JP2017179128A - Cured article of thermosetting resin composition, substrate having cured article and manufacturing method of electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a cured article using a resin composition capable of being cured on various substrates in a short time by irradiation with near infrared ray and an application thereof.SOLUTION: A cured film can be formed in a short time by applying near infrared ray to a resin composition containing an epoxy compound (A), an epoxy curing agent (B) and a photothermal conversion agent (C). The resulting cured film has no appearance defect, is excellent in adhesiveness with SUS304, aluminum, a glass substrate or the like and is good in saline water resistance, thermal impact resistance and further heat release property.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a cured product obtained by thermosetting a thermosetting resin composition. In more detail, the manufacturing method of the hardened | cured material obtained by irradiating a near-infrared ray to the thermosetting resin composition containing a specific compound and a photothermal conversion agent, manufacture of the board | substrate provided with the hardened | cured material, and the electronic component which has the said board | substrate Regarding the method.

  In recent years, technologies related to electronic devices such as smartphones and tablet terminals have been rapidly developed. With the development of such technology, rationalization of the manufacturing process, such as simplification of the manufacturing process and shortening of the manufacturing time, is being studied.

  For example, Patent Document 1 discloses a resin composition containing a polyester amide acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like used as a protective film such as an optical material or a transparent insulating film. However, in order to cure the coating film of the resin composition, a long time of about 30 to 90 minutes is required in an oven, and therefore, the manufacturing process is required to be shortened.

Means for shortening the curing time of the thermosetting resin composition include the use of a convection oven, far infrared rays, or a combination thereof. For example, Patent Documents 2 and 3 propose using near infrared light to form a cured film on a metal substrate.
However, the powder coating compositions proposed in Patent Documents 2 and 3 are limited in that it is necessary to use a near-infrared reflective material in order to obtain a smooth finish. For this reason, if only a near-infrared absorbing material such as carbon black is used, a problem occurs in smoothness and the like and an unacceptable appearance is obtained.

JP 2005-105264 A US Pat. No. 6,458,250 Special Table 2007-522329

  An object of the present invention is to provide a cured product and a cured product of a thermosetting resin composition that can efficiently produce a cured product by thermosetting the thermosetting resin composition on various substrates in a short time. An object of the present invention is to provide a substrate and an electronic component manufacturing method provided.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by irradiating a thermosetting resin composition having the following constitution with near-infrared rays to cause thermosetting, and the present invention has been completed.
The present invention relates to a manufacturing method including the following [1] to [20] as means for solving the above-described problems.

[1] Manufacture of hardened | cured material provided with the near-infrared hardening process which irradiates near infrared rays to the composition containing an epoxy compound (A), an epoxy hardening | curing agent (B), and a photothermal conversion agent (C), and hardens a composition. Method.
[2] The method for producing a cured product according to [1], wherein the epoxy compound (A) contains an epoxy compound having a fluorene skeleton.
[3] The method for producing a cured product according to the above [2], wherein an epoxy equivalent of the epoxy compound having a fluorene skeleton is 200 to 550 g / eq.
[4] The composition according to any one of [1] to [3], wherein the composition contains 1 to 50 parts by weight of the epoxy curing agent (B) with respect to 100 parts by weight of the epoxy compound (A). The manufacturing method of the hardened | cured material of description.
[5] The cured product according to any one of [1] to [4], wherein the composition contains a photothermal conversion material (C) having an absorption wavelength region of 750 to 1,500 nm. Method.
[6] The method for producing a cured product according to any one of [1] to [5], wherein the composition further contains a polyester amide acid (D).
[7] The method for producing a cured product according to [6], wherein the composition contains 1 to 60% by weight of the polyester amide acid (D) in a solid content of 100% by weight.
[8] The method for producing a cured product according to the above [6] or [7], wherein the polyester amic acid (D) has a weight average molecular weight of 2,000 to 30,000.
[9] Production of the cured product according to the above [6], [7] or [8], wherein the polyester amic acid (D) is a compound having a structural unit represented by the formula (1) or (2). Method.
(In the formula, R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is 2 having 1 to 20 carbon atoms. Valent organic group.)
[10] The above-mentioned polyester amic acid (D) is a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and polyvalent hydroxy compound (a3) as essential components. The method for producing a cured product according to any one of [6] to [9].
[11] The polyester amic acid (D) is obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3) and monohydric alcohol (a4) as essential components. The manufacturing method of the hardened | cured material of any one of said [6]-[10] which is a compound obtained.
[12] The polyester amic acid (D) comprises X moles of tetracarboxylic dianhydride (a1), Y moles of diamine (a2), and Z moles of polyvalent hydroxy compound (a3) of the formula (3) and The manufacturing method of the hardened | cured material of any one of said [6]-[11] which is a compound obtained by making it react by the ratio in which the relationship of Formula (4) is materialized.
0.2 ≦ Z / Y ≦ 8.0 (3)
0.2 ≦ (Y + Z) /X≦1.5 (4)
[13] The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride. Or at least one compound selected from the group consisting of 2,2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate), The manufacturing method of the hardened | cured material of any one of said [10]-[12].
[14] The above [10], wherein the diamine (a2) is one or more compounds selected from the group consisting of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. ] The manufacturing method of the hardened | cured material of any one of [13].
[15] The polyvalent hydroxy compound (a3) is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8. -The manufacturing method of the hardened | cured material of any one of said [10]-[14] which is 1 or more types of compounds selected from the group which consists of octanediol.
[16] The monohydric alcohol (a4) is one or more selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane. The manufacturing method of the hardened | cured material as described in said [11] which is a compound.
[17] The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, and the diamine (a2) is 3,3′-diaminodiphenylsulfone. The multivalent hydroxy compound (a3) is 1,4-butanediol, and the epoxy curing agent (B) is trimellitic anhydride, according to any one of [10] to [16] above. A method for producing a cured product.
[18] The method for producing a cured product according to any one of [1] to [17], wherein the composition further contains a solvent (E).

