dyes include “VALIFAST BLACK 3810”, “VALIFAST BLACK 3820”, “VALIFAST RED 3304”, “VALIFAST RED 3320”, “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industries, Ltd.), and Spiron. blue GNH (trade name; Hodogaya Chemical Industry Co., Ltd.).
One type of dye may be used alone, or two or more types may be mixed and used.

  The colorant (E) contained in the composition according to an embodiment of the present invention can provide, for example, a wiring pattern concealing property for an insulating film for protecting metal wiring and a light shielding property so that an inspection device can recognize it. From the viewpoint of being possible, the dye and pigment content is preferably at least 2 parts by weight, more preferably at least 3 parts by weight, based on 100 parts by weight of the resin solids excluding the solvent, the dye and the pigment of the composition. . Further, when the composition is supplied onto a substrate by an inkjet method, from the viewpoint that the jetting property of the composition becomes good, the solvent of the composition, 100 parts by weight of the resin solid content excluding dyes and pigments The dye and pigment content is preferably 15 parts by weight or less, more preferably 10 parts by weight or less.

  When a carbon black particle or a titanium compound particle-based inorganic pigment is used as the colorant (E), the jetting property of the composition is improved when the composition is supplied onto a substrate by an inkjet method. The average particle size is preferably 500 nm or less, more preferably 400 nm or less. In addition, the average particle diameter used in the present specification means a 50% volume particle diameter of a pigment dispersion, and is measured by a particle size distribution analyzer (for example, Nikkiso Microtrac UPA150) by a dynamic light scattering method / laser Doppler method. It is a value of the measured MV (volume average diameter).

1-6. Additives The composition of the present invention may contain additives other than the polyesteramic acid (A), the epoxy compound (B), the copolymer (C), the solvent (D), and the colorant (E), depending on the desired properties. An agent may be contained. Examples of the additive include a polyimide resin, a polymerizable monomer, an epoxy curing agent (F), an epoxy curing accelerator, an antistatic agent, a coupling agent, an ultraviolet absorber, an antioxidant, and a surfactant (i). No. Only one type of additive may be used, or two or more types may be used.

1.6.1. Polyimide resin The polyimide resin is not particularly limited as long as it has an imide group. One kind of polyimide resin may be used, or two or more kinds may be used.

  The polyimide resin is obtained, for example, by imidizing a polyamic acid obtained by reacting an acid dianhydride with a diamine. Examples of the acid dianhydride include a tetracarboxylic dianhydride (a1) that can be used for the synthesis of the polyester amide acid (A). Examples of the diamine include a diamine (a2) that can be used for the synthesis of the polyesteramic acid (A).

  When the composition of the present invention contains a polyimide resin, the concentration of the polyimide resin in the composition of the present invention is not particularly limited, but from the viewpoint of obtaining a cured film having better heat resistance and chemical resistance, The content of the composition of the present invention in 100 parts by weight of the solid content (the residue obtained by removing the solvent from the composition) is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. In the present invention, the polyimide resin does not include the copolymer (C) obtained by using an imide compound as a monomer.

1.6.2. Polymerizable monomer The composition of the present invention may contain a polymerizable monomer other than the polyesteramic acid (A), the epoxy compound (B), and the copolymer (C).
Examples of the polymerizable monomer include a monofunctional polymerizable monomer and a bifunctional (meth) acrylate. One type of polymerizable monomer may be used, or two or more types may be used.

  When the composition of the present invention contains a polymerizable monomer, the concentration of the polymerizable monomer in the composition of the present invention is not particularly limited, but the chemical resistance, the cured film having a better surface hardness can be obtained. Therefore, it is preferable that 1 to 40 parts by weight, preferably 1 to 30 parts by weight, be contained in 100 parts by weight of the solid content of the composition of the present invention (the residue obtained by removing the solvent from the composition). Is more preferred.

Examples of the monofunctional polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) 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, dicyclopentenyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate, Gurisero Mono (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, 3,4-epoxycyclohexyl (meth) acrylate, 3-methyl-3- (meth) ) Acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p- Vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2 − (Meth) acryloxymethi Luoxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide, N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene Macromonomer, polymethyl methacrylate 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, mono [2- (meth) acryloyloxyethyl succinate], mono [2- (meth) acryloyloxyethyl maleate], mono [2- (meth) acryloyloxycyclohexene-3,4-dicarboxylate Siethyl].

  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, and 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.

1.6.3 Epoxy curing agent (F)
When the composition of the present invention contains an epoxy curing agent (F), the epoxy curing agent (F) is a compound different from the polyesteramic acid (A), and specifically, an acid anhydride curing agent, Examples thereof include a polyamine-based curing agent, a polyphenol-based curing agent, and a catalyst-type curing agent, and an acid anhydride-based curing agent is preferred from the viewpoint of storage stability and solder heat resistance.
Only one epoxy curing agent (F) may be used, or two or more epoxy curing agents (F) may be used.

  Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; phthalic anhydride, trimellitic anhydride And styrene-maleic anhydride copolymers. Among these, trimellitic anhydride is particularly preferred from the viewpoint that a compound having excellent solubility in the solvent (D) can be obtained and a cured film having excellent heat resistance can be obtained.

  The content of the epoxy curing agent (F) is selected from the viewpoints that a cured film excellent in hardness, chemical resistance and adhesion to metals such as copper can be obtained in a well-balanced manner. The amount is preferably 35 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 25 parts by weight or less, and particularly preferably 20 parts by weight, based on 100 parts by weight (residue excluding the solvent from the composition). It is as follows.

