JPWO2017183226A1 - Thermosetting resin composition, cured film, substrate with cured film, and electronic component - Google Patents

Abstract

A thermosetting resin composition capable of forming a cured film having high hardness, high transparency, and adhesion to glass and ITO, and uses thereof.
The thermosetting resin composition includes a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton, an epoxy curing agent (C), a solvent (D), and silica having an average particle size of 50 nm or less. Since the fine particles (E) and the optically adjusted epoxy resin (F) are contained, a well-balanced cured film having high hardness, high transparency, and adhesion to glass and ITO can be formed.

Description

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

  In recent years, 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, and the like.

  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 is required to prevent outgassing, have high hardness, high transparency, and adherence to glass and ITO.

Various compositions have been studied for highly transparent insulating materials that can be used for such transparent insulating films or overcoats.
For example, Patent Literature 1 and Patent Literature 2 disclose resin compositions containing a polyester amide acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like. However, none of these patent documents discusses the adhesion and hardness of the cured film obtained from the composition to the ITO substrate.

  Patent Document 3 discloses a curable composition containing an epoxy compound having a fluorene skeleton and a curing agent. However, Patent Document 3 does not discuss the transparency of the cured film obtained from the composition, the adhesion to glass and ITO, and the hardness.

JP 2005-105264 A JP 2008-156546 A JP 2012-102228 A

  When manufacturing a touch panel type input device, it is considered that a resin composition that can be used for both the transparent insulating film and the overcoat is desirable from the viewpoint of simplification of the line and improvement of yield. Such a resin composition Has not been realized yet.

  An object of the present invention is to provide a thermosetting resin composition capable of forming a cured film having high hardness, high transparency, adhesion to glass and ITO, and use thereof.

The present inventors have intensively studied to solve the above problems.
For example, when the resin composition specifically described in the said patent document was examined, the cured film obtained from this composition had bad adhesiveness and hardness with respect to glass and ITO, especially ITO.

As a result of various investigations based on the above findings, the present inventors have found that the above problems can be solved by a thermosetting resin composition having the following configuration, and have completed the present invention.
That is, the present invention relates to the following [1] to [23], for example.

  [1] Polyesteramide acid (A), epoxy compound (B) having a fluorene skeleton or dicyclopentadiene skeleton, epoxy curing agent (C), solvent (D), silica fine particles (E) having an average particle size of 50 nm or less, and A thermosetting resin composition comprising an optically adjusted epoxy resin (F).

  [2] The thermosetting resin composition according to [1], wherein the optically adjusted epoxy resin (F) is an alicyclic epoxy compound.

  [3] The thermosetting resin according to [1] or [2], wherein a transmittance of a cured film having a thickness of 2.2 micrometers obtained from the thermosetting resin composition is 97% or more at a wavelength of 400 nm. Composition.

  [4] The thermosetting resin composition according to any one of [1] to [3], wherein an epoxy equivalent of the epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton is 150 to 550 g / eq. .

  [5] In any one of [1] to [4], the epoxy compound (B) having the fluorene skeleton or the dicyclopentadiene skeleton is included in an amount of 15 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A). The thermosetting resin composition as described in one.

  [6] The epoxy curing agent (C) is selected from the group consisting of acid anhydride curing agents, phenol resin curing agents, amine adducts, polycarboxylic acid curing agents, polyamine curing agents and catalytic curing agents. The thermosetting resin composition according to any one of [1] to [5], which is one or more compounds.

[7] The thermosetting according to any one of [1] to [6], wherein the content of the silica fine particles ( E ) is 140 parts by weight or less with respect to 100 parts by weight of the polyester amic acid (A). Resin composition.

  [8] The epoxy curing agent (C) is contained in an amount of 1 to 100 parts by weight with respect to a total of 100 parts by weight of the epoxy compound containing two or more oxirane rings or oxetane rings in the molecule in the thermosetting resin composition. The thermosetting resin composition according to any one of 1] to [7].

  [9] The thermosetting resin composition according to any one of [1] to [8], wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 30,000.

[10] The thermosetting resin according to any one of [1] to [9], wherein the polyester amic acid (A) is a compound having a structural unit represented by formulas (3) and (4). Composition.
(In the formula, 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 2 having 1 to 20 carbon atoms. Valent organic group.)

  [11] The polyester amic acid (A) is a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and a polyvalent hydroxy compound (a3) as essential components. ] The thermosetting resin composition as described in any one of [10].

  [12] The polyester amic acid (A) is obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3) and monohydric alcohol (a4) as essential components. The thermosetting resin composition according to any one of [1] to [11], which is a compound to be obtained.

[13] Polyester amide acid (A) is obtained by converting X mol of tetracarboxylic dianhydride (a1), Y mol of diamine (a2) and Z mol of polyvalent hydroxy compound (a3) into formula (i) and formula The thermosetting resin composition according to any one of [1] to [12], which is a compound obtained by reacting at a ratio such that the relationship (ii) is established.
0.2 ≦ Z / Y ≦ 8.0 (i)
0.2 ≦ (Y + Z) /X≦1.5 (ii)

  [14] The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride. Or at least one compound selected from the group consisting of 2,2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate), [11] The thermosetting resin composition according to any one of [13].

  [15] The diamine (a2) is one or more compounds selected from the group consisting of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone, [11] -The thermosetting resin composition as described in any one of [14].

  [16] The polyvalent hydroxy compound (a3) is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8. -The thermosetting resin composition according to any one of [11] to [15], which is one or more compounds selected from the group consisting of octanediol.

  [17] The monohydric alcohol (a4) is one or more selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane. The thermosetting resin composition according to any one of [11] to [16], which is a compound.

  [18] The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, and the diamine (a2) is 3,3′-diaminodiphenylsulfone. The heat according to any one of [11] to [17], wherein the polyvalent hydroxy compound (a3) is 1,4-butanediol and the epoxy curing agent (C) is trimellitic anhydride. Curable resin composition.

  [19] The thermosetting resin composition according to any one of [1] to [18], which is for a touch panel.

  [20] A cured film obtained from the thermosetting resin composition according to any one of [1] to [19].

  [21] A substrate with a cured film, comprising the cured film according to [20].

  [22] An electronic component having the cured film according to [20] or the substrate with the cured film according to [21].

  [23] The electronic component according to [22], which is a touch panel.

  According to the present invention, a cured film having high hardness, high transparency, adhesion to glass or ITO, and resistance to an ITO etching solution containing oxalic acid, and having these effects in a well-balanced manner can be formed. . For this reason, the thermosetting resin composition of the present invention is very practical, for example, it is possible to produce a transparent insulating film and an overcoat for a touch panel with high productivity. Can be suitably used.

