JP2017197616A - Thermosetting resin composition, and electronic device using cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition with a high refractive index and/or a high transmission.SOLUTION: The problem is solved by a thermosetting resin composition that contains a carboxyl group-containing compound (A) and inorganic fine particles (B) with a primary particle size of 1-100 nm. When formed into a cured film, the thermosetting resin composition has a refractive index (nD) of 1.6-3.0.

Description

  The present invention relates to a thermosetting resin composition, a cured film formed from the composition, a substrate with a cured film having the cured film, and an electronic device having the cured film or the substrate with the cured film.

  An organic electroluminescent element (organic EL element) is an electronic device, and is expected as a liquid crystal backlight or a self-luminous thin flat display device. However, organic EL elements are extremely susceptible to deterioration when exposed to moisture and oxygen. In other words, the interface between the metal electrode and the organic EL layer is peeled off due to the influence of moisture, the metal is oxidized to increase the resistance, or the light emitting material contained in the light emitting layer of the organic EL element is altered by moisture. I do. In addition to organic EL elements, many electronic devices use metals that can be eroded by moisture, oxygen, organic substances, and the like.

  Therefore, many methods for protecting electronic devices such as organic EL elements from moisture and oxygen have been reported. As one of the methods, a method of covering (surface sealing) an organic EL element with a sealant layer obtained by curing an epoxy resin composition is known (see Patent Documents 1 to 5). In these patent documents, resin compositions containing epoxy compounds having various structures and physical properties are proposed as sealants. In addition, as a protective film for an electronic device, a resin composition containing a polyesteramidic acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like has also been proposed (see Patent Document 6).

  Furthermore, in recent years, as an input device, a touch panel type input device in which a liquid crystal display element or an organic EL element 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. For example, in a touch panel type input device adopting a capacitance method, a capacitance change caused by a fingertip or the like using a device having a structure in which X and Y electrodes are arranged in a matrix on a glass substrate. Is detected as a change in current.

  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. In some cases, an insulating overcoat is provided to flatten the X and Y electrodes.

  A color filter is attached to the display portion side of the liquid crystal display element or the organic EL element. This color filter is a structure that allows coloration as a display device by patterning a transparent resin containing, for example, RGB three-color pigments and transmitting only red light, green light, and blue light from white light.

  Usually, electrodes such as ITO (indium tin oxide), fine silver wiring, and silver nanofibers are provided in the vicinity of the color filter. However, since the color filter has irregularities, a transparent overcoat for flattening is applied. ITO (indium tin oxide), fine silver wiring, and silver nanofibers may be patterned on this overcoat.

  The sealing agent, the transparent insulating film, the overcoat, and the like satisfy the respective roles described above, and for example, improve the light extraction efficiency, which is a problem of the top-emission type organic EL element that has been mainstream in recent years. Therefore, a high refractive index and / or a high transmittance as a material used for the optical system member is required.

International Publication No. 2006/104078 International Publication No. 2010/119706 JP 2006-179318 A JP 2010-126699 A JP 2013-166949 A JP 2005-105264 A

  The present invention has been made in view of the above situation. For example, it has a high refractive index and / or a high transmittance thermosetting property that can be used for a sealing agent, a transparent insulating film or an overcoat of an electronic device such as an organic EL element. It is an object of the present invention to provide a resin composition, more preferably a thermosetting resin composition having high storage stability.

  As a result of various studies to solve the above-mentioned problems, the present inventors are a thermosetting resin composition containing a carboxyl group-containing compound (A) and inorganic fine particles (B) having a primary particle diameter of 1 to 100 nm. The present inventors have found that the above object can be achieved by a thermosetting resin composition having a refractive index (nD) of 1.6 to 3.0 in the case of a cured film, and completed the present invention.

[1] A thermosetting resin composition containing a carboxyl group-containing compound (A) and inorganic fine particles (B) having a primary particle diameter of 1 to 100 nm, and having a refractive index (nD) of 1 when used as a cured film. Thermosetting resin composition which is .6 to 3.0.

（式（Ａ１）および式（Ａ２）中、Ｒ^１は独立に炭素数１〜３０の４価の有機基であり、Ｒ^２は炭素数１〜４０の２価の有機基であり、Ｒ^３は炭素数１〜２０の２価の有機基である。）

（式（Ａｉ−１）〜式（Ａｉ−３）、式（Ａｉｉ−１）〜式（Ａｉｉ−８）中、Ｘは独立に以下のいずれかの２価の基であり、

Ｙは独立に炭素数１〜３０の４価の有機基であり、Ｚは２価の有機基であり、「−ＣＯ−Ａ−ＣＯＯＨ」はジカルボン酸無水物またはテトラカルボン酸無水物の残基である。） [2] A compound in which the carboxyl group-containing compound (A) has at least one of a structural unit represented by the formula (A1) and a structural unit represented by the formula (A2), and formulas (Ai-1) to The thermosetting resin composition according to the above [1], which is at least one selected from compounds represented by formula (Ai-3) and formula (Aii-1) to formula (Aii-8).

(In Formula (A1) and Formula (A2), 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.)

(In the formulas (Ai-1) to (Ai-3) and (Aii-1) to (Aii-8), X is independently any one of the following divalent groups;

Y is independently a tetravalent organic group having 1 to 30 carbon atoms, Z is a divalent organic group, and “—CO—A—COOH” is a residue of a dicarboxylic acid anhydride or a tetracarboxylic acid anhydride. It is. )

[3] The thermosetting resin composition according to [1] or [2], further including an epoxy compound (C).

[4] The thermosetting resin composition according to any one of [1] to [3], further including an epoxy curing agent (D).

[5] Any one of [1] to [4], wherein the carboxyl group-containing compound (A) is a carboxyl group-containing compound (A) obtained by further reacting with a styrene-maleic anhydride copolymer. Thermosetting resin composition.

[6] The thermosetting resin composition according to any one of [1] to [5], further including an acrylic compound (E).

[7] The thermosetting resin composition according to any one of [1] to [6], further including a solvent (F).

[8] An inkjet ink comprising the thermosetting resin composition according to any one of [1] to [7].

[9] A resin composition for a slit die coater comprising the thermosetting resin composition according to any one of [1] to [7].

[10] An ink for screen printing comprising the thermosetting resin composition according to any one of [1] to [7].

[11] A cured product obtained by curing the thermosetting resin composition according to any one of [1] to [7].

[12] An electronic device having a cured product obtained by curing the thermosetting resin composition according to any one of [1] to [7].

  According to a preferred embodiment of the present invention, there is provided a thermosetting resin composition having a high refractive index and / or a high transmittance that can be used for a sealing agent, a transparent insulating film or an overcoat of an electronic device such as an organic EL element. For example, it is possible to improve the light extraction efficiency which is a problem of the top emission type organic EL element which has been mainstream in recent years. Furthermore, according to a preferred embodiment, since the thermosetting resin composition is excellent in storage stability, it is possible to realize an advantageous work process from this point.

1. Thermosetting resin composition of the present invention The thermosetting resin composition of the present invention comprises a carboxyl group-containing compound (A) and inorganic fine particles (B) having a primary particle diameter of 1 to 100 nm. And it is a thermosetting resin composition whose refractive index (nD) at the time of setting it as a cured film is 1.6-3.0.

（式（Ａ１）および式（Ａ２）中、Ｒ^１は独立に炭素数１〜３０の４価の有機基であり、Ｒ^２は炭素数１〜４０の２価の有機基であり、Ｒ^３は炭素数１〜２０の２価の有機基である。） 1.1 Carboxyl group-containing compound (A) (Part 1)
The carboxyl group-containing compound (A) used in the present invention is not particularly limited as long as it is a compound containing a carboxyl group, but is preferably a compound having an ester bond, an amide bond and a carboxyl group, for example, the formula (A1) The compound having at least one of the structural unit represented by formula (A2) and the structural unit represented by formula (A2) is more preferable. Only 1 type may be used for a carboxyl group-containing compound (A), and 2 or more types may be mixed and used for it.

(In Formula (A1) and Formula (A2), 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.)

From the viewpoints of obtaining a compound having good compatibility with other components in the composition and obtaining a cured film having a high refractive index and / or high transmittance, R ¹ is independently 4 having 2 to 25 carbon atoms. It is preferably a valent organic group, more preferably a tetravalent organic group having 2 to 20 carbon atoms, and even more preferably a group represented by the formula (A3).