  The content of the epoxy curing agent (F) is preferably 40 parts by weight or less based on 100 parts by weight of the total of the epoxy compound (B) and the copolymer (C) in the composition according to one embodiment of the present invention. The amount is more preferably 30 parts by weight or less, and even more preferably 3 to 20 parts by weight.

  The ratio of the total of the epoxy compound (B) and the copolymer (C) to be used and the epoxy curing agent (C) is used from the viewpoint that a cured film having excellent solder heat resistance and chemical resistance is obtained. The amount of oxiranyl and oxetanyl groups in the epoxy compound (B) and copolymer (C) is less than the amount of groups capable of reacting with epoxy groups such as acid anhydride groups and carboxyl groups in the epoxy curing agent. The equivalent is preferably 2 to 2 equivalents, more preferably 0.5 to 1.5 equivalents. Thereby, the chemical resistance of the obtained cured film is further improved. At this time, for example, one equivalent of a compound having one oxiranyl group is used as the epoxy compound (B) and the copolymer (C), and a compound having one acid anhydride group is used as the epoxy curing agent (F). When one equivalent is used, the amount of the epoxy curing agent (F) is assumed to be twice equivalent to the total amount of the epoxy compound (B) and the copolymer (C).

1.6.4. Epoxy curing accelerators Epoxy curing accelerators include, for example, tertiary amines, tertiary amine salts, imidazole, and the like, from the viewpoint of lowering the curing temperature of the composition of the present invention or shortening the curing time. Epoxy curing accelerators such as phosphines, phosphonium salts, thiols and the like can be used. Only one epoxy curing accelerator may be used, or two or more epoxy curing accelerators may be used.

  Examples of epoxy curing accelerators include “DBU”, “DBN”, “U-CAT”, “U-CAT SA1”, “U-CAT SA102”, “U-CAT SA506”, “U-CAT SA603”, “U-CAT SA810”, “U-CAT 5002”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT SA841”, “U-CAT SA851”, “U-CAT SA881”, “ U-CAT 891 "(trade name, manufactured by San Apro)," CP-001 "," NV-203-R4 "(trade name, manufactured by Osaka Gas Chemical Co., Ltd.)," Karenz MT PE1, "" Karenz MT " BD1 "," Karenz MT NR1 "," TPMB "," TEMB "(trade name, manufactured by Showa Denko KK) and the like.

  When the epoxy curing agent (F) is used, the content of the epoxy curing accelerator is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, based on 100 parts by weight of the epoxy curing agent (F). Preferably it is 30 to 150 parts by weight.

  When the epoxy curing agent (F) is not used, the content of the epoxy curing accelerator is preferably 1 to 20 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the epoxy compound (B) and the copolymer (C). Is 1 to 15 parts by weight, more preferably 1 to 10 parts by weight.

1.6.5. Antistatic agentAn antistatic agent can be used to prevent the composition of the present invention from being charged, and when the composition of the present invention contains an antistatic agent, 0 to 100 parts by weight of the composition of the present invention. It is preferably used in an amount of from 0.01 to 1 part by weight.

  As the antistatic agent, a known antistatic agent can be used. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, and tin oxide / indium oxide composite oxide; quaternary ammonium salts. Only one kind of antistatic agent may be used, or two or more kinds may be used.

1.6.6. Coupling Agent The coupling agent is not particularly limited, and a known coupling agent such as a silane coupling agent can be used for the purpose of improving the adhesion of a substrate such as metal or glass. When the composition of the present invention contains a coupling agent, the amount of the coupling agent is 10 parts by weight or less based on 100 parts by weight of the solid content of the composition of the present invention (the residue obtained by removing the solvent from the composition). It is preferable to use it after being added. One type of coupling agent may be used alone, or two or more types may be used.

  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-gly Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmeth 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, it includes γ- isocyanato propyl triethoxysilane.

  Among them, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are particularly preferable. In the present invention, among the silane compounds having an epoxy group, those used as a silane coupling agent are not included in the epoxy compound (B).

1.6.7. Ultraviolet Absorber When the composition of the present invention contains an ultraviolet absorber, the cured film obtained from the composition can be prevented from deteriorating when exposed to light. When the composition of the present invention contains an ultraviolet absorber, the ultraviolet absorber is added in an amount of 0.1 to 100 parts by weight of the solid content of the composition excluding the ultraviolet absorber (the residue obtained by removing the solvent from the composition). It is preferable to use by adding to 20 parts by weight. Only one UV absorber may be used, or two or more UV absorbers may be used.

  Examples of the ultraviolet absorber include benzotriazole-based and hydroxyphenyltriazine-based. Specifically, TINUVIN PS, TINUVIN99-2, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (all trade names, manufactured by BASF), LA-29, LA-29, LA-29, LA-29 31G, LA-31RG, LA-32, LA-36, LA-36RG, LA-46, LA-1413, LA-F70 (all trade names, manufactured by ADEKA Corporation) and the like.

1.6.8. Antioxidant When the composition of the present invention contains an antioxidant, the cured film obtained from the composition can be prevented from deteriorating when exposed to high temperature or light. When the composition of the present invention contains an antioxidant, the antioxidant is added in an amount of 0.1 to 100 parts by weight of the solid content of the composition excluding the antioxidant (the residue obtained by removing the solvent from the composition). It is preferable to add 10 to 10 parts by weight. One type of antioxidant may be used alone, or two or more types may be used.