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

1. Thermosetting resin composition The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene or dicyclopentadiene skeleton, an epoxy curing agent (C), a solvent (D), and an average particle size. Contains 50 nm or less of silica fine particles (E) and an optically adjusted epoxy resin (F). In addition to the above components, the composition of the present invention may contain additives, and may be colored or colorless.
According to such a composition of the present invention, it is possible to obtain a cured film having a good balance between high hardness, high transparency, adhesion to glass and ITO, and resistance to an ITO etching solution containing oxalic acid. 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 the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton, an epoxy curing agent (C), a solvent (D), and silica having an average particle size of 50 nm or less. Only when the fine particles (E) and the optically adjusted epoxy resin (F) are contained, a cured film having excellent effects can be obtained. In particular, the cured film having a pencil hardness of 3H or more and a transmittance of a cured film having a thickness of 2.2 micrometers is 97% or more at a wavelength of 400 nm, and a cured film having excellent adhesion to glass and ITO can be obtained.
In a conventional composition composed of polyester amide acid, or a composition composed of an epoxy compound having a fluorene skeleton and an epoxy curing agent, these substrates have a pencil hardness of 3H or more, and the transmittance is 97% or more. A cured film having excellent adhesion to glass and ITO was not obtained.
Therefore, the composition of the present invention is a composition having an effect that cannot be expected from the conventional composition, and is an epoxy compound, an epoxy curing agent, a solvent, an average particle having a polyesteramic acid, a fluorene skeleton or a dicyclopentadiene. A composition having a synergistic effect by combining silica fine particles having a diameter of 50 nm or less and an optically adjusted epoxy resin.

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.
For the first time by using such a polyester amic acid (A) in combination with a specific epoxy compound and an epoxy curing agent, it has high hardness, high transparency and excellent resistance to an ITO etching solution containing oxalic acid, A composition capable of forming a cured film having excellent adhesion to glass or 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. Preferably, it is 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 point that a compound having good compatibility with other components in the composition is obtained, and a cured film having high transparency and good adhesion to glass and ITO is obtained, 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 the formula (6), R ⁶ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ — or —O—ph—R ⁸ —ph—O—). (a ph is a benzene ^{ring, R} 8 _{is, -O -, - CO -,} - SO 2 -, - C (CF 3) 2 - or -R ⁷ -. a a) in which. Incidentally, ^{R 7} is Independently, it is an alkyl group having 1 to 4 carbon atoms.)

From the standpoint of obtaining a highly transparent cured film, R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, and is a group represented by the formula (7): —R ¹⁰ —NR ¹¹ -R ¹² - ^{(R 10} and ^{R 12} are independently an alkylene having 1 to 8 carbon ^{atoms, R 11} is hydrogen or at least one hydrogen which may be the number 1 to 8 carbon substituted by hydroxyl An alkyl having 2 to 15 carbon atoms, or at least one hydrogen 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 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 formulas 1 to 4.)

The polyester amic acid (A) is preferably a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and polyvalent hydroxy compound (a3) as essential components. A compound obtained by reacting dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3) and monohydric alcohol (a4) as essential components is also preferred.
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.
Each of these (a1) to (a5) may be used alone or in combination of two or more.

  When the polyester amic 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 amic acid (A) obtained using the monohydric alcohol (a4) tends to be a compound having excellent compatibility with the epoxy compound (B) and the epoxy curing agent (C), and has a composition excellent in coatability. There is a tendency to obtain things.

1.1.1. Tetracarboxylic dianhydride (a1)
Although it does not restrict | limit especially as tetracarboxylic dianhydride (a1), As a specific example, 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 Alicyclic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride and butanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides are listed.

  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, New Japan Rika Chemical Co., Ltd.) is preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are particularly preferred.

1.1.2. Diamine (a2)
Although it does not restrict | limit especially as a diamine (a2), As a specific example, 4,4'- diamino diphenyl sulfone, 3,3'- diamino diphenyl sulfone, 3,4'- diamino diphenyl sulfone, 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.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are preferable. Considering the compatibility of the resulting polyester amic acid (A) with the epoxy compound (B) and the epoxy curing agent (C) and the applicability of the resulting composition on glass or ITO, a monovalent alcohol ( As a4), benzyl alcohol is more preferable.

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. Examples include acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

Among these, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, methyl 3-methoxypropionate and N-methyl-2-pyrrolidone are 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.

  Moreover, in the case of the said reaction, in order to enlarge the weight average molecular weight of the obtained polyester amide acid (A), you may add the compound which has 3 or more acid anhydride groups, and may perform a synthetic reaction. 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 (i) and Formula (ii) is established between Z. By using each component in such an amount, a polyester amide acid (A) having high solubility in the following solvent (D) can be obtained, a composition having excellent coatability can be obtained, and a cured film having excellent flatness can be obtained. Can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (i)
0.2 ≦ (Y + Z) /X≦1.5 (ii)

  The relationship of formula (i) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. The relationship of formula (ii) is preferably 0.5 ≦ (Y + Z) /X≦0.9, and more preferably 0.7 ≦ (Y + Z) /X≦0.8.

  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 0.2 ≦ Z ′ / X ≦ 0.6, more preferably Is 0.3 ≦ Z ′ / X ≦ 0.5.

  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, amount of use, etc. of polyester amic acid (A) >>
The weight average molecular weight (polystyrene conversion) measured by the gel permeation chromatography (GPC) of the polyester amic acid (A) is soluble in the solvent (D), and particularly when used in combination with the epoxy compound (B). From the standpoint of obtaining a cured film having a good balance between adhesion to glass and ITO and chemical resistance, it is preferably 2,000 to 30,000, and preferably 3,000 to 28,000. More preferred.
Specifically, this weight average molecular weight can be measured by the method described in the Examples below.

  The viscosity of the polyester amic acid (A) is preferably 5 to 200 mPa · s at 25 ° C. from the viewpoint of easy handling of the obtained polyester amic acid (A) and adjusting the weight average molecular weight to the above preferred range. Preferably it is 10-150 mPa * s, More preferably, it is 15-100 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. Preferably it is 1-60 weight% with respect to weight%, More preferably, it is 5-55 weight%, More preferably, it is 10-50 weight%.

1.2. Epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton
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 or a dicyclopentadiene skeleton. Since such an epoxy compound (B) has a high decomposition temperature and excellent heat stability, it is possible to obtain a cured film having these effects in addition to the effects such as high transparency.
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 150 to 550 g / eq, more preferably 150 to 490 g / eq, and further preferably 160 to 480 g from the viewpoint that a cured film having excellent chemical resistance is obtained. / Eq.
The epoxy equivalent of the epoxy compound (B) can be measured, for example, by the method described in JIS K7236.

