WO2018190347A1

WO2018190347A1 - Heat curable resin composition, cured film, substrate with cured film, electronic component, and inkjet ink

Info

Publication number: WO2018190347A1
Application number: PCT/JP2018/015135
Authority: WO
Inventors: 彩子菊地; 智嗣古田; 信太諸越
Original assignee: Jnc株式会社
Priority date: 2017-04-13
Filing date: 2018-04-10
Publication date: 2018-10-18
Also published as: JPWO2018190347A1; TWI758461B; CN110494469A; KR20190132636A; TW201842066A; JP7092117B2; CN110494469B; KR20230110377A; KR102716106B1

Abstract

The heat curable resin composition according to the present invention is provided as a heat curable resin composition showing both high low-temperature curability and high storage stability such that the heat curable resin composition allows low-temperature curing at 120ºC or less and shows good storage stability before low-temperature curing. The heat curable resin composition comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, and a thiol compound (E) having a plurality of thiol groups in a molecule, and thus, the heat curable resin composition enables low-temperature curing while maintaining good storage stability until low-temperature curing.

Description

Thermosetting resin composition, cured film, substrate with cured film, electronic component and inkjet ink

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

In recent years, as an input device, 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. A touch panel type input device is an input device that detects a contact position when a finger or the tip of a pen is brought into contact with a display screen. There are various detection methods for touch panel type input devices, such as a resistance film method and a capacitance method.

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 of a fingertip or the like as a change in current. It is a method.

When forming the electrodes, in order to recognize the X and Y positions, a jumper is formed of ITO (Indium Tin Oxide) or the like at the overlapping portion of the X and Y electrodes, and 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 or ITO, etc., resistance to ethanol and isopropyl alcohol (IPA) used in the substrate cleaning process, low water absorption from the viewpoint of process Sex is required.

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

For touch panels, partial or total replacement from conventionally used glass to plastics such as PET (polyethylene terephthalate) is being considered for reasons such as reducing manufacturing costs. In addition, there is a demand for a material that can be cured at a low firing temperature in consideration of manufacturing energy saving and cost reduction.

Various compositions have been studied for highly transparent insulating materials that can be used for the transparent insulating film or overcoat.
For example, Patent Literature 1 discloses a thermosetting resin composition containing a polyester amide 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 polyester amide 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 with a biphenyl ether chain.

JP 2005-105264 A WO2015 / 012395 pamphlet Japanese Patent Laying-Open No. 2015-0778253

When replacing glass with plastic, for example, when considering the heat resistance of PET, low-temperature baking at 120 ° C. or lower is required.
However, Patent Documents 1 to 3 do not discuss 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 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 is required to be improved for use as a transparent insulating film. Further, as a result of examining the low-temperature curability of the thermosetting resin composition, when the property of forming a cured film having good properties by low-temperature firing property, that is, low-temperature firing is enhanced, the storage stability before curing is lowered. There is a tendency.
When manufacturing a touch panel type input device, a cured product with properties such as chemical resistance that can be used for both the transparent insulating film and the overcoat is formed by low-temperature firing in order to simplify the line and improve the yield. However, 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 and has good storage stability before low-temperature curing, and has both high low-temperature curability and high storage stability. In addition, it has high hardness, high transparency, adhesion to glass and ITO, low water absorption, and other cured films with good chemical resistance to ethanol and IPA used in the substrate cleaning process. It is in providing the thermosetting resin composition which can form, and its use.

The present inventors have intensively studied to solve the above problems. As a result, by incorporating a thiol compound in the thermosetting resin composition, low temperature curing is improved while maintaining high storage stability before curing, and a cured film having good chemical resistance and the like can be formed. I found it. The present invention is based on the findings and has the following configuration.

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

[2] The thiol compound (E) is pentaerythritol tetrakis (3-mercaptobutyrate), 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-mercaptopropio) ), 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 with respect to 100 parts by weight of all the epoxy compounds.

[4] The thermosetting resin composition according to [1], [2] or [3], wherein the epoxy compound (B) having the 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 the fluorene skeleton is 10 to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid (A). The thermosetting resin composition according to item.

[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 including a solvent (F).
[9] The thermosetting resin composition according to any one of [1] to [8], which is 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, comprising 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 type input device.
[14] An inkjet ink comprising the thermosetting resin composition according to any one of [1] to [9].

The thermosetting resin composition of the present invention can achieve both low-temperature curing at 120 ° C. or lower and storage stability before curing by containing the thiol compound (E). Moreover, the cured film with the balance which has a low water absorption and also has tolerance to ethanol and IPA can be formed. Furthermore, since a cured film excellent in heat resistance and mechanical properties can be formed, 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 of the present invention (hereinafter also referred to as “composition”), 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 polyester amide 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 colored or colorless. Hereinafter, the epoxy compound (B) having an fluorene skeleton and the epoxy compound (B) have the same meaning.
According to such a composition of the present invention, low temperature curing at 120 ° C. or lower is possible, and the storage stability of the composition is compatible, high hardness, high transparency, adhesion to glass and ITO, low water absorption A cured film having excellent balance in resistance to ethanol and IPA used in the substrate cleaning step can be obtained. For this reason, it is possible to produce the transparent insulating film and overcoat for touch panels with high productivity, and it can be used suitably for these uses.

