JPWO2018190347A1 - Thermosetting resin composition, cured film, substrate with cured film, electronic component and ink-jet ink - Google Patents

Abstract

The heat of the present invention, which is provided as a thermosetting resin composition that can be cured at a low temperature of 120 ° C. or lower and has good storage stability before curing at a low temperature, and has both high low-temperature curability and high storage stability. Since the curable resin composition contains a polyester amic acid (A), an epoxy compound (B) having a fluorene skeleton, and a thiol compound (E) having a plurality of thiol groups in the molecule, the curable resin composition before curing at low temperature can be used. Low temperature curing is possible while maintaining good storage stability.

Description

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

  2. Description of the Related Art In recent years, a touch panel type input device in which a liquid crystal display device or an organic electroluminescence device and a position detection device are combined has become widespread as an input device. The touch panel type input device is an input device that detects a contact position when a finger or a pen tip is touched on a display screen. There are various types of detection methods for the touch panel type input device, such as a resistance film type and a capacitance type.

  For example, the capacitance method uses a device having a structure in which X and Y electrodes are arranged in a matrix on a glass substrate, and detects a change in capacitance caused by contact with a fingertip or the like as a current change. It is a method.

  When forming the above-mentioned electrodes, a jumper is formed at the overlapping portion of the X and Y electrodes with ITO (indium tin oxide) or the like so that the X and Y electrodes are not in contact with each other. A transparent insulating film is provided. The transparent insulating film is required to have high hardness, high transparency, adhesion to glass and ITO, etc., and from the viewpoint of process, resistance to ethanol and isopropyl alcohol (IPA) used in a substrate cleaning step, low water absorption. Is required.

  In addition, the capacitive touch panel may be provided with an insulating overcoat, for example, to planarize the X and Y electrodes. In addition to flatness, this overcoat requires degassing prevention, high hardness, high transparency, adhesion to glass and ITO, resistance to ethanol and isopropyl alcohol (IPA) used in the substrate washing process, and low water absorption. Is done.

  For touch panels, some or all alternatives from conventionally used glass to plastics such as PET (polyethylene terephthalate) are being studied for reasons such as reducing manufacturing costs. In addition, a material that can be cured at a low firing temperature is required in consideration of energy saving and cost reduction in manufacturing.

Various compositions are being studied for highly transparent insulating materials that can be used for the transparent insulating film or the overcoat.
For example, Patent Document 1 discloses a thermosetting resin composition containing a polyesteramic acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like. Patent Document 2 discloses a thermosetting resin composition containing a polyesteramic acid having a specific structure, an epoxy compound having a fluorene skeleton, and a curing agent. Patent Document 3 discloses a thermosetting resin composition containing a polyimide precursor having a specific structural unit and an epoxy compound bonded to a fluorene structure via a biphenyl ether chain.

JP 2005-105264 A WO2015 / 012395 pamphlet JP-A-2005-078253

When replacing glass with plastic, for example, in consideration of the heat resistance of PET, low-temperature firing at 120 ° C. or lower is required.
However, Patent Documents 1 to 3 do not discuss at all the low-temperature curability of the thermosetting resin composition, the physical properties of the cured film obtained by low-temperature curing, the chemical resistance, and the like. Patent Document 2 describes that a thermosetting resin composition is heated at 120 ° C. to obtain a cured film, and the thermosetting resin composition is obtained by curing the thermosetting resin composition at a low temperature of 120 ° C. The cured film has poor chemical resistance to ethanol, IPA, and the like, has a high water absorption rate, and needs improvement in order to be used as a transparent insulating film. In addition, as a result of examining the low-temperature curability of the thermosetting resin composition, when the low-temperature baking property, that is, the property of forming a cured film having good properties by low-temperature baking is increased, the storage stability before curing is reduced. There is a tendency.
When manufacturing a touch panel type input device, a cured product having properties such as chemical resistance, which can be used for both the transparent insulating film and the overcoat, is formed by low-temperature firing from the viewpoint of line simplification and improvement in yield. Although it is considered that a thermosetting resin composition is desirable, such a thermosetting resin composition has not been realized yet.

  An object of the present invention is to provide a thermosetting resin composition that can be cured at a low temperature of 120 ° C. or lower, has good storage stability before curing at a low temperature, and has both high low-temperature curability and high storage stability. In addition, the cured film has properties such as high hardness, high transparency, adhesion to glass and ITO, and low water absorption, and has good chemical resistance to ethanol and IPA used in a substrate washing process. It is an object of the present invention to provide a thermosetting resin composition capable of forming a polymer and a use thereof.

  The present inventors have conducted intensive studies to solve the above problems. As a result, by adding a thiol compound to the thermosetting resin composition, it is possible to improve low-temperature curing while maintaining high storage stability before curing, and to form a cured film having good chemical resistance and the like. I found it. The present invention is based on this finding and has the following configuration.

[1] A thermosetting resin composition containing a polyester amic acid (A), an epoxy compound having a fluorene skeleton (B), and a thiol compound having a plurality of thiol groups in the molecule (E).

[2] The thiol compound (E) is pentaerythritol tetrakis (3-mercaptobutyrylate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryl) (Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropion) ), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and the following formula (8) From the group consisting of glycoluril derivatives A barre was one or more compounds, thermosetting resin composition according to [1].

[3]
The thermosetting resin composition according to [1] or [2], wherein the content of the thiol compound (E) is 0.1 to 35 parts by weight based on 100 parts by weight of the total epoxy compounds.

[4] The thermosetting resin composition according to [1], [2] or [3], wherein the epoxy compound (B) having a fluorene skeleton has an epoxy equivalent of 200 to 550 g / eq.

[5] Any one of [1] to [4], wherein the content of the epoxy compound (B) having a fluorene skeleton is 10 to 400 parts by weight based on 100 parts by weight of the polyesteramic acid (A). Item 3. The thermosetting resin composition according to item 1.

[6] The thermosetting resin composition according to any one of [1] to [5], wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 20,000.

[7] The heat according to any one of [1] to [6], wherein the polyester amic acid (A) is a compound having a structural unit represented by the following formulas (3) and (4). Curable resin composition.
(In the formulas (3) and (4), R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is It is a divalent organic group having 1 to 20 carbon atoms.)

[8] The thermosetting resin composition according to any one of [1] to [7], further comprising a solvent (F).
[9] The thermosetting resin composition according to any one of [1] to [8], which is used for a touch panel.

[10] A cured film obtained from the thermosetting resin composition according to any one of [1] to [9].
[11] A substrate with a cured film having the cured film according to [10].
[12] An electronic component having the cured film according to [10] or the substrate with the cured film according to [11].
[13] The electronic component according to [12], which is a touch panel input device.
[14] An inkjet ink comprising the thermosetting resin composition according to any one of [1] to [9].

  By containing the thiol compound (E), the thermosetting resin composition of the present invention can achieve both low-temperature curing at 120 ° C. or lower and storage stability before curing. Further, it is possible to form a cured film having a low balance of water absorption and resistance to ethanol and IPA. Further heat resistance, since it is possible to form a cured film excellent in mechanical properties, the thermosetting resin composition of the present invention is very practical, for example, a transparent insulating film for touch panels and The overcoat can be produced with high productivity and can be suitably used for these applications.

  Hereinafter, the thermosetting resin composition (hereinafter, also referred to as “composition”) of the present invention, a method for preparing the composition, a method for forming a cured film, a substrate with a cured film, and an electronic component will be described in detail.