（式（Ａ３）において、Ｒ^４は、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｒ^５−または−ＣＯＯ−Ｒ^５−ＯＣＯ−（Ｒ^５は独立に炭素数１〜４のアルキル基である。）である。）

(In the formula (A3), R ⁴ represents —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁵ — or —COO—R ⁵ —OCO— (R ⁵ represents Independently an alkyl group having 1 to 4 carbon atoms.)

Compatibility with other components in the composition may compound is obtained, from the viewpoint of the adhesion to glass and ITO is obtained a good cured film with high refractive index and / or high transmittance, R ² Is preferably a divalent organic group having 2 to 35 carbon atoms, more preferably a divalent organic group having 2 to 30 carbon atoms, and a group represented by the formula (A4). Further preferred.

（式（Ａ４）において、Ｒ^６は、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｒ^７−または−Ｏ−ｐｈ−Ｒ^８−ｐｈ−Ｏ−である（ｐｈはベンゼン環であり、Ｒ^８は、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−または−Ｒ^７−である。）。なお、Ｒ^７は独立に炭素数１〜４のアルキル基である。）

(In the formula (A4), 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 It is independently an alkyl group having 1 to 4 carbon atoms.)

In view of obtaining a cured film having a high refractive index and / or a high transmittance, R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, and is a group represented by the formula (A5). ^{, -R 10 -NR 11 -R 12 -} (R 10 and ^{R 12} is alkylene of 1 to 8 carbon atoms ^{independently, R 11} is hydrogen or at least one hydrogen may be substituted with a hydroxyl carbon 1 to 8 alkyl), alkylene having 2 to 15 carbons, or at least one hydrogen of alkylene having 2 to 15 carbons may be substituted with hydroxyl, and having —O—. More preferably, it is more preferably a divalent alkylene having 2 to 6 carbon atoms.

（式（Ａ５）において、Ｒ^９は、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｒ^７−または−ｐｈ−Ｒ^８−ｐｈ−である（ｐｈはベンゼン環であり、Ｒ^８は、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−または−Ｒ^７−である。）。なお、Ｒ^７は独立に炭素数１〜４のアルキル基である。）

(In the formula (A5), 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 a carbon number. 1-4 alkyl groups.)

  The carboxyl group-containing compound (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 acid dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3) and monohydric alcohol (a4) as essential components is also preferred. In addition, a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and, if necessary, monohydric alcohol (a4) as essential components, tetracarboxylic dianhydride (a1) ), A polyhydroxy compound (a3), and, if necessary, a compound obtained by reacting a monohydric alcohol (a4) as an essential component.

That is, in formulas (A1) and (A2), R ¹ is independently a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue. preferable. In this reaction, a reaction solvent (a5) or the like may be used. Each of these components (a1) to (a5) may be used alone or in combination of two or more.

  When the carboxyl group-containing compound (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 (C) and the epoxy curing agent (D) 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 ′ is obtained in that a compound having a good refractive index and / or transmittance can be obtained. -Diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG -100, manufactured by Shin Nippon Rika Co., Ltd.), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride Is 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 from the viewpoint of obtaining a compound having a good refractive index and / or transmittance, and 3,3 '-Diaminodiphenyl sulfone is particularly preferred.

1.1.3 Polyvalent hydroxy compound (a3)
The polyvalent hydroxy compound (a3) is not particularly limited as long as it is a compound having two or more hydroxy groups. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol having a molecular weight of 1,000 or less. , Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2- Pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2 , 6- 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 carboxyl group-containing compound (A) with the epoxy compound (C) and the epoxy curing agent (D), and the applicability of the resulting composition on glass or ITO, a monovalent alcohol (A4) is more preferably benzyl alcohol.

1.1.5 Reaction solvent (a5)
The reaction solvent (a5) is not particularly limited, but specific examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether. 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.

1.1.6 Synthesis of carboxyl group-containing compound (A) The method for synthesizing the carboxyl group-containing compound (A) is not particularly limited, but (Method 1) tetracarboxylic dianhydride (a1), diamine (a2), Method of reacting polyhydric hydroxy compound (a3) and, if necessary, monohydric alcohol (a4) as essential components, (Method 2) tetracarboxylic dianhydride (a1), diamine (a2), and 1 if necessary Method of reacting monohydric alcohol (a4) as an essential component, (Method 3) Reacting tetracarboxylic dianhydride (a1), polyvalent hydroxy compound (a3), and optionally monohydric alcohol (a4) as essential components And the like, and these reactions are preferably carried out in the reaction solvent (a5).

  The order of adding each component during this reaction is not particularly limited. That is, in the case of the above (Method 1), the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3) may be simultaneously added to the reaction solvent (a5) for reaction. The diamine (a2) and the polyvalent hydroxy compound (a3) may be dissolved in the reaction solvent (a5), and then the tetracarboxylic dianhydride (a1) may be added to react. The acid dianhydride (a1) and the diamine (a2) may be reacted in advance, and then the polyhydroxy compound (a3) may be added and reacted with the reaction product, and any method can be used. . The monohydric alcohol (a4) may be added at any point in the reaction. Further, the order of addition of each component in the above (Method 2) and (Method 3) can be freely changed in accordance with the description of (Method 1).

  Moreover, in the case of the said reaction, in order to enlarge the weight average molecular weight of the carboxyl group-containing compound (A) obtained, you may perform the synthetic reaction by adding the compound which has three or more acid anhydride groups. Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.

  The carboxyl group-containing compound synthesized in this way includes at least one of the structural unit represented by the above formula (A1) and the structural unit represented by the formula (A2), and the terminal thereof is a tetracarboxylic acid as a raw material. It is an acid anhydride group, an amino group or a hydroxy group derived from a dianhydride, a diamine or a polyvalent hydroxy compound, 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 the following mathematical formulas (1) and (2) is established between Z. By using each component in such an amount, a carboxyl group-containing compound (A) having high solubility in the following solvent (F) is obtained, a composition having excellent coatability is obtained, and a cured film having excellent flatness Can be obtained.
0.2 ≦ Z / Y ≦ 8.0 Formula (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)

  The relationship of Formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. Further, the relationship of the mathematical formula (2) 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.

1.1.7 Physical properties and use amount of carboxyl group-containing compound (A) The weight average molecular weight of the carboxyl group-containing compound (A) measured by gel permeation chromatography (GPC) is determined based on solubility in the solvent (F), In particular, from the viewpoint of obtaining a cured film having a balanced balance of refractive index and / or transmittance, adhesion to glass and ITO, and chemical resistance, in combination with the epoxy compound (C), 2,000 to It is preferably 20,000, more preferably 3,000 to 10,000. The weight average molecular weight can be specifically measured by the method described in the following examples.

  The viscosity of the carboxyl group-containing compound (A) is preferably 5 to 200 mPa · s at 25 ° C. from the viewpoint of adjusting the handleability of the resulting carboxyl group-containing compound (A) and adjusting the weight average molecular weight to the preferred range. More preferably, it is 10-150 mPa * s, More preferably, it is 15-100 mPa * s.

  The content of the carboxyl group-containing compound (A) is such that a cured film having a high refractive index and / or high transmittance and excellent chemical resistance is obtained, and the solid content of the composition of the present invention (from the composition) The amount is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, and still more preferably 10 to 50% by weight with respect to 100% by weight of the residue excluding the solvent.

1.2 Carboxyl group-containing compound (A) (part 2)
Examples of the carboxyl group-containing compound (A) also include at least one compound selected from the following amide acid (Ai) and the following carboxyl group-containing ester compound (Aii).
(I) An amic acid obtained by reacting an amino compound (a11) represented by the general formula (A6) described later and an acid anhydride (a12) (hereinafter also referred to as “amidic acid (Ai)”).
(Ii) An ester compound (hereinafter referred to as “carboxyl group”) obtained by reacting amic acid (Ai) or an imidized product thereof (hereinafter also referred to as “imidized product (Ai)”) and an acid anhydride (a12 ′). Containing ester compound (Aii) "or" ester compound (Aii) ")

  Since the carboxyl group-containing compound (A) has a carboxyl group, it acts as an epoxy curing agent. That is, by the heat treatment, the carboxyl group of the carboxyl group-containing compound (A) reacts with the epoxy of the epoxy compound (C), and curing proceeds to form a cured film. The cured film exhibits good adhesion to the substrate, has a small amount of warpage, and is excellent in electrical characteristics, alkali resistance characteristics, and thermal characteristics.