  Examples of the antioxidant include a hindered amine compound and a hindered phenol compound. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN ABA, and TINUVIN 52SF, TINUVIN5100 Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77γ, Adekastab LA-77G, Adekastab LA-81, Adekastab LA-82, Adekastab LA-87, Adekastab AO-20, ADK STAB AO-40, ADK STAB AO-50, ADK STAB Tab AO-60, Adekastab AO-80, Adekastab AO-330 (trade name, manufactured by ADEKA Corporation) and the like.

1.6.9. Surfactant (i)
When the composition of the present invention contains a surfactant, a composition having improved wettability, leveling property, and applicability to an underlying substrate can be obtained. When the composition of the present invention contains a surfactant, the surfactant is preferably used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the composition of the present invention. One surfactant may be used alone, or two or more surfactants may be used.

  As the surfactant, for example, polyflow No. 1 can be used from the viewpoint that the coating property of the composition of the present invention can be improved. 45, Polyflow KL-245, Polyflow No. 75, polyflow no. 90, polyflow no. 95 (all trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-335, BYK-341, BYK-342, BYK-344, BYK-346, BYK-354, BYK-358, BYK-361, BYK-361N, BYK-370, BYK-UV3500, BYK-UV3570 (all trade names; BYK-Chemie Japan KK), KP-112, KP-326, KP-341, KP- 58, KP-368, KF-96-50CS, KF-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Surflon-SC-101, Surflon-KH-40, Surflon-S611 (all AGC Seimi Chemical Co., Ltd.), FUJANTENT 222F, FUJANTENT 208G, FUJANTENT 250, FUJANTENT 251, FUJANTENT 710FL, FUJANTENT 710FM, FUJANTENT 710FS, FUJANTENT 601AD, FUJANTENT 602A, FUJANTENT 650A , DFX-18, FTX-218 (all trade names; Neos Corporation), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all trade names; Mitsubishi Materials Corporation), MegaFac F-171, MegaFac F-177, MegaFac F-410, MegaFac F-430, MegaFac F-444, MegaFac F-472SF , Megafac F-475, Megafac F-577, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Mega MEGAFAK R-30, MEGAFAC R-94, MEGAFAC RS-75, MEGAFAC RS-72-K, MEGAFAC RS-76-NS, MEGAFAC DS-21 (all trade names; DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TE GO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all trade names, Evonik Degussa Japan K.K.), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkyl Polyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, dimethylsiloxane bond Compounds, polyoxyethylene nonylphenyl ether, polyoxyethylene Tylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxy Ethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxy Ethylene naphthyl ether, alkyl benzene sulfonates, and alkyl diphenyl ether disulfonic acid salts.

2. Method for Preparing Thermosetting Resin Composition The composition of the present invention comprises a polyester amic acid (A), an epoxy compound (B), a copolymer (C), a solvent (D), and a colorant (E). It can be prepared by mixing with other additives used accordingly. Further, the composition of the present invention is prepared by reacting an epoxy compound (B), a solvent (D), a reaction solution or a mixed solution obtained at the time of synthesizing the polyester amide acid (A) or the copolymer (C), as it is. It can also be prepared by mixing the coloring agent (E) and other additives used as necessary.

3. Storage of the composition The composition of the present invention is preferably stored at a temperature in the range of -30 ° C to 25 ° C because the composition has good stability over time. If the storage temperature is -25 ° C to 10 ° C, it is more preferable that there is no precipitate.

4. Method for Producing Cured Film A method for producing a cured film using the composition according to one embodiment of the present invention is not limited. The method for manufacturing a cured film according to one embodiment of the present invention includes an arrangement step and a curing step described below.

4.1. Arranging Step In the arranging step, an uncured film made of the composition according to one embodiment of the present invention is arranged on a substrate in a predetermined shape. The uncured film may be disposed so as to cover the entire surface of the substrate, or may be disposed so as to form a pattern on the surface of the substrate.

  The method for supplying the composition according to one embodiment of the present invention onto a substrate is not limited. Conventionally known methods such as spray coating, spin coating, roll coating, dipping, slit coating, bar coating, gravure printing, flexo printing, offset printing, dispenser, screen printing, and inkjet printing. It can be done by a method.

  Among these methods, the ink jet method can greatly reduce the amount of ink used compared to other methods, and does not require the use of a photomask or the like. For this reason, according to the inkjet method, a large variety of cured films can be produced in large quantities, and the number of steps required for manufacturing these cured films is small. Therefore, when the uncured film has a pattern, the ink jet method may be particularly preferable. The composition according to the embodiment of the present invention is suitable as an inkjet ink composition.

  When the uncured film is formed so as to cover the entire surface of the substrate, a coating method such as a spin coating method, a slit coating method, a gravure printing method, a flexographic printing method, an offset printing method, a dispenser method, and a screen printing method. May be preferred.

  In any case where the disposing step is performed by any method, the composition may be repeatedly supplied onto the same position on the substrate. By performing such repeated supply, it is easy to increase the thickness of the uncured film disposed on the base material, so that it is easy to cope with an increase in the thickness of the cured film.

  Before disposing the composition according to one embodiment of the present invention on a substrate, a step of surface treating the substrate (surface treatment step) may be provided. By performing such a surface treatment step, it is possible to improve the shape stability of the uncured film on the substrate, or to improve the adhesion of the cured film on the substrate to the substrate. There is. Examples of the surface treatment performed in the surface treatment step include a silane coupling agent treatment, a UV ozone ashing treatment, a plasma treatment, an alkali etching treatment, an acid etching treatment, and a primer treatment.

