JP2016160420A - Thermosetting composition, cured film, substrate with cured film, electronic component, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that can form a cured film having excellent chemical resistance and adhesiveness to a substrate (adherend) such as glass in a well-balanced manner; a color ink for ink jet printing using the composition; and a touch panel using the color ink.SOLUTION: A thermosetting composition contains a resin (A) having styrene and a maleic anhydride structure, and an epoxy compound (B) having a 9,9-bisphenyl fluorene skeleton, and further contains a silsesquioxane-containing epoxy compound (D).SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting composition and use thereof. Specifically, the present invention relates to a thermosetting composition, a cured film obtained using the composition, the substrate with the cured film, the electronic component having the cured film or the substrate with the cured film, and a display device About.

  In recent years, as an input device, a touch panel type input device in which a liquid crystal display device or an organic electroluminescence device and a position detection device are combined has become widespread. A touch panel type input device is an input device that detects a contact position when a finger or the tip of a pen is brought into contact with a display screen.

  There are various detection methods for touch panel type input devices, such as a resistance film method and a capacitance method. For example, the capacitance method uses a device having a structure in which X and Y electrodes are arranged in a matrix on a glass substrate, and detects a change in capacitance caused by contact of a fingertip or the like as a change in current. It is a method. In recent years, such a capacitance method has become mainstream in small and mobile devices. Among them, a so-called OGS (one glass solution) type touch panel, in which a cover glass and a sensor substrate are integrated, is often used.

  In general, a cover glass or the like is provided on the outermost surface of the touch panel type input device, and the cover glass or the like is provided with a light shielding portion (generally, in order to suppress light leakage from the light source and hide peripheral wiring and the like. Is also referred to as a frame portion). The light shielding part is required to have light shielding properties for its use, and black is mainly used for cost reduction. In addition, various colors and patterns may be applied to the light shielding portion according to the design of the touch panel type input device.

  Conventionally, such a light shielding portion has been generally formed by screen printing. However, in screen printing, it is not usually possible to reduce the thickness of the light shielding portion obtained. For this reason, the light-shielding portion becomes thick, which causes problems such as an increase in the thickness of the entire touch panel type input device and an increase in manufacturing cost. There was also a risk of breaking existing wiring.

  On the other hand, inkjet printing is known as a technique for forming a thin film. This ink-jet printing is a plateless system, is on-demand printing, and can be manufactured at a low cost, so that it is desired to be used in various fields.

  For this ink jet printing, color ink compatible with ink jet is used, and examples of such color ink include color inks described in Patent Documents 1 and 2.

JP 2009-223127 A JP 2011-123331 A

  The light shielding part used in the OGS type touch panel is required to have chemical resistance since it is necessary to perform a manufacturing process of the ITO electrode by photolithography after the light shielding part is formed. However, the color inks described in the above-mentioned patent documents tend to be poor in chemical resistance and adhesion to a substrate (adhered body) such as glass, and therefore tend not to be used as such a light shielding part. It was.

  In addition, an insulating film is usually used for components such as electronic components used in electric / electronic devices and the like. For example, an application example of the capacitive touch panel includes an interlayer insulating film between an X electrode and an Y electrode of an ITO electrode. This insulating film is also required to have chemical resistance and adhesion to a substrate (adhered body) such as glass, like the light shielding portion.

  The object of the present invention has been made in view of the above requirements, and is capable of forming a cured film having excellent balance in chemical resistance and adhesion to a substrate (adhered body) such as glass. It is in providing a resin composition and its use.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a thermosetting composition having the following constitution, and have completed the present invention.

[1]
A thermosetting composition comprising a resin (A) having a structural unit represented by formula (1) and formula (2), and an epoxy compound (B) having a fluorene skeleton represented by formula (3).

（式（３）中、「＊」は結合手を示し、また同式中のベンゼン環上の水素原子はシアノ、ハロゲン原子、アルキルまたはメトキシフェニルによって置き換えられていてもよい。）

(In formula (3), “*” represents a bond, and the hydrogen atom on the benzene ring in the formula may be replaced by cyano, halogen atom, alkyl or methoxyphenyl.)

[2]
The thermosetting composition according to [1], wherein the resin (A) is a copolymer of styrene and maleic anhydride.

[3]
Furthermore, the thermosetting composition as described in [1] or [2] which has an epoxy compound (C) which does not have a fluorene skeleton and a silsesquioxane skeleton.

[4]
The thermosetting composition according to any one of [1] to [3], wherein the epoxy compound (B) having a fluorene skeleton is a compound represented by the formula (4).

（式中、Ｒ¹は独立して、シアノ、ハロゲン原子またはアルキルを示し、Ｒ²は独立して、水素、アルキルまたはメトキシフェニルを示し、Ｒ³は独立して、２価の有機基を示し、ｎは独立して、０〜４の整数を示し、ｍは独立して、０〜４の整数を示し、ｋは独立して、１〜４の整数を示す。）

(Wherein R ¹ independently represents cyano, halogen atom or alkyl, R ² independently represents hydrogen, alkyl or methoxyphenyl, and R ³ independently represents a divalent organic group. , N independently represents an integer of 0-4, m independently represents an integer of 0-4, and k independently represents an integer of 1-4.)

[5]
The thermosetting composition according to any one of [1] to [4], wherein the epoxy compound (B) having a fluorene skeleton is a compound represented by the formula (5).

（式中、Ｒ⁴は独立して、炭素数２〜４のアルキレンを示し、ｊは独立して、０〜４の整数を示し、Ｒ²は独立して、水素、アルキルまたはメトキシフェニルを示す。）

(In the formula, R ⁴ independently represents alkylene having 2 to 4 carbon atoms, j independently represents an integer of 0 to 4, and R ² independently represents hydrogen, alkyl or methoxyphenyl. .)

[6]
The thermosetting composition according to any one of [1] to [5], wherein the epoxy compound (B) having a fluorene skeleton is a compound represented by the formula (6).

（式中、ｊは独立して、０〜４の整数を示す。）

(In the formula, j independently represents an integer of 0 to 4.)

[7]
Furthermore, the thermosetting composition in any one of [1]-[6] containing the silsesquioxane (D) represented by Formula (7).

（式中、Ｒ⁵は独立して、炭素数１〜４５のアルキル、炭素数４〜８のシクロアルキル、炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキルから選択される基であり；炭素数１〜４５のアルキルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、隣接しない少なくとも１つの−ＣＨ₂−は、−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキル中のベンゼン環において、少なくとも１つの水素はハロゲンまたは炭素数１〜１０のアルキルで置き換えられてもよく、この炭素数１〜１０のアルキルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、また、炭素数１〜１０のアルキルの隣接しない少なくとも１つの−ＣＨ₂−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールアルキル中のアルキルの炭素数は１〜１０であり、隣接しない少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく；Ｒ⁶およびＲ⁷はそれぞれ独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり；Ｘは独立して、オキシラニル、オキシラニレン、３，４−エポキシシクロヘキシル、オキセタニルまたはオキセタニレンを有する基である。）

Wherein R ⁵ is independently a group selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms. Yes; in alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced with fluorine, and at least one non-adjacent —CH ₂ — may be replaced with —O— or —CH═CH—. In the benzene ring in aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; And at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ that is not adjacent to the alkyl having 1 to 10 carbons. - it may be replaced by -O- or -CH = CH-; number of carbon atoms in the alkyl in arylalkyl is 1-10, at least one -CH nonadjacent ₂ - is replaced by -O- R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl; X is independently oxiranyl, oxiranylene, 3,4-epoxy. A group having cyclohexyl, oxetanyl or oxetanylene.)