  The acid anhydride (a12 ′) to be reacted with the amide acid (Ai) or its imidized product (Ai) may be the same as or different from the acid anhydride (a12) used in the synthesis of the amide acid (Ai). .

  Hereinafter, the reaction raw materials such as the amino compound (a11), the acid anhydride (a12) and the acid anhydride (a12 ′), and the reaction solvent used in the synthesis of the carboxyl group-containing compound (A) will be described, and then the carboxyl group-containing The synthesis conditions for compound (A) will be described.

式（Ａ６）中、Ｚは二価の有機基である。二価の有機基としては、炭素数１〜２０のアルキレン、前記アルキレン中の任意のメチレンをフェニレンなどの芳香族基に置き換えた基、ポリエチレングリコール〔−（ＣＨ_２ＣＨ_２−Ｏ）_ｎ−ＣＨ_２ＣＨ_２−で表される基、ｎは１〜１０の整数である。〕などが挙げられる。炭素数１〜２０のアルキレンは、直鎖状であっても、分岐鎖状であってもよい。 1.2.1 Amino compound (a11)
The amino compound (a11) is represented by the following formula (A6).

In formula (A6), Z is a divalent organic group. Examples of the divalent organic group include alkylene having 1 to 20 carbon atoms, a group in which any methylene in the alkylene is replaced with an aromatic group such as phenylene, polyethylene glycol [— (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ -, a group represented by, n represents an integer of 1 to 10. And the like. The alkylene having 1 to 20 carbon atoms may be linear or branched.

  Examples of the amino compound (a11) include 2-aminoethanol, 5-amino-1-pentanol, 2- (4-aminophenyl) ethanol, 2- (2-aminoethoxy) ethanol and the like. Among these, 2- (2-aminoethoxy) ethanol and 2- (4-aminophenyl) ethanol are preferable.

1.2.2 Acid anhydride (a12)
The acid anhydride (a12) is not particularly limited as long as it has an acid anhydride group. In the present invention, from the viewpoint of obtaining a thermosetting resin composition having a low viscosity and a high concentration of the carboxyl group-containing compound (A), the number of acid anhydride groups in the acid anhydride (a12) is one or two. Preferably there is. That is, as the acid anhydride (a12), dicarboxylic acid anhydride and tetracarboxylic dianhydride are preferable.

1.2.2.1 Compound having one acid anhydride group Examples of the compound having one acid anhydride group include dicarboxylic acid anhydrides. Examples of the dicarboxylic acid anhydride include a compound represented by the general formula (A7), tetrapropenyl succinic anhydride, tetradecenyl succinic anhydride, octadecenyl succinic anhydride, 2-dodecen-1-yl succinic acid. Acid anhydride, 4-methylphthalic anhydride, 4-t-butylphthalic anhydride, 4-fluorophthalic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid An acid anhydride, glutaric acid anhydride, etc. are mentioned.

式（Ａ７）中、Ｘは独立に以下のいずれかの２価の基である。

In formula (A7), X is independently any one of the following divalent groups.

  Among dicarboxylic acid anhydrides, a general formula can be used in that a thermosetting resin composition having a high concentration of the carboxyl group-containing compound (A) (the composition can be suitably used as an inkjet ink) can be prepared. The compound represented by (A7), that is, succinic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride And cis-1,2-cyclohexanedicarboxylic anhydride are preferred; maleic anhydride, citraconic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride are particularly preferred.

1.2.2.2 Compound having two acid anhydride groups Examples of the compound having two acid anhydride groups include tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include compounds represented by general formula (A8), 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetra. Carboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 , 3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), methylcyclobutane tetracarboxylic dianhydride, Cyclopentanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, ethylenediaminetetracarboxylic dianhydride 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene succinic dianhydride and formula (a1-1) to formula And the compound represented by any one of (a1-73).

式（Ａ８）中、Ｙは独立に炭素数１〜４０の４価の有機基であり、好ましくは以下のいずれかの４価の基である。

ここで、Ｒ^１は、単結合、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、または以下のいずれかの２価の基であり、Ｒ^２は、単結合、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−の何れかである。

In formula (A8), Y is independently a tetravalent organic group having 1 to 40 carbon atoms, preferably any one of the following tetravalent groups.

Here, R ¹ is a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or any of the following: R ² is a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2. -Either.

  Among tetracarboxylic dianhydrides, compounds represented by general formula (A8), butanetetracarboxylic dianhydride, particularly compounds represented by general formula (A8) are soluble in solvent (F). As a result, a thermosetting resin composition having a high concentration of the carboxyl group-containing compound (A) (the composition can be suitably used as an inkjet ink). Can be prepared.

  Further, in order to obtain a higher refractive index and / or higher transmittance, the compound represented by the general formula (A8), butanetetracarboxylic dianhydride is preferable, pyromellitic dianhydride, 3, 3 ′ , 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropanoic dianhydride, cyclobutanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride are particularly preferred.

  As the acid anhydride (a12), only one type may be used, or two or more types may be mixed and used.

1.2.3 Acid anhydride (a12 ′)
The acid anhydride (a12 ′) to be reacted with the amide acid (Ai) or its imidized product (Ai) is not particularly limited as long as it has an acid anhydride group, and the same as the acid anhydride (a12) described above. Can be used. That is, the compound represented by general formula (A9) is mentioned.

式（Ａ９）中、Ａは式（Ａ７）中のＸと同義であるか、あるいは以下の式で表される２価の基である。

式中、Ｙは式（Ａ８）中のＹと同義である。

In formula (A9), A is synonymous with X in formula (A7) or is a divalent group represented by the following formula.

In the formula, Y has the same meaning as Y in formula (A8).

1.2.4 Reaction solvent When the carboxyl group-containing compound (A) is synthesized, a reaction solvent is usually used. As a reaction solvent, ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, aniso , Ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether ( -Ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1- Vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl -2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone and the like.

  Moreover, solvents other than the reaction solvent illustrated above can also be used by mixing with the reaction solvent. Only 1 type may be used for a reaction solvent, and 2 or more types may be mixed and used for it.

  By the way, when the reaction solvent remains when the synthesis of the carboxyl group-containing compound (A) is completed, the reaction solvent can be used as the solvent (F). Among the reaction solvents, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, 3-methyl-2-pyrrolidone, because the composition has good compatibility with other components in the thermosetting resin composition and the composition has a low viscosity. Methyl methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyrolactone are preferred.

1.2.5 Synthesis conditions of carboxyl group-containing compound (A)

1.2.5.1 Amic acid (Ai) or imidized product thereof (Ai)
The amic acid (Ai) can be synthesized by mixing the amino compound (a11) and the acid anhydride (a12) under mild reaction conditions. The mild reaction conditions are, for example, a normal pressure, a temperature of 5 to 60 ° C., a reaction time of 0.2 to 20 hours, preferably a temperature of 5 to 30 ° C. and a reaction time of 0.2 to 10 hours. The condition is that the acid anhydride group of the acid anhydride (a12) is allowed to react without activating the carboxyl formed by ring opening by the reaction. The activation of carboxyl is, for example, conversion to acid chloride.

  Under the above mild reaction conditions, the carboxyl produced by the reaction of the amino of the amino compound (a11) with the acid anhydride group of the acid anhydride (a12) reacts with the amine of the amino compound (a11) or imidizes. Therefore, an amic acid (Ai) having a free carboxyl can be obtained.

  The imidization of the amic acid (Ai) can be performed by a thermal method or a chemical method using a dehydration catalyst and a dehydrating agent, but it is preferable to proceed by a thermal method that can be used without performing a purification treatment. The imidation is, for example, heating at normal pressure and a temperature of usually 50 to 200 ° C., preferably 60 to 180 ° C., a reaction time of usually 0.2 to 20 hours, preferably 0.5 to 10 hours, and without using a catalyst. The process can proceed. The amic acid (Ai) can be converted into an imide structure by the heating step.

  Further, instead of the above mild reaction conditions, the synthesis of amic acid (Ai) and its imidization may be advanced by the heating step. That is, the imido compound (Ai) may be synthesized by mixing the amino compound (a11) and the acid anhydride (a12) and proceeding the reaction under the heating step.

  The preparation amount of the amino compound (a11) is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, per 1 mol of the acid anhydride group of the acid anhydride (a12).