[19] A method for manufacturing a substrate including a cured product that forms a cured product by the method for manufacturing a cured product according to any one of [1] to [18].
[20] A method for manufacturing an electronic component having a substrate provided with a cured product that forms the cured product by the method for manufacturing a cured product according to any one of [1] to [18].

  According to the present invention, the thermosetting resin composition containing (A), (B), and (C) is used to irradiate the thermosetting resin composition with near infrared rays, whereby the thermosetting resin composition. An object can be thermally cured in a short time. Therefore, it is possible to shorten the time required for forming a cured product such as a cured film and improve the production efficiency.

It is a graph which shows the drive waveform of the printer head in the inkjet printing used for the coating-film formation in the Example of this invention.

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

1. Thermosetting resin composition The thermosetting resin composition used in the production method of the present invention contains an epoxy compound (A), an epoxy curing agent (B), and a photothermal conversion agent (C). The composition of the present invention may contain additives in addition to the above components.
According to such a composition of the present invention, there is no appearance defect, high adhesion to SUS304, aluminum, glass substrate, etc., salt water resistance, good thermal shock resistance, heat dissipation characteristics A cured product having excellent properties such as being good can be efficiently produced by irradiation with near infrared rays. For this reason, the manufacturing method of the cured film using the composition of the present invention is very practical. For example, it is possible to produce an EMI shield, a light shielding member, etc. with high productivity by an inkjet method. is there.

The composition of the present invention contains an epoxy compound (A), an epoxy curing agent (B), and a photothermal conversion agent (C). Only when these components are combined, a cured product having the excellent effects described above is obtained by the near infrared irradiation step.
The composition containing (A), (B), and (C) forms a cured product having a good appearance with no salt defects or heat shock resistance in a short period of time, with only a near infrared irradiation step of irradiating near infrared rays. be able to. Not only this, but also a cured product with good heat dissipation characteristics and insulation can be obtained. The cured product having various excellent properties described above is considered to have been obtained by a synergistic effect by using the composition of the present invention comprising a combination of specific components and thermally curing by irradiating near infrared rays. .

  The composition of the present invention can also be used as a thermosetting inkjet ink composition ejected by an inkjet method. In this specification, discharging ink by an ink jet method is also called jetting, and the characteristic is also called discharging property or jetting property. Having the characteristics suitable for the use of the inkjet ink composition is said to have good jetting properties.

1.1. Epoxy compound (A)
The epoxy compound (A) used for this invention will not be specifically limited if it has an epoxy group. Examples of epoxy compounds include bisphenol A type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, epoxy compounds having a fluorene skeleton, polymers of monomers having an oxirane ring, monomers having an oxirane ring and other monomers And a copolymer.

  Examples of the epoxy compound (A) include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyltriethoxysilane. Is mentioned. These exemplified silanes are not included in the silane coupling agent as an additive component described later. As described above, the above silane corresponds to the epoxy compound (A) and is distinguished from other compounds generally used as a silane coupling agent. That is, in the specification, among compounds generally used as silane coupling agents, those having an epoxy group correspond to the epoxy compound (A).

  The epoxy compound having a fluorene skeleton is, for example, an epoxy compound containing two or more oxirane rings or oxetane rings in the molecule. Only one kind of epoxy compound having a fluorene skeleton may be used, or two or more kinds may be used.

The epoxy equivalent of the epoxy compound (A) having a fluorene skeleton is preferably 200 to 550 g / eq, more preferably 220 to 490 g / eq, from the viewpoint of obtaining a cured product (cured film) excellent in chemical resistance. eq, more preferably 240 to 480 g / eq.
The epoxy equivalent of the epoxy compound (A) having a fluorene skeleton can be measured, for example, by the method described in JIS K7236. In the present invention, the epoxy equivalent refers to a measured value obtained using the above method.

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

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

  Preferred examples of the polymer of the monomer having an oxirane ring and the copolymer of the monomer having an oxirane ring and another monomer include polyglycidyl methacrylate, a copolymer of methyl methacrylate and glycidyl methacrylate, benzyl methacrylate and glycidyl methacrylate. A copolymer of n-butyl methacrylate and glycidyl methacrylate, a copolymer of 2-hydroxyethyl methacrylate and glycidyl methacrylate, a copolymer of (3-ethyl-3-oxetanyl) methyl methacrylate and glycidyl methacrylate. Examples thereof include a polymer and a copolymer of styrene and glycidyl methacrylate. When the composition of this invention contains these epoxy compounds, since the heat resistance of the cured film formed from the said composition becomes further favorable, it is preferable.