1. Thermosetting resin composition The composition of the present invention contains a polyesteramic acid (A), an epoxy compound (B) having a fluorene skeleton, and a thiol compound (E). The composition of the present invention may contain additives in addition to the above components, and the additives may be either colored or colorless. Hereinafter, the epoxy compound (B) having a fluorene skeleton and the epoxy compound (B) have the same meaning.
According to such a composition of the present invention, curing at a low temperature of 120 ° C. or less is possible, and storage stability of the composition is also compatible, high hardness, high transparency, adhesion to glass and ITO, and low water absorption. In addition, it is possible to obtain a cured film having a good balance of resistance to ethanol and IPA used in the substrate washing step. Therefore, a transparent insulating film and an overcoat for a touch panel can be manufactured with high productivity, and can be suitably used for these applications.

The composition of the present invention becomes excellent in the above effects by containing the polyester amic acid (A), the epoxy compound (B), and the thiol compound (E). In particular, a cured film that can be fired at a low temperature of 120 ° C. or lower and has both good storage stability and low water absorption and excellent resistance to ethanol and IPA can be obtained.
A conventional composition comprising a polyester amide acid and a composition comprising an epoxy compound having a fluorene skeleton and an epoxy curing agent can be fired at a low temperature of 120 ° C. or lower and have both storage stability, low water absorption, ethanol and A cured film having excellent IPA resistance was not obtained.
Therefore, the composition of the present invention is a composition having an effect unexpected from conventional compositions, and comprises a polyesteramic acid (A) and an epoxy compound (B) having a fluorene skeleton. By adding the thiol compound (E) to the composition, an effect different from that of a composition containing a conventional epoxy curing agent is exhibited.

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. Specifically, the compound is represented by Formulas (3) and (4). More preferably, the compound has a structural unit represented by the formula:
By using such a polyester amic acid (A) in combination with a specific epoxy compound (B) and a thiol compound (E), the polyester amide acid (A) has excellent resistance to a cleaning solution for a substrate such as ethanol or IPA, and further has a high hardness. Thus, a composition capable of forming a cured film having high transparency and excellent adhesion to glass and ITO can be obtained.
The polyester amic acid (A) may be used alone or in combination of two or more.

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

From the viewpoint that a compound having good compatibility with other components in the composition is obtained and a highly transparent cured film is obtained, R ¹ is independently a tetravalent organic group having 2 to 25 carbon atoms. It is preferably a tetravalent organic group having 2 to 20 carbon atoms, 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 is Independently, it is an alkyl group having 1 to 4 carbon atoms.))

From the viewpoint that a compound having good compatibility with other components in the composition is obtained, and a cured film having high transparency and good adhesion to glass or ITO is obtained, R ² has 2 to 2 carbon atoms. It is preferably a divalent organic group having 35, more preferably a divalent organic group having 2 to 30 carbon atoms, and still more 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— (Ph is a benzene ring, and R ⁸ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ — or —R ⁷ —), where R ⁷ is Independently, it is an alkyl group having 1 to 4 carbon atoms.)

From the viewpoint of obtaining a highly transparent cured film, 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 an alkylene having 1 to 8 carbon ^{atoms, R 11} is hydrogen or at least one hydrogen which may be the number 1 to 8 carbon substituted by hydroxyl An alkylene group having 2 to 15 carbon atoms, or a group in which at least one hydrogen atom of the alkylene group having 2 to 15 carbon atoms may be substituted with hydroxyl and may have -O-. More preferably, it is more preferably a divalent alkylene having 2 to 6 carbon atoms.

(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 alkyl group of the 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). Preferably, a component containing the tetracarboxylic dianhydride (a1), a component containing the diamine (a2), a component containing the polyhydric hydroxy compound (a3), and a component containing the monohydric alcohol (a4) are reacted. Is also preferred.
That is, in the formulas (3) and (4), 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) or the like may be used.
The component containing the tetracarboxylic dianhydride (a1) only needs to contain the tetracarboxylic dianhydride (a1), and may contain other compounds other than this compound. This is the same for the other components described above.
Each of these (a1) to (a5) and the like may be used alone or in combination of two or more.

  When the polyester amide acid (A) has an acid anhydride group at a molecular terminal, it is preferably a compound obtained by reacting a monohydric alcohol (a4) if necessary. Polyester amic acid (A) obtained using monohydric alcohol (a4) tends to be a compound having excellent compatibility with epoxy compound (B) and thiol compound (E), and also has excellent coating properties. 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′-benzophenone tetracarboxylic dianhydride and 2,2 ′, 3,3′-benzophenone tetraanhydride. 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'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic 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 butanetetracarboxylic acid And aliphatic tetracarboxylic dianhydrides such as acid dianhydride.

  Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether are preferred in terms of obtaining a compound having good transparency. Tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name: TMEG-100, Shin Nihon Rika) (3), and 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride are particularly preferable.

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 from the viewpoint that a compound having good transparency is obtained, and 3,3′-diaminodiphenylsulfone is preferred. 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 1,8-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 these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferable, and 1,4-octanediol is preferable. 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, borneol, maltol, linalool, Terpineol, dimethylbenzylcarbinol and 3-ethyl- - include hydroxymethyl oxetane.

  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 polyester amide acid (A), the epoxy compound (B) and the thiol compound (E), and the applicability of the obtained composition to glass or ITO, the monohydric alcohol (a4 ) Is more preferably benzyl alcohol.

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, 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.

<< Synthesis of polyester amic acid (A) >>
The method for synthesizing the polyester amide 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) A method of reacting as an essential component is preferable, 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 polyhydric hydroxy compound (a3) may be simultaneously added to the reaction solvent (a5) and reacted, or the diamine (a2) and the polyhydric hydroxy compound may be added. 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 the 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 way contains the structural units represented by the above formulas (3) and (4), and its terminal is derived from the starting material, tetracarboxylic dianhydride, diamine or polyhydric hydroxy 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 polyvalent hydroxy 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 (1) and (2) be established between Z. By using each component in such an amount, a polyesteramic acid (A) having high solubility in the following solvent (F) 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 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)

  The relationship of the expression (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, more preferably 1.3 ≦ Z / Y ≦ 7.0. Further, the relation of the expression (2) 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 by the solubility in the solvent (F), and particularly by using it together with the epoxy compound (B) and the thiol compound (E). From the viewpoint of obtaining a cured film having a good balance of transparency, adhesion to glass and ITO, and chemical resistance, it is preferably 2,000 to 30,000, and more preferably 3,000 to 30,000. Is more preferable.
Specifically, the weight average molecular weight can be measured by a method described in Examples described later.

  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-mentioned preferable ranges. Is 10 to 150 mPa · s, more preferably 15 to 100 mPa · s.

  The content of the polyester amic acid (A) is 100% from the solid content of the composition of the present invention (the residue obtained by removing the solvent from the composition) from the viewpoint that a cured film having high transparency and excellent chemical resistance is obtained. The amount is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, and still more preferably 5 to 50% by weight with respect to the weight%.

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

The epoxy equivalent of the epoxy compound (B) is preferably 200 to 550 g / eq, more preferably 220 to 490 g / eq, and still more preferably 240 to 480 g, from the viewpoint that a cured film having excellent chemical resistance is obtained. / Eq.
The epoxy equivalent of the epoxy compound (B) can be measured, for example, by the method described in JIS K7236.