1.2.5.2 Carboxyl group-containing ester compound (Aii)
Hydroxyl derived from the amino compound (a11) exists in the amic acid (Ai) or its imidized product (Ai). Therefore, by reacting amic acid (Ai) or its imidized product (Ai) with an acid anhydride (a12 ′), hydroxyl derived from amino compound (a11) and acid of acid anhydride (a12 ′) Reaction with an anhydride group produces carboxyl. Thus, an amide acid having an ester or an imidized product having an ester, that is, a carboxyl group-containing ester compound (Aii) can be synthesized. The esterification can be carried out, for example, under normal pressure at a temperature of usually 50 to 200 ° C., preferably 60 to 180 ° C., a reaction time of usually 0.2 to 20 hours, preferably 0.5 to 10 hours.

  The amic acid (Ai) or imidized product (Ai) obtained as described above may be isolated by a purification treatment and then reacted with an acid anhydride (a12 ′), and a solution containing them. An acid anhydride (a12 ′) may be added to and reacted with the acid anhydride (a12 ′).

The charging amount of the acid anhydride (a12 ′) is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, relative to 1 mol of hydroxyl of the amic acid (Ai) or imidized product (Ai) thereof. . From the viewpoint of total charge, in the synthesis of the carboxyl group-containing compound (A), the number of moles of the amino compound (a11) is defined as _na11 , the total number of moles of the acid anhydrides (a12) and (a12 ′). When n _a12 is set, the molar ratio (n _a11 / n _a12 ) is usually set to 0.3 to 5.0, preferably 0.35 to 4.0, more preferably 0.40 to 3.0. Good. From the viewpoint of the compatibility of the carboxyl group-containing compound (A) in the thermosetting resin composition and the adhesion between the cured film formed from the thermosetting resin composition and the metal, the molar ratio is preferable.

  The total amount of the reaction solvent is usually 100 parts by weight with respect to a total of 100 parts by weight of the amino compound (a11), the acid anhydride (a12) and the acid anhydride (a12 ′) from the viewpoint of smoothly proceeding the reaction. As mentioned above, Preferably it is 100-500 weight part.

  The reaction solution or mixed solution obtained as described above contains the carboxyl group-containing compound (A) and the reaction solvent. The reaction solution or mixed solution containing the carboxyl group-containing compound (A) may be used as it is, or the carboxyl group-containing compound (A) may be isolated and used.

  The carboxyl group-containing compound (A), including the epoxy compound (C), can be contained in the thermosetting resin composition of the present invention at a high concentration, and the composition has a low viscosity. Therefore, when the thermosetting resin composition of the present invention is, for example, an inkjet ink, a relatively thick cured film (2 μm or more) can be formed by one jetting.

1.2.5.3 Order of addition of reaction raw materials to reaction system The order of addition of reaction raw materials to the reaction system is not particularly limited.

  In the synthesis of the amic acid (Ai), for example, a method in which the amino compound (a11) and the acid anhydride (a12) are simultaneously added to the reaction solvent, the acid anhydride (a12) is dissolved in the reaction solvent, and then the amino compound ( Any method such as a method of adding a11) or a method of adding an acid anhydride (a12) after dissolving the amino compound (a11) in a reaction solvent can be used.

  In the synthesis of the carboxyl group-containing ester compound (Aii), for example, the amino compound (a11) and the acid anhydride (a12) are mixed and reacted as described above, and then the obtained amide acid (Ai) or A method of isolating the imidized product (Ai) and mixing them with an acid anhydride (a12 ′) and a reaction solvent, mixing an amino compound (a11) and an acid anhydride (a12) as described above. Any method such as a method of adding an acid anhydride (a12 ′) after the reaction can be used. Further, the amino compound (a11), the acid anhydride (a12) (a part of which corresponds to the acid anhydride (a12 ′)) and the reaction solvent are mixed to obtain the amic acid (Ai) and the ester compound. The synthesis of (Aii) may proceed simultaneously.

1.2.6 Specific Example of Amide Acid (Ai) and Carboxyl Group-Containing Ester Compound (Aii) As a specific example of the amide acid (Ai), any one of formulas (Ai-1) to (Ai-3) However, it is not limited to these.

Specific examples of the carboxyl group-containing ester compound (Aii) include compounds represented by any one of formulas (Aii-1) to (Aii-8), but are not limited thereto.

In formula (Ai-1) to formula (Ai-3) and formula (Aii-1) to formula (Aii-8), X is synonymous with X in formula (A7), and Y is in formula (A8). Z is synonymous with Z in formula (A6), and “—CO—A—COOH” is a residue of a dicarboxylic anhydride or tetracarboxylic anhydride, for example, represented by formula (A7). Or a residue of the compound represented by the formula (A8), that is, A has the same meaning as X in the formula (A7), or the following formula (wherein Y represents Y in the formula (A8)) Which is synonymous.).

1.3 Inorganic fine particles (B)
The inorganic fine particles (B) are not particularly limited, but Si, Al, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr Y, Zr, Nb, Mo, Tc, Ru, Ag, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Oxides such as Tb, Dy, Ho, Er, Tm, Yb, and Lu, single salts such as sulfates, carbonates and fluorides, or double salts (such as MgAl ₂ O ₄ ).

  Among these, the inorganic fine particles (B) are preferably oxide particles of Group 4 element of the periodic table, and by adding fine particles having a high refractive index, the refractive index of the resulting cured film is further increased. be able to. Specific examples thereof include titanium oxide, zirconium oxide, hafnium oxide, and composite particles of these metal oxides and silicon oxide or tin oxide. From the viewpoint of increasing the refractive index of the resulting cured film, titanium oxide and Zirconium oxide is preferred.

  Since titanium oxide has photocatalytic activity, it is preferable to coat the particle surface with silicon oxide for use in optical applications. Titanium oxide has an anatase type and a rutile type depending on the crystal type, but a rutile type is preferred because of its high refractive index and excellent light resistance.

  When light is incident on the composition in which the inorganic fine particles (B) are dispersed in the thermosetting resin, Rayleigh scattering is caused by the dispersed particles. If this Rayleigh scattering is reduced, the irradiated light is not scattered in the composition. Can penetrate. For example, when the composition is cured to produce an electronic device sealant or the like, the light extraction efficiency as described above can be improved. Further, when the optical waveguide is produced by curing the composition, the light propagation loss of the optical waveguide is reduced because the scattering of the optical signal propagating through the optical waveguide is small. Since Rayleigh scattering is proportional to the cube of the particle size of the dispersed particles, the primary particle size of the inorganic fine particles (B) in the composition is preferably small in order to suppress the scattering.

  The primary particle diameter of the inorganic fine particles (B) in the thermosetting resin composition is 1 to 100 nm, preferably 1 to 50 nm, more preferably 5 to 15 nm. If the primary particle diameter is less than 1 nm, secondary aggregation is likely to occur and the cured film may be whitened. If it exceeds 100 nm, the surface uniformity during the formation of the thin film may be impaired. The inorganic fine particles (B) in the composition include those in the state of primary particles in which aggregation is completely loosened, and those in the state where a plurality of primary particles are aggregated. Here, the primary particle diameter of the inorganic fine particles (B) is the particle diameter of the particles that are not aggregated, and the particle diameter of the aggregate in which the primary particles are aggregated is the aggregated particle diameter. As a method of measuring the primary particle diameter of the inorganic fine particles (B) in the composition, a method of directly observing particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), or a light scattering method is used. There are methods.

  The refractive index (refractive index nD as a bulk material, not nanoparticles) of the inorganic fine particles (B) is 1.6 to 3.5, preferably 1.8 to 3.0, more preferably 2. 0 to 2.8.

  The inorganic fine particles (B) may be in the form of powder or a solvent dispersion. Examples of the dispersion medium include methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether and the like.

  Examples of commercially available products that can be used as the inorganic fine particles (B) include, for example, a titanium oxide nanofiller dispersion (ND-139 manufactured by Teika Co., Ltd., C007M manufactured by Gokoku Dye Co., Ltd.), and a zirconium oxide nanofiller dispersion (Gokoku). MHI B642M manufactured by Dye Co., B943M manufactured by Gokoku Dye Co., Ltd., ZR-011 manufactured by Solar Co., Ltd.), silicon oxide-coated anatase-type titanium oxide-methanol dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., Optorike series), oxidation Examples include silicon-coated tin oxide-containing rutile titanium oxide-methanol dispersion sol (manufactured by Teika, TS series), zirconium oxide-methyl ethyl ketone dispersion sol (manufactured by Osaka Cement, HXU-120JC), and the like.