  The substrate on which the uncured film is disposed is not particularly limited, and a member made of a known material can be used. The shape of the substrate is not limited, and may be, for example, a plate, that is, a substrate. Specific examples of the substrate include a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, a paper epoxy substrate, a green epoxy substrate, and a BT that conform to various standards such as FR-1, FR-3, FR-4, and CEM-3. (Bismaleimide triazine) resin substrate; a substrate made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless steel (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), aluminum titanate, barium titanate , Lead titanate (PT), lead zirconate titanate ( ZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (berylia), silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride ( A substrate made of an inorganic substance such as silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, forsterite, spinel or spodumene (a substrate having a layer containing these inorganic substances on its surface, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene terephthalate), PPS (polyphenylene sulfide), polycarbonate Made of resin such as polyacetal, polyphenylene ether, polyimide, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer or liquid crystal polymer (It 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; an electrode material such as tin oxide, zinc oxide, ITO or ATO (antimony tin oxide). Substrates having (wiring) formed on the surface; gel sheets such as αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel), and γGEL (gamma gel) (all of which are registered trademarks of Taika Co., Ltd.). Preferred examples of the substrate include a glass epoxy substrate, a copper substrate, a silicon wafer, a glass substrate, an ITO substrate, and a resin film substrate.

  The cured film in the member with a cured film according to one embodiment of the present invention can be appropriately attached to the base material. Therefore, even when an external force is applied to the cured film, the cured film is hardly peeled off from the substrate (that is, excellent in adhesion), and even when the member with the cured film is immersed in boiling water, the cured film is peeled off. Hard (that is, excellent in water resistance). Therefore, the member with a cured film according to one embodiment of the present invention can maintain an excellent appearance even when placed in various environments.

4.2. Curing Step In the curing step, the uncured film formed on the substrate by the above-described arrangement step is cured to obtain a cured film on the substrate.

  The method for curing the uncured film is not limited. It is set appropriately according to the composition of the composition. Specific examples include heating, irradiation with ionizing radiation such as ultraviolet rays, ion beams, electron beams, and gamma rays.

  In the case of curing by heating, the heating method is not limited. The uncured film may be heated together with the substrate on a hot plate or an oven, or may be heated by irradiating the uncured film with infrared rays. By heating as described above, the solvent in the uncured film volatilizes (drying treatment), and the ring-opening reaction of the oxiranyl and oxetanyl of the epoxy compound (B) and the copolymer (C) proceeds (curing treatment). ), A cured film is formed from the uncured film.

  The conditions of the drying treatment are different depending on the type and the mixing ratio of each component contained in the composition to be used when drying by heating, but usually, the heating temperature is 70 to 120 ° C., and the heating time is 5 to 15 in an oven. Minutes or 1-10 minutes on a hot plate. By such a drying treatment, it is possible to form a coating film on the base material from the uncured film to an extent that the shape can be maintained.

  After forming this coating film, it is usually subjected to a curing treatment at 80 to 300C, preferably 100 to 250C. At this time, a cured film can be obtained by performing a heat treatment usually for 10 to 120 minutes when using an oven, and usually for 5 to 60 minutes when using a hot plate.

  When the uncured film is cured using ionizing radiation, the above-described drying treatment may be performed by heating, and the coating film may be irradiated with ionizing radiation to perform the curing treatment.

  In the method for manufacturing a cured film according to an embodiment of the present invention, a step group including an arrangement step and a curing step may be performed a plurality of times. By performing such a process group a plurality of times, a cured film having a laminated structure can be formed on the substrate. By having such a laminated structure, it is easy to increase the thickness of the cured film. A process group consisting of an arranging process and a drying process in a curing process is repeated, a coating film is laminated, and a curing process in a curing process is performed on the obtained laminate of the coating film to form a cured film having a laminated structure. May be obtained.

  The cured film thus produced may be peeled off from the substrate or used as it is without being peeled off from the substrate, depending on the desired use or the substrate to be used.

5. Substrate with cured film A substrate (member) with a cured film according to one embodiment of the present invention includes a base material and the above-described cured film provided on the base material. As one specific example of the substrate with a cured film according to one embodiment of the present invention, an insulating film for a wiring substrate is given. In addition, since the insulating film also functions as a light shielding member, the concealing property of the wiring is good, and the substrate with the cured film is also excellent in design.

  The thickness of the cured film in the member with the cured film according to one embodiment of the present invention is not limited. If the thickness is excessively thin, a desired color tone may not be easily exhibited, and if the thickness is excessively large, manufacturing efficiency may decrease (specifically, an increase in manufacturing time and an increase in manufacturing cost may be exemplified). The thickness of the cured film is appropriately set in consideration of the occurrence of From the viewpoint of obtaining a cured film exhibiting a dark color tone more stably, the thickness of the cured film in the member with the cured film according to one embodiment of the present invention is preferably 3 μm or more because excellent flux resistance can be obtained. In some cases, it is preferable that the thickness is 4 μm or more, and in some cases, it is particularly preferable that it is 5 μm or more. From the viewpoint of more stably avoiding a decrease in the production efficiency of the cured film, the thickness of the cured film in the member with the cured film according to one embodiment of the present invention may be preferably 20 μm or less, and 15 μm or less. May be more preferable.