[8]
The thermosetting composition according to [7], wherein R ⁵ in the formula (7) is cyclohexyl or phenyl, and X is a group represented by any one of formulas (a) to (d).

（式（ａ）〜（ｄ）中、「＊」は結合手を示す。）

(In formulas (a) to (d), “*” represents a bond.)

[9]
The thermosetting composition according to [8], wherein R ⁵ in the formula (7) is phenyl, R ⁶ and R ⁷ are methyl, and X is a group represented by the formula (b).

[10]
Furthermore, the thermosetting composition in any one of [1]-[9] which has a black pigment (E).

[11]
The thermosetting according to [10], wherein the black pigment (E) is at least one selected from carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black and titanium black. Composition.

[12]
The thermosetting composition according to [10], wherein the black pigment (E) is at least one selected from carbon black and titanium black.

[13]
The thermosetting composition according to any one of [10] to [12], wherein the black pigment (E) has an average particle size of 10 to 3000 nm.

[14]
The thermosetting composition according to any one of [10] to [12], wherein the average particle size of the black pigment (E) is 20 to 1500 nm.

[15]
The thermosetting composition according to any one of [10] to [12], wherein the average particle size of the black pigment (E) is 30 to 800 nm.

[16]
Furthermore, the thermosetting composition in any one of [1]-[15] containing a solvent (F).

[17]
The thermosetting composition according to any one of [1] to [16], which is an inkjet ink.

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

[19]
The board | substrate with a cured film which has a board | substrate and the cured film as described in [18].

[20]
An electronic component having at least one selected from the cured film according to [18] and the substrate with the cured film according to [19].

[21]
A display device having a light transmissive portion and a light shielding portion, wherein the light shielding portion includes the cured film according to [18].

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting composition which can form the cured film which is excellent in chemical-resistance and the adhesiveness to substrates (adhered bodies), such as glass, can be obtained.
Further, according to the present invention, a thermosetting composition (color ink) having excellent jetting properties, in particular, a cured film having excellent light shielding properties and excellent effects as described above can be formed while having excellent jetting properties. A thermosetting composition can be obtained.
Therefore, this thermosetting composition is used for forming an insulating film used for electronic parts used in electric / electronic devices, etc., and for light shielding formed on a cover glass of a display device such as a touch panel type input device. An electronic component that is suitably used for forming a portion (frame portion) and that is excellent in terms of performance, durability, thickness reduction, low cost, and the like can be easily obtained.

1. Thermosetting Composition The thermosetting composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) contains a specific resin (A) and an epoxy compound (B) having a specific fluorene skeleton. If it does not specifically limit.
Thus, since the composition of this invention contains resin (A) and an epoxy compound (B), it can form the cured film which is excellent in chemical resistance and the adhesiveness to substrates, such as glass, with good balance. it can. Such an effect is an effect found for the first time using the resin (A) and the epoxy compound (B) at the same time.

  Usually, the chemical resistance of the cured film obtained from the thermosetting composition is improved as the crosslinking density of the cured film is increased. On the other hand, when a composition that increases the crosslink density of the cured film is used, curing shrinkage tends to occur when the cured film is formed, and as a result, it has sufficient adhesion to a substrate such as glass. A cured film cannot be obtained. In other words, there is a trade-off between the chemical resistance of the cured film and the adhesion to a substrate such as glass, and when a conventional composition is used, a cured film having these characteristics cannot be obtained. It was. Therefore, the composition of the present invention has a remarkably excellent effect over the conventional composition, and has a synergistic effect exceeding the additive effect of the resin (A) and the compound (B).

  In particular, the cured film obtained from the composition of the present invention is excellent in adhesion to a substrate such as glass even after an etching step or a resist stripping step, which can be performed when forming a wiring or the like. For this reason, a cured film such as an insulating film or a light shielding film obtained from the composition of the present invention can be suitably used also when a wiring is formed on a substrate having the cured film. That is, by using the composition of the present invention, not only a cured film can be formed on a substrate on which a wiring has been previously formed, but also a wiring can be formed on a substrate on which a cured film has been previously formed. In the case of using a conventional insulating film forming composition, when an insulating film is first formed on a substrate and then wiring is formed, the insulating film after wiring formation has poor adhesion to the substrate, An electronic component excellent in desired performance, particularly durability, could not be obtained. On the other hand, by using the composition of the present invention, even if a wiring is formed on a substrate on which a cured film has been formed in advance, the cured film after the wiring is formed has excellent adhesion to the substrate. An electronic component having excellent properties can be obtained. Therefore, by using the composition of the present invention, the variation of the manufacturing procedure of the electronic component is greatly increased, and the electronic component can be manufactured by various methods according to the desired application, the shape of the electronic component, etc. The composition of the present invention is particularly useful in the manufacture of electronic components.

  Furthermore, since the composition of this invention contains the said resin (A) and an epoxy compound (B), it is excellent in jetting property. Therefore, by using the composition of the present invention, it is possible to form a desired thickness, particularly a cured film of a thin film, at a low production cost in a predetermined place by inkjet printing.

  The composition of the present invention is represented by the epoxy compound (C) having no fluorene skeleton and silsesquioxane skeleton, and the formula (7) from the viewpoint of further improving the chemical resistance of the resulting cured film. Silsesquioxane (D), a black pigment (E) for imparting light-shielding properties to the resulting cured film, and a solvent (F) for adjusting the viscosity of the composition may be blended.

  If necessary, the composition of the present invention may further comprise a polymer compound other than the resin (A), a surfactant, an antistatic agent, a coupling agent, an epoxy curing agent other than the resin (A), a curing accelerator, pH. An adjusting agent, a rust inhibitor, a preservative, an antifungal agent, an antioxidant, a reduction inhibitor, an evaporation accelerator, a chelating agent, and a pigment or dye other than black may be included.

1-1. Resin (A) having structural units represented by formula (1) and formula (2)
Resin (A) (hereinafter also referred to as “component (A)”) having structural units represented by formula (1) and formula (2) is a structural unit represented by formulas (1) and (2). If there is, it is not particularly limited.
By using the component (A), a cured film having excellent heat resistance and chemical resistance can be obtained.

  Component (A) can be produced using styrene and maleic anhydride, and can also be produced using styrene, maleic anhydride and a monomer having an ethylenically unsaturated bond.

Examples of the monomer having an ethylenically unsaturated bond include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, Cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2 -(Meth) acryloyloxyethyl], cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl], tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , Benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, methylstyrene, vinyltoluene, chloromethylstyrene, (meth) acrylamide, methyl (meth) acrylate, butyl (meth) Acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloylmorpholine, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-oxiranecyclohexylmethyl (meth) acrylate, 3-methyl-3- (meta ) Acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane and 3-e It may be mentioned-3- (meth) acryloxy ethyl oxetane.

  In the present specification, “(meth) acrylate” indicates both or one of acrylate and methacrylate.

Component (A) may be a resin having a structural unit in which the ring in formula (2) is opened. For example, a half ester having a structural unit in which the ring in formula (2) is opened with an alcohol It may be a mold resin.
In this case, from the viewpoint of obtaining the component (A) having excellent solubility, the number of moles of total OH groups in the alcohol used for the ring-opening reaction is different from the formula (2) in the component (A). It is preferably 10 mol% or more, and more preferably 30 mol% or more.