  The content of the inorganic fine particles (B) is preferably 30 to 80% by weight with respect to the solid component in the thermosetting resin composition. When the content is 30% by weight or more, the refractive index change rate and the linear expansion coefficient depending on the temperature of the obtained cured product can be further reduced. A more preferable content is 50% by weight or more. When the content is 80% by weight or less, the obtained cured product becomes tough and cracks are hardly generated. In addition, when pattern processing is performed by a photolithography method, the residue of unexposed portions during development is reduced. A more preferable content is 70% by weight or less.

1.4 Refractive Index of Thermoplastic Resin Composition The refractive index of the thermoplastic resin composition is defined as the refractive index (nD) when the composition is a cured film, and is 1.6 to 3.0. Preferably it is 1.63-2.50, More preferably, it is 1.63-2.00, More preferably, it is 1.65-1.90, Most preferably, it is 1.65-1.85 Most preferably, it is 1.68 to 1.80. A refractive index (nD) is a refractive index with respect to the D line | wire of sodium and the light of wavelength 589.3nm, and the measuring method is as showing in an Example.

1.5 Epoxy compound (C)
The epoxy compound (C) is not particularly limited as long as it is a compound having oxirane or oxetane, but a compound having two or more oxiranes is preferable.

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

式（Ｃ１）中、ｐは１〜５０の整数である。

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

  Examples of the monomer having oxirane include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

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

  Preferred examples of the polymer of the monomer having oxirane and the copolymer of the monomer having oxirane and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, and benzyl methacrylate-glycidyl methacrylate copolymer. , N-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate copolymer, etc. Is mentioned. Use of these epoxy compounds is preferable because the cured film formed from the thermosetting resin composition of the present invention has good heat resistance.

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

  Commercially available products of the epoxy compound (C) include “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 828EL”, “Epicoat 190P”, “Epicoat”. "191P" (manufactured by Yuka Shell Epoxy Co., Ltd.), trade names "Epicoat 1001", "Epicoat 1004", "Epicoat 1256" (manufactured by Japan Epoxy Resin Co., Ltd.), trade names "Araldite CY177", Trade names “Araldite CY184” (available from The Ciba-Geigy Chemical Corp. (available from Huntsman Japan)), trade names “Celoxide 2021P”, “Celoxide 3000”, “EHPE-3150” (Daicel Chemical Industries ( Product name) "Techmore VG3101L" ( Made well Chemical Co., Ltd.), and the like. Among these, the product name “Araldite CY184”, the product name “Celoxide 2021P”, the product name “Techmore VG3101L”, the product name “Epicoat 828”, and the product name “Epicoat 828EL” have particularly good flatness of the resulting cured film. Therefore, it is preferable.

  As for an epoxy compound (C), only 1 type may be used and 2 or more types may be mixed and used for it.

  Although the density | concentration of the epoxy compound (C) in the thermosetting resin composition of this invention is not specifically limited, 1 to 80 weight% is preferable and 10 to 60 weight% is further more preferable. Within this concentration range, the cured film formed from the thermosetting resin composition of the present invention has good heat resistance, chemical resistance and flatness. In addition, the density | concentration of an epoxy compound (C) is a density | concentration with respect to the whole composition.

1.6 Epoxy curing agent (D)
The thermosetting resin composition of the present invention may further contain an epoxy curing agent (D) other than the carboxyl group-containing compound (A). Examples of the epoxy curing agent (D) include an acid anhydride curing agent, a phenol resin curing agent, an amine adduct, a polycarboxylic acid curing agent, a polyamine curing agent, and a catalyst curing agent. From the viewpoint of coloring and heat resistance, an acid anhydride curing agent is preferred.

  When the epoxy curing agent (D) is used, the epoxy curing agent (D) in the thermosetting resin composition is usually more than 0 parts by weight and 50 parts by weight with respect to 100 parts by weight of the carboxyl group-containing compound (A). Hereinafter, it is preferably contained in an amount exceeding 0 part by weight and not more than 40 parts by weight, more preferably exceeding 0 part by weight and not more than 30 parts by weight.

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

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

  Examples of the amine adduct include, but are not limited to, a reaction product of an amine and an epoxy, and three reaction products of a diamine, an acid anhydride, and an epoxy.

  Specific examples of reaction products of amines and epoxies include reaction products of S510 (manufactured by JNC) and 4-benzylpiperidine, and S510 (manufactured by JNC) and 3,5-dimethylpiperidine. Reaction product, reaction product of Epicoat 828EL (Oilized Shell Epoxy Co., Ltd.) and 3,5-dimethylpiperidine, reaction product of Epicoat 828EL (Oilized Shell Epoxy Co., Ltd.) and 4-hydropiperidine Things.

  Specific examples of the three reaction products of diamine, acid anhydride, and epoxy include a reaction product of 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of maleic anhydride. , S510 (manufactured by JNC Corporation) with 2 moles of reaction product, 1 mole of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 3- (triethoxysilyl) propyl succinic anhydride 1 Reaction product of 1 mol of reactant and 2 mol of S510 (manufactured by JNC), 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of maleic anhydride And a reaction product of 2 moles of N-glycidyl phthalimide, 1 mole of Polea SL-100A (Ihara Chemical Industry Co., Ltd.) and 1 mole of maleic anhydride, Such as 10 (manufactured by JNC (Ltd.)) the reaction product of two moles and the like.

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

1.7 Acrylic compound (E)
The acrylic compound (E) is not particularly limited as long as it is a compound such as a resin having an acrylic group or a methacryl group. The acrylic compound as the resin is, for example, a monofunctional polymerizable monomer having hydroxyl, a monofunctional polymerizable monomer having no hydroxyl, a bifunctional (meth) acrylate or a trifunctional or higher polyfunctional (meth) acrylate homopolymer, Or the copolymer of these monomers is mentioned. Acrylic compound (E) may use only 1 type and may mix and use 2 or more types.

  Specific examples of the monofunctional polymerizable monomer having hydroxyl include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono ( Mention may be made of (meth) acrylates. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferable from the viewpoint that the formed film can be made flexible.

Specific examples of the monofunctional polymerizable monomer having no hydroxyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3-methyl-3- (meth) acryloxy. Methyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl- 3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) ) Acryloxymethyl oxetane, (meth) acrylic acid, Chill (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, (meth) acrylamide, tricyclo [5.2.1. 0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate , Polystyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloylmorpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, (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] And mono [2- (meth) acryloyloxyethyl maleate] and mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate.

  Specific examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol. Diacrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol diacrylate, trimethylolpropane diacrylate, dipentaerythritol diacrylate Mention may be made of the over door.

  Specific examples of trifunctional or higher polyfunctional (meth) acrylates are trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified Trimethylolpropane 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, Pentaerythritol 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, Mention may be made of ethylene oxide-modified phosphoric acid tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, urethane (meth) acrylate.

  Although the density | concentration of the acrylic compound (E) in the thermosetting resin composition of this invention is not specifically limited, 0.1-20 weight% is preferable and 1-10 weight% is further more preferable. Within such a concentration range, the cured film formed from the thermosetting resin composition of the present invention has good heat resistance, chemical resistance and flatness.

1.8 Solvent (F)
The thermosetting resin composition of the present invention preferably further contains a solvent (F). The solvent (F) is not particularly limited as long as it can dissolve the carboxyl group-containing compound (A) and the epoxy compound (C). Even if the solvent alone does not dissolve the carboxyl group-containing compound (A) or the epoxy compound (C), the carboxyl group-containing compound (A) or the epoxy compound (C) is dissolved by mixing with another solvent. In such a case, such a mixed solvent can be used as the solvent (F).

  The boiling point of the solvent (F) is usually 150 to 300 ° C, preferably 150 to 250 ° C.

  As the solvent (F), ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Mechi Ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butyl ether) Xyl-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene Glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2 -Pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1 3-dimethyl-2-imidazolidinone, etc. γ- butyrolactone.

  Among the solvents (F), N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, because compatibility with other components in the thermosetting resin composition is good and the composition has a low viscosity. Preferred are methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyrolactone.

  Only 1 type may be used for a solvent (F), and 2 or more types may be mixed and used for it.