The composition of this invention becomes the thing excellent in the said effect by containing a polyester amide acid (A), an epoxy compound (B), and a thiol compound (E). In particular, a cured film excellent in resistance to low water absorption, ethanol and IPA, which can be fired at a low temperature of 120 ° C. or lower and also has the storage stability of the composition, is obtained.
Conventional compositions composed of polyester amide acid, and compositions composed of an epoxy compound having a fluorene skeleton and an epoxy curing agent, can be baked at a low temperature of 120 ° C. or less and have both storage stability, low water absorption, ethanol and A cured film excellent in IPA resistance was not obtained.
Therefore, the composition of the present invention is a composition having an effect which cannot be expected from the conventional composition, and is a composition containing polyester amic 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 the conventional composition containing an epoxy curing agent is obtained.

1.1. Polyester amide acid (A)
The polyester amide acid (A) used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond, and a carboxyl group, and specifically represented by formulas (3) and (4). It is more preferable that the compound has a structural unit.
By using such a polyester amic acid (A) in combination with a specific epoxy compound (B) and a thiol compound (E), it has excellent resistance to a substrate cleaning solution such as ethanol and IPA, and also has high hardness. Thus, a composition capable of forming a cured film having high transparency and excellent adhesion to glass and ITO can be obtained.
Polyester amide acid (A) may use only 1 type, and may mix and use 2 or more types.

(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.)

R ¹ is independently a tetravalent organic group having 2 to 25 carbon atoms 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. 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 represents Independently, it is an alkyl group having 1 to 4 carbon atoms.)

From the viewpoints of obtaining a compound having good compatibility with other components in the composition and obtaining a cured film having high transparency and good adhesion to glass and ITO, R ² has 2 to 2 carbon atoms. A divalent organic group of 35 is preferable, a divalent organic group having 2 to 30 carbon atoms is more preferable, and a group represented by the formula (6) is more preferable.

(In Formula (6), R ⁶ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ — or —O—ph—R ⁸ —ph—O—). (a ph is a benzene ^{ring, R} 8 _{is, -O -, - CO -,} - SO 2 -, - C (CF 3) 2 - or -R ⁷ -. a a) in which. Incidentally, ^{R 7} is Independently, it is an alkyl group having 1 to 4 carbon atoms.)

From viewpoint of high transparency of the cured film is obtained, ^{R 3} is preferably a divalent organic group having 2 to 15 carbon atoms, 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 carbon atoms which may be have 1-8 substituted with a hydroxyl An alkylene group having 2 to 15 carbon atoms, or at least one hydrogen atom of alkylene 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— (ph Is a benzene ring, and R ⁸ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ — or —R ⁷ —.) Note that R ⁷ is independently carbon (It is an alkyl group of the number 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 obtained by reacting a component containing tetracarboxylic dianhydride (a1), a component containing diamine (a2), a component containing polyvalent hydroxy compound (a3) and a component containing monohydric alcohol (a4). It is also preferable that it is a compound obtained.
That is, in 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. The same applies to the other components described above.
Each of (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 the molecular end, it is preferably a compound obtained by reacting a monohydric alcohol (a4) if necessary. The polyester amide acid (A) obtained by using the monohydric alcohol (a4) tends to be a compound having excellent compatibility with the epoxy compound (B) and the 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, 2,2 ′, 3,3′-benzophenone tetra Carboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2 , 2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl) ] 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, Cycloaliphatic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride and butanetetracarboxylic Aliphatic tetracarboxylic dianhydrides such as acid dianhydrides may be mentioned.

Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether is used because a compound having good transparency can be obtained. Tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name TMEG-100, Shin Nippon Rika (3), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are particularly preferable.

1.1.2. Diamine (a2)
The diamine (a2) is not particularly limited, and specific examples thereof include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 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 is mentioned.

Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable, and 3,3′-diaminodiphenylsulfone is preferable from the viewpoint of obtaining a compound having good transparency. 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- Xanthriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2 , 8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decane Examples include triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.

Among 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- Butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferable 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, 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, dimethylbenzyl carbinol and 3-ethyl- - it includes hydroxymethyl oxetane.

Of these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyl oxetane are preferable. Considering the compatibility of the resulting polyester amic acid (A) with the epoxy compound (B) and the thiol compound (E) and the applicability of the resulting composition on glass or ITO, a monovalent 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, propylene glycol monomethyl ether. Acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

Among these, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, methyl 3-methoxypropionate and N-methyl-2-pyrrolidone are preferable from the viewpoint of solubility.
Specific examples of the reaction solvent (a5) include these solvents, but if these solvents are in a proportion of 30% by weight or less with respect to the total amount of the solvent used in the reaction, other than the solvent A mixed solvent obtained by mixing other solvents can also be used.

<< Synthesis of Polyesteramide Acid (A) >>
The method for synthesizing the polyester amic acid (A) is not particularly limited, but the tetracarboxylic dianhydride (a1), the diamine (a2), the polyvalent hydroxy compound (a3), and, if necessary, the monohydric alcohol (a4). A method of reacting as an essential component is preferred, and this reaction is more preferably carried out in the reaction solvent (a5).

The order of adding each component during this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3) may be simultaneously added to the reaction solvent (a5) to cause the reaction, or the diamine (a2) and the polyvalent hydroxy compound may be reacted. After (a3) is dissolved in the reaction solvent (a5), the reaction may be carried out by adding tetracarboxylic dianhydride (a1), or tetracarboxylic dianhydride (a1) and diamine ( After reacting a2) in advance, the polyhydroxy compound (a3) may be added to the reaction product for reaction, and either method can be used.
The monohydric alcohol (a4) may be added at any point in the reaction.