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

The epoxy compound (B) may be obtained by synthesis or may be a commercially available product.
Commercial products of the epoxy compound (B) include, for example, OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.64, epoxy equivalent 260 g / eq), and OGSOL CG-500 (trade name, Osaka Gas Chemical Co., Ltd., refractive index 1.70, epoxy equivalent 310 g / eq), OGSOL EG-200 (trade name, Osaka Gas Chemical Co., Ltd., refractive index 1.62, epoxy equivalent 290 g / eq), OGSOL EG-250 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.58, epoxy equivalent: 395 g / eq), OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.56) , Epoxy equivalent 460 g / eq), OGSOL CG-400 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.53, epoxy equivalent 540 g / eq) q), and the like.

  The content of the epoxy compound (B) is selected from the viewpoint of obtaining a cured film excellent in heat resistance, chemical resistance, and adhesion to glass and ITO in a well-balanced manner. It is preferably 1 to 90 parts by weight, more preferably 3 to 80 parts by weight, and still more preferably 5 to 70 parts by weight, based on 100 parts by weight of the solvent except for the solvent. The amount is preferably 10 to 400 parts by weight, more preferably 20 to 350 parts by weight, and still more preferably 30 to 300 parts by weight.

1.3. Thiol compound (E)
The thiol compound (E) used in the present invention is not particularly limited as long as it has a plurality of thiol groups in the molecule, but is preferably a compound containing an oxygen atom in addition to the thiol group. By using the thiol compound (E) in combination with the polyesteramic acid (A) having a specific structure and the epoxy compound (B), a cured film can be formed at a low temperature of 120 ° C. or less, and the storage stability of the composition And can be compatible. In addition, a composition capable of forming a cured film having a low water absorption and a balance having resistance to ethanol and IPA can be obtained. Since the thiol compound (E) has both the action of reacting itself to cure the epoxy and the action of assisting the epoxy reaction without reacting, the thiol compound (E) has an epoxy curing agent (C) in the epoxy curing reaction. ) And the epoxy curing accelerator (i). As the thiol compound (E), only one kind may be used, or two or more kinds may be used.

Examples of the thiol compound (E) include pentaerythritol tetrakis (3-mercaptobutyrylate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and glycol of the following chemical formula (8) And uryl derivatives.

  Among these, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane tris (3-mercaptobutyrate) are preferred because a composition having good storage stability can be obtained. Also, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione, trimethylolpropane tris (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -Ethyl] -isocyanurate, trimethylolpropane tris (3-mercaptopropionate), and glycoluril derivatives represented by the formula (8) are preferable because a cured film having excellent heat resistance can be obtained.

The thiol compound (E) may be obtained by synthesis or may be a commercially available product.
Commercial products of the thiol compound (E) include, for example, “Karenz MT PE1”, “Karenz MT BD1”, “Karenz MT NR1”, “TPMB” (all trade names, manufactured by Showa Denko KK), and “DPMP” , “PEMP”, “TEMPIC”, “TMMP” (trade name, manufactured by SC Organic Chemicals, Inc.) and “TS-G” (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.).

  The content of the thiol compound (E) is set to be lower than 120 ° C. in terms of low-temperature curability, storage stability of the composition, resistance to ethanol and IPA, etc., and a cured film excellent in low water absorption can be obtained. Preferably 0.1 to 20 parts by weight, more preferably 0.15 to 18 parts by weight, based on 100 parts by weight of the solid content of the composition according to the embodiment (the residue obtained by removing the solvent (solvent) from the composition). More preferably, it is 0.2 to 15 parts by weight.

  The content of the thiol compound (E) is preferably 0.1 to 35 parts by weight, more preferably 0.2 to 30 parts by weight, based on 100 parts by weight of the total epoxy compounds contained in the solid content of the composition. More preferably, it is 0.3 to 25 parts by weight.

  When the composition contains the epoxy curing agent (C), the content of the thiol compound (E) is preferably 1 to 350 parts by weight, more preferably 2 to 320 parts by weight, per 100 parts by weight of the epoxy curing agent (C). Parts by weight, more preferably 3 to 300 parts by weight.

1.4. Additives The composition of the present invention may contain additives other than the polyesteramic acid (A), the epoxy compound (B) and the thiol compound (E), depending on the desired properties. Examples of additives include an epoxy curing agent (C), a solvent (F), an epoxy compound (e), a polyimide resin, a polymerizable monomer, an antistatic agent, a coupling agent (f), a pH adjuster, and a rust inhibitor. Preservatives, fungicides, antioxidants (g), surfactants (h), epoxy curing accelerators (i), reduction inhibitors, evaporation accelerators, chelating agents, and water-soluble polymers. Further, a pigment or a dye may be contained depending on a desired use. One type of additive may be used alone, or two or more types may be used in combination.

1.4.1. Epoxy curing agent (C)
The composition of the present invention may be blended with an epoxy curing agent (C) that promotes a curing reaction of epoxy by reacting itself. By blending the epoxy curing agent (C), a cured film having excellent heat resistance and chemical resistance can be obtained. In the present invention, the thiol compound (E) is not included in the epoxy curing agent (C).
The epoxy curing agent (C) is a compound different from the polyester amic acid (A), and specifically includes an acid anhydride-based curing agent, a polyamine-based curing agent, a polyphenol-based curing agent, and a catalyst-based curing agent. However, acid anhydride-based curing agents are preferred from the viewpoints of coloring resistance and heat resistance.
The epoxy curing agent (C) may be used alone or in combination of two or more.

  Specific examples of the acid anhydride-based curing agent include, for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride (active hydrogen equivalent 64 0.0), 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride (active hydrogen equivalent: 77.5), 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (active hydrogen amount) 111.0), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (active hydrogen equivalent 75.0) And styrene-maleic anhydride copolymers. Among these, trimellitic anhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 4,4 ′, from the viewpoint that a composition having excellent solubility in the solvent (F) can be obtained. -(Hexafluoroisopropylidene) diphthalic anhydride is particularly preferred. Further, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride is particularly preferable from the viewpoint that a cured film having a high glass transition temperature can be obtained.

  Specific examples of the carboxylic curing agent include maleic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and dimer acid.

  The dimer acid is obtained by, for example, polymerizing an unsaturated fatty acid using a Lewis acid and a Bronsted acid as catalysts. The dimer acid can be produced by a known method (eg, JP-A-9-112712).

  As unsaturated fatty acids, for example, crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadolinic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, eleostearic acid, Mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, boseopentaenoic acid, ozbondic acid, sardic acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid Is mentioned. The carbon number of the unsaturated fatty acid is usually 4 to 24, preferably 14 to 20.

  For example, when dimer acid is produced using linoleic acid, the resulting mixture generally contains a dimer acid having 36 carbon atoms as a main component, but a monomer acid having 18 carbon atoms and a trimer acid having 54 carbon atoms are also minor components. In general, and includes various structures derived from raw materials.

  The content of the epoxy curing agent (C) is determined according to the composition of the present invention from the viewpoint that a cured film having a high surface hardness can be obtained, which has good chemical resistance to chemicals such as ethanol and IPA, good adhesion to glass and ITO, and the like. It is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, and still more preferably 0 to 30 parts by weight, based on 100 parts by weight of the solid content of the product (the residue obtained by removing the solvent from the composition). The amount is preferably 0 to 300 parts by weight, more preferably 0 to 200 parts by weight, and still more preferably 0 to 100 parts by weight, based on 100 parts by weight of all epoxy compounds.

  The ratio of the total epoxy compound to the epoxy curing agent (C) used is such that a composition having excellent solubility in the solvent (F) can be obtained, and a cured film having high transparency, excellent heat resistance, chemical resistance, and low water absorption. Is obtained, the amount of the group capable of reacting with the epoxy group such as an acid anhydride group or a carboxyl group in the epoxy curing agent is 0 to 1.5 times the amount of the epoxy group in all the epoxy compounds used. It is preferably equivalent, more preferably 0 to 1.2 times equivalent, and even more preferably 0 to 0.8 times equivalent, because the chemical resistance of the obtained cured film is further improved. At this time, for example, when one equivalent of a compound having one epoxy group is used as the total epoxy compound and one equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (C), It is assumed that the amount of the epoxy curing agent (C) with respect to is twice equivalent.