  As the component (A), a styrene-maleic anhydride copolymer is preferable from the viewpoint of obtaining a cured film excellent in chemical resistance and heat resistance.

  Examples of commercially available components (A) include SMA1000, SMA2000, SMA3000, SMA EF30, SMA EF40, SMA EF60, SMA EF80, SMA1440, SMA17352, SMA2625, and SMA3840 (trade names: manufactured by cray valley).

  These components (A) may be a single compound or two or more compounds.

The weight average molecular weight of the component (A) is 1,000 to 20,000 from the viewpoint of the viscosity of the resulting composition, which gives a polymer excellent in compatibility with other components and solubility in a solvent. Is preferable, and 2,000 to 15,000 are more preferable.
The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method.

In the component (A), the ratio of the formula (1) to the formula (2) (the number of moles of the structural unit represented by the formula (1) / the number of moles of the structural unit represented by the formula (2)) is the heat resistance. In addition, a cured film having excellent chemical resistance is obtained, and a polymer having excellent compatibility with other components and solubility in a solvent is obtained. ~ 8/1 is more preferred.
The said ratio can be judged from the usage-amount of styrene and maleic anhydride used in the case of the synthesis | combination of a component (A), for example.

Component (A) is preferably from 5 to 70% by weight, more preferably from 10 to 60% by weight, based on the solid content of the composition of the present invention, in that a cured film having excellent chemical resistance and heat resistance can be obtained.
In addition, the “solid content” in the present invention refers to the total amount of components in the composition of the present invention obtained by subtracting the solvent from the composition.

1-2. Epoxy compound (B) having a fluorene skeleton represented by formula (3)
The epoxy compound (B) having a fluorene skeleton (hereinafter also referred to as “component (B)”) used in the present invention is not particularly limited as long as it is an epoxy compound having a fluorene skeleton represented by the formula (3).

（式（３）中、「＊」は結合手を示し、また同式中のベンゼン環上の水素原子はシアノ、ハロゲン原子、アルキルまたはメトキシフェニルによって置き換えられていてもよい。）

(In formula (3), “*” represents a bond, and the hydrogen atom on the benzene ring in the formula may be replaced by cyano, halogen atom, alkyl or methoxyphenyl.)

  By using such a component (B), a cured film having excellent heat resistance, chemical resistance and adhesion to a substrate such as glass can be obtained.

  The component (B) is preferably a compound represented by the formula (4) from the viewpoint of obtaining a cured film having excellent heat resistance, chemical resistance and adhesion to a substrate such as glass. The compound represented by 5) is more preferred, and the compound represented by formula (6) is particularly preferred.

（式中、Ｒ¹は独立して、シアノ、ハロゲン原子またはアルキルを示し、Ｒ²は独立して、水素、アルキルまたはメトキシフェニルを示し、Ｒ³は独立して、２価の有機基を示し、ｎは独立して、０〜４の整数を示し、ｍは独立して、０〜４の整数を示し、ｋは独立して、１〜４の整数を示す。）

(Wherein R ¹ independently represents cyano, halogen atom or alkyl, R ² independently represents hydrogen, alkyl or methoxyphenyl, and R ³ independently represents a divalent organic group. , N independently represents an integer of 0-4, m independently represents an integer of 0-4, and k independently represents an integer of 1-4.)

（式中、Ｒ⁴は独立して、炭素数２〜４のアルキレンを示し、ｊは独立して、０〜４の整数を示し、Ｒ²は独立して、水素、アルキルまたはメトキシフェニルを示す。）

(In the formula, R ⁴ independently represents alkylene having 2 to 4 carbon atoms, j independently represents an integer of 0 to 4, and R ² independently represents hydrogen, alkyl or methoxyphenyl. .)

（式中、ｊは独立して、０〜４の整数を示す。）

(In the formula, j independently represents an integer of 0 to 4.)

  Component (B) may be obtained by synthesis or may be a commercially available product.

  Examples of commercially available components (B) include OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), OGSOL CG-500 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), and OGSOL EG-200. (Trade name, manufactured by Osaka Gas Chemical Co., Ltd.), OGSOL EG-250 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), and OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.).

  These components (B) may be a single compound or two or more compounds.

  The content of the component (B) is from 5 to 60% by weight of the solid content of the composition of the present invention in that a cured film having excellent heat resistance, chemical resistance and adhesion to a substrate such as glass can be obtained. Is preferable, and 5 to 50 weight% is more preferable.

1-3. Epoxy compound having no fluorene skeleton and silsesquioxane skeleton (C)
An epoxy compound having no fluorene skeleton and silsesquioxane skeleton (hereinafter also referred to as “component (C)”) is an oxirane group other than components (A), (B), (D) and alkoxysilanes. Or a compound having an oxetane group is not particularly limited, but a compound having two or more oxirane groups is preferable.

  By adding a component (C) to the composition of this invention, the cured film which is further excellent in heat resistance and chemical resistance can be obtained.

  In the present invention, a polymer comprising a monomer having an oxirane group or an oxetane group even if it has an acryloyl group or a methacryloyl group is the component (C), and alkoxysilanes containing an oxirane group or an oxetane group are It is a coupling agent.

  In the present specification, acrylate or methacrylate is referred to as (meth) acrylate.

  Examples of the component (C) include bisphenol A type epoxy compounds, novolak type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol methane type epoxy compounds, dicyclopentadiene type epoxy compounds, biphenyl type epoxy compounds, polycyclic aromatic compounds. Type epoxy compound, mesogen skeleton-containing epoxy compound, glycidyl ester type epoxy compound, alicyclic epoxy compound, polymer of monomer having oxirane group or oxetane group, copolymerization of monomer having oxirane group or oxetane group and other monomer Examples include coalescence.

  Specific examples of the monomer having an oxirane group or an oxetane group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) ) Acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (meth) acryloxyethyloxetane, 3-methyl-3 -(Meth) acryloxymethyloxetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) Acryloxymethyl oxetane.

  Specific examples of other monomers copolymerized with a monomer having an oxirane group or an oxetane group include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene , Methylstyrene, chloromethylstyrene, N-cyclohexylmaleimide and N-phenylmaleimide.

  Preferable specific examples of a polymer of a monomer having an oxirane group or oxetane group, and a copolymer of a monomer having an oxirane group or oxetane group and another monomer include polyglycidyl (meth) acrylate and methyl (meth) acrylate. -Glycidyl (meth) acrylate copolymer, benzyl (meth) acrylate-glycidyl (meth) acrylate copolymer, n-butyl (meth) acrylate-glycidyl (meth) acrylate copolymer, 2-hydroxyethyl (meth) acrylate -Glycidyl (meth) acrylate copolymer, (3-ethyl-3-oxetanyl) methyl (meth) acrylate-glycidyl (meth) acrylate copolymer, and styrene-glycidyl (meth) acrylate copolymer

  Specific examples of the component (C) include trade names “jER807”, “jER815”, “jER825”, “jER825”, “jER828”, “jER190P”, “jER191P”, “jER1004”, “jER1256”, “jER157S70”. ”,“ JER1032H60 ”(Mitsubishi Chemical Corporation), trade names“ EPICLON HP-4032D ”,“ EPICLON HP-4700 ”,“ EPICLON EXA-7240 ”,“ EPICLON HP-7200 ”,“ EPICLON HP-7200H ”, “EPICLON HP-7200HH”, “EPICLON EXA-7260”, “EPICLON EXA-7335”, “EPICLON EXA-4770”, “EPICLON EXA-4850” (DIC Corporation), Product names “Araldite CY177”, “Araldite CY184” (Huntsman Japan Co., Ltd.), product names “Celoxide 2021P”, “Celoxide 3000”, “EHPE-3150” (Daicel Corporation), product names “TECHMORE VG3101L” ( (Printintech), N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N ′, N'-tetraglycidyl-4,4'-diaminodiphenylmethane is mentioned. Among these, from the viewpoint of heat resistance and chemical resistance, jER157S70, jER1032H60, EPICLON HP-7200, EPICLON HP-7200H, EPICLON HP-7200HH, EPICLON HP-4850, Araldite CY184, Celoxide 2021P, and TECHMORE VG3101L are preferred.