  Specific examples of the epoxy compound include “807”, “815”, “825”, “827”, “828”, “828EL”, “871”, “872”, “190P”, “191P”, “1001”. ”,“ 1004 ”,“ 1004AF ”,“ 1007 ”,“ 1256 ”,“ 157S70 ”,“ 1032H60 ”(above product name, manufactured by Mitsubishi Chemical Corporation),“ Araldite CY177 ”,“ Araldite CY184 ”(above products) Name, manufactured by BASF), “Celoxide 2021P”, “Celoxide 3000”, “Celoxide 8000”, “EHPE-3150” (trade name, manufactured by Daicel Corporation), “TECHMORE VG3101L” (trade name, Inc.) Made by Printec), "HP7200", "HP7200H", "HP7200HH" IC Co., Ltd.), “NC-3000”, “NC-3000H”, “EPPN-501H”, “EOCN-102S”, “EOCN-103S”, “EOCN-104S”, “EPPN-501H”, “EPPN-501H” "EPPN-501HY", "EPPN-502H", "EPPN-201-L" (trade names, manufactured by Nippon Kayaku Co., Ltd.), "TEP-G" (trade names, manufactured by Asahi Organic Materials Co., Ltd.) , “MA-DGIC”, “Me-DGIC”, “TG-G” (trade name, manufactured by Shikoku Chemicals Co., Ltd.), “TEPIC-VL” (trade name, manufactured by Nissan Chemical Industries, Ltd.), “FLEP-10”, “FLEP-50”, “FLEP-60”, “FLEP-80” (trade name, manufactured by Toray Rethiocol Co., Ltd.), N, N, N ′, N′-tetraglycidyl-m -Xylenediamine, 1,3-bi (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.) Epoxy equivalent 259 g / eq), OGSOL CG-500 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent 311 g / eq), OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent 292 g / eq), OGSOL EG-250 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent 417 g / eq), OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent 467 g / eq), OGSOL CG-400 (epoxy equivalent 540 g / eq) is mentioned. Among these, the composition containing the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “TECHMORE VG3101L”, and the trade name “828” can provide a cured film with particularly good flatness. Is preferable. Further, a composition containing the trade name “OGSOL EG-200”, the trade name “OGSOL EG-280”, and the trade name “157S70” is preferable in that a cured film having particularly good adhesion to glass or metal can be obtained. .

  The concentration of the epoxy compound used as the epoxy compound (A) in the composition of the present invention is not particularly limited, but from the standpoint of obtaining a cured film having a well-balanced appearance of the cured film, salt water resistance, and thermal shock resistance, etc. The content of the composition of the present invention is preferably 20 to 80% by weight and more preferably 20 to 70% by weight in the solid content (residue obtained by removing the solvent from the composition).

  In the case of using an epoxy compound having a fluorene skeleton, the solid content of the composition of the present invention (from the viewpoint of obtaining a cured film having excellent adhesion to glass, SUS304, aluminum and other metals, salt water resistance, and thermal shock resistance) It is preferably 1 to 90% by weight, more preferably 3 to 80% by weight, and still more preferably 5 to 70% by weight with respect to 100% by weight of the residue obtained by removing the solvent from the composition.

1.2. Epoxy curing agent (B)
The composition of the present invention is blended with an epoxy curing agent (B), whereby a cured film having excellent salt water resistance and thermal shock resistance is obtained.
The epoxy curing agent (B) is a compound different from the polyester amide acid (D), and specific examples include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent. However, an acid anhydride curing agent is preferable from the viewpoint of coloring resistance and heat resistance.
As the epoxy curing agent (B), only one type may be used, or two or more types may be used.

  Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; phthalic anhydride, trimellitic anhydride And aromatic polycarboxylic acid anhydrides such as styrene-maleic anhydride copolymer. Among these, trimellitic anhydride is particularly preferable from the viewpoints of obtaining a compound having excellent solubility in the solvent (E) and obtaining a cured film having excellent heat resistance.

  The content of the epoxy curing agent (B) is such that a cured film having good adhesion to glass, SUS304 or aluminum and having excellent balance of salt water resistance and thermal shock resistance can be obtained. Preferably it is 1-50 weight part with respect to 100 weight part of epoxy compounds (A), More preferably, it is 2-50 weight part, More preferably, it is 3-40 weight part.

The ratio of the epoxy compound (A) and the epoxy curing agent (B) contained in the composition is such that the amount of the group capable of reacting with the epoxy group in the epoxy curing agent (B) is in the epoxy compound (A). It is preferable that it is 0.1-2 times equivalent of the epoxy group of. Thereby, the cured film excellent in heat resistance and chemical resistance is obtained. Moreover, it is preferable that the quantity of the group which can react with an epoxy group is 0.2-1 times equivalent of an epoxy group from a viewpoint of improving the chemical resistance of a cured film further. Examples of the group capable of reacting with the epoxy group include an acid anhydride group and a carboxyl group.
In this case, for example, when 1 equivalent of a compound having one epoxy group is used as the epoxy compound (A) and 1 equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (B), The amount of the epoxy curing agent (B) relative to the compound (A) is assumed to be 2 times equivalent.