1.4.2. Solvent (F)
The composition of the present invention can be obtained, for example, by dissolving a polyesteramic acid (A), an epoxy compound (B) and a thiol compound (E) in a solvent (F). Therefore, the solvent (F) is preferably a solvent that can dissolve the polyesteramic acid (A), the epoxy compound (B), and the thiol compound (E). Further, even a solvent which does not dissolve the polyesteramic acid (A), the epoxy compound (B) and the thiol compound (E) by itself can be used as the solvent (F) by mixing with another solvent. May be.
As the solvent (F), only one type may be used, or two or more types may be mixed and used.

  Examples of the solvent (F) 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, and ethylene glycol monoethyl ether. Acetate, propylene glycol monomethyl ether acetate, 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 Nomethyl 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 monoethyl ether (ECa), diethylene glycol monobutyl ether (DB ), Ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl Ether, tetraethylene glycol dimethyl ether (MTEM), tetramethylene glycol monovinyl ether, 2-methoxyethanol, 2-ethoxyethanol, 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-hexanolact , Methyl ethyl sulfoxide, methyl 2-hydroxyisobutyrate (HBM), dimethyl sulfoxide and Idemitsu Kosan Co. Ekuamido (trade name).

  Among these, in view of the solubility of the polyester amic acid (A), the epoxy compound (B) and the thiol compound (E), 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, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, γ-butyrolactone, diethylene glycol monoethyl ether (ECa), diethylene glycol monobutyl ether (DB), methyl 2-hydroxyisobutyrate (HBM) ), Tetraethylene glycol dimethyl ether (MTEM), dimethyl sulfoxide and Idemitsu Kosan Co., Ltd. At least one member selected from the group consisting of Ekuamido (trade name), is preferably contained as the solvent (F).

1.4.3. Epoxy compound (e)
In the present invention, a compound having at least one oxirane ring or oxetane ring is referred to as an epoxy compound. In the present invention, the epoxy compound (e) refers to an epoxy compound other than the epoxy compound (B).
As the epoxy compound (e), a compound having two or more oxirane rings is preferably used, and as the epoxy compound (e), only one kind may be used, or two or more kinds may be used in combination.

  Examples of the epoxy compound (e) include bisphenol A type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, silica fine particle-containing epoxy compounds, polymers of monomers having an oxirane ring, monomers having an oxirane ring, and others. And a copolymer with the above monomer.

Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and a compound represented by the following formula (9).
In the present invention, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acryl refers to acryl and / or methacryl.

In the formula (9), R is independently a group selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl and arylalkyl; One hydrogen may be replaced by fluorine, and any non-adjacent —CH ₂ — may be replaced by —O— or —CH ＝ CH—; the alkyl in arylalkyl has 1 to 10 carbon atoms. , Any non-adjacent —CH ₂ — of the alkyl may be replaced by —O—; R ¹ and R ² are each independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl X ¹ is any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl and oxetanylene It is a group having one.

  Other monomers that copolymerize with the monomer having an oxirane ring include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloro Examples include methylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

  Preferred specific examples of the polymer of the monomer having an oxirane ring and the copolymer of the monomer having an oxirane ring and another monomer include polyglycidyl methacrylate, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of benzyl methacrylate and glycidyl methacrylate. A copolymer of n-butyl methacrylate and glycidyl methacrylate, a copolymer of 2-hydroxyethyl methacrylate and glycidyl methacrylate, and a copolymer of (3-ethyl-3-oxetanyl) methyl methacrylate and glycidyl methacrylate. Examples of the polymer include a copolymer of styrene and glycidyl methacrylate. It is preferable that the composition of the present invention contains these epoxy compounds, because the heat resistance of a cured film formed from the composition is further improved.

  Specific examples of the epoxy compound (e) include, for example, the epoxy compound “jER807” (epoxy equivalent 160 to 175 g / eq), “jER815”, “jER825” (epoxy equivalent 170 to 180 g / eq), “jER827” (epoxy (Equivalent 180-190 g / eq), "jER828" (epoxy equivalent 184-194 g / eq), "jER190P", "jER191P", "jER1001" (epoxy equivalent 450-500 g / eq), "jER1002" (epoxy equivalent 600- 700 g / eq), "jER1004" (epoxy equivalent 875-975 g / eq), "jER1004AF" (epoxy equivalent 875-975 g / eq), "jER1007" (epoxy equivalent 1750-2200 g / eq), "jER1010" (epoki) (Equivalent 3000-5000 g / eq), "jER157S70" (epoxy equivalent 200-220 g / eq), "jER1032H60" (epoxy equivalent 163-175 g / eq), "jER1256" (epoxy equivalent 7500-8500 g / eq) (trade name) , Manufactured by Mitsubishi Chemical Corporation), "Celoxide 2021P" (epoxy equivalent: 128 to 145 g / eq), "Celoxide 3000", "EHPE-3150" (epoxy equivalent: 170 to 190 g / eq), "EHPE-3150CE" (epoxy) (Equivalent: 147 to 157 g / eq) (trade name, manufactured by Daicel Co., Ltd.), “TECHMORE VG3101L” (trade name, manufactured by Printtech, epoxy equivalent: 210 g / eq), “HP7200” (epoxy equivalent: 254 to 264 g) / Eq), “HP 7200H "(epoxy equivalent 272-284 g / eq)," HP7200HH "(epoxy equivalent 274-286 g / eq) (trade name, manufactured by DIC Corporation)," NC-3000 "(epoxy equivalent 265-285 g / eq) , "NC-3000H" (epoxy equivalent: 280-300 g / eq), "EOCN-102S" (epoxy equivalent: 205-217 g / eq), "EOCN-103S" (epoxy equivalent: 209-219 g / eq), "EOCN-104S" "(Epoxy equivalent 213-223 g / eq)," EPPN-501H "(epoxy equivalent 162-172 g / eq)," EPPN-501HY "(epoxy equivalent 163-175 g / eq)," EPPN-502H "(epoxy equivalent 158). 178 g / eq), “EPPN-201” (epoxy 180-200 g / eq) (trade name, manufactured by Nippon Kayaku Co., Ltd.), "TEP-G" (epoxy equivalent: 160-180 g / eq) (trade name, manufactured by Asahi Organic Materials Co., Ltd.), "MA -DGIC (epoxy equivalent 140 g / eq) "," DA-MGIC "(epoxy equivalent 265 g / eq)," TG-G "(epoxy equivalent 92 g / eq) (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), “TEPIC-VL” (epoxy equivalent: 125 to 145 g / eq) (trade name, manufactured by Nissan Chemical Industries, Ltd.), “NANOPOX C620” (trade name, manufactured by EVONIK, epoxy equivalent: about 220 g / eq), “ADEKARESIN EP- 4088S "(trade name, manufactured by ADEKA Corporation, epoxy equivalent: 170 g / eq), N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, γ-glycidoxypropyltrimethoxysilane (epoxy equivalent 194 g / eq), γ -Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane. "NANOPOX C620" is a compound obtained by reacting celloxide 2021P (60 parts by weight) with hydroxyl group-containing silica (40 parts by weight). Among these, a composition containing “NANOPOX C620” is preferable because a cured film having a high hardness can be obtained. Further, a composition containing "ADEKARESIN EP-4088S" is preferable because a cured film having particularly good chemical resistance can be obtained.