  Specific examples of the component (C) further include compounds represented by the following formulas (I) to (VI). Among these, compounds represented by the following formulas (I), (V) and (VI) are preferable because a cured film having particularly good film surface uniformity can be obtained.

In the formula (V), R ^f , R ^g and R ^h are each independently hydrogen or an organic group having 1 to 30 carbon atoms. As this C1-C30 organic group, a C1-C30 hydrocarbon group is mentioned, for example.

In formula (VI), R ^c is an organic group having 2 to 100 carbon atoms. As this C2-C100 organic group, the group containing a C2-C100 hydrocarbon group and a C6-C40 aromatic group is mentioned, for example.

In the formula (VI), R ^d is independently an organic group having 1 to 30 carbon atoms. As this C1-C30 organic group, a C1-C30 linear or branched hydrocarbon group is mentioned, for example, C1-C1 which may contain a ring structure or oxygen is included. Thirty hydrocarbon groups are preferred. Examples of the ring structure include phenyl, cyclohexyl, naphthyl, cyclohexenyl and tricyclo [5.2.1.0 ^2,6 ] decanyl.

In the formula (VI), R ^e is independently an organic group having oxetane, oxirane or 1,2-epoxycyclohexane, preferably an organic group selected from the group consisting of the following formulas (VII) to (IX) .

In the formula (VII), R ⁱ is hydrogen or alkyl having 1 to 3 carbon atoms.

  Preferable examples of the compound represented by the formula (VI) include a compound represented by the following formula (X).

  Only 1 type may be used for a component (C), and 2 or more types may be used for it.

  When the component (C) is contained in the composition of the present invention, the content of the component (C) in the composition is not particularly limited, but a cured film having excellent chemical resistance, heat resistance, and film surface uniformity. Is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight of the solid content of the composition of the present invention.

1-4. Silsesquioxane (D) represented by formula (7)
By adding the silsesquioxane represented by formula (7) (hereinafter also referred to as “component (D)”) to the composition of the present invention, a cured film having further excellent chemical resistance can be obtained.

（式（７）中、Ｒ⁵は独立して、炭素数１〜４５のアルキル、炭素数４〜８のシクロアルキル、炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキルから選択される基であり；炭素数１〜４５のアルキルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、隣接しない少なくとも１つの−ＣＨ₂−は、−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキル中のベンゼン環において、少なくとも１つの水素はハロゲンまたは炭素数１〜１０のアルキルで置き換えられてもよく、この炭素数１〜１０のアルキルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、また、炭素数１〜１０のアルキルの隣接しない少なくとも１つの−ＣＨ₂−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールアルキル中のアルキルの炭素数は１〜１０であり、隣接しない少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく；Ｒ⁶およびＲ⁷はそれぞれ独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり；Ｘは独立して、オキシラニル、オキシラニレン、３，４−エポキシシクロヘキシル、オキセタニルまたはオキセタニレンを有する基である。）

(In the formula (7), R ⁵ is independently selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 14 carbon atoms, and arylalkyl having 7 to 24 carbon atoms. In alkyl having 1 to 45 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent —CH ₂ — may be replaced by —O— or —CH═CH—. In the benzene ring in aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms. In 1-10 alkyl, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent of alkyl having 1-10 carbons. CH ₂ - is -O- or -CH = CH- may be replaced by; from 1 to 10 carbon number of the alkyl in arylalkyl, at least one -CH nonadjacent ₂ - replaced by -O- R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl; X is independently oxiranyl, oxiranylene, 3,4 -A group having epoxycyclohexyl, oxetanyl or oxetanylene.)

From the viewpoint of obtaining a cured film having excellent chemical resistance, R ⁵ is preferably cyclohexyl or phenyl, and X is preferably a group represented by any one of formulas (a) to (d). More preferably, ⁵ is phenyl, R ⁶ and R ⁷ are methyl, and X is a group represented by the formula (b).

（式中、「＊」は結合手を示す。）

(In the formula, “*” indicates a bond.)

  Component (D) can be produced with reference to the method described in International Publication No. 2004/024741.

  These components (D) may be a single compound or two or more compounds.

  The content of the component (D) is preferably 5 to 60% by weight, more preferably 5 to 50% by weight from the viewpoint of obtaining a cured film having excellent chemical resistance.

1-5. Black pigment (E)
By adding a black pigment (E) (hereinafter also referred to as “component (E)”) to the composition of the present invention, a cured film having a light shielding property can be obtained.
Since the composition of the present invention contains components (A) and (B), even if it contains component (E), it has excellent jetting properties and can form a cured film.

  Examples of the component (E) include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  These components (E) may be one kind of compound or two or more kinds of compounds.

  The average particle size of the component (E) is not particularly limited, but generally, when the particle size of the particles to be blended in the composition becomes small, the viscosity of the resulting composition tends to increase and the storage stability tends to decrease. On the other hand, when the particle size of the particles increases, particle sedimentation due to an increase in the specific gravity of the composition, and the particle packing density in the resulting cured film decreases, so that the properties of the particles themselves, such as light shielding properties, are obtained. It tends to be difficult to appear.

  Considering these, the average particle size of the component (E) is preferably 10 nm to 3000 nm, more preferably 20 nm to 1500 nm, further preferably 30 nm to 1000 nm, and particularly preferably 30 to 800 nm.

  The average particle diameter of the present invention is a value measured on a volume basis using a laser diffraction scattering type particle size distribution measuring apparatus LA-950V2 manufactured by HORIBA, Ltd. and utilizing analysis by Mie's scattering theory.

  The content of the component (E) is preferably 20 to 90% by weight, preferably 30 to 80% by weight of the solid content of the composition of the present invention from the viewpoint of obtaining a cured film having excellent light shielding properties and insulating properties. %, More preferably 35 to 70% by weight.

  In addition, when the composition of the present invention is used as an inkjet ink, the content of the component (E) is such that a cured film having excellent light shielding properties and insulating properties can be obtained, and a composition having excellent discharge properties can be obtained. The solid content of the composition of the present invention is preferably 20 to 70% by weight, more preferably 30 to 65% by weight, and even more preferably 35 to 60% by weight.

  When preparing the composition of the present invention, the black pigment may be used alone, but if a dispersion in which the black pigment is dispersed in a dispersant or solvent is used, the black pigment is uniformly mixed with the other components. Therefore, it is preferable.