1.3. Photothermal conversion agent (C)
The composition of the present invention contains a photothermal conversion agent (C). It is considered that the photothermal conversion agent in the present invention generates heat by absorbing near infrared rays and promotes the reaction between the epoxy compound (A) and the epoxy curing agent (B). Therefore, it is preferable to select a photothermal conversion agent that efficiently absorbs the near-infrared wavelength range used in the near-infrared curing step. Those having an absorption wavelength region in the range of 750 to 1,500 nm are more preferable, and those having a light absorption spectrum peak in the region of the wavelength of 750 to 1,500 nm are more preferable.

  Examples of the photothermal conversion agent (C) include inorganic colorants and organic colorants. Organic dyes, organic pigments, and inorganic pigments that are excellent in light-shielding rate, salt water resistance, and thermal shock resistance are preferred because they require high light-shielding rates for light-shielding inks and high salt water resistance and thermal shock resistance for EMI shields. Organic pigments and inorganic pigments having high light absorption efficiency are preferable in that they can be cured in a short time.

  Examples of the inorganic pigment include silicon carbide, alumina, magnesia, silica, zinc oxide, titanium oxide, titanium black, graphite, and carbon black. Only 1 type may be used for an inorganic pigment, and 2 or more types may be mixed and used for it.

Examples of the organic pigment include C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment violet 23, C.I. I. Pigment orange 43, C.I. I. Pigment black 1, C.I. I. And pigments with a color index number such as CI Pigment Black 7.
Only one organic pigment may be used, or two or more organic pigments may be mixed and used.

Examples of the dye include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Examples of azo dyes include “VALIFAST BLACK 3810”, “VALIFAST BLACK 3820”, “VALIFAST RED 3304”, “VALIFAST RED 3320”, “OIL BLACK 860” (above, trade name, manufactured by Orient Chemical Industries, Ltd.), “ spilon blue GNH "(trade name; Hodogaya Chemical Co., Ltd.).
Only one type of dye may be used, or two or more types may be mixed and used.
A commercial item may be used for the photothermal conversion agent (C).

  When a pigment component comprising a titanium compound such as titanium black and / or carbon black is blended as the photothermal conversion agent (C) in the composition of the present invention, the content as the pigment component is 100% by weight of the composition. 1 to 20% by weight is preferable, and 1 to 15% by weight is more preferable. By setting the pigment content in the above range, a composition having good storage stability and jetting properties can be obtained.

  When the cured film (cured product) obtained by curing the composition of the present invention is used as a light-shielding member (a substrate provided with a cured product, an electronic component), the photothermal conversion agent (C) is an inorganic pigment, particularly titanium black and carbon. Black is preferred.

  The inorganic pigment is preferably 1 to 130 parts by weight, more preferably 5 to 120 parts by weight, based on 100 parts by weight of the solid content in the composition. When titanium black or carbon black is used as the inorganic pigment, by setting the above range, the adhesion to various base materials can be maintained, the curing with near infrared rays is sufficient, and the heat radiation characteristics are also good. A membrane can be provided.

1.4. Polyester amide acid (D)
The polyester amide acid (D) used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond and a carboxyl group. Specifically, a compound having a structural unit represented by the following formula (1) or (2) is more preferable.
For the first time by using such a polyester amic acid (D) in combination with a specific epoxy compound and an epoxy curing agent, it is excellent in balance in hardness and resistance to an ITO etching solution containing oxalic acid. A composition capable of forming a cured film having excellent adhesion to ITO is obtained.
Polyester amide acid (D) may use only 1 type and may use 2 or more types.

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

Since a compound having good compatibility with other components in the composition is obtained, R ¹ is preferably independently a tetravalent organic group having 2 to 25 carbon atoms, and 4 having 2 to 20 carbon atoms. A valent organic group is more preferable, and a group represented by Formula (5) is more preferable.

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

R ² in the formula (1) is the number of carbons from the viewpoint that a compound having good compatibility with other components in the composition is obtained and a cured film having good adhesion to glass or ITO is obtained. A divalent organic group having 2 to 35 carbon atoms is preferable, a divalent organic group having 2 to 30 carbon atoms is more preferable, and a group represented by formula (6) is more preferable.

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

R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, the group represented by formula (7), —R ¹⁰ —NR ¹¹ —R ¹² — (R ¹⁰ and R ¹² are independently , Alkylene having 1 to 8 carbon atoms, and R ¹¹ is hydrogen or alkyl having 1 to 8 carbon atoms in which at least one hydrogen may be substituted with hydroxyl.), Alkylene having 2 to 15 carbon atoms, Alternatively, at least one hydrogen of alkylene having 2 to 15 carbons may be substituted with hydroxyl, and more preferably a group which may have -O-, More preferably it is.

(In Formula (7), R ⁹ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ —, or —ph—R ⁸ —ph— (ph Is a benzene ring, and R ⁸ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ — or —R ⁷ —.) Note that R ⁷ is independently carbon (Alkylene of the number 1 to 4.)