In the reaction, a synthetic reaction may be performed by adding a compound having 3 or more acid anhydride groups in order to increase the weight average molecular weight of the obtained polyesteramic acid (A). Specific examples of the compound having 3 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 the ends thereof are derived from the raw materials tetracarboxylic dianhydride, diamine or polyhydroxy compound, respectively. It is 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 tetracarboxylic dianhydride (a1), diamine (a2) and 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 of Formula (1) and Formula (2) is established between Z. By using each component in such an amount, a polyester amide 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 formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. The relationship of the formula (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 used is not particularly limited, but is 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 usage of polyester amide acid (A) >>
The weight average molecular weight measured by gel permeation chromatography (GPC) of the polyester amic acid (A) is soluble in the solvent (F), and particularly in combination with the epoxy compound (B) and the thiol compound (E). From the viewpoint of obtaining a cured film having a balance of transparency, adhesion to glass and ITO, and chemical resistance, it is preferably 2,000 to 30,000, preferably 3,000 to 30,000. It is more preferable.
Specifically, this weight average molecular weight can be measured by the method described in Examples described later.

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

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

1.2. Epoxy compound having a 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. For this reason, in addition to the said effects, such as high transparency, the cured film which has these effects together can be obtained.
The epoxy compound (B) may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy compound (B) is preferably 200 to 550 g / eq, more preferably 220 to 490 g / eq, still more preferably 240 to 480 g from the viewpoint that a cured film having excellent chemical resistance can be 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 excellent in high transparency. More preferably, it is 1.54 to 1.71.
The refractive index of the epoxy compound (B) can be measured by, for example, the method described in JIS K7105 or JIS K7142.

The epoxy compound (B) may be obtained by synthesis or may be a commercially available product.
Examples of commercially available epoxy compounds (B) include OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.64, epoxy equivalent 260 g / eq), 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 / q), and the like.

The content of the epoxy compound (B) is such that a cured film having excellent balance of heat resistance, chemical resistance and adhesion to glass and ITO can be obtained, and the solid content of the composition of the present invention (from the composition) Residue excluding solvent) is preferably 1 to 90 parts by weight, more preferably 3 to 80 parts by weight, still more preferably 5 to 70 parts by weight, and 100 parts by weight of polyester amic acid (A) with respect to 100 parts by weight. On the other hand, it is preferably 10 to 400 parts by weight, more preferably 20 to 350 parts by weight, 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 preferably includes an oxygen atom in addition to the thiol group. By using the thiol compound (E) in combination with the polyester amide acid (A) and the epoxy compound (B) having a specific structure, a cured film can be formed at a low temperature of 120 ° C. or less and the storage stability of the composition And both. Moreover, the composition which can form the cured film provided with the balance which has low water absorption and also has tolerance to ethanol and IPA is 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 itself, the epoxy curing agent (C ) And epoxy curing accelerator (i). Only 1 type may be used for a thiol compound (E), and 2 or more types may be used for it.

As the thiol compound (E), 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 glycol of the following chemical formula (8) Examples include uril 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. 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 a glycoluril derivative 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.
Examples of commercially available thiol compounds (E) include “Karenz MT PE1”, “Karenz MT BD1”, “Karenz MT NR1”, “TPMB” (trade name, manufactured by Showa Denko KK), “DPMP”. , “PEMP”, “TEMPIC”, “TMMP” (trade name, manufactured by SC Organic Chemical Co., Ltd.) and “TS-G” (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.).

The content of the thiol compound (E) is as follows: low-temperature curability at 120 ° C. or lower, storage stability of the composition, resistance to ethanol and IPA, 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 form (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, with respect to 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 an 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 per 100 parts by weight of the epoxy curing agent (C). Part 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 polyester amic acid (A), the epoxy compound (B) and the thiol compound (E) depending on the intended properties. Examples of the additive 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. , Antiseptics, antifungal agents, antioxidants (g), surfactants (h), epoxy curing accelerators (i), reduction inhibitors, evaporation accelerators, chelating agents, water-soluble polymers. Moreover, you may contain a pigment or dye according to a desired use. Only one type of additive may be used, or two or more types may be mixed and used.

1.4.1. Epoxy curing agent (C)
The composition of the present invention may contain an epoxy curing agent (C) that accelerates the epoxy curing reaction by reacting itself. By adding 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 amide acid (A). Specific examples include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent. However, acid anhydride curing agents are preferred from the standpoint of color resistance and heat resistance.
As the epoxy curing agent (C), only one kind may be used, or two or more kinds may be mixed and used.

Specific examples of the acid anhydride curing agent include, for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride (active hydrogen content equivalent of 64 0.0), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (active hydrogen content equivalent 77.5), 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (active hydrogen content) Equivalent 111.0), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (active hydrogen equivalent 75.0) And aromatic polycarboxylic anhydrides such as styrene-maleic anhydride copolymers. Of these, trimellitic anhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4 ′, and the like are obtained because a composition having excellent solubility in the solvent (F) can be obtained. -(Hexafluoroisopropylidene) diphthalic anhydride is particularly preferred. Further, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride is particularly preferable from the viewpoint of obtaining a cured film having a high glass transition temperature.

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

The dimer acid can be obtained, for example, by polymerizing an unsaturated fatty acid using a Lewis acid and a Bronsted acid as a catalyst. Dimer acid can be produced by a known method (eg, JP-A-9-12712).