6. Electronic / Electric Component An electronic / electric component according to one embodiment of the present invention includes the member with a cured film according to one embodiment of the present invention. An electronic / electric component according to an embodiment of the present invention includes a semiconductor package and a printed wiring board used in electronic devices such as a smartphone and a tablet terminal.

  The embodiments described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Tetracarboxylic acid used in the synthesis of epoxy compound (B), solvent (D), colorant (E), epoxy curing agent (F), surfactant (i), and polyesteramic acid (A) used in Examples. Synthesis of dianhydride (a1), diamine (a2), polyhydroxy compound (a3), monohydric alcohol (a4), reaction solvent (a5), polyanhydride (a6), and copolymer (C) The names and abbreviations of the monomer (c1), polymerization initiator (c2) and reaction solvent (c3) to be used are shown below. This abbreviation will be used in the following description.

<Polyester amic acid (A)>
<Tetracarboxylic dianhydride (a1)>
ODPA: 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride <Diamine (a2)>
DDS: 3,3'-diaminodiphenyl sulfone <Polyhydric hydroxy compound (a3)>
BDOH: 1,4-butanediol <monohydric alcohol (a4)>
BzOH: benzyl alcohol <reaction solvent (a5)>
MPM: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate EDM: diethylene glycol methyl ethyl ether <Acid anhydride (a6)>
SM: SMA1000 (trade name, manufactured by Kawahara Yuka Co., Ltd.)

<Epoxy compound (B)>
EHPE3150: EHPE3150 (trade name, manufactured by Daicel Corp.), 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2-bis (hydroxymethyl) -1-butanol (epoxy equivalent 177, weight average molecular weight) 2,400)
157S70: 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), special novolak type epoxy resin (epoxy equivalent: 200 to 220, weight average molecular weight: 3,000 or less)
C620: NANOPOX C620 (trade name, manufactured by EVONIK), an epoxy resin containing 40% of nanosilica (epoxy equivalent 220)
VG3101L: TECHMORE VG3101L (trade name, manufactured by Printec Co., Ltd.), highly heat-resistant trifunctional epoxy resin (epoxy equivalent 210, molecular weight 592 to 1129, mixture of monomer and dimer)
EG200: OGSOL EG200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy resin having a fluorene skeleton (epoxy equivalent 292, weight average molecular weight 2,000 or less)
EG280: OGSOL EG280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), epoxy resin having a fluorene skeleton (epoxy equivalent: 467, weight average molecular weight: 2,000 or less)
FLEP-60: FLEP-60 (trade name, manufactured by Toray Thiokol Co., Ltd.), a mixture of a polysulfide-modified epoxy resin and a bisphenol F type epoxy resin (epoxy equivalent 280, weight average molecular weight 3,000 or less)

<Copolymer (C)>
<Monomer (c1)>
NPM: N-phenylmaleimide (N-substituted maleimide)
GMA: glycidyl methacrylate BMA: n-butyl methacrylate (monofunctional methacrylate)

<Polymerization initiator (c2)>
AIBN: azobisisobutyronitrile

<Reaction solvent (c3)>
PGMEA: Propylene glycol monomethyl ether acetate

<Adhesion improver>
AddBond LTH: TEGO AddBond LTH (trade name, manufactured by Evonik Japan KK), polyester resin

<Solvent (D)>
GBL: γ-butyrolactone (boiling point 204 ° C., high boiling point solvent)
MTM: Highsolve MTM (trade name, manufactured by Toho Chemical Industry Co., Ltd.), triethylene glycol dimethyl ether (boiling point: 216 ° C., high boiling solvent)
PGME: Propylene glycol monomethyl ether (trade name, Nippon Emulsifier Co., Ltd.)

<Colorant (E)>
Marco 2004: Marco 2004 Black (trade name, manufactured by Tokushiki Co., Ltd.), solid content: 38.4% by weight, pigment solid content: 30.7% by weight DPMA: dipropylene glycol methyl ether acetate dispersion, laser diffraction -The 50% volume average diameter based on the particle size distribution measurement by the scattering method is 140 nm)
Marco 2011: Marco 2011 Black (trade name, manufactured by Tokushiki Co., Ltd., solid content of 37.3% by weight, of which 30.0% by weight of pigment solid content is DPMA dispersion, based on particle size distribution measurement by laser diffraction / scattering method) (50% volume average diameter is 100 nm)

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

<Surfactant (i)>
RS-72K: Megafac RS-72-K (trade name, manufactured by DIC Corporation), oligomer containing fluorine-containing group, hydrophilic group, lipophilic group, and UV-reactive group F-444: Megafac F-444 ( Trade name, DIC Corporation), perfluoroalkyl ethylene oxide adduct

<Polyester amic acid (A)>
Polyester amic acid (A) was synthesized by the following method (Synthesis Examples 1 and 2).

[Synthesis Example 1]
In a 1000 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging port, and a nitrogen gas inlet, MPM 446.6 g as a reaction solvent, 183.20 g of ODPA, 31.93 g of BDOH, and 25.54 g of BzOH were charged and dried. The mixture was stirred at 130 ° C. for 3 hours under a nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C, 29.33 g of DDS and 183.4 g of MPM were added, and the mixture was stirred at 20 to 30 ° C for 2 hours and then at 115 ° C for 1 hour. Thereafter, the mixture was cooled to 30 ° C. or lower to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid.

  The rotational viscosity of this solution was 29 mPa · s. Here, the rotational viscosity is a value measured at 25 ° C. using an E-type viscometer (trade name: VISCONIC END, manufactured by Tokyo Keiki Co., Ltd.) (the same applies hereinafter).