The refractive index of the epoxy compound (B) is preferably 1.40 to 1.75, more preferably 1.45 to 1.73, from the viewpoint of obtaining a cured film excellent in high transparency. More preferably, it is 1.48 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 products of the epoxy compound (B) include OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.64, epoxy equivalent 259 g / eq), OGSOL CG-500 (trade name, Osaka Gas Chemical Co., Ltd., refractive index 1.70, epoxy equivalent 311 g / eq), OGSOL EG-200 (trade name, Osaka Gas Chemical Co., Ltd., refractive index 1.62, epoxy equivalent 292 g / eq), OGSOL EG-250 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.58, epoxy equivalent 417 g / eq), OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.56) , Epoxy equivalent 467 g / eq), OGSOL CG-400 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.53, epoxy equivalent 540 g / q), EP-4088S (trade name, manufactured by ADEKA, refractive index 1.50, epoxy equivalent 170 g / eq), EP-4088L (trade name, manufactured by ADEKA, refractive index 1.50, epoxy equivalent) 165 g / eq).

  When using a compound having a refractive index of 1.60 or more and an epoxy equivalent of less than 280 g / eq, for example, OGSOL PG-100, as the epoxy compound (B), other components in the composition of the epoxy compound (B) From the standpoint of solubility, etc., it is preferable to use an epoxy compound (B) having a refractive index of 1.70 or less and an epoxy equivalent of more than 280 g / eq, and in this case, all epoxy compounds contained in the composition of the present invention In (B), the content of the compound having a refractive index of 1.60 or more and an epoxy equivalent of less than 280 g / eq is preferably 70% by weight or less, more preferably 65% by weight or less, and 60% by weight or less. More preferably.

  When the epoxy compound (B) is a compound having a refractive index of 1.68 or more and an epoxy equivalent of 400 g / eq or less, such as OGSOL CG-500, the cured film obtained from the composition of the present invention has particularly high hardness. Become. On the other hand, since transparency tends to decrease, a cured film having a good balance of hardness and transparency can be obtained by using an epoxy compound (B) having a refractive index of less than 1.68 and an epoxy equivalent of 200 g / eq or more. It is done. At this time, in all the epoxy compounds (B) contained in the composition of the present invention, the content of the compound having a refractive index of 1.68 or more and an epoxy equivalent of 400 g / eq or less is preferably 90% by weight or less, More preferably, it is 80% by weight or less, and further preferably 70% by weight or less.

  As the epoxy compound (B), when a compound having a refractive index of less than 1.60 and an epoxy equivalent of 300 g / eq or more, for example, OGSOL EG-280, a cured film obtained from the composition of the present invention is particularly glass or Adhesiveness and transparency to ITO are improved. On the other hand, since the resistance to acids such as an oxalic acid aqueous solution tends to be reduced, by using an epoxy compound (B) having a refractive index of 1.60 or more and an epoxy equivalent of less than 400, adhesion to glass or ITO, A cured film having a good balance between transparency and resistance to acids such as an aqueous oxalic acid solution can be obtained. At this time, it is preferable that the compounding amount of the compound having a refractive index of less than 1.60 and an epoxy equivalent of 300 g / eq or more in all the epoxy compounds (B) contained in the resin composition of the present invention is 70% by weight or less. , 60% by weight or less, more preferably 50% by weight or less.

  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 3 to 60% by weight, more preferably 5 to 50% by weight, and still more preferably 7 to 50% by weight with respect to 100% by weight, and 100 parts by weight of polyester amic acid (A) The amount is preferably 1 to 400 parts by weight, more preferably 20 to 300 parts by weight, and still more preferably 20 to 250 parts by weight.

1.3. Epoxy curing agent (C)
The composition of the present invention is blended with an epoxy curing agent (C), whereby a cured film having excellent heat resistance and chemical resistance is obtained.
The epoxy curing agent (C) is a compound different from the polyester amide acid (A), and specifically includes an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent. Although mentioned, an acid anhydride type hardening | curing agent is preferable from points, such as coloring 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 acid anhydride curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride Aliphatic dicarboxylic acid anhydrides such as phthalic acid; aromatic polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these, trimellitic anhydride is particularly preferable from the viewpoints of obtaining a compound having excellent solubility in the solvent (D) and obtaining a cured film having excellent heat resistance.

  The content of the epoxy curing agent (C) is the composition of the present invention in terms of chemical resistance to chemicals such as an oxalic acid aqueous solution, good adhesion to glass and ITO, and a cured film having high surface hardness. It is preferably 1 to 20% by weight, more preferably 2 to 17% by weight, still more preferably 3 to 15% by weight based on 100% by weight of the solid content of the product (residue obtained by removing the solvent from the composition) Preferably it is 5-30 weight part with respect to 100 weight part of all the epoxy resins containing an epoxy compound (B), More preferably, it is 7-29 weight part, More preferably, it is 7-28 weight part.

  Moreover, the ratio of the epoxy compound (B) to be used and the epoxy curing agent (C) is based on the amount of epoxy groups in the epoxy compound (B) to be used from the viewpoint of obtaining a cured film having excellent heat resistance and chemical resistance. On the other hand, the amount of the group capable of reacting with an epoxy group such as an acid anhydride group or a carboxyl group in the epoxy curing agent is preferably 0.2 to 2 times equivalent, and 0.5 to 1.5 times equivalent. Further, the chemical resistance of the resulting cured film is further improved, which is further preferable. At this time, for example, when 1 equivalent of a compound having one epoxy group is used as the epoxy compound (B) and 1 equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (C), The amount of the epoxy curing agent (C) with respect to the compound (B) is assumed to be 2 times equivalent.

1.4. Solvent (D)
The composition of the present invention can be obtained, for example, by dissolving the polyester amide acid (A), the epoxy compound (B) and the epoxy curing agent (C) in the solvent (D). Therefore, the solvent (D) is preferably a solvent that can dissolve the polyester amide acid (A), the epoxy compound (B), and the epoxy curing agent (C). Moreover, even if it is a solvent that does not dissolve polyester amic acid (A), epoxy compound (B) and epoxy curing agent (C) alone, it can be used as solvent (D) by mixing with other solvents. It may become.
As the solvent (D), only one kind may be used, or two or more kinds may be mixed and used, or the reaction solvent (a5) may be used as it is.