Examples of unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic 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, bosepentaenoic acid, ozbond acid, succinic acid, tetracosapentanoic acid, docosahexaenoic acid, nisic 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 dimer acid having 36 carbon atoms as a main component, but monomer acid having 18 carbon atoms and trimer acid having 54 carbon atoms are also minor components. As a general rule, a small amount is included, and various structures derived from raw materials are included.

The content of the epoxy curing agent (C) is the composition of the present invention from the viewpoints of having good chemical resistance to chemicals such as ethanol and IPA, good adhesion to glass and ITO, and obtaining a cured film with high surface hardness. It is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight, still more preferably 0 to 30 parts by weight based on 100 parts by weight of the solid content of the product (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 with respect to 100 parts by weight of the total epoxy compound.

Moreover, the ratio of the total epoxy compound to be used and the epoxy curing agent (C) is such that a composition having excellent solubility in the solvent (F) is obtained, and a cured film having high transparency, excellent heat resistance, chemical resistance, and low water absorption. The amount of groups capable of reacting with epoxy groups such as acid anhydride groups and carboxyl groups in the epoxy curing agent is 0 to 1.5 times the amount of epoxy groups in all epoxy compounds used. It is preferably an equivalent, more preferably 0 to 1.2 times equivalent, and more preferably 0 to 0.8 times equivalent, since the chemical resistance of the resulting cured film is further improved. At this time, for example, when 1 equivalent of a compound having one epoxy group is used as the total epoxy compound and 1 equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (C), all the epoxy compounds It is assumed that the amount of the epoxy curing agent (C) is 2 times equivalent.

1.4.2. Solvent (F)
The composition of the present invention can be obtained, for example, by dissolving the polyester amide acid (A), the epoxy compound (B), and the thiol compound (E) in the solvent (F). Therefore, the solvent (F) is preferably a solvent that can dissolve the polyester amide acid (A), the epoxy compound (B), and the thiol compound (E). Moreover, even if it is a solvent which does not dissolve polyester amide acid (A), epoxy compound (B) and thiol compound (E) alone, it can be used as solvent (F) by mixing with other solvents. There is a case.
Only 1 type may be used for a solvent (F), and 2 or more types may be mixed and used for it.

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-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene Glico Monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol 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-Hexanolac Emissions, methyl ethyl sulfoxide, methyl 2-hydroxyisobutyrate (HBM), dimethyl sulfoxide and Idemitsu Kosan Co. Ekuamido (trade name).

Among these, in terms of the solubility of the polyester amide acid (A), the epoxy compound (B), and the thiol compound (E), the composition of the present invention includes 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 manufacturing Ekuamido (trade name), it 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 the epoxy compound (e) may be used alone or in combination of two or more.

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, 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; in alkyl having 1 to 45 carbons, at least 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 of 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl a group; ^{X 1} is oxiranyl, Okishiraniren, 3,4-epoxycyclohexyl, or oxetanyl and Okisetaniren 1 It is a group having one.

Other monomers that copolymerize with monomers 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 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, 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 thereof include a polymer and a copolymer of styrene and glycidyl methacrylate. It is preferable that the composition of the present invention contains these epoxy compounds since the heat resistance of the cured film formed from the composition is further improved.

Specific examples of the epoxy compound (e) include, for example, an epoxy compound “jER807” (epoxy equivalent 160 to 175 g / eq), “jER815”, “jER825” (epoxy equivalent 170 to 180 g / eq), “jER827” (epoxy 180-190 g / eq), “jER828” (epoxy equivalents 184-194 g / eq), “jER190P”, “jER191P”, “jER1001” (epoxy equivalents 450-500 g / eq), “jER1002” (epoxy equivalents 600- 700 g / eq), “jER1004” (epoxy equivalents 875-975 g / eq), “jER1004AF” (epoxy equivalents 875-975 g / eq), “jER1007” (epoxy equivalents 1750-2200 g / eq), “jER1010” (epoch (Equivalent 3000 to 5000 g / eq), “jER157S70” (epoxy equivalent 200 to 220 g / eq), “jER1032H60” (epoxy equivalent 163-175 g / eq), “jER1256” (epoxy equivalent 7500 to 8500 g / eq) 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 equivalents 147 to 157 g / eq) (trade name, manufactured by Daicel Corporation), “TECHMORE VG3101L” (trade name, manufactured by Printec Co., Ltd., epoxy equivalent 210 g / eq), “HP7200” (epoxy equivalents 254— 264g / eq), " P7200H "(epoxy equivalent 272 to 284 g / eq)," HP7200HH "(epoxy equivalent 274 to 286 g / eq) (above trade name, manufactured by DIC Corporation)," NC-3000 "(epoxy equivalent 265 to 285 g / eq) , “NC-3000H” (epoxy equivalent 280 to 300 g / eq), “EOCN-102S” (epoxy equivalent 205 to 217 g / eq), “EOCN-103S” (epoxy equivalent 209 to 219 g / eq), “EOCN-104S” (Epoxy equivalents 213 to 223 g / eq), "EPPN-501H" (epoxy equivalents 162 to 172 g / eq), "EPPN-501HY" (epoxy equivalents 163 to 175 g / eq), "EPPN-502H" (epoxy equivalents 158 ~ 178g / eq), "EPPN-201" (epoxy Equivalent 180-200 g / eq) (above trade name, Nippon Kayaku Co., Ltd.), “TEP-G” (epoxy equivalent 160-180 g / eq) (above trade name, 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) , “TEPIC-VL” (epoxy equivalent 125-145 g / eq) (trade name, manufactured by Nissan Chemical Industries, Ltd.), “NANOPOX C620” (trade name, manufactured by EVONIK, epoxy equivalent approximately 220 g / eq), “Adeka Resin EP -4088S "(trade name, manufactured by ADEKA Corporation, epoxy equivalent 170 g / eq), N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3- (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, γ-glycidoxypropyltrimethoxysilane (epoxy equivalent 194 g / eq) , Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyltriethoxysilane. “NANOPOX C620” is a compound obtained by reacting Celoxide 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 high hardness can be obtained. A composition containing “ADEKA RESIN EP-4088S” is preferable because a cured film having particularly good chemical resistance can be obtained.