The polyester amic acid (D) is a compound obtained by reacting a component containing a tetracarboxylic dianhydride (a1), a component containing a diamine (a2) and a component containing a polyvalent hydroxy compound (a3). Preferably obtained by reacting a component containing tetracarboxylic dianhydride (a1), a component containing diamine (a2), a component containing polyvalent hydroxy compound (a3) and a component containing monohydric alcohol (a4). It is also preferable that it is a compound obtained.
That is, in formulas (1) and (2), R ¹ is independently a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue. Is preferred.
In this reaction, a reaction solvent (a5), an acid anhydride (a6) or the like may be used.
The component containing the tetracarboxylic dianhydride (a1) may contain other compounds having three or more acid anhydride groups other than this compound. The same applies to the component containing the diamine (a2), and the component may contain another compound having 3 or more amino groups.
Each of these (a1) to (a6) may be used alone or in combination of two or more.

  When the polyester amic acid (D) has an acid anhydride group at the molecular end, it is preferably a compound obtained by reacting a monohydric alcohol (a4) if necessary. The polyester amide acid (D) obtained using the monohydric alcohol (a4) tends to be a compound having excellent compatibility with the epoxy compound (A) and the epoxy curing agent (B), and has a composition excellent in coatability. There is a tendency to obtain things.

1.4.1. Tetracarboxylic dianhydride (a1)
The tetracarboxylic dianhydride (a1) is not particularly limited, but specific examples include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetra. 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) ] Hexafu Aromatic tetracarboxylic dianhydrides such as oropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.); cyclobutanetetracarboxylic dianhydride, Cycloaliphatic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride and butanetetracarboxylic Aliphatic tetracarboxylic dianhydrides such as acid dianhydrides may be mentioned.

  Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′ is used because a compound having good adhesion to a glass substrate can be obtained by using in combination with an epoxy compound. , 4,4'-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.) is preferable, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetra Carboxylic dianhydride is particularly preferred.

1.4.2. Diamine (a2)
The diamine (a2) is not particularly limited, and specific examples thereof include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-amino Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4 -Aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane is mentioned.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) are used in combination with an epoxy compound having a fluorene skeleton to obtain a compound having good adhesion to a glass substrate. Phenyl] sulfone is preferred, and 3,3′-diaminodiphenylsulfone is particularly preferred.

1.4.3. 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).

1.4.4. 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, dipropylene glycol methyl ether acetate, 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-3-hydroxymethyl oxetane and the like.

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

1.4.5. 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, dipropylene glycol methyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

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

1.4.6. Acid anhydride (a6)
The acid anhydride is not particularly limited, and specific examples thereof include carboxylic acid anhydrides such as 3- (triethoxysilyl) propyl succinic acid anhydride and maleic acid anhydride. Moreover, polyhydric anhydrides, such as a copolymer containing a carboxylic acid anhydride, can also be used. Examples of commercially available polyhydric anhydrides include SMA (trade name, manufactured by Kawa Crude Co., Ltd.), which is a styrene / maleic anhydride copolymer.

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

The order of adding each component during this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2), the polyvalent hydroxy compound (a3) and the acid anhydride (a6) may be simultaneously added to the reaction solvent (a5) and reacted. After dissolving a2) and the polyvalent hydroxy compound (a3) in the reaction solvent (a5), the tetracarboxylic dianhydride (a1) and the acid anhydride (a6) may be added and reacted. Alternatively, tetracarboxylic dianhydride (a1), acid anhydride (a6), and diamine (a2) are reacted in advance, and then the polyhydroxy compound (a3) is added to the reaction product for reaction. Either method can be used.
The monohydric alcohol (a4) may be added at any point in the reaction.

  Moreover, in the case of the said reaction, in order to enlarge the weight average molecular weight of the polyester amic acid (D) obtained, you may add and carry out a synthesis reaction by adding the compound which has 3 or more acid anhydride groups. Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.

  The polyester amide acid (D) synthesized in this way contains the structural units represented by the above formulas (1) and (2), and the terminal thereof is a tetracarboxylic dianhydride, diamine or polyvalent hydroxy compound as a raw material. It is an acid anhydride group, an amino group or a hydroxy group derived from each of them, or a group derived from a component other than these compounds (for example, a monohydric alcohol residue).

When the amounts of tetracarboxylic dianhydride (a1), diamine (a2) and polyvalent hydroxy compound (a3) used in the reaction are X mol, Y mol and Z mol, respectively, X, Y and It is preferable that the relationship of Formula (3) and Formula (4) is established between Z. By using each component in such an amount, a polyester amide acid (D) having high solubility in the following solvent (E) can be obtained. Therefore, the composition has excellent coatability and a cured film having excellent flatness. Can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (3)
0.2 ≦ (Y + Z) /X≦1.5 (4)

  The relationship of Formula (3) is more preferably 0.7 ≦ Z / Y ≦ 7.0, and further preferably 1.3 ≦ Z / Y ≦ 7.0. The relationship of the formula (4) is more preferably 0.3 ≦ (Y + Z) /X≦1.2, and further preferably 0.4 ≦ (Y + Z) /X≦1.0.