1-6. Solvent (F)
The viscosity can be adjusted by adding a solvent (F) (hereinafter also referred to as “component (F)”) to the composition of the present invention.

  As the component (F), only one type may be used, or two or more types may be used.

  Examples of the component (F) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, methyl 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, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol Dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether , Triethylene glycol 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, γ-butyrolactone, α-acetyl-γ-butyrolactone, ε-caprolactone, γ-hexanolactone, δ- Hexanolactone, methylethylsulfoxy De, dimethyl sulfoxide and Idemitsu Kosan Co. Ekuamido (trade name).

  Among these, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, N in view of solubility of components (A) and (B) and film surface uniformity of the resulting cured film It is preferable that at least one selected from the group consisting of -methyl-2-pyrrolidone, dipropylene glycol methyl ether acetate and diethylene glycol monobutyl ether acetate is included as the solvent (F).

  The content of the component (F) depends on the viscosity of the target composition, but from the viewpoint of the viscosity of the obtained composition and the uniformity of the film surface of the obtained cured film, the content of the composition of the present invention is 5 to 90. It is preferable that it is weight%, and it is more preferable that it is 10 to 85 weight%.

  Moreover, when using the composition of this invention as an inkjet ink, it is preferable that content of a component (F) is 20 to 90 weight% of the composition of this invention from viewpoints, such as a viscosity of the composition obtained. 30 to 85% by weight is more preferable.

1-7. Additives The composition of the present invention may contain additives other than the components (A) to (F) within a range not impairing the effects of the present invention, depending on the intended properties. Examples of such additives include polymer compounds other than the component (A), surfactants, antistatic agents, coupling agents, epoxy curing agents other than the component (A), curing accelerators, pH adjusters, Examples include rust preventives, antiseptics, antifungal agents, antioxidants, anti-reduction agents, evaporation accelerators, chelating agents, and pigments or dyes other than black.

  These additives may be used alone or in combination of two or more depending on the intended properties.

1-7-1. The polymer compound is not particularly limited as long as it is a compound other than the component (A). For example, acrylic resin, polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, polyvinyl alcohol, poly Examples include oxyethylene and water-soluble polymers. As a high molecular compound, only 1 type may be used and 2 or more types may be used.

  The weight average molecular weight of the polymer compound is preferably 1,000 to 200,000, more preferably 1,000 to 180,000, and still more preferably 1,000 from the viewpoint of excellent solubility. It is -160,000, Most preferably, it is 1,000-150,000.

When a polymer compound having a weight average molecular weight of 1,000 or more is used, the polymer compound does not evaporate when forming a cured film from the composition of the present invention, and is chemically and mechanically stable. A cured film is obtained.
The weight average molecular weight of the polymer compound can be measured by a gel permeation chromatography (GPC) method.

  The content of the polymer compound in the composition of the present invention is from 0 to the solid content of the composition of the present invention in terms of obtaining a cured film having good film surface uniformity, heat resistance, and mechanical properties. 40 weight% is preferable and 0-30 weight% is further more preferable.

1-7-1-1. Acrylic resin The acrylic resin is not particularly limited as long as it is a polymer having an acryloyl group or a methacryloyl group. For example, a monofunctional polymerizable (meth) acrylate having a hydroxyl group; a monofunctional polymerizable (meth) having no hydroxyl group Examples include homopolymers of monomers such as acrylates; bifunctional (meth) acrylates; trifunctional or higher polyfunctional (meth) acrylates; and copolymers of these monomers. Moreover, these monomers, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide, N-phenylmaleimide, polystyrene macromonomer, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamon Polymers obtained by copolymerizing monomers such as acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid may also be used.

  The case where the number of polymerizable groups is one is expressed as monofunctional and the case where there are two groups is expressed as bifunctional. Trifunctional and polyfunctional meanings are also expressions based on the number of polymerizable groups.

  Specific examples of the monofunctional polymerizable (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth). Examples include acrylate and 1,4-cyclohexanedimethanol mono (meth) acrylate. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferable because the formed cured film can be flexible.

Specific examples of the monofunctional polymerizable (meth) acrylate having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and iso-butyl (meth) acrylate. , Tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, ω-carboxypolycarbonate Prolactone mono (meth) acrylate, polymethyl methacrylate macromonomer, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl] and cyclohexene-3,4- Examples include dicarboxylic acid mono [2- (meth) acryloyloxyethyl], N- (meth) acryloylmorpholine, and (meth) acrylamide.

  Specific examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 2 n- butyl-2-ethyl-1,3-propanediol di (meth) acrylate and trimethylolpropane di (meth) acrylate.

  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, Examples include ethylene oxide-modified tri (meth) acrylate phosphate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.

  Only one type of acrylic resin may be used, or two or more types may be used.

  When an acrylic resin is contained in the composition of the present invention, the content of the acrylic resin in the composition is not particularly limited, but a cured film having excellent film surface uniformity, heat resistance and mechanical properties can be obtained. From the point, 0 to 40% by weight of the solid content of the composition of the present invention is preferable, and 0 to 30% by weight is more preferable.

1-7-2. Surfactant The composition of the present invention is intended to improve wettability to an object to be coated such as a substrate, leveling property, film surface uniformity, or ejection property when the composition of the present invention is subjected to inkjet printing or the like. Further, a surfactant may be included.

  As the surfactant, for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK” can be used for improving the discharge properties when the composition of the present invention is subjected to inkjet printing or the like. -310 ”,“ BYK-341 ”,“ BYK-342 ”,“ BYK-344 ”,“ BYK-361N ”,“ BYK-370 ”(BIC Chemie Japan Co., Ltd.) and other silicon surfactants; Acrylic surfactants such as names “BYK-354”, “BYK-358”, “BYK-361” (BIC Chemie Japan Co., Ltd.); trade names “DFX-18”, “Factent 250”, “Footer” Fluorosurfactants such as “Gent 251” (Neos Co., Ltd.).

  Only one type of surfactant may be used, or two or more types may be used.

  When a surfactant is contained in the composition of the present invention, the content of the surfactant in the composition is preferably 0.01 to 1% by weight of the solid content of the composition of the present invention.

1-7-3. Antistatic agent The antistatic agent is used to prevent the composition of the present invention from being charged. The antistatic agent is not particularly limited, and a known antistatic agent can be used. Specifically, tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide can be used. And metal oxides such as quaternary ammonium salts.

  Only one type of antistatic agent may be used, or two or more types may be used.

  When the antistatic agent is contained in the composition of the present invention, the content of the antistatic agent in the composition is preferably 0.01 to 1% by weight of the composition of the present invention.

1-7-4. The coupling agent is not particularly limited, and a known coupling agent can be used, and a silane coupling agent is preferably used. Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds.

  Examples of trialkoxysilane compounds or dialkoxysilane compounds include γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, and γ-acryloylpropylmethyldisilane. Ethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-aminopropylmethyldimethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxy Silane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercapto Propylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Cypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane etc. are mentioned.

  Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferred.

  Only one type of coupling agent may be used, or two or more types may be used.

  When a coupling agent is contained in the composition of the present invention, the concentration of the coupling agent in the composition is 0.01 to 10% by weight of the solid content of the composition of the present invention.