  Examples of the solvent (D) 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, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene Glico Monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, tripropylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, Pyrene glycol monoethyl ether, dipropylene glycol monomethyl ether acetate, triethylene glycol divinyl ether, triethylene glycol butyl methyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethanol, 2- Ethoxyethanol, methyl 2-hydroxyisobutyrate, 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-diethylacetate Toamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, α-acetyl-γ-butyrolactone, ε-caprolactone, γ-hexano Examples include lactone, δ-hexanolactone, methyl ethyl sulfoxide, dimethyl sulfoxide, and equamide (trade name) manufactured by Idemitsu Kosan Co., Ltd.

  Among these, the composition of the present invention includes ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether in terms of solubility in the polyester amic acid (A), the epoxy compound (B), and the epoxy curing agent (C). Ether acetate, diethylene glycol monoethyl butel acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether, methyl 3-methoxypropionate, .gamma.-butyrolactone, at least one member selected from the group consisting of dimethyl sulfoxide and Idemitsu Kosan Co. Ekuamido (trade name), is preferably contained as the solvent (D).

1.5 Silica fine particles (E)
The silica fine particles (E) used in the present invention are not particularly limited as long as the average particle diameter is 50 nm or less, but is preferably 40 nm or less, and more preferably 25 nm or less. By containing such silica fine particles (E), a cured film having excellent heat resistance, high transparency, high hardness and the like can be obtained.
The silica fine particles (E) may be used alone or in combination of two or more.
The average particle diameter of the silica described above is the significance of the equivalent sphere diameter evaluated by the dynamic light scattering method.

  The content of the silica fine particles (E) in the composition is preferably 35 parts by weight or more with respect to 100 parts by weight of the polyester amic acid (A) because a cured film having high hardness is obtained, and 50 parts by weight. More preferably, it is more preferably 70 parts by weight or more. Further, since a cured film having good adhesion to ITO is obtained, it is preferably 150 parts by mass or less, more preferably 145 parts by mass or less, based on 100 parts by mass of the polyester amic acid (A). More preferably, it is 140 parts by mass or less.

  The silica fine particles (E) may be added to the composition as an epoxy resin containing silica dispersed in the optically adjusted epoxy resin (F). Specific examples of the epoxy resin (E) containing silica include NANOPOX C450, NANOPOX C460, NANOPOX C620, NANOPOX F400, NANOPOX E500, NANOPOX E601, NANOPOX F631, NANOPOX F640 (above, manufactured by EVONIK), Examples include Composeran E205 and Composeran E206 (trade names, manufactured by Arakawa Chemical Co., Ltd.). Among these, NANOPOX C620 is particularly preferable because a cured film having high transparency and high hardness can be obtained.

1.6. Optical adjustment epoxy resin (F)
The optically adjusted epoxy resin (F) used in the present invention is an epoxy resin of a type different from the above-described epoxy resin (B), which is blended in order to adjust the optical properties of the cured film obtained by curing the composition. is there. The optically adjusted epoxy resin (F) may be added to the composition separately from the silica fine particles (E), or may be used as a dispersion medium for dispersing the silica fine particles (E) in advance. The dispersion state of the silica fine particles (E) can be improved by dispersing the silica fine particles (E) in advance in the optically adjusted epoxy resin (F) and then adding the silica fine particles (E) to the composition.

  As the optical adjustment epoxy resin (F), bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin, polymer of monomer having oxirane ring, monomer having oxirane ring and others And a copolymer with the above monomer. Among these, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane is obtained because a cured film having high transmittance and excellent transparent optical properties and having good adhesion to glass and ITO can be obtained. An alicyclic epoxy compound such as carboxylate is preferred.

  By using an alicyclic epoxy compound as the optically adjusted epoxy resin (F), a highly transparent cured film can be obtained. For example, when the film thickness is 2.2 μm, a highly transparent cured film having a transmittance at a wavelength of 400 nm of 97% or more can be obtained. Further, by adjusting the blending amount of the composition, a cured film having a transmittance of 98% or more and a cured film having 99% or more can be obtained.

1.7. Additives The composition of the present invention comprises a polyester amic acid (A), an epoxy compound (B), an epoxy curing agent (C), silica fine particles (E), and an optically-adjustable epoxy resin (F) depending on the intended properties. You may contain additives other than. Examples of additives include other epoxy resins (f), polyimide resins, oxetane resins, polymerizable monomers, antistatic agents, coupling agents (g), pH adjusters, rust preventives, antiseptics, and antifungal agents. , Antioxidant (h), surfactant (i), epoxy resin curing accelerator (j), reduction inhibitor, evaporation accelerator, chelating agent, and water-soluble polymer. 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.

1.7.1. Other epoxy resins (f)
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 other epoxy resin (f) refers to an epoxy resin other than the epoxy compound (B) having the fluorene skeleton or the dicyclopentadiene skeleton and the optically adjusted epoxy resin (F).
As the other epoxy resin (f), a compound having two or more oxirane rings is preferably used, and the other epoxy resin (f) may be used alone or in combination of two or more. Also good.

  Other epoxy resins (f) include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, polymers of monomers having an oxirane ring, monomers having an oxirane ring. And copolymers with other monomers.

Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and compounds represented by the following structure.

In the formula (1), R is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl and arylalkyl; The hydrogen in can be replaced with fluorine, and any non-adjacent —CH ₂ — can be replaced with —O— or —CH═CH—; in alkylene in arylalkyl, the number of carbon atoms is one And any non-adjacent —CH ₂ — may be replaced by —O—; R ¹ and R ² are independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl And X ¹ is any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl and oxetanylene. A group having one.
In the present invention, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acryl refers to acryl and / or methacryl.

  Other monomers that copolymerize with monomers having an oxirane ring include, 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, 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. When the composition of this invention contains these epoxy resins, since the heat resistance of the cured film formed from the said composition becomes further favorable, it is preferable.

  Specific examples of the other epoxy resins (f) include “jER806”, “jER807”, “jER815”, “jER825”, “jER825”, “jER828”, “jER871”, “jER872”, “jER190P”, “ “jER191P”, “jER1004”, “jER1004AF”, “jER1007”, “jER1010”, “jER1256”, “jER157S70”, “jER1032H60” (trade names, manufactured by Mitsubishi Chemical Corporation), “Araldite CY177”, “Araldite” “CY184” (trade name, manufactured by BASF), “Celoxide 2021P”, “Celoxide 3000”, “Celoxide 8000”, “EHPE-3150”, “EHPE-3150CE” (all trade names, manufactured by Daicel Chemical Industries, Ltd.) Name “TECHMORE VG3101L” (trade name, manufactured by Printec Co., Ltd.), “HP7200, HP7200H, HP7200HH (trade name, manufactured by DIC Corporation)”, “NC-3000”, “NC-3000H”, “EPPN” -501H "," EOCN-102S "," EOCN-103S "," EOCN-104S "," EPPN-501H "," EPPN-501HY "," EPPN-502H "," EPPN-201-L " Name, Nippon Kayaku Co., Ltd.), "TEP-G" (trade name, manufactured by Asahi Organic Materials Co., Ltd.), "MA-DGIC", "Me-DGIC", "TG-G" (above Trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), “TEPIC-VL” (trade name, manufactured by Nissan Chemical Industries, Ltd.), “FLEP-10”, “FLEP-50”, “F LEP-60 "," FLEP-80 "(trade name, manufactured by Toraythiol Co., Ltd.), N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N -Diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane. Among these, a composition containing a trade name “Araldite CY184”, a trade name “Celoxide 2021P”, a trade name “TECHMORE VG3101L”, and an epoxy resin “jER828” can obtain a cured film with particularly good flatness. preferable.