  When the amount of the monohydric alcohol (a4) used in the reaction is Z ′ mol, the amount used is not particularly limited, but is preferably 0.1 ≦ Z ′ / X ≦ 5.0, more preferably Is 0.2 ≦ Z ′ / X ≦ 4.0.

  When the reaction solvent (a5) is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyvalent hydroxy compound (a3), the reaction proceeds smoothly. Therefore, it is preferable.

  The reaction is preferably performed at 40 to 200 ° C. for 0.2 to 20 hours.

<< Physical properties, amount of use, etc. of polyester amic acid (D) >>
The weight average molecular weight of the polyester amic acid (D) measured by gel permeation chromatography (GPC) is the solubility in the solvent (E), and particularly in combination with the epoxy compound (B) having a fluorene skeleton, From the standpoint of obtaining a cured film having a good balance between adhesion to ITO and chemical resistance, it is preferably 2,000 to 30,000, more preferably 3,000 to 30,000.
Specifically, this weight average molecular weight can be measured by the method described in Examples described later.

  The viscosity of the polyester amic acid (D) is preferably 5 to 200 mPa · s, more preferably 25 ° C., from the viewpoints of handling the polyester amic acid (D) to be obtained and adjusting the weight average molecular weight to the above preferred range. Is 10 to 150 mPa · s, more preferably 15 to 100 mPa · s.

  The content of the polyester amic acid (D) is such that a cured film excellent in salt water resistance and thermal shock resistance can be obtained, and so on. The solid content of the composition of the present invention (residue obtained by removing the solvent from the composition) is 100. In the wt%, it is preferably 1 to 60 wt%, more preferably 2 to 55 wt%, still more preferably 3 to 50 wt%.

1.5. Solvent (E)
The composition of the present invention can be obtained, for example, by dissolving or dispersing the epoxy compound (A), the epoxy curing agent (B), and the photothermal conversion agent (C) in the solvent (E). Therefore, the solvent (E) is preferably a solvent that can dissolve the epoxy compound (A) and the epoxy curing agent (B) and can dissolve or disperse the photothermal conversion agent (C). Even if the solvent alone does not dissolve the epoxy compound (A) and the epoxy curing agent (B), or the solvent does not dissolve or disperse the photothermal conversion agent (C), the solvent ( E) may be possible to use.
Only 1 type may be used for a solvent (E) and 2 or more types may be used for it.

  Examples of the solvent (E) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether. Acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene Glycol Nomethyl ether, ethylene glycol monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, 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, triplicate Pyrene 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, methyl ethyl sulfoxide, Dimethyl sulfoxide and Idemitsu Kosan Co., Ltd. Amide (trade name) and the like.

  Among these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether in terms of solubility in the epoxy compound (A) and the epoxy curing agent (B) and solubility or dispersibility of the photothermal conversion agent (C). , Diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, methyl 3-methoxypropionate, γ-butyrolactone, dimethyl sulfoxide, and equamide manufactured by Idemitsu Kosan Co., Ltd. The composition of the present invention contains at least one selected from the group consisting of (trade name) as the solvent (E). Door is preferable.

  The content of the solvent is preferably 45 to 90% by weight, more preferably 50 to 80% by weight in 100% by weight of the composition from the viewpoint that the jetting property of the composition becomes good. .

1.6. Additives The composition of the present invention comprises an epoxy compound (A), an epoxy curing agent (B), a photothermal conversion agent (C), a polyester amic acid (D), and a solvent (E), depending on the intended properties. An additive may be contained. Examples of additives include polyimide resins, polymerizable monomers, antistatic agents, coupling agents, pH adjusters, rust inhibitors, preservatives, antifungal agents, antioxidants, polyester resins, surfactants, and epoxy curing agents. Accelerators, reduction inhibitors, evaporation accelerators, chelating agents, and water-soluble polymers. Only 1 type may be used for an additive and 2 or more types may be used for it.

1.6.1. The polyimide resin is not particularly limited as long as it has an imide group.
Only one type of polyimide resin may be used, or two or more types may be used.
The polyimide resin can be obtained, for example, by imidizing polyamic acid obtained by reacting acid dianhydride and diamine. As an acid dianhydride, the tetracarboxylic dianhydride (a1) which can be used for the synthesis | combination of a polyester amide acid (D) is mentioned, for example. Examples of the diamine include diamine (a2) that can be used for the synthesis of polyester amic acid (D).

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

1.6.2. Polymerizable monomer Examples of the polymerizable monomer include monofunctional polymerizable monomers, bifunctional (meth) acrylates, and trifunctional or higher polyfunctional (meth) acrylates.
Only 1 type may be used for a polymerizable monomer and it may use 2 or more types.

  In the case where the composition of the present invention contains a polymerizable monomer, the concentration of the polymerizable monomer in the composition is not particularly limited, but from the viewpoint of obtaining a cured film having better chemical resistance and surface hardness, etc. The solid content of the composition of the invention (the residue obtained by removing the solvent from the composition) is preferably 10 to 80% by weight, and more preferably 20 to 70% by weight.