The weight average molecular weight of the obtained polyester amide acid was 4,300.
In addition, the weight average molecular weight of the polyester amide acid was measured as follows. The obtained polyester amide acid is diluted with N, N-dimethylformamide (DMF) so that the concentration of the polyester amide acid becomes about 1% by weight, and GPC apparatus: Chrom Nav (differential refraction, manufactured by JASCO Corporation). The diluent was measured by a GPC method using a rate meter (RI-2031 Plus) as a developing agent, and the value was obtained by polystyrene conversion. As the columns, three columns GF-1G7B, GF-510HQ and GF-310HQ manufactured by Showa Denko KK were used in this order, and the measurement was performed under the conditions of a column temperature of 40 ° C. and a flow rate of 0.5 ml / min. .

[Synthesis Example 2]
In a 300 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging inlet, and a nitrogen gas inlet, 134.4 g of PGMEA as a reaction solvent, 12.72 g of ODPA, 2.46 g of BDOH, 14.78 g of BzOH, and 38.7 g of SM were placed. , And 25.58 g of EDM, and the mixture was stirred at 125 ° C. for 2 hours under a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C., a solution in which 3.39 g of DDS was dissolved in 7.92 g of EDM was charged, and the mixture was stirred at 20 to 30 ° C. for 2 hours, and then at 120 ° C. for 1 hour. Thereafter, the mixture was cooled to 30 ° C. or lower to obtain a 30% by weight solution of a pale yellow transparent polyesteramic acid.

  The rotational viscosity of this solution was 35 mPa · s, and the weight average molecular weight of the obtained polyesteramic acid was 24,000.

<Copolymer (C)>
The copolymer (C) was synthesized by the method shown below (Synthesis Example 3).
[Synthesis Example 3]
In a four-necked flask equipped with a stirrer, PGME: propylene glycol monomethyl ether 116.67 g as a reaction solvent, NPM: N-phenylmaleimide 10 g as a monomer, GMA: glycidyl methacrylate 35 g and BMA: n-butyl methacrylate 5 g, as a polymerization initiator AIBN: 0.4 g of azobisisobutyronitrile was charged and stirred at 80 ° C. for 60 minutes to confirm dissolution of the contents, and then heated to 100 ° C. over 30 minutes. Subsequently, polymerization was performed by heating at 100 ° C. for 3 hours. Thereafter, the mixture was cooled to 30 ° C. or lower to obtain a 30% by weight solution of the copolymer (C). The rotational viscosity of this solution was 320 mPa · s, and the weight average molecular weight of the obtained copolymer (C) was 43,000. The proportion of the monomers constituting the copolymer (C) was 20 mol% of N-phenylmaleimide, 70 mol% of glycidyl methacrylate, and 10 mol% of n-butyl methacrylate.

[Example 1]
The 300 ml three-necked flask equipped with stirring blades was purged with nitrogen, and 5.00 g of the polyesteramic acid (A) solution obtained in Synthesis Example 1 (the amount of the polyesteramic acid (A) in the solution was 1. 50 g), 2.40 g of EHPE3150 (epoxy compound (B)), 1.00 g of the copolymer (C) solution obtained in Synthesis Example 3 (the amount of the copolymer (C) is 0.30 g), MTM 6.53 g (solvent (D), high boiling point solvent) were charged.
Thereafter, the mixture was stirred at room temperature (25 ° C.) for 1 hour to uniformly dissolve each component. Next, 0.97 g of Marco 2011 (0.291 g of pigment (solid content) contained therein) as a coloring agent (E), 0.30 g of TMA as an epoxy curing agent, and 0% of RS-72K as a surfactant were used. 0.03 g was added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a membrane filter (material: PTFE, pore size: 5 μm) to obtain a thermosetting resin-containing composition as a filtrate.

[Examples 2 to 14]
In Examples 2 to 14, a thermosetting resin composition was prepared in the same manner as in Example 1 except that the types and charge amounts of the components were changed as shown in Tables 3 and 4.

[Comparative Examples 1 to 7]
In Comparative Examples 1 to 7, thermosetting resin compositions were prepared in the same manner as in Example 1 except that the types and charged amounts of each component were changed as shown in Table 4.

Using the thermosetting resin compositions according to Examples 1 to 14 and Comparative Examples 1 to 7, a coating film was formed and cured under the following conditions to obtain a sample substrate.
Substrate: Copper substrate (4cm square)
Coating method: inkjet printing Printer: DMP-2831 (manufactured by FUJIFILM Dimatix)
Head: DMC-11610 (manufactured by FUJIFILM Dimatix)
Printing conditions: head temperature 30 ° C., voltage 18 V, driving waveform Dimatix Model Fluid 2, driving frequency 1 kHz, space between dots 12 to 15 μm, single-sided two-layer printing Curing conditions: inkjet printing, drying, and baking on a glass substrate In this way, a cured film was obtained.
Drying process Hot plate EC-1200N manufactured by AS ONE Corporation
Temperature setting: 80 ° C, 5 minutes Main firing step Clean oven DT-610 manufactured by Yamato Scientific Co., Ltd.
Temperature setting: 170 ° C, 60 minutes

  First, the evaluation of the ink-jet property regarding the discharge of the ink-jet was performed, and then the following evaluations were performed using the sample substrates obtained as described above, each of which had a cured film formed on the substrate.