1-7-5. Epoxy curing agent The epoxy curing agent is not particularly limited as long as it is a compound other than the component (A). As the epoxy curing agent, known epoxy curing agents can be used. Specifically, organic acid dihydrazide compounds, imidazole and its derivatives, phenols, dicyandiamides, aromatic amines, polyvalent carboxylic acids, polyvalent carboxylic acids. An acid anhydride or the like can be used.

  The polyvalent carboxylic acid refers to a compound having two or more carboxyl groups in one molecule.

  More specifically, as the epoxy curing agent, trade names “Marcalinker M S-1”, “Marcalinker S-2”, “Marcalinker S-4”, “Marcalinker H-2” (Maruzen Petroleum ( Ltd.), trade names "MEH-7500", "MEH-7600-4H", "MEH-7785SS" (Maywa Kasei Co., Ltd.) and the like; dicyandiamides such as dicyandiamide; adipic acid dihydrazide, 1,3 Organic acid dihydrazide compounds such as bis (hydrazinocarboethyl) -5-isopropylhydantoin; 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 Imidazole derivatives such as dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2-undecylimidazole; phthalic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride And polyvalent carboxylic acid anhydrides such as trimellitic acid. Among these, Marcalinker MS-1, Marcalinker S-2, Marcalinker S-4, Marcalinker H-2, trimellitic anhydride, trimellitic acid, 2,3-dihydro-1H-pyrrolo [1 , 2-a] benzimidazole, 2-undecylimidazole, and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are preferred.

  Only one epoxy curing agent may be used, or two or more epoxy curing agents may be used.

  When an epoxy curing agent is contained in the composition of the present invention, the content of the epoxy curing agent in the composition is preferably 1 to 50% by weight of the solid content of the composition of the present invention.

1-7-6. Curing accelerator The curing accelerator is not particularly limited, and known curing accelerators can be used. Specifically, tertiary amines, imidazole and derivatives thereof, Lewis acids, organic acids, phosphines and the like can be used. Can be used.

  In addition, imidazole and its derivative are the above 1-6-7. Compounds similar to imidazole and derivatives thereof that can be used as epoxy curing agents may be used, not only as epoxy curing agents but also as curing accelerators.

More specifically, examples of the curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-trisdimethylaminomethylphenol; 2,4-diamino-6- [2′-ethylimidazolyl- ( 1 ′)]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2- a] imidazole derivatives such as benzimidazole and 2-undecylimidazole; Lewis acids such as BF ₃ monoethylamine; organic acids such as salicylic acid; and phosphines such as triphenylphosphine. Among these, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2-undecylimidazole, and triphenylphosphine are preferable.

  Only one type of curing accelerator may be used, or two or more types may be used.

  When a curing accelerator is contained in the composition of the present invention, the content of the curing accelerator in the composition is the total amount of component (B), component (C) and component (F) of the composition of the present invention. 0.1 to 10% by weight is preferable.

2. Preparation method of thermosetting composition The composition of the present invention is prepared by mixing the components (A) and (B) and, if necessary, the components (C) to (F) and other additives. Can be prepared.

3. Forming method of cured film The cured film of the present invention is not particularly limited as long as it is a film obtained using the composition of the present invention. The cured film of the present invention can be obtained, for example, by applying the composition of the present invention on a substrate and heating.
The cured film formed on the substrate may be peeled off from the substrate depending on the desired application, but the resulting cured film is excellent in adhesion to the substrate, so it does not peel off from the substrate, The obtained cured film-coated substrate is preferably used as it is for various applications.

3-1. Application method of thermosetting composition Application of the composition of the present invention on a substrate is performed by spray coating, spin coating, roll coating, dipping, slit coating, bar coating, gravure printing, flexographic printing. Can be performed by a conventionally known method such as a method, an offset printing method, a dispenser method, a screen printing method, and an ink jet printing method.

  For example, from the composition of the present invention, when forming a light-shielding part (frame part) in a touch panel, a gravure printing method, a flexographic printing method, an offset printing method, a dispenser method, a screen printing method in that pattern formation is easy. Printing methods such as inkjet printing are preferred.

  In particular, inkjet printing is more preferable because it can be made thin, and cost can be reduced by plateless and on-demand printing.

  Further, for example, in the case where an insulating film is formed on the entire surface of the substrate of the composition of the present invention, the entire surface printing is easy, so that the spin coating method, the slit coating method, the gravure printing method, the flexographic printing method, and the offset printing method are used. Application methods such as a dispenser method and a screen printing method are preferred.

The substrate is not particularly limited, and a known substrate can be used, and a portion where the cured film of the present invention is to be formed can be used as the substrate.
Examples of the substrate include a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, a paper epoxy substrate, a green epoxy substrate, and a BT conforming to various standards of FR-1, FR-3, FR-4, or CEM-3. (Bismaleimide triazine) resin substrate; a substrate made of metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or stainless steel (a substrate having a layer made of these metals on the surface) Indium tin oxide (ITO), aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate , Lead titanate (PT), zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia), silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (Silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spodumene, etc., a substrate having a layer containing these inorganic materials on its surface. PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene terephthalate), PPS (polyphenylene sulfide), polycarbonate From resins such as silicate, polyacetal, polyphenylene ether, polyamide, polyimide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer or liquid crystal polymer A substrate (which may be a substrate having a layer containing these resins on its surface); a semiconductor substrate such as silicon, germanium or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO or ATO (antimony tin oxide), etc. A substrate on which an electrode material (wiring) 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.); Can be mentioned.

  The composition of the present invention is preferably applied on a glass substrate, an ITO substrate or a resin film substrate.

3-2. Curing method of thermosetting resin composition After applying the composition of the present invention, a cured film can be obtained by heating the composition applied on the substrate. As a method for forming a cured film in this manner, preferably, the composition of the present invention is applied on a substrate and then heated by a hot plate or an oven to remove the solvent by evaporation (drying). Treatment) and then further heating (curing treatment) is used.

  The conditions for the drying treatment vary depending on the types and blending ratios of the components contained in the composition to be used, but the heating temperature is usually 70 to 120 ° C., and the heating time is 5 to 15 minutes for an oven and 1 for a hot plate. 10 minutes. By such a drying process, a coating film to the extent that the shape can be maintained can be formed on the substrate.

  After the coating film is formed, a curing treatment is usually performed at 120 to 300 ° C, preferably 150 to 250 ° C. At this time, when the oven is used, the cured film can be usually obtained by heat treatment for 10 to 120 minutes, and when the hot plate is used, usually 5 to 60 minutes.

  The curing treatment is not limited to heat treatment, and may be performed by ultraviolet rays, near infrared rays, ion beams, electron beams, gamma ray irradiation, or the like.

4). Substrate with cured film The substrate with a cured film of the present invention is not particularly limited as long as it has the cured film of the present invention. However, at least one selected from the group consisting of the substrate, particularly a glass substrate, an ITO substrate, and a resin film substrate. It is preferable to have the above-mentioned cured film on a kind of substrate, and since the cured film of the present invention is particularly excellent in adhesion to the glass substrate, it is more preferable to have the above-mentioned cured film on the glass substrate.

  Such a substrate with a cured film is, for example, applied on the entire surface or a predetermined pattern (such as a line) by applying the composition of the present invention on a substrate such as glass, ITO, PET, PEN, etc. Then, it can form by passing through the drying process and hardening process which were demonstrated above.

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

  The touch panel can be manufactured, for example, by combining a liquid crystal display device or an organic electroluminescence device and a position detection device.