Although the density | concentration of the epoxy compound (e) in the composition of this invention is not specifically limited, From the point of being able to obtain the cured film which is excellent in heat resistance and the adhesiveness with respect to glass or ITO, etc. of the composition of this invention. It is preferably contained in an amount of 0 to 50% by weight and more preferably 0 to 40% by weight in 100% by weight of the solid content (residue obtained by removing the solvent from the composition).

1.4.4. The polyimide resin is not particularly limited as long as it has an imide group.
A polyimide resin may use only 1 type and may mix and use 2 or more types.

The polyimide resin can be obtained, for example, by imidizing polyamic acid obtained by reacting acid dianhydride and diamine. As an acid dianhydride, the tetracarboxylic dianhydride (a1) which can be used for the synthesis | combination of a polyester amide acid (A) is mentioned, for example. Examples of the diamine include diamine (a2) that can be used for the synthesis of 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. In this respect, 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 monofunctional polymerizable monomers, bifunctional (meth) acrylates, and trifunctional or higher polyfunctional (meth) acrylates.
As the polymerizable monomer, only one type may be used, or two or more types may be mixed and used.

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 cured film having a better chemical resistance and surface hardness can be obtained. From 10 to 80% by weight, preferably 20 to 70% by weight is contained in 100% by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). Is more preferable.

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) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl- 3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) Acryloxime Tyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide , N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethylmethacrylate macromonomer, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid , Itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl] , And chlorohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl].

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

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

1.4.6. The 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 0.01 to 1% by weight.
A known antistatic agent can be used as the antistatic agent. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; and quaternary ammonium salts.
Only one type of antistatic agent may be used, or a mixture of two or more types may be used.

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 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 a coupling agent (f), the coupling agent (f) is based on 100% by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). It is preferable to add and use so that it may become 10 weight% or less.
Only 1 type may be used for a coupling agent (f), and 2 or more types may be mixed and used for it.

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-aminopropyltri 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-aminopropyltri Ethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltri Examples include ethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyltriethoxysilane.

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

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

Examples of the antioxidant (g) include hindered amine compounds and hindered phenol compounds. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (above trade names, manufactured by BASF), Adeka Stub AO-20, Adeka Stub AO-40, Ade 40 A-40 Adeka Stub AO-60, Adeka Stub AO-80, Adeka Stub AO-330 (trade name, manufactured by ADEKA Corporation) and the like.

1.4.9. Surfactant (h)
When the composition of the present invention contains the surfactant (h), a composition having improved wettability, leveling properties and coatability to the base substrate can be obtained, and the composition of the present invention is a surfactant. When (h) is included, 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.
Only 1 type may be used for surfactant (h), and 2 or more types may be mixed and used for it.

As the surfactant (h), for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-” can be used, for example, in order to improve the coating property of the composition of the present invention. 310 ”,“ BYK-341 ”,“ BYK-344 ”,“ BYK-370 ”(manufactured by Big Chemie Japan Co., Ltd.) and other silicon surfactants; trade names“ BYK-354 ”,“ BYK-358 ” Acrylic surfactants such as “BYK-361” (manufactured by Big Chemie Japan Co., Ltd.); trade names “DFX-18”, “Factent 250”, “Factent 251” (manufactured by Neos), Fluorosurfactants such as “Megafac RS-72-K” (manufactured by DIC Corporation) can be used.

1.4.10. Epoxy curing accelerator (i)
The epoxy curing accelerator (i) refers to an agent that accelerates the epoxy curing reaction 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), “DBU”, “U-CAT”, “U-” can be used because the curing temperature of the composition of the present invention can be lowered or the curing time can be shortened. "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 ( Etc.).
Each of the epoxy curing accelerators (i) may be used alone or in combination of two or more.

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

2. The composition of the preparation the present invention thermosetting resin composition, polyester amide acid (A), epoxy compound (B) and a thiol compound (E), an epoxy curing agent optionally (C) and solvent (D ) And other additives.
In addition, the composition of the present invention is an epoxy compound (B), a thiol compound (E), and an epoxy curing agent that is used as necessary, with the reaction solution or mixed solution obtained during the synthesis of the polyester amide acid (A) as it is. It can also be prepared by mixing with (C), solvent (F), other additives and the like.

3. Forming method of cured film The cured film of the present invention is not particularly limited as long as it is a film obtained 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.
Hereinafter, the coating method and the curing method in the method for 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 on a substrate can be performed by spray coating, spin coating, roll coating, dipping, slit coating, bar coating, gravure printing, flexographic printing. It can be performed by a conventionally known method such as a printing method, an offset printing method, a dispenser method, a screen printing method and an ink jet printing method.

For example, from the composition of the present invention, in the case of forming a transparent insulating film provided 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, 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.