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

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

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

1.6.3. The antistatic agent can be used for preventing the charge of the composition of the present invention. When the composition of the present invention contains an antistatic agent, 0.01 to It is preferably used in an amount of 1% by weight.
A known antistatic agent can be used as the antistatic agent. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; quaternary ammonium salts, and the like.
Only one type of antistatic agent may be used, or two or more types may be used.

1.6.4. 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. When the composition of the present invention contains a coupling agent, the amount of the coupling agent is 10% by weight or less with respect to 100% by weight of the solid content of the composition of the present invention (residue obtained by removing the solvent from the composition). It is preferable to add and use as described above.
Only one type of coupling agent may be used, or two or more types may be used.

  Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldi Toxisilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxy Silane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxy Examples thereof include silane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyltriethoxysilane.

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

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

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

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

  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.

1.6.7. Polyester resin The composition which improved salt water tolerance can be obtained because the composition of this invention contains a polyester resin. The polyester resin does not contain polyester amic acid (D). When the composition of the present invention contains a polyester resin, 0.1 to 5 parts by weight is added to 100 parts by weight of the solid content of the composition excluding the polyester resin (residue obtained by removing the solvent from the composition). It is preferable to use it.
Only one type of polyester resin may be used, or two or more types may be used.

1.6.8. Surfactant When the composition of the present invention contains a surfactant, it is possible to obtain a composition having improved wettability, leveling properties and coatability to the base substrate. When the composition of the present invention contains a surfactant, the surfactant is preferably used in an amount of 0.01 to 1% by weight with respect to 100% by weight of the composition of the present invention.
Only one type of surfactant may be used, or two or more types may be used.

  As the surfactant, for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-310”, from the viewpoint that the coating property of the composition of the present invention can be improved. “BYK-341”, “BYK-344”, “BYK-370” (above, manufactured by Big Chemie Japan Co., Ltd.), “KP-112”, “KP-326”, “KP-341” (above, Shin-Etsu) Silicone surfactants such as Chemical Industry Co., Ltd .; acrylic surfactants such as “BYK-354”, “BYK-358”, “BYK-361” (manufactured by Big Chemie Japan) Fluorine-based interfaces such as trade names “DFX-18”, “Furgent 250”, “Furgent 251” (manufactured by Neos Co., Ltd.), “Megafuck RS-72K” (trade name, produced by DIC Corporation) Active agent It is.

2. Preparation method of thermosetting resin composition The composition of the present invention comprises an epoxy compound (A), an epoxy curing agent (B), a photothermal conversion agent (C), and, if necessary, a polyester amide acid (D), a solvent ( It can be prepared by mixing E) and other additives.
In addition, the composition of the present invention is prepared by using the reaction solution or mixed solution obtained during the synthesis of the polyester amide acid (D) as it is, the epoxy compound (A), the epoxy curing agent (B), and a solvent (if necessary) It can also be prepared by mixing with E) and other additives.

3. Forming method of cured film The cured film produced by the production method of the present invention is not particularly limited as long as it is a film obtained by irradiating the composition of the present invention with near infrared rays. The cured film of this invention can be obtained by the near-infrared hardening process which apply | coats the composition of this invention to a board | substrate, and irradiates near infrared rays.
Hereinafter, the coating method and the curing method of the composition of the present invention will be described.

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

  For example, when a light shielding member is formed using the composition of the present invention, the amount of ink used is overwhelmingly small compared to conventional coating methods, and it is not necessary to use a photomask or the like. The method is preferred. According to the ink jet method, a wide variety of cured films can be produced in large quantities, and the number of steps required to produce these cured films is small.

  When an EMI shield or a light shielding member is formed from the composition of the present invention using an ink jet method, a step of forming a coating film by applying on the substrate by an ink jet method (forming step, A manufacturing method having a coating film forming step) and a step of irradiating the coating film with near infrared rays to form a cured film (near infrared irradiation step, light baking step) can be used. In this method, before the composition of the present invention is applied to a substrate, a step of surface-treating the substrate (surface treatment step) is provided, and the composition of the present invention is applied onto the surface-treated substrate to form a coating film. Is preferably formed.

  When the coating film is formed in a pattern, the cured film is also formed in a pattern. In the present specification, unless otherwise specified, the “cured film” includes a patterned cured film.

  A cured product such as a cured film produced in this manner may be used after being peeled off from the substrate or may be used as it is without being peeled off from the substrate, depending on the desired application and the substrate used.

  By including the surface treatment step, the wettability of the substrate surface becomes uniform, so that the reproducibility of the printed pattern is improved. Moreover, the cured film excellent in adhesiveness with a board | substrate can be obtained. Examples of the surface treatment include silane coupling agent treatment, UV ozone ashing treatment, plasma treatment, alkali etching treatment, acid etching treatment, and primer treatment.

  In addition, for example, in the case of forming an insulating film provided so as not to contact the electrode from the composition of the present invention, the gravure printing method, the flexographic printing method, the offset printing method, the dispenser method in that the pattern formation is easy. Printing methods such as screen printing and ink jet printing are preferred.