  The concentration of the other epoxy resin (f) in the composition of the present invention is not particularly limited, but the composition of the present invention is obtained from the viewpoint of obtaining a cured film having excellent balance in heat resistance and adhesion to glass and ITO. It is preferably contained in an amount of 0 to 40% by weight, more preferably 0 to 30% by weight in the solid content of the product (residue obtained by removing the solvent from the composition).

1.7.2. Oxetane resin The optically adjusted epoxy resin (F) includes an oxetane resin as one aspect thereof. Specific examples of the oxetane resin include “OXT-101”, “OXT-121”, “OXT-212”, and “OXT-221” (trade names, manufactured by Toagosei Co., Ltd.). Among these, a composition containing the trade name “OXT-101” is preferable because a cured film having high transparency can be obtained.
The concentration of the oxetane resin in the composition of the present invention is not particularly limited, but the solid content (from the composition) of the composition of the present invention is obtained in that a cured film having better heat resistance and transparency can be obtained. It is preferable that 0 to 40% by weight is contained in the residue excluding the solvent, and more preferably 0 to 30% by weight.

  The “epoxy compound containing two or more oxirane rings or oxetane rings in the molecule in the thermosetting resin composition” as referred to in [8] in the section of means for solving the above-mentioned problems means The combination of “epoxy compound (B) having fluorene skeleton or dicyclopentadiene skeleton”, “optically adjusted epoxy resin (F)” and “other epoxy resin (f)” contained in the thermosetting resin composition It means all epoxy compounds contained in.

1.7.3. 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 an amic acid obtained by reacting an acid dianhydride and a 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 the composition of the present invention is not particularly limited, but a cured film having better heat resistance and chemical resistance can be obtained. 0.1-20 weight% is preferable and 0.1-10 weight% is further more preferable.

1.7.4. 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. Therefore, the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition) is preferably 0.1 to 40% by weight, and preferably 1 to 30% by weight. Further preferred.

Examples of the monofunctional polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate, Gurisero Mono (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, 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- (meta Acrylic Cymethyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexyl Maleimide, N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethyl methacrylate macromonomer, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric Acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl ] And cyclohexene-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-propanedio Distearate (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate.

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

1.7.5. The antistatic agent can be used for preventing the charge of the composition of the present invention. When the composition of the present invention contains an antistatic agent, 0.01 to It is preferably used in an amount of 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.

1.7.6. Coupling agent (g)
The coupling agent (g) 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. When the composition of the present invention contains a coupling agent (g), the coupling agent (g) 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 (g), 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-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyl Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-amino Propyltrimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Methyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyana DOO propyl methyl diethoxy silane, include γ- isocyanato propyl triethoxysilane.

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

1.7.7. Antioxidant (h)
When the composition of the present invention contains the antioxidant (h), the cured film obtained from the composition can be prevented from being deteriorated when exposed to high temperature or light. When the composition of the present invention contains the antioxidant (h), the antioxidant (h) is a solid content of the composition excluding the antioxidant (h) (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 (h), and 2 or more types may be mixed and used for it.

  Examples of the antioxidant (h) 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), Adekastab AO-20, Adekastab AO-40, Adeka 50 Examples include ADK STAB AO-60, ADK STAB AO-80, ADK STAB AO-330 (trade name, manufactured by ADEKA Corporation), and the like.

1.7.8. Surfactant (i)
When the composition of the present invention contains the surfactant (i), 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 (i) is included, the surfactant (i) is preferably used in an amount of 0.01 to 1% by weight with respect to 100% by weight of the composition of the present invention.
As the surfactant (i), only one type may be used, or two or more types may be mixed and used.

  As the surfactant (i), for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-” can be used, for example, because the coating property of the composition of the present invention can be improved. 310 "," BYK-341 "," BYK-344 "," BYK-370 "(above trade names, manufactured by Big Chemie Japan Co., Ltd.)," KP-112 "," KP-326 "," KP-341 " (Such as a product of Shin-Etsu Chemical Co., Ltd.), etc .; trade names “BYK-354”, “BYK-358”, “BYK-361” (above trade names, Big Chemie Japan Co., Ltd.) Acrylic surfactants such as “DFX-18”, “Furgent 250”, “Furgent 251” (named above, manufactured by Neos Co., Ltd.), “Megafac F-444”, “ Mega fuck Fluorine-based surfactants such as “F-477” and “Megafac RS-72-K” (trade name, manufactured by DIC Corporation) can be used.

1.7.9. Epoxy resin curing accelerator (j)
As the epoxy resin curing accelerator (j), “DBU”, “DBN”, “U-CAT” can be used because the curing temperature of the composition of the present invention can be lowered or the curing time can be shortened. "," U-CAT SA1 "," U-CAT SA102 "," U-CAT SA506 "," U-CAT SA603 "," U-CAT SA810 "," U-CAT 5002 "," U-CAT 5003 " , "U-CAT 18X", "U-CAT SA841 / 851", "U-CAT SA881", "U-CAT 891" (trade name, manufactured by San Apro Co., Ltd.), "CP-001", "NV -203-R4 "(above trade name, manufactured by Osaka Gas Chemical Co., Ltd.)," Karenz MT PE1 "," Karenz MT BD1 "," Karenz MT NR1 "(above trade name, Showa Den Made Co., Ltd.), and the like.
Each of the epoxy resin curing accelerators (j) may be used alone or in combination of two or more.

  The content of the epoxy resin curing accelerator (j) 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). It is.