  The solvent (F) is preferably used in such a proportion that the solid content concentration in the thermosetting resin composition of the present invention is 30 to 80% by weight, particularly 30 to 75% by weight. In addition, solid content means all components other than the solvent (F) in a thermosetting resin composition. When the reaction solution or mixed solution obtained at the time of synthesizing the carboxyl group-containing compound (A) was mixed with other components as it was, the solvent (F) was used at the time of synthesizing the carboxyl group-containing compound (A). A reaction solvent is also included.

1.9 Other Additives The thermosetting resin composition of the present invention may contain additives depending on the intended characteristics. Examples of the additive include an antistatic agent, a coupling agent, a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, a surfactant, a filler, an antireductant, an evaporation accelerator, and a chelate. And a water-soluble polymer. Only one type of additive may be used, or two or more types may be mixed and used.

<Antistatic agent>
The antistatic agent can be used to prevent the composition from being charged, and is preferably used in an amount of 0 to 20% by weight in the composition. 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.

<Coupling agent>
The coupling agent is not particularly limited, and a known coupling agent such as a silane coupling agent can be used for the purpose of improving adhesion to glass or ITO. The silane coupling agent mainly serves as an adhesion aid for favorably bonding a cured film obtained from a thermosetting resin composition to an organic EL panel, a protective substrate, or the like. The coupling agent is preferably added and used so that the solid content of the composition (residue obtained by removing the solvent from the composition) is 100 parts by weight. A coupling agent may use only 1 type and may mix and use 2 or more types.

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

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

  Moreover, you may use the polycondensation product of these compounds. Specifically, Coatosil MP200 (product name: MOMENTIVE) is mentioned.

<Antioxidant>
When the thermosetting resin composition contains an antioxidant, it is possible to prevent deterioration when a cured film obtained from the composition is exposed to high temperature or light. The antioxidant is preferably added in an amount of 0 to 3 parts by weight with respect to 100 parts by weight of the solid content of the composition excluding the antioxidant (residue obtained by removing the solvent from the composition). Only 1 type may be used for antioxidant and 2 or more types may be mixed and used for it.

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

<Surfactant>
When the thermosetting resin composition contains a surfactant, it is possible to obtain a composition with improved wettability, leveling properties, and applicability to the base substrate. The surfactant is preferably used in an amount of 0.01 to 1% by weight based on the total weight of the composition. Only one surfactant may be used, or two or more surfactants may be mixed and used.

  As the surfactant, for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-310”, “BYK-” can be used from the viewpoint of improving the coating property of the composition. Silicone surfactants such as “341”, “BYK-344”, “BYK-370” (manufactured by BYK Japan Japan); trade names “BYK-354”, “BYK-358”, “BYK-361” Acrylic surfactants (such as Big Chemie Japan Co., Ltd.) and the like; Fluorosurfactants such as trade names “DFX-18”, “Fargent 250”, “Furgent 251” (manufactured by Neos) Is mentioned.

<Filler>
The thermosetting resin composition of the present invention may contain a filler as long as the high refractive index and / or high transmittance is not impaired. The filler is not particularly limited, for example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, Examples include inorganic fillers such as glass beads, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. .

1.10 Preparation Method of Thermosetting Resin Composition The thermosetting resin composition of the present invention comprises a carboxyl group-containing compound (A), inorganic fine particles (B), and an epoxy compound (C), epoxy as necessary. It can be prepared by uniformly mixing the curing agent (D), the acrylic compound (E), the solvent (F), and other additives. The thermosetting resin composition of the present invention can also be prepared by uniformly mixing the reaction solution or mixed solution obtained during the synthesis of the carboxyl group-containing compound (A) with other components as it is. . In the reaction solution or mixed solution, at least one carboxyl group-containing compound (A) selected from amic acid (Ai) and a carboxyl group-containing ester compound (Aii), an imidized product (Ai), a reaction solvent, and the like Is included.

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

  The obtained coating film is then heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 120 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  For example, in the case of forming a transparent insulating film provided from the thermosetting resin composition so that the X and Y electrodes do not come into contact with each other, a gravure printing method, a flexographic printing method, and an offset printing method are used in that pattern formation is easy. Printing methods such as a printing method, a dispenser method, a screen printing method and an ink jet printing method are preferred. Further, for example, when the overcoat is formed from a thermosetting resin composition, the spin coating method, the slit die coating method, the gravure printing method, the flexographic printing method, the offset printing method, Coating methods such as a dispenser method and a screen printing method are preferred.

2. Ink-jet ink When the thermosetting resin composition of the present invention is used as an ink-jet ink, various parameters such as viscosity, surface tension, and boiling point of the solvent can be optimized and used for ink-jet printing. Ink jet printability (for example, drawability) is exhibited and storage stability is also excellent.

2.1 Viscosity of inkjet ink The viscosity at the temperature (ejection temperature) when ejecting the inkjet ink of the present invention from the inkjet head is usually 1 to 50 mPa · s, preferably 5 to 20 mPa · s, more preferably 8 ~ 15 mPa · s. When the viscosity is in the above range, jetting accuracy by the ink jet coating method is improved. If the viscosity is less than 15 mPa · s, ink jet ejection defects do not occur.

  Since jetting is often performed at room temperature (25 ° C.), the viscosity of the inkjet ink of the present invention at 25 ° C. is usually 1 to 50 mPa · s, preferably 5 to 20 mPa · s, more preferably 8 to 15 mPa · s. s. If the viscosity at 25 ° C. is less than 15 mPa · s, ink jet ejection defects do not occur.

2.2 Surface Tension of Inkjet Ink The surface tension of the inkjet ink of the present invention at 25 ° C. is usually 20 to 70 mN / m, preferably 20 to 40 mN / m. When the surface tension is in the above range, good droplets can be formed by jetting and a meniscus can be formed.

2.3 Ink-jet ink application method The ink-jet ink application method of the present invention comprises the steps of applying the above-described ink-jet ink by the ink-jet application method to form a coating film, and curing the coating film. Have.

  The ink of the present invention can be ejected by various methods by appropriately selecting the contained components. According to the inkjet coating method, the inkjet ink of the present invention is applied in a predetermined pattern. Can do.

  When the ink of the present invention is applied by an ink jet application method, there are various types depending on the ink discharge method. Examples of the discharge method include a piezoelectric element type, a bubble jet (registered trademark) type, a continuous injection type, and an electrostatic induction type.

  A preferred ejection method when coating using the inkjet ink of the present invention is a piezoelectric element type. The piezoelectric element-type head includes a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite to the nozzles, and ink filling the periphery of the pressure generating element. An on-demand ink jet coating head displaces a pressure generating element by an applied voltage and ejects a small droplet of ink from a nozzle.

  The ink jet coating apparatus is not limited to the configuration in which the coating head and the ink storage unit are separated from each other, and may be configured such that they are integrated so as not to be separated. The ink container is integrated with the coating head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the apparatus via an ink supply member such as a tube. It may be in the form of supplying ink to the coating head.

  Further, when the ink tank is provided with a configuration for applying a preferable negative pressure to the coating head, a configuration in which an absorber is disposed in the ink storage portion of the ink tank, or a flexible ink storage bag and this On the other hand, it is possible to adopt a form having a spring portion for applying an urging force in the direction of expanding the internal volume. In addition to the serial coating method, the coating apparatus may take the form of a line printer in which coating elements are aligned over a range corresponding to the entire width of the coating medium.

3. Cured film or patterned cured film The cured film or patterned cured film of the present invention is a process in which the thermosetting resin composition of the present invention is used as, for example, an inkjet ink and is applied by an inkjet coating method to form a coating film. And a step of curing the coating film. Heat treatment such as a hot plate or an oven can be used for forming the cured film.

  After forming the above-mentioned coating film, the solvent is usually removed by vaporization or the like by heating with a hot plate or oven, that is, drying. The drying conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 120 ° C., and 5 to 15 minutes when using an oven, and 1 to 5 minutes when using a hot plate. By such drying, a coating film having a shape capable of holding the shape on the substrate is formed. In addition, the formation of the cured film is not limited to heat treatment, and treatment such as UV treatment, ion beam, electron beam, and gamma ray can also be used.

  When ink is printed in a pattern using an ink jet coating method, a patterned cured film (patterned cured film) is formed. In the present specification, unless otherwise stated, hereinafter, the cured film includes a patterned cured film.

  The insulating film made of the cured film of the present invention, for example, for printed wiring board use or semiconductor use, exhibits good adhesion with a substrate, has high heat resistance and high electrical insulation, has sufficient mechanical strength, The amount of warpage is small, and the reliability and yield of electronic devices can be improved.