[Evaluation method]
[Jetting characteristics]
(I) Evaluation of inkjet ejection stability (continuous ejection stabilization time)
The ejection of the ink (thermosetting resin composition) from the inkjet head was started, and the ejection state was observed with a CCD camera attached to the printer. The time from the start of ejection, such as non-ejection or an oblique ejection direction, to the time when a defective ejection nozzle was found was defined as the continuous ejection stabilization time.
In Tables 5 and 6, in the column of the continuous discharge stabilization time, “> X” means that no defective nozzle was generated at the time when X minutes passed, and “≦ X” at the time when X minutes passed. This means that a defective nozzle has occurred.

(Ii) Generation of Satellite A state in which the ink (thermosetting composition) was discharged under the above discharge conditions was observed. When the liquid column at the time of jetting is ejected in the vertical direction and ink is dropped from the nozzle, a minute droplet is generated in addition to the ink droplet that contributes to pattern formation or the like (that is, it is not ejected exactly as one droplet). A state in which the phenomenon of satellite did not occur was regarded as normal ejection, and evaluated according to the following criteria.
〇: No satellite was generated.
Δ: Contact with the adjacent liquid column or a little satellite was generated.
X: Many contact with the adjacent liquid column or satellite occurred.

[Printability]
The wetting and spreading of the ink on the glass substrate in the case of inkjet printing was evaluated according to the following criteria.
Large: The wet spread is large.
Small: Wet spread is small.

[Flux resistance]
In order to evaluate the flux resistance of the cured film, 1.5 g of a flux (trade name: WF-6317, manufactured by Senju Metal Co., Ltd.) was uniformly applied to the surfaces of the sample substrates of Examples and Comparative Examples, and 260 After standing at 6 ° C. for 6 minutes and washing with water, a cross-cut test (JIS-K-5400: 1990) was conducted by peeling off the tape of the cured film, and the adhesion between the substrate and the cured film was evaluated by counting the number of remaining films.
Cuts were made in the cured film at 1 mm intervals using a cutter knife to produce 100 1-mm squares, and # 600 manufactured by 3M Co. was used as a tape for peeling. The number of grids remaining after the tape was peeled off (remaining number / 100) was evaluated (one time). 0 times in Tables 5 and 6 are the results of a grid test of the sample substrate before the application of the flux. Twice and three times, the flux was washed with water, and then the flux was applied again. This shows the results of evaluating the sample substrate obtained by repeating the process of allowing it to stand for 6 minutes twice and three times by the above-described grid test.

[Solder heat resistance]
In order to evaluate the solder heat resistance of the cured film, a flux was applied to the surfaces of the sample substrates of Examples and Comparative Examples, immersed in a 260 ° C. solder bath for 10 minutes, washed with water, air-dried, and peeled. Whether or not swelling occurred was examined by microscopic observation, and evaluated using the following criteria. The results are shown in Tables 5 and 6.
〇: No peeling occurred.
×: Peeling occurred.

[chemical resistance]
In order to evaluate the solder resistance of the cured film, the sample substrates of Examples and Comparative Examples were applied, immersed in the solutions shown in Table 7 at the temperatures and times shown in Tables 5 and 6, and washed with water. After the evaluation, the results of the evaluation by the grid test are shown in Tables 5 and 6.

[OD value (Optical Density)]
For the curable resin compositions of Examples and Comparative Examples, a cured film having a thickness of 4 μm was formed on a glass substrate, and the Y value was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation. did. The OD value was calculated from the Y value by the following equation.
OD = -log (Y / 100)
By dividing this value by the thickness of the cured film, the OD value per unit μm, that is, per μm of the cured film thickness was calculated.

[Flux resistance]
As shown in Tables 5 and 6, any cured film (sample substrate) obtained from the inks (curable resin compositions) according to Examples 1 to 14 and Comparative Examples 1 to 7 was subjected to the flux resistance test. Before (0 time), the number of crosses remaining after the tape was peeled off was 100, and it was confirmed that the cured film had excellent adhesion to the copper substrate. However, after the flux resistance test (first time), in each of Examples 1 to 14 in which the copolymer (C) was blended, the number of crosses remaining was 100, whereas the copolymer (C) In any of the cured films formed from the inks according to Comparative Examples 1 to 7 in which no was blended, the number of remaining crosses was 0. From this result, it is understood that the flux resistance of the cured film is improved by blending the copolymer (C).

The cured film formed from the ink according to Example 14 had zero crossings after the flux resistance test (second time). Since the ink of Example 14 contained a large amount of the coloring agent, it is considered that the coloring agent (E) affected the flux resistance of the cured film.
In the cured films formed from the inks of Examples 3 and 10, the number of remaining cross-cuts in the flux resistance test (second time) and (third time) was zero. Since the inks according to these examples contained the epoxy compound (B) containing 40% by weight of the nanosilica, it is considered that the nanosilica affected the flux resistance of the cured film.

[Solder heat resistance]
None of the cured films (sample substrates) obtained from the inks (curable resin compositions) according to Examples 1 to 14 peeled off after the solder heat resistance test. On the other hand, the cured films (sample substrates) obtained from the inks of Comparative Examples 1 to 7 all peeled off after the solder heat resistance test. From this result, it is understood that the solder heat resistance of the cured film is improved by blending the copolymer (C).

  From the results of the flux resistance and the solder heat resistance described above, it can be said that the epoxy compound (B) preferably has an epoxy equivalent of about 150 to 270.