1.7.10. Examples of the pigment or dye pigment include one or more compounds selected from the group consisting of boron nitride, aluminum nitride, silicon carbide, alumina, magnesia, silica, rutile titanium oxide, zinc oxide, lower titanium oxide, and graphite. Can be mentioned. Rutile titanium oxide refers to white titanium oxide represented by TiO ₂ . Low-order titanium oxide refers to black titanium oxide such as Ti ₃ O ₅ , Ti ₂ O ₃ and TiO. For example, low-order titanium oxide (black) known as titanium black includes Tirac D (trade name) manufactured by Ako Kasei Co., Ltd., 12S, 13M, 13M-C, and SC-13M manufactured by Mitsubishi Materials Corporation. (Trade name) and Tokoshi Co., Ltd. Mark 2004 Black (trade name). Examples of graphite include Marco 2003, Black Marco 2011 Black, Marco 2020 Black, and Marco 2021 Black (trade name) manufactured by Tokushi Corporation.
Examples of the dye include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Examples of azo dyes include “VALIFAST BLACK 3810”, “VALIFAST BLACK 3820”, “VALIFAST RED 3304”, “VALIFAST RED 3320”, and “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industry Co., Ltd.). It is done.
Each of the pigment and the dye may be used alone or in combination of two or more.

2. Preparation Method of Thermosetting Resin Composition The composition of the present invention comprises a polyester amide acid (A), an epoxy compound having a fluorene skeleton or a dicyclopentadiene skeleton and an epoxy curing agent (C), a solvent (D), silica fine particles ( E), and can be prepared by mixing an optically adjusted epoxy resin (F) and other additives.
In addition, the composition of the present invention is prepared by using the reaction solution or mixed solution obtained at the time of synthesizing the polyester amide acid (A) as it is, the epoxy compound (B), the epoxy curing agent (C), and a solvent (if necessary) D), silica fine particles (E), optical adjustment epoxy resin (F), and other additives may be mixed to prepare.

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

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

  For example, 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 is used 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, when the overcoat is formed from the composition of the present invention, the entire surface printing is easy, so that the spin coating method, the slit coating method, the gravure printing method, the flexographic printing method, the offset printing method, the dispenser. A coating method such as a printing method or 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 the surface); a semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO, or A substrate on which an electrode material (wiring) such as ATO (antimony tin oxide) is formed; αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel) or γGEL (gamma gel) (above, ( ) Registered trademark of Tayca), such gel sheet; 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 treatment vary depending on the types and blending ratios of the components contained in the composition to be used, but the heating temperature is usually 70 to 120 ° C., and the heating time is 5 to 15 minutes for an oven and 1 for a hot plate. 10 minutes. By such a drying process, a coating film to the extent that the shape can be maintained can be formed on the substrate.

After forming the coating film, curing treatment is usually performed at 100 to 300 ° C, preferably 100 to 250 ° C. At this time, when the oven is used, the cured film can be usually obtained by heat treatment for 10 to 120 minutes, and when the hot plate is used, usually 5 to 30 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.

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), which is usually formed in a pattern by a printing method or the like, and usually the entire surface by a coating method or the like by using the composition of the present invention. 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.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. Tetracarboxylic dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3), monohydric alcohol (a4), reaction solvent (a5), fluorene skeleton or dicyclopentadiene used in Examples and Comparative Examples Epoxy compound (B) having skeleton, epoxy curing agent (C), solvent (D), silica fine particles (E), optically adjusted epoxy resin (F), coupling agent (g), antioxidant (h) and interface The names of the activator (i) and the epoxy curing accelerator (j) and their abbreviations are shown. This abbreviation is used in the following description.

<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 PGMEA: propylene glycol monomethyl ether acetate EDM: diethylene glycol methyl ethyl ether <styrene-maleic anhydride copolymer>
SMA1000: styrene component / maleic anhydride component: 50/50, weight average molecular weight: 5,500 (trade name, manufactured by Sartomer Co., Ltd.)

<Epoxy compound (B) having fluorene skeleton or dicyclopentadiene skeleton>
EG-200: OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
EG-280: OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
4088S: EP-4088S (trade name, manufactured by ADEKA Corporation)

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

<Solvent (D)>
EDM: diethylene glycol methyl ethyl ether DB: diethylene glycol monobutyl ether MTEM: tetraethylene glycol dimethyl ether Eca: diethylene glycol monoethyl ether EDGAC: diethylene glycol monoethyl ether acetate PGME: propylene glycol monomethyl ether DEGBEA: diethylene glycol monobutyl ether acetate MTM: triethylene glycol dimethyl ether

<Silica fine particles (E)>
C450: NANOPOX C450 (trade name, manufactured by EVONIK), average particle size: 20 nm
C460: NANOPOX C460 (trade name, manufactured by EVONIK), average particle size: 20 nm
C620: NANOPOX C620 (trade name, manufactured by EVONIK), average particle size: 20 nm
C680: NANOPOX C680 (trade name, manufactured by EVONIK), average particle size: 20 nm

<Optical adjustment epoxy resin (F)>
BPA: Bisphenol A type epoxy resin (C450 dispersion medium)
BPF: Bisphenol F type phenol resin (C460 dispersion medium)
CEL2021P: Celoxide 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (dispersion medium of C620) OXT-101: OXT-101 (trade name) , Manufactured by Toagosei Co., Ltd.), Oxetane resin (C680 dispersion medium)

<Other epoxy resins (f)>
EHPE3150: EHPE3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.), 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol SQ: JP Compound represented by formula (1-1) synthesized by the method described in 2009-167390

<Coupling agent (g)>
GMS: γ-glycidoxypropyltrimethoxysilane

<Antioxidant (h)>
I1010: IRGANOX 1010 (trade name, manufactured by BASF)

<Surfactant (i)>
BYK344: BYK-344 (trade name, manufactured by Big Chemie Japan Co., Ltd.)

<Epoxy resin curing accelerator (j)>
PE1: Karenz MT PE1 (trade name, manufactured by Showa Denko KK)
SA506: U-CAT SA506 (trade name, manufactured by San Apro Co., Ltd.)

  First, a polyester amic acid solution was synthesized as shown below (Synthesis Examples 1 and 2). Table 1 summarizes Synthesis Examples 1 and 2.

[Synthesis Example 1]
A 1000 ml separable flask equipped with a thermometer, stirring blade, raw material charging inlet and nitrogen gas inlet was charged with 466.6 g of dehydrated and purified MPM, 31.93 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 183.4 g of MPM were added, and the mixture was 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 28.1 mPa · s. Here, the rotational viscosity is a viscosity measured at 25 ° C. using an E-type viscometer (trade name; VISCONIC END, manufactured by Tokyo Keiki 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).