Further, for example, in the case of forming an overcoat from the composition of the present invention, spin coating, slit coating, gravure printing, flexographic printing, offset printing, dispenser, 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. Epoxy substrate, glass composite substrate, paper phenol substrate, paper epoxy substrate, green epoxy substrate, BT (bismaleimide triazine) resin substrate; copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or A substrate made of metal such as stainless steel (may be a substrate having a layer made of these metals on the surface); indium tin oxide (ITO), aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium Silicate (zircon), magnesium oxide (magnesia), titanium Aluminum, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia) ), Silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spojumen Substrates made of inorganic substances (may be substrates having a layer containing these inorganic substances on the surface); PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene) Terephthalate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, polyphenylene ether, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer Or a substrate made of a resin such as a liquid crystal polymer (may be a substrate having a layer containing these resins on its surface); a semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO, or 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) (above 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 for forming a cured film in this manner, preferably, after applying the composition of the present invention, the solvent is removed by heating (drying treatment) by heating with a hot plate or an oven, etc. Further, a method of further heating (curing treatment) is used.

The conditions for the drying process vary depending on the types and blending ratios of the components contained in the composition to be used. 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 process, a coating film to the extent that the shape can be maintained can be formed on the substrate.

After forming the coating film, a curing treatment is usually performed at 80 to 300 ° C, preferably 90 to 200 ° C. At this time, in the case of using an oven, a cured film can be obtained usually by heat treatment for 10 to 120 minutes.
Note that the curing process is not limited to the heat treatment, and may be a process such as ultraviolet ray, ion beam, electron beam, or gamma ray irradiation.
Since the composition of this invention contains the polyester amide acid (A), an epoxy compound (B), and a thiol compound (E), low temperature curability is favorable. For this reason, the cured film which is excellent in chemical-resistance etc. can be formed by low-temperature baking of 120 degrees C or less. Therefore, it is possible to form a cured film even on a resin film substrate such as PET that is difficult to perform the curing process 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 at least one selected from the group consisting of the above-mentioned substrates, particularly glass substrates, ITO substrates, and resin film substrates. It is preferable to have the above-mentioned cured film on a kind of substrate.
Such a substrate with a cured film, for example, on the substrate of glass, ITO, PET, PEN, etc., the composition of the present invention is applied to the entire surface or a predetermined pattern (line shape, etc.) by the coating method, Then, it can form by passing through the drying process and hardening process which were demonstrated above.

5). Electronic component An electronic component of the present invention is an electronic component having the above-described cured film or substrate with a cured film. Examples of such electronic components include color filters, various optical materials such as LED light emitting elements and light receiving elements, and touch panels.

The touch panel can be manufactured, for example, by combining a liquid crystal display device or an organic electroluminescence device and a position detection device.
Here, as the position detection 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. Then, 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. It is done.

In the production of such a device, the cured film (transparent insulating film) usually formed in a pattern by a printing method or the like by using the composition of the present invention, and usually the front surface by a coating method or the like. The overcoat formed can be formed of a single composition. Therefore, by using the composition of the present invention, it is possible to simplify the line and improve the yield when manufacturing electronic components.

Hereinafter, the present invention will be described by way of 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), polyvalent hydroxy compound (a3), monohydric alcohol (a4) used for the synthesis of polyester amic acid (A) ), Names of the reaction solvent (a5) and polyhydric acid anhydride (a6) and their abbreviations. This abbreviation is used in the following description.

<Polyester amide acid (A)>
<Tetracarboxylic dianhydride (a1)>
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride <Diamine (a2)>
DDS: 3,3′-diaminodiphenylsulfone <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 containing 40% nanosilica EP4088S: Adeka Resin EP-4088S (trade name, manufactured by ADEKA Corporation)
S510: 3-Glycidoxypropyltrimethoxysilane (trade name: Sila Ace S510, manufactured by JNC Corporation)

<Epoxy curing agent (C)>
TMA: trimellitic anhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic 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 Karenz 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 Karenz 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 Co., Ltd.)
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 Chemicals Co., Ltd.)

<Solvent (F)>
MTM: Triethylene glycol dimethyl ether (trade name: Hisolv 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-toluenesulfonate of diazabicycloundecene (DBU) (trade name U-CAT SA506, manufactured by San Apro Co., Ltd.)
2E4MZ: 1-cyanoethyl-2-ethyl-4-methylimidazole (trade name 2E4MZ-CN, manufactured by Shikoku Kasei Co., Ltd.)
C11Z: 2-Undecylimidazole (trade name Curesol C11Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.)

<Antioxidant (g)>
I1010: Irganox 1010 (trade name, manufactured by BASF)
<Surfactant (h)>
RS-72K: Fluorine-based liquid repellent (trade name: Mega-Fac RS-72K, manufactured by DIC Corporation)

<Polyester amide acid (A)>
First, polyester amic acid was synthesized as shown below (Synthesis Example 1).
[Synthesis Example 1]
A 1000 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging inlet and a nitrogen gas inlet was charged with 46.96 g of dehydrated and purified MP31.93 g of BDOH, 25.54 g of BzOH and 183.20 g of ODPA under a dry nitrogen stream. Stir 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 stirred at 20 to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour. Thereafter, by cooling to 30 ° C. or lower, a pale yellow transparent 30% by weight solution of polyester amic acid was obtained.

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.) (hereinafter the same).