Here, as the position detection device, a conventionally known position detection device can be exemplified. For example, a so-called OGS type position having a structure in which a cover glass and a sensor substrate are integrated is manufactured as follows. A detection device is preferred.
Manufacturing method: A light shielding part is formed with the cured film of the present invention on a cover glass for installation on the outermost surface. Thereafter, a wiring (X electrode) made of a conductive material such as ITO is formed on the side of the cover glass where the light shielding portion is formed, a transparent insulating film is formed so as to cover the wiring, and then orthogonal to the X electrode. Thus, a wiring (Y electrode) made of a conductive material such as ITO is formed, and then an overcoat is formed so as to cover the entire surface of the substrate.

Since the composition of the present invention is excellent in jetting properties, the light shielding part having a desired thickness can be easily formed at a desired position, in a desired shape, and at a low cost. It is preferable to form.
The light-shielding portion obtained in this way is excellent in adhesion to a substrate such as glass even after an etching step or a resist stripping step, which can be performed when forming a wiring or the like. For this reason, by using the composition of the present invention, not only the light shielding portion can be formed on the substrate on which the wiring is previously formed, but also the wiring can be formed on the substrate on which the light shielding portion has been previously formed.

  As a material used for forming the transparent insulating film, a conventionally known material can be used, but the composition of the present invention may be used.

6). Display Device The display device of the present invention has a light transmission part and a light shielding part comprising the cured film of the present invention. Specifically, a so-called OGS type touch panel having a structure in which a cover glass and a sensor substrate are integrated is preferable. As this touch panel, the touch panel described in the column of the electronic component is preferable except that the cured film of the present invention is used as the light shielding portion.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.

  The names of reaction raw materials and solvents used in Examples and Comparative Examples are indicated by abbreviations. This abbreviation is used in the following description.

Ingredient (A)
"SMA1000": SMA1000 (trade name): manufactured by Cray Valley, a styrene-maleic anhydride copolymer (weight average molecular weight 5500),
"SMA EF30": SMAEF30 (trade name): styrene-maleic anhydride copolymer (weight average molecular weight 9500) manufactured by Cray Valley
"SMA17352": SMA17352 (trade name): a compound represented by formula (8), manufactured by Cray Valley

Ingredient (B)
-"PG100": OGSOL PG-100 (trade name): manufactured by Osaka Gas Chemical Co., Ltd.-"EG200": OGSOL EG-200 (trade name): manufactured by Osaka Gas Chemical Co., Ltd.

Ingredient (C)
"JER157": jER157S70 (trade name): Mitsubishi Chemical Corporation, special novolac type polyfunctional epoxy resin "HP4700": EPICLON HP4700 (trade name): DIC Corporation, naphthalene type epoxy resin-"VG3101L" ]: TECHMORE VG3101L (trade name): manufactured by Printec Co., Ltd., 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- [2,3 -Epoxypropoxy] phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2 , 3 Epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol

（式（９）中、Ｍｅはメチルを示し、Ｐｈはフェニルを示す。） Ingredient (D)
"Compound (9)": Compound represented by the formula (9)

(In the formula (9), Me represents methyl and Ph represents phenyl.)

Ingredient (E)
"TiB": Titanium black dispersion SC13M-T / MTM (trade name): manufactured by Mitsubishi Materials Corporation, titanium black dispersion (solvent: triethylene glycol dimethyl ether, solid content 34.4% by weight, average particle size 283 nm )

Ingredient (F)
・ "MTM": Highsolve MTM (trade name): manufactured by Toho Chemical Industry Co., Ltd., triethylene glycol dimethyl ether

Coupling agent “S510”: Silaace S-510 (trade name): 3-glycidoxypropyltrimethoxysilane, manufactured by JNC Corporation

Curing agent "TMA": Trimellitic anhydride (trade name): Wako Pure Chemical Industries, Ltd.

[Synthesis Example 1]
<Production of Compound (9)>
Compound (9) was produced based on the following reaction mechanism.

  Compound (a) (21.0 g) synthesized by the method disclosed in International Publication No. 2004/024741 in a reaction vessel having an internal volume of 200 ml equipped with a thermometer, a dropping funnel and a reflux condenser in a nitrogen atmosphere And dry toluene (20 g) were charged and sealed with dry nitrogen. While stirring with a magnetic stirrer, the reaction temperature was heated to 60 ° C. Pt catalyst (21 μL) was added using a microsyringe, and CEL2000 (10 g) manufactured by Daicel Corporation was slowly dropped from the dropping funnel, followed by stirring for 3 hours. The contents of the reaction vessel were transferred to an evaporator and concentrated to obtain crude crystals. Acetone was added to the obtained crude crystals to make a 20 wt% solution. Further, 3% by weight of activated carbon was added to the crude crystals and stirred for 1 hour. Thereafter, the activated carbon was filtered, 10 times the amount of crude crystals of hexane was added to the filtrate, and the mixture was stirred at 25 ° C. for 2 hours. Thereafter, filtration was performed, and the filtrate was concentrated with an evaporator. 1.25 times as much hexane as the obtained crude crystals was added and dissolved by heating to 60 ° C., followed by recrystallization at 25 ° C. As a result of NMR measurement, the obtained crystal (yield 22 g, yield 76%) was found to be compound (9).

¹ H-NMR (CDCl 3): δ (ppm); 0.01 (s, 24 H), 0.40 to 0.46 (m, 8 H), 0.58 to 0.63 (m, 2 H), 0. 83-0.87 (m, 4H), 0.95-1.26 (m, 18H), 1.45-1.49 (m, 2H), 1.59-1.81 (m, 6H), 1.98 (dd, 4H), 2.91-3.03 (m, 8H), 7.14 (t, 8H), 7.25 (t, 8H), 7.33 (t, 4H), 7 .38-7.43 (m, 12H), 7.45 (d, 8H).
²⁹ Si-NMR (CDCl 3): δ (ppm); −106.92, −79.41, −79.18, 11.26, 11.28, 11.34, 11.36.

[Example 1]
SMA1000 [1.65 g] as component (A), EG200 [1.13 g] as component (B), MTM [7.50 g] as component (F), jER157 [0.75 g] as component (C), coupling S510 [0.20 g] as an agent was stirred until a uniform solution was obtained to obtain a mixed solution 1. Next, mixed solution 1 was added and stirred in TiB [14.70 g] as component (E), and then filtered through a membrane filter (manufactured by PTFE, 5.0 μm), and the filtrate (thermosetting composition 1) was obtained. Obtained.

  The viscosity of the thermosetting composition 1 measured at 25 ° C. using an E-type viscometer (trade name: TV-22, manufactured by Toki Sangyo Co., Ltd.) was 10.2 mPa · s.

(Production of substrate with cured film)
A 4 cm square glass substrate (trade name: EAGLE XG, manufactured by Corning) was prepared. The thermosetting composition 1 is injected into an ink jet cartridge, which is mounted on an ink jet apparatus (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.), and an ejection voltage (piezo voltage) is used using an ink jet head for 10 pl. ) A pattern of 3 cm × 2 cm was applied under discharge conditions of 20 V, a head temperature of 30 ° C., a drive frequency of 5 kHz, a discharge interval of 35 μm, and a single application. This substrate was dried at 80 ° C. for 3 minutes using a hot plate (manufactured by AS ONE, Ultra Hot Plate HI-200A (trade name)), and then Tranjap Oven (manufactured by Kato Corporation, TRO-51DPN ( Product name)) was heated at 230 ° C. for 30 minutes to obtain a substrate with a cured film.