[Synthesis Example 2]
A 500 ml flask equipped with a thermometer and a stirring blade was purged with nitrogen and dehydrated and purified 179.2 g of PGMEA, ODPA 16.96 g, SMA 1000 51.6 g, BzOH 19.7 g, BDOH 3.28 g, and EDM 34. 2 was stirred and stirred at 125 ° C. for 2 hours under a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C., 4.52 g of DDS and 10.6 g of EDM were added, and the mixture was stirred at 20 to 30 ° C. for 2 hours, and then stirred at 120 ° C. for 1 hour. Thereafter, by cooling to 30 ° C. or lower, a pale yellow transparent 30% by weight solution of polyester amic acid (A) was obtained.
The rotational viscosity of this solution was 35.3 mPa · s. The weight average molecular weight measured by GPC was 24,000 (polystyrene conversion).

[Example 1]
A 100 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 4.8 g of the polyester amic acid solution obtained in Synthesis Example 1, 1.44 g of EG-200, 1.44 g of C620, 0.43 g of TMA, 0.2 g of GMS, 0.02 g of I1010 and 11.6 g of dehydrated and purified MTM were charged and stirred for 1 hour at room temperature to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to obtain a filtrate (thermosetting resin composition).

[Examples 2 to 25]
In Examples 2 to 25, thermosetting 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.
As described in Example 1, the silica fine particles (E) were added as an epoxy resin containing silica dispersed in the optically adjusted epoxy resin (F). For this reason, in Table 2 and Table 3, it is divided into the silica fine particles (E) and the optically adjusted epoxy resin (F) constituting the epoxy resin containing dispersed silica, and the blending amount of each component is described. . Table 5 shows the type and amount of the epoxy resin (NANOPOX) containing dispersed silica containing the silica fine particles (E) and the optically adjusted epoxy resin (F).

[Example 26]
A 100 ml three-necked flask equipped with stirring blades was purged with nitrogen, and in the flask, 4.79 g of the polyester amic acid solution obtained in Synthesis Example 1, 0.72 g of EG-200, 1.44 g of C620, EHPE3150 (0.72 g), TMA (0.43 g), GMS (0.23 g), I1010 (0.02 g) and dehydrated and purified MTM (11.6 g) were charged, and the mixture was stirred at room temperature for 1 hour to uniformly dissolve each component. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to obtain a filtrate (thermosetting resin composition).

[Examples 27 to 28]
In Examples 27 to 28, thermosetting resin compositions were prepared in the same manner as in Example 26 except that the types and amounts of each component were changed as shown in Table 3.

[Example 29]
A 100 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 4.8 g of the polyester amic acid solution obtained in Synthesis Example 1, 1.44 g of EG-200, 1.44 g of C620, 0.35 g of TMA, 0.22 g of GMS, 0.02 g of I1010, 0.16 g of SA506 and 11.3 g of dehydrated and purified MTM were charged and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to obtain a filtrate (thermosetting resin composition).

[Examples 30 to 32]
In Examples 30 to 32, thermosetting resin compositions were prepared in the same manner as in Example 29 except that the types and amounts of each component were changed as shown in Table 3.

[Comparative Example 1]
A 100 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 4.80 g of the polyester amic acid solution obtained in Synthesis Example 1, 2.88 g of C620, 0.43 g of TMA, and GMS were added to the flask. 0.23 g, I1010 0.02 g, and 11.6 g of dehydrated and purified MTM were charged and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to obtain a filtrate (thermosetting resin composition).

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

[Comparative Example 3]
A 100 ml three-necked flask equipped with stirring blades was purged with nitrogen, and the polyester amic acid solution obtained in Synthesis Example 1 was added to the flask by 4.79 g, EG-200 2.88 g, TMA 0.43 g, 0.23 g of GMS, 0.02 g of I1010 and 11.6 g of dehydrated and purified MTM were charged and stirred for 1 hour at room temperature to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to obtain a filtrate (thermosetting resin composition).

[Comparative Examples 4 to 5]
In Comparative Examples 4 to 5, thermosetting resin compositions were prepared in the same manner as in Comparative Example 3 except that the types and amounts of each component were changed as shown in Table 4.

  The thermosetting resin composition obtained by the adjustment method described above was spin-coated on the glass substrate and the ITO substrate so that the thickness of the cured film obtained was as shown in Table 6, and then on the hot plate. A coating film was formed by drying at 5 ° C. for 5 minutes. Then, about Examples 1-28 and Comparative Examples 1-5, it heated for 30 minutes at 150 degreeC using oven, and obtained the cured film. About Examples 29-32, the cured film was obtained by heating at 120 degreeC for 30 minute (s) using oven. The cured film thus obtained was evaluated for transparency, adhesion, surface hardness and chemical resistance. These evaluation results are shown in Table 3.

[Evaluation method]
(I) Transparency Using the obtained glass substrate with a cured film, the transmittance of the cured film was measured with a spectrophotometer V-670 (manufactured by JASCO Corporation) at a wavelength of 400 nm.

(Ii) Adhesiveness After the obtained glass substrate with a cured film and the ITO substrate with a cured film were immersed in ultrapure water at 60 ° C. for 60 minutes, a cross-cut test (JIS-K-5400) by tape peeling was performed. The adhesion between the substrate and the cured film was evaluated by counting the remaining number. Using a cutter knife, incisions were made in the cured film at intervals of 1 mm to produce 100 1 mm square grids, and # 600 manufactured by 3M was used as a tape for peeling after making close contact with the grids. Of the 100 grids of the cured film formed on the substrate, the number remaining on the substrate after tape peeling (remaining number / 100) is 100/100, and the case is 99/100 or less Was marked with x.

(Iii) Surface hardness Using the obtained glass substrate with a cured film, the hardness of the surface of the cured film was measured with a pencil hardness meter in accordance with JIS-K-5400.

(Iv) Chemical resistance The obtained glass substrate with a cured film and the ITO substrate with a cured film were immersed in an aqueous 3.5% oxalic acid solution at 40 ° C. for 6 minutes. And the film thickness change of the cured film before and after immersion is measured using a stylus type film thickness meter XP-200 (manufactured by AMBIOS TECHNOLOGY), and when the film thickness change is less than ± 3%, ○, ± 3% The case where it was above was set as x. Further, the transmittance was observed in the same manner as in (i) before and after the immersion, and the case where the change in transmittance was less than ± 1% was marked as ◯, and the case where it was ± 1% or more was marked as x.

From comparison between Examples 1 to 32 and Comparative Examples 3 to 5, it was found that a cured film having high hardness can be obtained by blending silica fine particles (E) into the thermosetting resin composition.
As is clear from the results shown in Table 6, the cured films formed from the thermosetting resin compositions obtained in Examples 1 to 16 and 26 to 32 are excellent in adhesion to glass and ITO, and further at 400 nm. The transmittance was as high as 97% or higher, and the surface hardness was as high as 3H or higher. Furthermore, the tolerance with respect to the oxalic acid aqueous solution was also good, and high transparency, high hardness, adhesion to glass and ITO, and resistance against the oxalic acid aqueous solution were balanced.
On the other hand, the cured film formed from the thermosetting resin composition obtained in Examples 17 to 23 has a low transmittance of 95% or less at 400 nm, and Examples 24 to 25 and Comparative Examples 1 to 2 have low transparency. The cured film had poor adhesion to ITO, and the cured films of Comparative Examples 3 to 5 had a surface hardness as low as H or less.