Moreover, the weight average molecular weight of the obtained polyester amide acid was 4,200. The weight average molecular weight of the polyester amide acid was measured as follows.
The obtained polyester amic acid was diluted with N, N-dimethylformamide (DMF) so that the concentration of the polyester amic acid was about 1% by weight, and GPC apparatus: manufactured by JASCO Corporation, Chrom Nav (differential refraction). Using a ratio meter (RI-2031 Plus), the diluted solution was measured by a GPC method using a developing agent, and determined by polystyrene conversion. Three columns GF-1G7B, GF-510HQ and GF-310HQ manufactured by Showa Denko Co., Ltd. were connected in this order, and the column was measured under conditions of a column temperature of 40 ° C. and a flow rate of 0.5 ml / min. (same as below).

[Example 1]
A 100 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 7.37 g of the polyester amic acid (A) solution obtained in Synthesis Example 1 (the amount of the polyester amic acid (A) in the solution was 2. 21g), 8.85 g of EG-200 (the amount of the 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 for each.
Then, it stirred at 25 degreeC (room temperature) for 1 hour, and dissolved each component uniformly. Next, 0.31 g of PE1 was added and stirred at 25 ° C. for 1 hour, followed by filtration with 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 amounts of each component were changed as shown in Tables 2 and 3. In addition, the preparation amount of each component in the table indicates 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 type and amount 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 instead of the thiol compound (E).

[viscosity]
For the thermosetting resin compositions of Examples 1 to 13 and Comparative Examples 1 to 6 (hereinafter referred to as “composition” as appropriate), the viscosity (rotational viscosity) immediately after production was measured. As shown in Tables 2 to 3, the thermosetting resin compositions of the 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 immediately after the addition of the epoxy curing accelerator (i) except for Comparative Example 2. In this case, a solid was deposited, and an ink usable for inkjet could not be prepared (indicated by x in Table 4). From this result, the composition containing the polyester amic acid (A) and the epoxy compound (B) having a fluorene skeleton cannot be prepared by adding the epoxy curing accelerator (i), or the storage stability is increased. It can be said that there is a tendency to get worse.

[Storage stability (viscosity)]
The viscosities were measured after the compositions of Examples 1 to 13 and Comparative Examples 1 and 2 were stored 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 was observed with the passage of time after production. However, the composition of Comparative Example 2, which had a low viscosity immediately after production, increased in viscosity after storage for 7 days at 45 ° C. by about 2.3 times. In contrast, the compositions of Examples 1 to 13 containing the thiol compound (E) all had a viscosity of about 1.3 times or less immediately after production after being stored at 45 ° C. for 7 days. From this result, it was found that the use of the thiol compound (E) resulted in a composition having better storage stability than the case where the epoxy curing accelerator (i) was blended.

[Water absorption rate]
The compositions obtained in Examples 1 to 13 and Comparative Example 2 were applied on the 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 an aluminum foil with a cured film having a thickness of 50 to 100 μm. In the composition of Comparative Example 1, the cured film was easily broken after firing at 120 ° C. for 30 minutes or 100 ° C. for 60 minutes, and it was not possible to extract the aluminum foil in a certain size. The rate was not measured.

<Curing conditions>
Using a hot plate, the mixture was kept at 80 ° C. for 30 minutes 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, Comparative Examples 1 and 2: 120 ° C., 30 minutes Table 5
Example 2-1 and 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 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 using the method described above was peeled off to obtain a single film of the cured film after firing the composition. After measuring the weight (A) before immersion of this single membrane, it was immersed in ultrapure water at room temperature for 24 hours to wipe off water droplets 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 formula.
Water absorption rate (%) = [(BA) / A] × 100
Tables 2 to 4 show the results of measuring the water absorption of the single cured films formed using the compositions of Examples and Comparative Examples.

All of the examples shown in Tables 2 to 3 have lower water absorption than Comparative Example 2, and it was found that a cured film having low water absorption can be obtained by using the thiol compound (E). Further, 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, the composition containing the thiol compound (E) is blended with TMA which is an acid anhydride. It can be said that it is preferable not to.

[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 to obtain a substrate on which a coating film before curing was formed.
Substrate: Glass substrate (10cm square)
Application method: inkjet printing Printer: DMP-2831 (manufactured by FUJIFILM Dimatix)
Head: DMC-11610 (manufactured by FUJIFILM Dimatix)
Printing conditions: Head temperature 30 ° C., voltage 20V, drive waveform Dimatix Model Fluid 2, drive frequency 5 kHz, dot spacing 15-20 μm, single-sided two-layer printing

Thereafter, the composition was cured by drying and main firing under the following conditions to obtain a sample substrate having a cured film formed on the substrate. About the cured film of the obtained sample board | substrate, weight reduction temperature and chemical resistance were evaluated by the method mentioned later.
<Curing conditions>
・ Baking process Yamato Scientific Co., Ltd. clean oven DT-610
・ Temperature setting tables 2 and 3
Examples 1 to 13: Table 5 at 120 ° C. for 30 minutes
-Example 2-1 and 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 reduction temperature (Td1) and 5% weight reduction temperature (Td5) of the cured film were measured. Further, the glass transition temperature (Tg) of the cured film was also measured. The measurement results of each example are shown in Table 2 and Table 3. When the results of Examples 1 to 8 and Examples 9 to 13 shown in Table 2 and Table 3 were compared, Td1 and Td5 tended to increase due to the absence of TMA. From this result, it can be said that it is preferable that the composition containing the thiol compound (E) does not contain TMA which is an acid anhydride in order to form a cured product having good thermal stability.