  The concentration of the epoxy compound (e) in the composition of the present invention is not particularly limited. However, from the viewpoint of obtaining a cured film excellent in heat resistance and adhesion to glass and ITO in a well-balanced manner, the composition of the composition of the present invention can be obtained. It is preferably contained in an amount of 0 to 50% by weight, more preferably 0 to 40% by weight, based on 100% by weight of the solid content (the residue obtained by removing the solvent from the composition).

1.4.4. 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 alone, or two or more kinds may be used in combination.

  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 polyester amic acid (A).

  When the composition of the present invention contains a polyimide resin, the concentration of the polyimide resin in 100% by weight of the composition of the present invention is not particularly limited, but a cured film having better heat resistance and chemical resistance can be obtained. From the viewpoint, 0.1 to 20% by weight is preferable, and 0.1 to 10% by weight is more preferable.

1.4.5. Polymerizable monomer Examples of the polymerizable monomer include a monofunctional polymerizable monomer, a bifunctional (meth) acrylate, and a trifunctional or higher polyfunctional (meth) acrylate.
One type of polymerizable monomer may be used alone, or two or more types may be mixed and 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 a point that a cured film having more favorable chemical resistance and surface hardness can be obtained. Therefore, the composition of the present invention preferably contains 10 to 80% by weight, and more preferably 20 to 70% by weight, in 100% by weight of the solid content (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, 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-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) Acryloxime Tiloxetane, 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 , Clohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl] is mentioned.

  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.

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

1.4.6. Antistatic agent An antistatic agent can be used to prevent the composition of the present invention from being charged. When the composition of the present invention contains an antistatic agent, 0% in 100% by weight of the composition of the present invention. It is preferably used in an amount of from 0.01 to 1% 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; and quaternary ammonium salts.
One kind of antistatic agent may be used alone, or two or more kinds may be used in combination.

1.4.7. Coupling agent (f)
The coupling agent (f) 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 to glass or ITO. In the present invention, the coupling agent (f) excludes a coupling agent containing an oxirane ring. When the composition of the present invention contains the coupling agent (f), the coupling agent (f) is used in an amount of 100% by weight based on 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 by adding so as to be 10% by weight or less.
As the coupling agent (f), only one type may be used, or two or more types may be mixed and 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-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane Methoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldi Toxisilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Ethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltri Ethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane are exemplified.

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

1.4.8. Antioxidant (g)
When the composition of the present invention contains the antioxidant (g), it is possible to prevent the cured film obtained from the composition from deteriorating when exposed to high temperature or light. When the composition of the present invention contains an antioxidant (g), the antioxidant (g) is a solid content of the composition excluding the antioxidant (g) (a residue obtained by removing a solvent from the composition). It is preferable to add 0.1 to 3 parts by weight based on 100 parts by weight.
As the antioxidant (g), one type may be used alone, or two or more types may be used in combination.

  Examples of the antioxidant (g) 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 (all trade names, manufactured by BASF), Adekastab AO-20, Adekastab AO-40, Adekastab AO-40 ADK STAB AO-60, ADK STAB AO-80, ADK STAB AO-330 (trade name, manufactured by ADEKA Corporation) and the like.

1.4.9. Surfactant (h)
When the composition of the present invention contains a surfactant (h), a composition having improved wettability, leveling property and applicability to an underlying substrate can be obtained. When (h) is contained, the surfactant (h) is preferably used in an amount of 0.01 to 1% by weight based on 100% by weight of the composition of the present invention.
The surfactant (h) may be used alone or in combination of two or more.

  Examples of the surfactant (h) include, for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, and “BYK-” from the viewpoint that the coatability of the composition of the present invention can be improved. 310 "," BYK-341 "," BYK-344 "," BYK-370 "(manufactured by BYK Japan KK) and the like; trade names" BYK-354 "," BYK-358 " And acrylic surfactants such as "BYK-361" (manufactured by BYK-Chemie Japan KK); trade names "DFX-18", "Futagent 250", and "Futagent 251" (manufactured by Neos Corporation); Fluorinated surfactants such as “MegaFac RS-72-K” (manufactured by DIC Corporation) are exemplified.

1.4.10. Epoxy curing accelerator (i)
The epoxy curing accelerator (i) refers to one that promotes the curing reaction of epoxy without reacting itself. In the present invention, the thiol compound (E) is not included in the epoxy curing agent (C).
As the epoxy curing accelerator (i), from the viewpoint that the curing temperature of the composition of the present invention can be lowered or the curing time can be shortened, “DBU”, “U-CAT”, “U-CAT” can be used. “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 SA881 "," U-CAT 891 "(trade name, manufactured by Sun Apro Co., Ltd.)," CP-001 "," NV-203-R4 "(trade name, Osaka Gas Chemical ( Co., Ltd.).
Only one epoxy curing accelerator (i) may be used, or two or more epoxy curing accelerators (i) may be used.

  The content of the epoxy curing accelerator (i) is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, and still more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the epoxy curing agent (C). is there.

1.4.11. Pigments or dye pigments include silicon carbide, alumina, magnesia, silica, zinc oxide, lower titanium oxide and graphite.
Examples of the dye include an azo dye, an azomethine dye, a xanthene dye, and a quinone dye. Examples of the azo dye include “VALIFAST BLACK 3810”, “VALIFAST BLACK 3820”, “VALIFAST RED 3304”, “VALIFAST RED 3320”, and “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industry Co., Ltd.). Can be
Each of the pigment and the dye may be used alone or in combination of two or more.

2. Method for Preparing Thermosetting Resin Composition The composition of the present invention comprises a polyesteramic acid (A), an epoxy compound (B) and a thiol compound (E), and, if necessary, an epoxy curing agent (C) and a solvent (D). ) And other additives.
In addition, the composition of the present invention comprises an epoxy compound (B), a thiol compound (E), and an epoxy curing agent used as needed, with the reaction solution or mixed solution obtained during the synthesis of the polyesteramic acid (A) as it is. It can also be prepared by mixing with (C), the solvent (F), and other additives.

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

3.1. Application method of thermosetting resin composition Application of the composition of the present invention onto a substrate is performed by spray coating, spin coating, roll coating, dipping, slit coating, bar coating, gravure printing, flexo printing, etc. It can be performed by a conventionally known method such as a printing method, an offset printing method, a dispenser method, a screen printing method, and an inkjet printing method.

  For example, when a transparent insulating film is formed from the composition of the present invention so that the X and Y electrodes are not in contact with each other, a gravure printing method, a flexographic printing method, an offset printing method is preferred in that pattern formation is easy. Printing methods such as a dispenser method, a screen printing method and an ink jet printing method are preferred.

  Also, for example, when forming an overcoat from the composition of the present invention, in that the entire surface is easily printed, a spin coating method, a slit coating method, a gravure printing method, a flexographic printing method, an offset printing method, a dispenser method, A coating method such as a screen printing method is preferred.

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

3.2. Curing Method of Thermosetting Resin Composition After applying the composition of the present invention, a cured film can be obtained by heating the composition applied on the substrate. As a method of forming a cured film in this manner, preferably, the composition of the present invention is applied and then heated on a hot plate or an oven to vaporize and remove the solvent (drying treatment). Further, a method of further heating (curing treatment) is used.

  The conditions of the drying treatment vary depending on the type and the mixing ratio of each component contained in the composition to be used, but usually, the heating temperature is 70 to 120 ° C., and the heating time is 5 to 15 minutes for an oven and 1 for a hot plate. 10 minutes. By such a drying treatment, it is possible to form a coating film on the substrate that can keep the shape.