[Examples 2 to 4, Comparative Examples 1 to 3]
Except having used the raw material shown in Table 1, after preparing the thermosetting composition on the same conditions as Example 1, the board | substrate with a cured film was created and following evaluation (1)-(3) was performed. The results are shown in Table 1.

  Using the obtained thermosetting composition, the viscosity of the composition was measured in the same manner as in Example 1. The results are shown in Table 1.

(1) Light shielding (OD)
The light-shielding property of the obtained cured film was evaluated by OD (optical density) of the cured film. OD was measured based on the following formula using the Y value calculated from the measured transmittance using a UV-visible spectrophotometer V-670 (light source: D65) manufactured by JASCO Corporation.
OD = -log (Y / 100)
The Y value is Y of the tristimulus value of the object due to transmission in the XYZ color system.

Since the light shielding property is proportional to the film thickness, an OD / film thickness value obtained by standardizing the OD by the film thickness was also obtained. In addition, the film thickness of a cured film is the value measured using the stylus type film thickness meter XP-200 (made by AMBIOS TECHNOLOGY).
The light shielding required as a light shielding part provided on a cover glass of a display device such as a touch panel is usually required to have an OD / film thickness value of 1.5 or more.

(2) Chemical resistance Using the obtained substrate with cured film, three tests (i) to (iii) were performed, respectively, and the film thickness change of the cured film before and after the test was measured with a stylus type film thickness meter XP-200. It measured using. The case where the change in film thickness was less than ± 3% was rated as “◎”, the case where it was ± 3% or more and less than ± 5%, and the case where it was ± 5% or more.

Test (i): A substrate with a cured film was immersed in a Nagase resist strip N300 (trade name, manufactured by Nagase ChemteX Corp.), a resist remover, at 80 ° C. for 15 minutes. Test (ii): 10% nitric acid A substrate with a cured film was immersed in an aqueous solution at 50 ° C. for 15 minutes. Test (iii): A substrate obtained by immersing the substrate with a cured film in a 5% NaOH aqueous solution at 40 ° C. for 5 minutes and then a 10% nitric acid aqueous solution Was immersed at 50 ° C. for 5 minutes, and then the substrate obtained on Nagase Strip N300 was immersed at 80 ° C. for 5 minutes.

(3) Adhesion (2) Chemical resistance tests (i) to (iii) Using a substrate with a cured film after each test, a cross-cut test (JIS-K-5400) by tape peeling was performed on the substrate. The adhesion between the substrate and the cured film was evaluated by counting the number of remaining cured films. The case where the remaining number / 100 was 100/100 was evaluated as ◯, and the case where it was 99/100 or less was evaluated as ×.

As can be seen from Table 1, the cured film formed from the thermosetting composition of the present invention is excellent in light-shielding property, chemical resistance and adhesion. On the other hand, Comparative Examples 1 to 3 have light shielding properties, but have poor chemical resistance or adhesion to the substrate.
As mentioned above, only the cured film of the thermosetting composition which has a component (A) and an epoxy compound (B) was favorable in light-shielding property, chemical-resistance, and adhesiveness.

  The composition of the present invention can be suitably used for forming an insulating film used for electronic parts and the like, particularly for forming a light shielding part for a touch panel.

Claims (21)

A thermosetting composition comprising a resin (A) having a structural unit represented by formula (1) and formula (2), and an epoxy compound (B) having a fluorene skeleton represented by formula (3).

(In formula (3), “*” represents a bond, and the hydrogen atom on the benzene ring in the formula may be replaced by cyano, halogen atom, alkyl or methoxyphenyl.)   The thermosetting composition according to claim 1, wherein the resin (A) is a copolymer of styrene and maleic anhydride.   Furthermore, the thermosetting composition of Claim 1 or 2 which has an epoxy compound (C) which does not have a fluorene skeleton and a silsesquioxane skeleton. The thermosetting composition according to any one of claims 1 to 3, wherein the epoxy compound (B) having a fluorene skeleton is a compound represented by the formula (4).

(Wherein R ¹ independently represents cyano, halogen atom or alkyl, R ² independently represents hydrogen, alkyl or methoxyphenyl, and R ³ independently represents a divalent organic group. , N independently represents an integer of 0-4, m independently represents an integer of 0-4, and k independently represents an integer of 1-4.) The thermosetting composition according to any one of claims 1 to 4, wherein the epoxy compound (B) having a fluorene skeleton is a compound represented by the formula (5).

(In the formula, R ⁴ independently represents alkylene having 2 to 4 carbon atoms, j independently represents an integer of 0 to 4, and R ² independently represents hydrogen, alkyl or methoxyphenyl. .) The thermosetting composition according to any one of claims 1 to 5, wherein the epoxy compound (B) having a fluorene skeleton is a compound represented by the formula (6).

(In the formula, j independently represents an integer of 0 to 4.) Furthermore, the thermosetting composition of any one of Claims 1-6 containing the silsesquioxane (D) represented by Formula (7).

Wherein R ⁵ is independently a group selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms. Yes; in alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced with fluorine, and at least one non-adjacent —CH ₂ — may be replaced with —O— or —CH═CH—. In the benzene ring in aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; And at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ that is not adjacent to the alkyl having 1 to 10 carbons. - it may be replaced by -O- or -CH = CH-; number of carbon atoms in the alkyl in arylalkyl is 1-10, at least one -CH nonadjacent ₂ - is replaced by -O- R ⁶ and R ⁷ are each independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl; X is independently oxiranyl, oxiranylene, 3,4-epoxy. A group having cyclohexyl, oxetanyl or oxetanylene.) The thermosetting composition according to claim 7, wherein R ⁵ in the formula (7) is cyclohexyl or phenyl, and X is a group represented by any one of the formulas (a) to (d).

(In formulas (a) to (d), “*” represents a bond.) The thermosetting composition according to claim 8, wherein R ⁵ in the formula (7) is phenyl, R ⁶ and R ⁷ are methyl, and X is a group represented by the formula (b).   Furthermore, the thermosetting composition of any one of Claims 1-9 which has a black pigment (E).   The thermosetting according to claim 10, wherein the black pigment (E) is at least one selected from carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black and titanium black. Composition.   The thermosetting composition according to claim 10, wherein the black pigment (E) is at least one selected from carbon black and titanium black.   The thermosetting composition of any one of Claims 10-12 whose average particle diameter of a black pigment (E) is 10-3000 nm.   The thermosetting composition according to any one of claims 10 to 12, wherein the average particle diameter of the black pigment (E) is 20 to 1500 nm.   The thermosetting composition according to any one of claims 10 to 12, wherein the average particle size of the black pigment (E) is 30 to 800 nm.   Furthermore, the thermosetting composition of any one of Claims 1-15 containing a solvent (F).   The thermosetting composition according to any one of claims 1 to 16, which is an inkjet ink.   The cured film obtained using the thermosetting composition of any one of Claims 1-17.   The board | substrate with a cured film which has a board | substrate and the cured film of Claim 18.   An electronic component having at least one selected from the cured film according to claim 18 and the substrate with a cured film according to claim 19.   19. A display device having a light transmission part and a light shielding part, wherein the light shielding part includes the cured film according to claim 18.