[chemical resistance]
The cured films of Examples 1 to 14 have sufficient resistance to any of 10% by weight aqueous sodium hydroxide solution, 10% by weight aqueous hydrochloric acid solution, 10% by weight aqueous sulfuric acid solution and high-temperature water (80 ° C.). Met.

[Jetting properties]
In the ink of Example 14 in which the amount of the coloring agent (E) was increased, the continuous discharge stabilization time was slightly shorter than that of the other inks, and the generation of satellite was recognized. From this result, it can be said that increasing the amount of the coloring agent (E) containing a pigment contributes to a decrease in the jetting property of the ink.
In the ink of Example 12 containing propylene glycol monomethyl ether (PGME, boiling point: 120 ° C.) as the solvent (D), the continuous discharge stabilization time was short, and generation of a large number of satellites was observed. On the other hand, Examples 1 to 11 and 13 containing γ-butyrolactone (GBL, boiling point 204 ° C.) or triethylene glycol dimethyl ether (MTM, boiling point 216 ° C.) as the solvent (D) have a continuous discharge stabilization time of 10 minutes. As described above, no generation of satellite was observed. Therefore, it can be said that by mixing a high boiling point solvent having a boiling point of 200 ° C. or higher, an ink having good jetting properties can be obtained.

[Printability]
Among Examples 1 to 14, the inks of Example 11 and Example 12 had a small spread on the substrate. Since the ink of Example 11 had good jetting properties, γ-butyrolactone is preferred as the solvent (D) from the viewpoint of forming a fine pattern on a copper substrate by suppressing wet spreading during inkjet printing. It can be said that.

[OD value]
The cured films formed by the inks of Examples 1 to 14 had an OD value of 1.3 and had a color of sufficient density to carry out accurate inspection using an optical inspection device. there were.

  The thermosetting composition of the present invention has excellent heat resistance, moisture resistance, insulation, adhesion to a substrate and a circuit, flux resistance, solder resistance, solvent resistance, heat resistance and insulation in a thin film, In addition, even a thin film having a thickness of 20 μm or less has a dark black color enough to shield the underlying circuit and can be stably printed with an ink jet head having a small nozzle size, and thus can be used as an ink composition for ink jet.

Claims (21)

  A polyesteramic acid (A), an epoxy compound (B) having a weight average molecular weight of less than 10,000, and a copolymer (C) having oxiranyl or oxetanyl and having a weight average molecular weight of 10,000 or more. Characteristic thermosetting resin composition. The copolymer (C) having oxiranyl or oxetanyl is
A copolymer (C1) of a radical polymerizable monomer (c1) having an oxiranyl group and another radical polymerizable monomer (c3), and / or
The thermosetting resin composition according to claim 1, which is a copolymer (C2) of a radical polymerizable monomer (c2) having an oxetanyl group and another radical polymerizable monomer (c3).   The radical polymerizable monomer (c1) having an oxiranyl group is at least one selected from the group consisting of glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. The thermosetting resin composition according to claim 1 or 2, wherein   When the radical polymerizable monomer (c2) having an oxetanyl group is 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2- Selected from the group consisting of trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane The thermosetting resin composition according to claim 1 or 2, which is one or more types. The thermosetting composition according to claim 1, wherein the copolymer (C) is obtained by copolymerizing a monomer composition containing three kinds of an N-substituted maleimide compound, a compound having oxiranyl or oxetanyl, and a methacrylate compound. Resin composition.   The thermosetting resin composition according to claim 5, wherein the methacrylate compound is a monofunctional methacrylate compound.   6. The monomer composition of the copolymer (C), wherein glycidyl methacrylate is 15 to 50 parts by weight and n-butyl methacrylate is 2 to 10 parts by weight based on 10 parts by weight of phenylmaleimide. 3. The thermosetting resin composition according to item 1.   The thermosetting resin composition according to any one of claims 1 to 7, further comprising a solvent (D).   9. The thermosetting resin composition according to claim 8, wherein 100 parts by weight of the solvent (D) contains 50 parts by weight or more of a high boiling point solvent having a boiling point of 200 ° C. or more.   The thermosetting resin composition according to claim 8, wherein the solvent (D) is γ-butyrolactone.   The thermosetting resin composition according to any one of claims 1 to 10, further comprising a coloring agent (E).   The thermosetting resin composition according to claim 11, wherein the colorant (E) contains titanium compound particles and / or carbon black particles.   The thermosetting resin composition according to claim 11, wherein the content of the coloring agent (E) is 2 to 15 parts by weight based on 100 parts by weight of a resin solid content in the thermosetting resin composition.   The thermosetting resin composition according to any one of claims 1 to 13, wherein the weight average molecular weight of the copolymer (C) is 10,000 or more and 100,000 or less. The thermosetting resin composition according to any one of claims 1 to 13, wherein the polyester amic acid (A) is a compound having a structural unit represented by Formulas (1) and (2).


(Wherein, R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is independently a divalent organic group having 1 to 40 carbon atoms, and R ³ is independently a carbon atom having 1 carbon atom. ~ 20 divalent organic groups.)   The thermosetting resin composition according to any one of claims 1 to 15, further comprising an epoxy curing agent (F).   The thermosetting resin composition according to claim 16, wherein the epoxy curing agent (F) is an acid anhydride-based curing agent.   A cured film obtained from the thermosetting resin composition according to claim 1.   A substrate with a cured film having the cured film according to claim 18.   An electronic component comprising the cured film according to claim 18 or the cured film-attached substrate according to claim 19.   An ink-jet ink composition comprising the thermosetting resin composition according to claim 1.