After forming the coating film, a curing treatment is usually performed at 80 to 300 ° C, preferably 90 to 200 ° C. At this time, when an oven is used, a cured film can be obtained by generally performing heat treatment for 10 to 120 minutes.
Note that the curing treatment is not limited to the heat treatment, and may be a treatment such as irradiation with ultraviolet light, an ion beam, an electron beam, or a gamma ray.
Since the composition of the present invention contains the polyesteramic acid (A), the epoxy compound (B) and the thiol compound (E), the composition has good low-temperature curability. Therefore, a cured film excellent in chemical resistance and the like can be formed by firing at a low temperature of 120 ° C. or lower. Therefore, a cured film can be formed even on a resin film substrate made of PET or the like, for which it is difficult to perform the curing treatment at a high temperature.

4. Substrate with Cured Film The substrate with a cured film of the present invention is not particularly limited as long as it has the cured film of the present invention, but is preferably at least one selected from the group consisting of the above-mentioned substrates, particularly, a glass substrate, an ITO substrate, and a resin film substrate. It is preferable to have the above-mentioned cured film on a kind of substrate.
For example, such a substrate with a cured film is formed by applying the composition of the present invention on the entire surface or in a predetermined pattern (such as a line) on a substrate such as glass, ITO, PET, or PEN by the coating method or the like. Thereafter, it can be formed through the drying process and the curing process as described above.

5. Electronic Component The electronic component of the present invention is an electronic component having the above-described cured film or substrate with a cured film. Examples of such electronic components include various optical materials such as a color filter, an LED light emitting element and a light receiving element, and a touch panel.

The touch panel can be manufactured, for example, by combining a liquid crystal display device or an organic electroluminescence device with a position detection device.
Here, as the position detecting device, for example, a cured film (transparent insulating film) of the present invention is formed on a substrate on which a wiring (X electrode) made of a conductive material such as ITO is formed so as to cover the wiring. Next, there is an apparatus in which a wiring (Y electrode) made of a conductive material such as ITO is formed so as to be orthogonal to the X electrode, and then an overcoat is formed with the cured film of the present invention so as to cover the entire surface of the substrate. Can be

  When the composition of the present invention is used in manufacturing such an apparatus, the cured film (transparent insulating film) which is usually formed in a pattern by a printing method or the like, and the front surface is usually formed by a coating method or the like. The overcoat formed as described above can be formed with one type of composition. Therefore, by using the composition of the present invention, it is possible to simplify the line and improve the yield in the production of electronic components.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Epoxy compound (B) having a fluorene skeleton, epoxy compound (e), epoxy curing agent (C), thiol compound (E), solvent (F), epoxy curing accelerator (i), antioxidant used in Examples (G), surfactant (h), tetracarboxylic dianhydride (a1), diamine (a2), polyhydroxy compound (a3), monohydric alcohol (a4) used in the synthesis of polyester amic acid (A) ), Reaction solvent (a5) and polyanhydrides (a6) and their abbreviations. 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 <Polyvalent hydroxy compound (a3)>
BDOH: 1,4-butanediol <monohydric alcohol (a4)>
BzOH: benzyl alcohol <reaction solvent (a5)>
MPM: methyl 3-methoxypropionate

<Epoxy compound (B)>
EG-200: OGSOL EG200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), epoxy resin having a fluorene skeleton (epoxy equivalent: 290, weight average molecular weight: 2,000 or less)

<Epoxy compound (e)>
C620: NANOPOX C620 (trade name, manufactured by EVONIK), epoxy resin EP4088S containing 40% nanosilica: Adekaresin EP-4088S (trade name, manufactured by ADEKA Corporation)
S510: 3-glycidoxypropyltrimethoxysilane (trade name: Sail Ace S510, manufactured by JNC)

<Epoxy curing agent (C)>
TMA: trimellitic anhydride ODPA: 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride 6FDA: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride TDA: 4- (2,5 -Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride P-1025: Pripol 1025

<Thiol compound (E)>
PE1: pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karens MT PE1, manufactured by Showa Denko KK)
PE1 AG: pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT PE1 AG, a refined product of PE1, manufactured by Showa Denko KK)
BD1: 1,4-bis (3-mercaptobutyryloxy) butane (trade name Karens MT BD1, manufactured by Showa Denko KK)
NR1: 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1, Showa Denko (Made by Corporation)
TPMB: trimethylolpropane tris (3-mercaptobutyrate)
DPMP: dipentaerythritol hexakis (3-mercaptopropionate)
PEMP: pentaerythritol tetrakis (3-mercaptopropionate)
TEMPIC: tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate TMMP: trimethylolpropane tris (3-mercaptopropionate) TSG: glycoluril derivative represented by the following chemical formula (8) (trade name: TS) -G, manufactured by Shikoku Chemical Industry Co., Ltd.)

<Solvent (F)>
MTM: Triethylene glycol dimethyl ether (trade name: Highsolve MTM, manufactured by Toho Chemical Industry Co., Ltd.)
EDM: diethylene glycol ethyl methyl ether HBM: methyl 2-hydroxyisobutyrate GBL: γ-butyrolactone

<Epoxy curing accelerator (i)>
SA506: p-toluenesulfonic acid salt of diazabicycloundecene (DBU) (trade name: U-CAT SA506, manufactured by San Apro Corporation)
2E4MZ: 1-cyanoethyl-2-ethyl-4-methylimidazole (trade name 2E4MZ-CN, manufactured by Shikoku Chemicals Co., Ltd.)
C11Z: 2-undecylimidazole (trade name: Curesol C11Z, manufactured by Shikoku Chemicals Co., Ltd.)

<Antioxidant (g)>
I1010: Irganox1010 (trade name, manufactured by BASF)
<Surfactant (h)>
RS-72K: a fluorine-based liquid repellent having a surfactant activity (trade name: Megafac RS-72K, manufactured by DIC Corporation)

<Polyester amic acid (A)>
First, a polyesteramic acid was synthesized as shown below (Synthesis Example 1).
[Synthesis Example 1]
A dehydrated and purified MPM (446.96 g), BDOH (31.93 g), BzOH (25.54 g), and ODPA (183.20 g) were charged into a 1000 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging port, and a nitrogen gas inlet, and dried under a nitrogen stream. Stirred at 130 ° C. for 3 hours. Thereafter, the reaction solution was cooled to 25 ° C., 29.33 g of DDS and 183.04 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 solution 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 28.2 mPa · s. Here, the rotational viscosity is a value measured at 25 ° C. using an E-type viscometer (trade name TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) (the same applies hereinafter).

The weight average molecular weight of the obtained polyester amide acid was 4,200. 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 (manufactured by JASCO Corporation) (differential refraction) The diluent was measured by a GPC method using a rate meter (RI-2031 Plus) as a developing agent, and determined 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. (same as below).

[Example 1]
The 100 ml three-necked flask equipped with stirring blades was purged with nitrogen, and 7.37 g of the polyesteramic acid (A) solution obtained in Synthesis Example 1 (the amount of the polyesteramic acid (A) in the solution was 2.37 g). 21g), 8.85 g of EG-200 (the amount of epoxy compound (B) is 4.43 g), 0.35 of S510, 0.66 g of TMA, 22.42 g of HBM, 0.04 g of I1010, RS- 0.08 g of 72K was charged.
Thereafter, the mixture was stirred at 25 ° C. (room temperature) for 1 hour to uniformly dissolve each component. Next, 0.31 g of PE1 was added, the mixture was stirred at 25 ° C. for 1 hour, and then filtered through a membrane filter (material: PTFE, pore size: 1 μm) to obtain a thermosetting resin-containing composition as a filtrate.