[Mechanical properties]
All cured films formed using the compositions of Examples 1 to 13 had good mechanical properties. For example, the 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%. Moreover, 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 this result, 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 composition of Example 2 and Comparative Examples 1 and 2 were applied to the entire area of one surface of the 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. Then, the film thickness (A) before the treatment of the cured film was measured.
<Curing conditions>
・ Baking process Yamato Scientific Co., Ltd. clean oven DT-610
Temperature setting table 5
-Example 2, Comparative Examples 1 and 2: 120 ° C, 30 minutes-Example 2-1, Comparative Examples 1-1 and 2-1: 100 ° C, 60 minutes-Example 2-2, Comparative Example 1-2 And 2-2: 120 ° C., 60 minutes Table 6 to Table 10
Examples 14-32, Example 42, Comparative Examples 7 and 8: 100 ° C., 60 minutes

Thereafter, the glass substrate with a cured film was 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 referred to as IPA treatment). (Abbreviation) was applied separately, and the film thickness (B) after immersion of the cured film was measured. In the chemical resistance test under the condition of applying ultrasonic waves, an ASU-10M ultrasonic washer made by ASONE was used, and the mode of washing strength was set to strong (Hi).

Then, heat processing were performed for 5 minutes at 150 degreeC, and the film thickness (C) after the heating of a cured film was measured. Using the film thickness before treatment (A), the film thickness after immersion (B), and the film thickness after heating (C), the remaining film ratio (%) after the immersion treatment and after the heat treatment in the chemical resistance test is as follows: It calculated | required using the formula of.
Remaining film rate after immersion treatment (%)
= [Film thickness after immersion (B) / film thickness before treatment (A)] × 100
Remaining film rate after immersion treatment and heat treatment (%)
= [Film thickness after heating (C) / Film thickness before treatment (A)] × 100
Moreover, the film thickness (D) of the blank of the cured film which performed only the heat processing, without performing an immersion process was measured.
Blank, remaining film ratio after heating (%)
= [Blank film thickness (D) / film thickness before processing (A)] × 100

The results of evaluating chemical resistance, water absorption and thermal stability of Examples 2, 2-1 and 2-2 and Comparative Examples 1, 1-1, 1-2, 2, 2-1, and 2-2 are shown. Table 5 shows.

As shown in Table 5, the cured films of Examples 2 and 2-1 were compared with the cured films of Comparative Examples 1 and 1-1 with respect to both the EtOH treatment and the IPA treatment. The rate has increased. From this result, it was found that the chemical resistance of the dura was improved by adding the thiol compound (E) to the composition.
In addition, the cured films of Examples 2, 2-1 and 2-2 yielded cured films having a lower water absorption than the cured films of Comparative Examples 1-2, 2, 2-1, and 2-2. It was. From this result, it was found that a cured film having a low water absorption can be obtained by blending 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 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 amounts of each component were changed as shown in Tables 6 and 7.

For the Examples and Comparative Examples, the viscosity, storage stability (viscosity), chemical resistance and thermal stability 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 for either EtOH treatment or IPA treatment. However, the remaining film rate became high. From this result, it was found that the chemical resistance of the cured film was improved by blending a certain amount or more of the thiol compound (E) into the composition. From the results of Examples 14 to 22, the content of the thiol compound (E) is above 0.025 parts by weight in 40 parts by weight of the composition (above 0.063 parts by weight in 100 parts by weight of the composition). ) Is preferred. 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 (residue obtained by removing the solvent from the composition), and the total epoxy compound (the epoxy in the solids) This corresponds to 0.564 parts by weight in 100 parts by weight of the total of the compounds. Therefore, it can be said that the content of the thiol compound (E) is preferably higher than 0.312 parts by weight in 100 parts by weight of the solid content, and preferably higher than 0.564 parts by weight in 100 parts by weight of the total epoxy compound.

As shown in Table 6, from the results of Examples 14 and 15 and Examples 18 and 19, the composition in which the thiol compound (E) was blended had TMA as an acid anhydride as the epoxy curing agent (C). It turned out that it becomes the composition which can form hardened | cured material with high heat stability, when it does not contain.

Further, as shown in Tables 6 and 7, any of Examples 14 to 17 and 22 containing TMA and Examples 18 to 21 containing no TMA were compared with Comparative Examples 7 and 8 containing no thiol compound (E). The storage stability was comparable. From this result, 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). If it is inside, it can be said that the storage stability of a composition can be maintained favorable. 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 the solid content, and 0.4 to 0.4 in 100 parts by weight of the total epoxy compound. It can be said that it is preferable to be within 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 amounts of the components were changed as shown in Tables 8 to 10.
About an Example and a comparative example, the viscosity, storage stability (viscosity), chemical-resistance, and thermal stability were evaluated using the evaluation method mentioned above. The results are shown in Tables 8 to 10.

As shown in Tables 8 to 10, it was found that a composition having excellent storage stability was obtained by blending various thiol compounds (E). 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). I found out that

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

Claims

Thermosetting resin composition containing polyester amide acid (A), epoxy compound (B) having a fluorene skeleton, and thiol compound (E) having a plurality of thiol groups in the molecule.
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 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 with respect to 100 parts by weight of all the epoxy compounds.
The thermosetting resin composition according to claim 1, 2 or 3, wherein the epoxy compound (B) having a fluorene skeleton has an epoxy equivalent of 200 to 550 g / eq.
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 with respect to 100 parts by weight of the polyester amic acid (A). Curable resin composition.
6. The thermosetting resin composition according to claim 1, 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 any one of claims 1 to 9.
A substrate with a cured film, comprising the cured film according to claim 10.
An electronic component having 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 ink-jet ink comprising the thermosetting resin composition according to any one of claims 1 to 9.