4). Substrate with cured film The substrate with a cured film of the present invention has a film substrate or a silicon wafer substrate, and a cured film or a patterned cured film formed on the substrate by the above-described method for forming a cured film. For example, the inkjet ink of the present invention is applied to the entire surface or a predetermined pattern (line shape, etc.) by an inkjet application method on a substrate such as a polyimide film or a silicon wafer substrate on which wiring is formed, and then described above. As described above, the substrate is dried and further heated to form a cured film.

  The cured film of the present invention is preferably formed on the above-described film substrate or silicon wafer substrate, but the type of the substrate is not particularly limited to these and can be formed on a known substrate.

  As a substrate applicable to the present invention, for example, a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, conforming to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668, Examples include paper epoxy substrates, green epoxy substrates, and BT resin substrates.

  Other substrates applicable to the present invention include, for example, a substrate made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless steel (these metals on the surface) Aluminium oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate, titanic acid Lead (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 A substrate made of ceramics such as zinc oxide, boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel, or spodumene (may be a substrate having such ceramics on the surface); PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylenedimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, Polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic A substrate made of a resin such as a lastomer or a liquid crystal polymer (may be a substrate having such a resin on its surface); a semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO, Or a substrate on which an electrode material such as ATO is formed; a gel sheet such as αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel), or γGEL (gamma gel) (which is a registered trademark of Taika Co., Ltd.) It is done.

5. Electronic Device An electronic device of the present invention is an electronic device having the above-mentioned substrate with a cured film. A flexible electronic device can be obtained by using the substrate with a cured film of the present invention. Moreover, a semiconductor electronic device is obtained by applying the cured film of this invention to a silicon wafer substrate.

6). Optical waveguide Since the cured product obtained from the thermosetting resin composition of the present invention has a high refractive index, it is preferably used for an optical waveguide. The optical waveguide is formed on a circuit board such as an electronic device and has a function of transmitting an optical signal between ICs mounted on the board. The optical waveguide includes a core part through which an optical signal propagates and a cladding part having a lower refractive index than the core part surrounding the core part. Examples of the optical waveguide include a channel type optical waveguide having a structure in which a cladding portion surrounds a linear core portion, and a slab type optical waveguide having a structure in which a layered cladding portion covers the upper and lower sides of a layered core portion. However, the cured product obtained from the thermosetting resin composition of the present invention can be used in either case, and may be used in both the core part and the cladding part, or only in one of them. Also good.

  The refractive index and thickness of the cladding portion and the core portion of the optical waveguide can be arbitrarily selected depending on the optical waveguide to be designed. In the case of a multimode optical waveguide, it is suitable to increase the refractive index difference between the core part and the cladding part to make the core part thicker. In the case of a single mode optical waveguide, the difference in refractive index between the core portion and the cladding portion is reduced, and the core portion is thinned so that single mode propagation is realized.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. The names of components used in Examples and Comparative Examples are indicated by abbreviations. This abbreviation is used in the following description.

<Evaluation of resin composition>
The measurement method or evaluation method for each evaluation item was according to the following method.

(1) Viscosity Viscosity at 25 ° C. was measured using a viscometer TVE-25 manufactured by Toki Sangyo Co., Ltd.

(2) Weight average molecular weight The weight average molecular weights of (poly) esteramic acid, (poly) amic acid and polyimide were measured as follows.
The obtained (poly) esteramidic acid, (poly) amidic acid or polyimide is diluted with N, N-dimethylformamide (DMF) so that its concentration is about 1% by weight, and GPC apparatus: JASCO Corporation , Manufactured by Chrom Nav (differential refractometer RI-2031 Plus), measured by the GPC method using the diluent as 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 measured under conditions of a column temperature of 40 ° C. and a flow rate of 0.5 mL / min. .

(3) Evaluation of storage stability Storage stability was evaluated using a test tube. Storage stability was evaluated by visual inspection after preparing the finger and after being stored at room temperature of 25 ° C., and confirmed whether there was precipitation or whether it was cloudy. When there was no change, it was marked as ◯, when precipitation occurred, it was marked as ×, and when clouding was progressing, it was marked as △.

(4) Film thickness After applying a resin on a glass substrate and thinning it by spin coating, it is dried on a hot plate at 80 ° C. for 5 minutes and baked at 120 ° C. for 30 minutes in a hot air circulating oven, or a metal halide lamp Was fired at ² J / cm ² to prepare a cured film. The thickness of this cured film was measured using a stylus type film thickness meter Alpha Step P-17 (manufactured by KLA-Tencor). Moreover, the sample in which the fine crack was contained in the cured film was set to “crack” in the evaluation result column.

(5) Optical characteristics Spectrophotometer V-670 (manufactured by JEOL Ltd.), reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.), and Heizometer haze-gard plus (manufactured by BYK Co., Ltd.) ) Was used to measure the transmittance (400 nm), total light transmittance, refractive index (nD), and haze value of the cured film.

(6) Curability The cured film was immersed in propylene glycol monomethyl ether (PGME) for 10 minutes together with the glass substrate, and the appearance of the film was observed. No change was indicated as ◯, and dissolved and white turbidity was indicated as X. In addition, the thing of subsequent physical-property measurement has not been implemented for the thing of evaluation of sclerosis | solid.

<Preparation of Invention Composition and Comparative Composition>
Next, a method for preparing the inventive composition and the comparative composition according to the present invention will be described.

Synthesis Example (1): Polyester amide acid 30% by weight solution (a)
To a 1000 mL separable flask equipped with a thermometer, stirring blades, raw material charging inlet and nitrogen gas inlet, dehydrated and purified MMP (446.96 g), 1,4-butanediol (31.93 g), benzyl alcohol ( 25.54 g) and ODPA (183.20 g) were charged and stirred at 130 ° C. for 3 hours under a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 ° C., DDS (29.33 g) and MMP (183.04 g) 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 less, a pale yellow transparent polyester amic acid 30 wt% solution (a) was obtained. The viscosity of this solution was 28.1 mPa · s. Moreover, the weight average molecular weight of the obtained polyester amide acid was 4,200.

Synthesis Example (2): 25% by weight polyamic acid solution (b)
In a 1000 mL separable flask equipped with a thermometer, stirring blades, raw material charging inlet and nitrogen gas inlet, dehydrated and purified EDM (483.6 g), FM-3311 (45.2 g), S330 (60.00 g) Was charged and dissolved. Thereafter, ODPA (56.0 g) was added, and the mixture was stirred at 40 ° C. for 5 hours under a dry nitrogen stream. As a result, a pale yellow transparent polyamic acid 25 wt% solution (b) was obtained. The viscosity of this solution was 7.3 mPa · s. Moreover, the weight average molecular weight of the obtained polyamic acid was 3,400.

Synthesis Example (3): 30% by weight solution of ester amic acid (c)
AEE (2.393 g) and EDM (21 g) were placed in a screw tube bottle, and MA (2.232 g) was further added, followed by stirring for 3 hours. Thereafter, TMA (4.374 g) was added and stirred for 3 hours on a hot stirrer at 110 ° C. to obtain a uniform 30% by weight solution (c) of ester amic acid. The viscosity of this solution was 41.8 mPa · s. Moreover, the weight average molecular weight of the obtained ester amide acid was 539.

Synthesis Example (4): 30% by weight solution of ester amic acid (d)
AEE (4.188 g) and EDM (21 g) were placed in a screw tube bottle, and MA (3.906 g) was further added, followed by stirring for 3 hours. Thereafter, MA (3.906 g) was added and stirred on a hot stirrer at 110 ° C. for 3 hours to obtain a uniform 30% by weight solution (d) of ester amic acid. The viscosity of this solution was 7.3 mPa · s. Moreover, the weight average molecular weight of the obtained ester amide acid was 450.

Synthesis Example (5): 30% by weight solution of amic acid (e)
BAPP (3.7652 g) and EDM (21 g) were placed in a screw tube bottle and stirred until dissolved, then MA (0.8994 g) was added and stirred for 3 hours. Thereafter, S510 (4.3354 g) was added and stirred for 3 hours on a hot stirrer at 110 ° C. to obtain a uniform 30 wt% solution (e) of amic acid. The viscosity of this solution was 5.08 mPa · s.