Thermosetting resins of Examples 1 to 16 and 24-32 containing 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, which is an alicyclic epoxy compound, as the optically adjusted epoxy resin (F) All of the cured films formed from the composition had high transparency with a transmittance of 97% or more at 400 nm. On the other hand, the cured film formed from the thermosetting resin composition of Comparative Examples 1 and 2 did not have sufficient adhesion to ITO. From this, it was found that in order to form a cured film with good adhesion to ITO, the thermosetting resin composition requires an epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton. From the results of Examples 4 and 5, when the epoxy compound (B) content is 25 parts by weight or more based on 100 parts by weight of the polyester amic acid (A), it is effective for forming a cured film having high adhesion to ITO. You can say that.
As described above, since Synthesis Examples 1 and 2 are 30% by weight solutions of polyester amide acid (A), the amount of polyester amide acid (A) contained in the thermosetting composition is shown in Tables 2-4. 30% by weight of the blending amounts of Synthesis Examples 1 and 2 described.

  In order to form a cured film having high adhesion to the ITO substrate, it is preferable that the content of the silica fine particles (E) with respect to the polyester amic acid (A) is not excessively increased. From the results of Examples 24 and 25, the content of the silica fine particles (E) is preferably 140 parts by weight or less, more preferably 130 parts by weight or less with respect to 100 parts by weight of the polyester amide acid (A).

  As described above, only the cured film obtained from the composition containing the polyester amic acid, the epoxy resin having a fluorene skeleton or the dicyclopentadiene skeleton, the silica fine particles, the optical adjustment epoxy resin and the epoxy curing agent has all the desired properties. I was satisfied.

  The composition of the present invention is for forming protective films for various optical materials such as color filters, LED light-emitting elements, and light-receiving elements because it can form a cured film having excellent properties as an optical material such as adhesion and transparency. In addition, it can be used for forming a touch panel (for forming an insulating film for a transparent electrode or an overcoat film used for a touch panel).

Claims (23)

  Polyester amide acid (A), epoxy compound (B) having fluorene skeleton or dicyclopentadiene skeleton, epoxy curing agent (C), solvent (D), silica fine particles (E) having an average particle diameter of 50 nm or less, and optical adjustment A thermosetting resin composition containing an epoxy resin (F).   The thermosetting resin composition according to claim 1, wherein the optically adjusted epoxy resin (F) is an alicyclic epoxy compound.   The thermosetting resin composition according to claim 1 or 2, wherein a transmittance of a cured film having a thickness of 2.2 micrometers obtained from the thermosetting resin composition is 97% or more at a wavelength of 400 nm.   The thermosetting resin composition according to any one of claims 1 to 3, wherein an epoxy equivalent of the epoxy compound (B) having the fluorene skeleton or the dicyclopentadiene skeleton is 150 to 550 g / eq.   The heat according to any one of claims 1 to 4, comprising 15 to 400 parts by weight of the epoxy compound (B) having the fluorene skeleton or dicyclopentadiene skeleton with respect to 100 parts by weight of the polyester amic acid (A). Curable resin composition.   The epoxy curing agent (C) is one or more selected from the group consisting of an acid anhydride curing agent, a phenol resin curing agent, an amine adduct, a polycarboxylic acid curing agent, a polyamine curing agent, and a catalytic curing agent. The thermosetting resin composition according to any one of claims 1 to 5, which is a compound of   The thermosetting resin composition according to any one of claims 1 to 6, wherein the content of the silica fine particles (E) is 140 parts by weight or less with respect to 100 parts by weight of the polyester amic acid (A).   The said epoxy hardening | curing agent (C) is contained in 1-100 weight part with respect to a total of 100 weight part of the epoxy compound which contains two or more oxirane rings or oxetane rings in the molecule | numerator in a thermosetting resin composition. 8. The thermosetting resin composition according to any one of 7 above.   The thermosetting resin composition according to any one of claims 1 to 8, wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 30,000. The thermosetting resin composition according to any one of claims 1 to 9, wherein the polyester amic acid (A) is a compound having structural units represented by formulas (3) and (4).

(In the formula, 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 2 having 1 to 20 carbon atoms. Valent organic group.)   The said polyester amide acid (A) is a compound obtained by making tetracarboxylic dianhydride (a1), diamine (a2), and a polyvalent hydroxy compound (a3) react as an essential component. The thermosetting resin composition according to any one of the above.   The polyester amic acid (A) is a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3) and monohydric alcohol (a4) as essential components. The thermosetting resin composition according to any one of claims 1 to 11. The polyester amic acid (A) is converted into X moles of tetracarboxylic dianhydride (a1), Y moles of diamine (a2) and Z moles of polyhydric hydroxy compound (a3) with formulas (i) and (ii). The thermosetting resin composition according to any one of claims 1 to 12, which is a compound obtained by reacting at a ratio such that the relationship is established.
0.2 ≦ Z / Y ≦ 8.0 (i)
0.2 ≦ (Y + Z) /X≦1.5 (ii)   The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2 , 2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and one or more compounds selected from the group consisting of ethylene glycol bis (anhydrotrimellitate). The thermosetting resin composition according to any one of ˜13.   The diamine (a2) is one or more compounds selected from the group consisting of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. The thermosetting resin composition according to any one of the above.   The polyvalent hydroxy compound (a3) is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol. The thermosetting resin composition according to any one of claims 11 to 15, which is at least one compound selected from the group consisting of:   The monohydric alcohol (a4) is at least one compound selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. The thermosetting resin composition according to any one of claims 11 to 16.   The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine (a2) is 3,3′-diaminodiphenylsulfone, The thermosetting resin composition according to any one of claims 11 to 17, wherein the divalent hydroxy compound (a3) is 1,4-butanediol and the epoxy curing agent (C) is trimellitic anhydride. .   The thermosetting resin composition according to any one of claims 1 to 18, which is used for a touch panel.   The cured film obtained from the thermosetting resin composition of any one of Claims 1-19.   The board | substrate with a cured film which has a cured film of Claim 20.   An electronic component having the cured film according to claim 20 or the substrate with the cured film according to claim 21.   The electronic component according to claim 22, wherein the electronic component is a touch panel.