[Examples 2 to 13]
In Examples 2 to 13, curable resin compositions were prepared in the same manner as in Example 1 except that the types and charge amounts of each component were changed as shown in Tables 2 and 3. In addition, the charged amount of each component in the table indicates the weight (g) (the same applies to the following tables).

[Comparative Examples 1 to 8]
In Comparative Examples 1 to 8, curable resin compositions were prepared in the same manner as in Example 1 except that the types and charge amounts of each component were changed as shown in Table 4. In Comparative Examples 2 to 6, each reaction accelerator shown in Table 4 was blended in place of the thiol compound (E).

[viscosity]
With respect to the thermosetting resin compositions of Examples 1 to 13 and Comparative Examples 1 to 6 (hereinafter, appropriately referred to as “compositions”), the viscosity (rotational viscosity) immediately after the production was measured. As shown in Tables 2 and 3, the viscosities of the thermosetting resin compositions of Examples were suitable as inks for inkjet.
On the other hand, the compositions of Comparative Examples 2 to 6 to which the epoxy curing accelerator (i) was added instead of the thiol compound (E) were obtained immediately after the addition of the epoxy curing accelerator (i) except for Comparative Example 2. , And an ink usable for inkjet could not be produced (indicated by X in Table 4). From these results, it was found that the composition containing the polyester amide acid (A) and the epoxy compound (B) having a fluorene skeleton could not be prepared with the addition of the epoxy curing accelerator (i), and the storage stability was poor. Is likely to be worse.

[Storage stability (viscosity)]
The viscosities of the compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were measured after storage at 45 ° C for 7, 14 and 30 days. As shown in Table 4, in Comparative Example 1 containing no reaction accelerator, no increase in viscosity over time after production was observed. However, the viscosity of the composition of Comparative Example 2, which had a low viscosity immediately after production, was about 2.3 times that after storage for 7 days at 45 ° C. In contrast, all of the compositions of Examples 1 to 13 containing the thiol compound (E) had a viscosity of about 1.3 times or less immediately after production after storage at 45 ° C for 7 days. From these results, it was found that the use of the thiol compound (E) resulted in a composition having better storage stability than the addition of the epoxy curing accelerator (i).

[Water absorption]
The compositions obtained in Examples 1 to 13 and Comparative Example 2 were applied on an aluminum foil surface to form a coating film so that the film thickness after drying was 30 to 70 µm. Thereafter, each coating film was cured under the following conditions to obtain a cured film-coated aluminum foil having a thickness of 50 to 100 μm. After baking at 120 ° C. for 30 minutes or 100 ° C. for 60 minutes, the cured film of the composition of Comparative Example 1 was easily broken and could not be collected in a certain size from the aluminum foil. No rate was measured.

<Curing conditions>
The composition was kept at 80 ° C. for 30 minutes using a hot plate to evaporate the solvent in the composition, and then fired under the following conditions.
Yamato Scientific Co., Ltd. Clean Oven DT-610
Temperature setting table 2-4
-Examples 1 to 13 and Comparative Examples 1 and 2: Table 5 at 120 ° C for 30 minutes
Example 2-1 and Comparative Examples 1-1 and 2-1: 100 ° C. for 60 minutes Example 2-2 and Comparative Examples 1-2 and 2-2: 120 ° C. and 60 minutes The cured film was evaluated for water absorption, glass transition temperature, and mechanical properties.

The aluminum foil of the aluminum foil with a cured film produced by the method described above was peeled off, and a single cured film was obtained after firing the composition. After measuring the weight (A) of the single membrane before immersion, the membrane was immersed in ultrapure water at room temperature for 24 hours to wipe off water drops adhering to the membrane surface with a nonwoven fabric, and the weight of the single membrane after immersion ( B) was measured. Using the measurement results of A and B, the water absorption was determined by the following equation.
Water absorption (%) = [(BA) / A] × 100
Tables 2 to 4 show the results of measuring the water absorption of a single cured film formed using each composition of the examples and comparative examples.

  In all of the examples shown in Tables 2 and 3, it was found that the water absorption was lower than that of Comparative Example 2, and that a cured film having low water absorption was obtained by using the thiol compound (E). Also, from the results of Examples 1 to 8 and Examples 9 to 13, in order to form a cured product having a low water absorption, TMA, which is an acid anhydride, was added to the composition containing the thiol compound (E). It can be said that it is preferable not to do so.

[Thermal stability]
A coating film was formed using the compositions according to Examples 1 to 13 and Comparative Examples 1 to 6 under the following conditions, and a substrate having a coating film before curing was formed on the surface.
Substrate: Glass substrate (10 cm square)
Coating method: inkjet printing Printer: DMP-2831 (FUJIFILM Dimatix)
Head: DMC-11610 (manufactured by FUJIFILM Dimatix)
Printing conditions: head temperature 30 ° C., voltage 20 V, drive waveform Dimatix Model Fluid 2, drive frequency 5 kHz, space between dots 15 to 20 μm, single-sided two-layer printing

Thereafter, the composition was cured by performing drying and main baking under the following conditions to obtain a sample substrate having a cured film formed on the substrate. With respect to the cured film of the obtained sample substrate, the weight reduction temperature and the chemical resistance were evaluated by the methods described below.
<Curing conditions>
・ Baking process Clean oven DT-610 manufactured by Yamato Scientific Co., Ltd.
・ Temperature setting tables 2 and 3
-Examples 1 to 13: 120 ° C, 30 minutes Table 5
-Example 2-1, Comparative Examples 1-1 and 2-1: 100 ° C, 60 minutes-Example 2-2, Comparative Examples 1-2 and 2-2: 120 ° C, 60 minutes Tables 6, 8 to 10
-Examples 14 to 19, 23 to 42, Comparative Examples 7 to 9: 100 ° C, 60 minutes

  The 1% weight loss temperature (Td1) and the 5% weight loss temperature (Td5) of the cured film were measured. The glass transition temperature (Tg) of the cured film was also measured. Tables 2 and 3 show the measurement results of the examples. Comparing the results of Examples 1 to 8 and Examples 9 to 13 shown in Tables 2 and 3, it was found that Td1 and Td5 tended to increase by not blending TMA. From these results, it can be said that in order to form a cured product having good thermal stability, it is preferable that the composition containing the thiol compound (E) does not contain TMA which is an acid anhydride.

[Mechanical properties]
The cured films formed using the compositions of Examples 1 to 13 all had good mechanical properties. For example, a cured film formed using the composition of Example 1 had an elastic modulus of 1627 (MPa), a strength of 78.7 (MPa), and an elongation of 11.5%. The cured film formed using the composition of Example 9 had an elastic modulus of 1619 (MPa), a strength of 81.0 (MPa), and an elongation of 10.1%. From these results, it was found that the composition containing the thiol compound (E) can form a cured film having good mechanical properties regardless of whether or not it contains TMA.