Synthesis Example (6): 20% by weight solution of amic acid (f)
FM-3311 (3.344 g) and EDM (16 g) were placed in a screw tube bottle and further reacted with MA (0.6559 g). As a result, a uniform 20% by weight solution of amic acid (f) Got. The viscosity of this solution was 2.54 mPa · s.

Synthesis Example (7): 40% by weight solution of amic acid (h)
Dehydrated and purified EDM (600.0 g) and S330 (168.42 g) were charged and dissolved in a 2000 mL separable flask equipped with a thermometer, a stirring blade, a raw material charging inlet and a nitrogen gas inlet. Thereafter, TESA (231.57 g) was slowly added, and the mixture was stirred at 25 ° C. for 3 hours under a stream of dry nitrogen to obtain a 40% by weight solution (h) of a pale yellow transparent amic acid. The viscosity of this solution was 8.0 mPa · s. Moreover, the weight average molecular weight of the obtained amic acid was 1,200.

Preparation Example (1): Composition (A)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and the ester amic acid solution (c) (10.39 g) obtained in Synthesis Example (3) was obtained in Synthesis Example (4). Ester amic acid solution (d) (10.39 g), VG3101L (26.60 g), TMA (4.051 g), amic acid solution (e) (3.463 g) obtained in Synthesis Example (5), synthesis The amic acid solution (f) (0.050 g) obtained in Example (6) and dehydrated and purified EDM (45.05 g) were charged and stirred at room temperature for 1 hour to dissolve each component uniformly. Subsequently, it filtered with the membrane filter (0.2 micrometer) and obtained the composition (A). The viscosity of this composition (A) was 8.1 mPa · s.

Preparation Example (2): Composition (B)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and the polyester amic acid solution (a) (11.57 g) obtained in Synthesis Example (1) and EG-200 (13.96 g) were added to the flask. , TMA (1.041 g), S510 (0.555 g), Irganox 1010 (0.0583 g), U-cat SA506 (0.4000 g), PGME (1.200 g) and dehydrated and purified MTM (21.11 g) The mixture was stirred at room temperature for 1 hour to dissolve each component uniformly. Next, the polyamic acid solution (b) (0.1 g) obtained in Synthesis Example (2) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to obtain the composition (B). Obtained. The viscosity of this composition (B) was 8.0 mPa · s.

Preparation Example (3): Composition (C)
A 100 mL three-necked flask equipped with a stirring blade was purged with nitrogen, and the ester amic acid solution (c) (10.39 g) obtained in Synthesis Example (3) was obtained in Synthesis Example (4). Ester amide acid solution (d) (10.39 g), amide acid solution (e) (3.463 g) obtained in Synthesis Example (5), VG3101L (26.60 g), TMA (4.051 g), EDM ( 45.00 g) and the amic acid solution (f) (0.05 g) obtained in Synthesis Example (6) were charged and stirred at room temperature for 1 hour to dissolve each component uniformly. Subsequently, it filtered with the membrane filter (0.2 micrometer), and obtained the composition (C). The viscosity of this composition (C) was 12.0 mPa · s.

Example 1: Invention composition (1)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and ND-139 (25.00 g) and the composition (A) (25.00 g) obtained in Preparation Example (1) were charged into the flask. The mixture was stirred at room temperature for 1 hour to uniformly dissolve each component, and the invention composition (1) was obtained. The evaluation results of the inventive composition (1) are shown in Table 2.

Examples 2 to 9: Invention compositions (2) to (9)
As shown in Table 2, invention compositions (2) to (9) were prepared under the same conditions as in Example 1. Table 2 shows the evaluation results of the inventive compositions (2) to (9).

Comparative Example 1: Comparative composition (1)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and the composition (A) (25.00 g) obtained in Preparation Example (1) was charged into the flask and stirred at room temperature for 1 hour. A composition (1) was obtained. Table 2 shows the evaluation results of the comparative composition (1).

Comparative Example 2: Comparative composition (2)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and the composition (B) (25.00 g) obtained in Preparation Example (2) was charged into the flask, and stirred at room temperature for 1 hour. A composition (2) was obtained. The evaluation results of the comparative composition (2) are shown in Table 2.

Comparative Example 3: Comparative composition (3)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and the composition (C) (25.00 g) obtained in Preparation Example (3) was charged into the flask and stirred at room temperature for 1 hour. A composition (3) was obtained. The evaluation results of the comparative composition (3) are shown in Table 2.

Comparative Example 4: Comparative composition (4)
A 100 mL three-necked flask equipped with a stirring blade was purged with nitrogen, and ND-139 (25.00 g), EG-200 (7.500 g) and TMA (2.500 g) were charged into the flask at room temperature. The mixture was stirred for 1 hour to uniformly dissolve each component, thereby obtaining a comparative composition (4). The evaluation results of the comparative composition (4) are shown in Table 2.

Comparative Example 5: Comparative composition (5)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and B943M (25.00 g) and the amic acid solution (h) (10.00 g) synthesized in Synthesis Example (8) were charged into the flask. The mixture was stirred at room temperature for 1 hour to uniformly dissolve each component, thereby obtaining a comparative composition (5). The evaluation results of the comparative composition (5) are shown in Table 2.

Comparative Example 6: Comparative composition (6)
A 100 mL three-necked flask equipped with stirring blades was purged with nitrogen, and ND-139 (25.00 g), M-208 (10.00 g) and IRGACURE 184 (1 g) were charged into the flask for 1 hour at room temperature. Stirring and dissolving each component uniformly to obtain a comparative composition (6). The evaluation results of the comparative composition (6) are shown in Table 2. In addition, this composition was hardened | cured by exposing at 2000 mJ / cm < ² > after drying at 80 degreeC for 5 minutes.

  As mentioned above, invention composition (1)-(9) not only is excellent in storage stability and sclerosis | hardenability, but the cured film has a high refractive index and transparency. On the other hand, the cured films obtained from the comparative compositions (1) to (3) and (6) had a poor refractive index, and the cured films obtained from the comparative compositions (4) and (5) had a poor curability.

  The curable resin composition of the present invention is a high refractive index and / or high transmittance thermosetting resin composition that can be used, for example, as a sealant for an electronic device such as an organic EL element, a transparent insulating film, or an overcoat. For example, it is possible to improve the light extraction efficiency, which is a problem of the top emission type organic EL element which has been mainstream in recent years. Furthermore, according to a preferred embodiment, since the thermosetting resin composition is excellent in storage stability, it is possible to realize an advantageous work process from this point.

Claims (12)

  A thermosetting resin composition containing a carboxyl group-containing compound (A) and inorganic fine particles (B) having a primary particle diameter of 1 to 100 nm, and having a refractive index (nD) of 1.6 to 1.6 when a cured film is formed. A thermosetting resin composition of 3.0. The compound having a carboxyl group-containing compound (A) having at least one of a structural unit represented by formula (A1) and a structural unit represented by formula (A2), and formula (Ai-1) to formula (Ai) -3) The thermosetting resin composition according to claim 1, which is at least one selected from compounds represented by formulas (Aii-1) to (Aii-8).

(In Formula (A1) and Formula (A2), 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.)

(In the formulas (Ai-1) to (Ai-3) and (Aii-1) to (Aii-8), X is independently any one of the following divalent groups;

Y is independently a tetravalent organic group having 1 to 30 carbon atoms, Z is a divalent organic group, and “—CO—A—COOH” is a residue of a dicarboxylic acid anhydride or a tetracarboxylic acid anhydride. It is. )   Furthermore, the thermosetting resin composition of Claim 1 or 2 containing an epoxy compound (C).   Furthermore, the thermosetting resin composition in any one of Claims 1-3 containing an epoxy hardening | curing agent (D).   The thermosetting resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing compound (A) is a carboxyl group-containing compound (A) obtained by further reacting with a styrene-maleic anhydride copolymer. object.   Furthermore, the thermosetting resin composition in any one of Claims 1-5 containing an acrylic compound (E).   Furthermore, the thermosetting resin composition in any one of Claims 1-6 containing a solvent (F).   An ink-jet ink comprising the thermosetting resin composition according to claim 1.   The resin composition for slit die coaters containing the thermosetting resin composition in any one of Claims 1-7.   Screen printing ink containing the thermosetting resin composition in any one of Claims 1-7.   Hardened | cured material which hardened the thermosetting resin composition in any one of Claims 1-7.   An electronic device having a cured product obtained by curing the thermosetting resin composition according to claim 1.