[chemical resistance]
The compositions of Example 2 and Comparative Examples 1 and 2 were applied to the entire surface of one surface of a glass plate so that the film thickness after firing was about 1 μm, and fired under the following conditions to obtain a glass substrate with a cured film. The thickness (A) of the cured film before the treatment was measured.
<Curing conditions>
・ Baking process Clean oven DT-610 manufactured by Yamato Scientific Co., Ltd.
Temperature setting table 5
Example 2, Comparative Examples 1 and 2: 120 ° C. for 30 minutes Example 2-1 and Comparative Examples 1-1 and 2-1 at 100 ° C. for 60 minutes Example 2-2, Comparative Example 1-2 And 2-2: 120 ° C., 60 minutes Tables 6 to 10
-Examples 14 to 32, Example 42, Comparative Examples 7 and 8: 100 ° C, 60 minutes

  Thereafter, the glass substrate with the cured film is immersed in ethanol at 50 ° C. for 10 minutes (hereinafter abbreviated as EtOH treatment), and immersed in isopropyl alcohol at 50 ° C. for 10 minutes (hereinafter IPA treatment). Abbreviations) were separately applied, and the film thickness (B) of the cured film after immersion was measured. In the chemical resistance test under the condition where ultrasonic waves were applied, an ASU-10M ultrasonic cleaning machine manufactured by AS ONE was used, and the mode of cleaning intensity was set to high (Hi).

Thereafter, a heat treatment was performed at 150 ° C. for 5 minutes, and the thickness (C) of the cured film after heating was measured. Using the film thickness before treatment (A), the film thickness after immersion (B), and the film thickness after heating (C), the residual film ratio (%) after the immersion treatment and after the heat treatment in the chemical resistance test is as follows. It calculated using the formula of.
Residual film rate after immersion treatment (%)
= [Thickness after immersion (B) / Thickness before treatment (A)] × 100
Remaining film rate after immersion and heat treatment (%)
= [Thickness after heating (C) / Thickness before treatment (A)] × 100
Further, the thickness (D) of the blank of the cured film subjected to only the heat treatment without performing the immersion treatment was measured.
Blank, residual film rate after heating (%)
= [Thickness of blank (D) / Thickness before treatment (A)] × 100

  With respect to Examples 2, 2-1 and 2-2 and Comparative Examples 1, 1-1, 1-2, 2, 2-1 and 2-2, the results of evaluating chemical resistance, water absorption and thermal stability are shown. It is shown in Table 5.

As shown in Table 5, the cured films of Examples 2 and 2-1 were different from the cured films of Comparative Examples 1 and 1-1 in both the EtOH treatment and the IPA treatment. The rate has increased. From these results, it was found that the chemical resistance of the hardened film was improved by adding the thiol compound (E) to the composition.
In addition, the cured films of Examples 2, 2-1 and 2-2 had lower water absorption than the cured films of Comparative Examples 1-2, 2, 2-1 and 2-2. Was. From these results, it was found that a cured film having a low water absorption was obtained by mixing the thiol compound (E) with the composition.

[Examples 14 to 22]
In Examples 14 to 22, curable resin compositions were prepared in the same manner as in Example 1 except that the types and charge amounts of each component were changed as shown in Tables 6 and 7.

[Comparative Examples 7 to 9]
In Comparative Examples 7 to 9, curable resin compositions were prepared in the same manner as in Example 1 except that the types and charge amounts of each component were changed as shown in Tables 6 and 7.

  The viscosity, storage stability (viscosity), chemical resistance, and thermal stability of the examples and comparative examples were evaluated using the evaluation methods described above. The results are shown in Tables 6 and 7.

  As shown in Tables 6 and 7, the cured films of Examples 14 to 16, 18 to 20, and 22 were compared with the cured films of Comparative Examples 7 and 8 with respect to any of the EtOH treatment and the IPA treatment. However, the residual film ratio increased. From this result, it was found that the chemical resistance of the cured film was improved by adding a certain amount or more of the thiol compound (E) to the composition. From the results of Examples 14 to 22, the content of the thiol compound (E) was more than 0.025 parts by weight in 40 parts by weight of the composition (more than 0.063 parts by weight in 100 parts by weight of the composition). ) Is preferable. 0.063 parts by weight in 100 parts by weight of the composition corresponds to 0.312 parts by weight in 100 parts by weight of the solid content (the residue obtained by removing the solvent from the composition). 0.564 parts by weight in 100 parts by weight of the compound). Therefore, it can be said that the content of the thiol compound (E) is preferably more than 0.312 parts by weight in 100 parts by weight of solids, and more preferably more than 0.564 parts by weight in 100 parts by weight of all epoxy compounds.

  As shown in Table 6, from the results of Examples 14 and 15 and Examples 18 and 19, the composition containing the thiol compound (E) was obtained by using TMA which is an acid anhydride as the epoxy curing agent (C). It was found that a composition containing no such a composition was able to form a cured product having high heat stability.

  Further, as shown in Tables 6 and 7, Examples 14 to 17 and 22 containing TMA and Examples 18 to 21 not containing TMA were all the same as Comparative Examples 7 and 8 containing no thiol compound (E). The storage stability was comparable. From these results, the content of the thiol compound (E) in 40 parts by weight of the composition is in the range of 0.02 to 0.69 parts by weight (0.05 to 1.8 parts by weight in 100 parts by weight of the composition). Within this range, it can be said that the storage stability of the composition can be favorably maintained. From the same viewpoint, the content of the thiol compound (E) is in the range of 0.3 to 8.7 parts by weight in 100 parts by weight of solids, and 0.4 to It can be said that the content is preferably in the range of 13.9 parts by weight.

[Examples 23 to 42]
In Examples 23 to 42, curable resin compositions were prepared in the same manner as in Example 1 except that the types and charge amounts of each component were changed as shown in Tables 8 to 10.
The viscosity, storage stability (viscosity), chemical resistance, and thermal stability of Examples and Comparative Examples were evaluated using the above-described evaluation methods. The results are shown in Tables 8 to 10.

  As shown in Tables 8 to 10, it was found that a composition excellent in storage stability was obtained by blending various thiol compounds (E). In addition, even when various thiol compounds (E) are blended, the composition tends to be a composition that can form a cured product having high thermal stability when it does not contain the acid anhydride TMA as the epoxy curing agent (C). It turned out that there was.

  The thermosetting resin composition of the present invention is suitable as an ink composition for inkjet having excellent storage stability, and can form a cured product having excellent chemical resistance and heat stability.

Claims (14)

  A thermosetting resin composition containing a polyester amic acid (A), an epoxy compound (B) having a fluorene skeleton, and a thiol compound (E) having a plurality of thiol groups in a molecule. When the thiol compound (E) is pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and represented by the following formula (8) Selected from the group consisting of glycoluril derivatives Is one or more compounds, the thermosetting resin composition of claim 1.
  The thermosetting resin composition according to claim 1 or 2, wherein the content of the thiol compound (E) is 0.1 to 35 parts by weight based on 100 parts by weight of all epoxy compounds in total.   4. The thermosetting resin composition according to claim 1, wherein the epoxy compound (B) having a fluorene skeleton has an epoxy equivalent of 200 to 550 g / eq. 5.   The heat according to any one of claims 1 to 4, wherein the content of the epoxy compound (B) having a fluorene skeleton is 10 to 400 parts by weight based on 100 parts by weight of the polyester amic acid (A). Curable resin composition.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 20,000. The thermosetting resin composition according to any one of claims 1 to 6, wherein the polyester amic acid (A) is a compound having a structural unit represented by the following formulas (3) and (4).
(In the formulas (3) and (4), R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is It is a divalent organic group having 1 to 20 carbon atoms.)   The thermosetting resin composition according to any one of claims 1 to 7, further comprising a solvent (F).   The thermosetting resin composition according to any one of claims 1 to 8, which is used for a touch panel.   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 10.   An electronic component comprising the cured film according to claim 10 or the substrate with the cured film according to claim 11.   The electronic component according to claim 12, which is a touch panel type input device.   An inkjet ink comprising the thermosetting resin composition according to claim 1.