  Further, for example, when the overcoat is formed from the composition of the present invention, the entire surface printing is easy, so that the spin coating method, the slit coating method, the gravure printing method, the flexographic printing method, the offset printing method, the dispenser. A coating method such as a printing method or a screen printing method is preferred.

The substrate is not particularly limited and a known substrate can be used. For example, a glass epoxy substrate conforming to various standards such as FR-1, FR-3, FR-4, or CEM-3, Glass composite substrate, paper phenol substrate, paper epoxy substrate, green epoxy substrate, BT (bismaleimide triazine) resin substrate; iron, copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or stainless steel A substrate made of a metal such as (may be a substrate having a layer made of these metals on its surface); indium tin oxide (ITO), aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium Acid salt (zircon), magnesium oxide (magnesia), aluminum titanate , Barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia) , Silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spodumene A substrate comprising a layer containing these inorganic substances (may be a substrate having a surface containing these inorganic substances); PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylenedimethylene terephthalate) Rate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, polyphenylene ether, polyimide, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic A substrate made of a resin such as an elastomer or a liquid crystal polymer (may be a substrate having a layer containing these resins on its surface); a semiconductor substrate such as silicon, germanium or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO or A substrate on which an electrode material (wiring) such as ATO (antimony tin oxide) is formed; αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel) or γGEL (gamma gel) Gel sheet registered trademark) of Tayca; and the like.
The composition of the present invention is preferably applied on a glass substrate, a SUS304 (stainless steel made of iron, chromium, nickel) substrate, an aluminum substrate or a resin film substrate.

3.2. Curing method of thermosetting resin composition (near infrared curing process)
After apply | coating the composition of this invention, a cured film can be obtained by irradiating the near infrared rays to the composition apply | coated on the board | substrate. As a method for forming a cured film, the composition of the present invention is applied and then heated with a hot plate or an oven to remove the solvent by evaporating (drying treatment) and then irradiating near infrared rays. A method of curing (curing treatment) can also be used.

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

  After forming the coating film, it is cured by irradiating near infrared rays. The near infrared ray used at this time is a wavelength region of 750 to 1500 nm, preferably 750 to 1200 nm. The wavelength region in this range is preferable because it has high transparency, and it is difficult to cause a defect that only the coating film surface seen by curing with far infrared rays is cured. As a near infrared irradiation device, for example, there is a near infrared lamp manufactured by Adphos. Adpho's near-infrared lamp has a wavelength at which the radiant intensity reaches a maximum depending on the output. For example, when the output is 100%, the wavelength at which the radiant intensity has a maximum exists at 750 to 1200 nm, which is suitable for the production method of the present invention. Can be used for

According to the near-infrared irradiation process, a cured film (cured product) having good insulation and heat dissipation characteristics can be formed, so that it is possible to simultaneously impart insulation and heat dissipation to an electronic component. Conventionally, in order to improve the characteristics of an electronic component, a film having desired characteristics has been attached by hand. Generally, a polyimide or epoxy resin film is used for imparting insulation, and a metal foil, a heat sink, or a heat conductive film is used for imparting heat dissipation. For this reason, in order to provide an electronic component with insulating properties and heat dissipation properties, two steps of attaching different films are necessary. However, according to the near-infrared irradiation process, the function that conventionally required two processes can be imparted to the electronic component in one process. Therefore, the manufacturing method of the present invention is effective for rationalizing the manufacturing process of electronic components.
Moreover, since the near infrared irradiation process can form a cured film or the like having two functions of insulation and heat dissipation, a portion where two conventional films are used can be replaced with one cured film. Therefore, the manufacturing method of the present invention is also effective for reducing the size of electronic components.

The film thickness of the coating film formed by the forming step is preferably 1 μm to 40 μm, preferably 1 μm to 35 μm from the viewpoint that curing proceeds until adhesion, saltwater resistance, and thermal shock resistance are sufficient. Is more preferable, and it is further more preferable that it is 1 micrometer-30 micrometers.
From the same viewpoint, the thickness of the cured film after being cured by the near infrared curing step is preferably 0.5 μm to 25 μm, more preferably 0.5 μm to 20 μm, and 1 μm to 20 μm. More preferably it is.

4). Substrate with cured product (substrate with cured product)
The substrate with a cured product obtained by the production method of the present invention is not particularly limited as long as it has a cured product such as a cured film, but is selected from the group consisting of a substrate, particularly a glass substrate, SUS304, an aluminum substrate, and a resin film substrate. It is preferable to have the above-mentioned cured product on at least one kind of substrate.
Such a substrate with a cured product is, for example, a glass, SUS304, aluminum substrate, ITO, PET, PEN or the like on the entire surface or a predetermined pattern (line shape or the like) of the composition of the present invention by the coating method or the like. ) (Formation step), and then through a drying process and a curing process (near infrared curing process) as described above.

5. Electronic component The electronic component obtained by the manufacturing method of the present invention is an electronic component having the above-described cured product or a substrate with a cured product. Examples of such electronic components include various optical materials such as color filters, LED light emitting elements and light receiving elements, touch panels, smartphone housings, and EMI shields.

  Electromagnetic waves generated from transistors built into smartphones and tablet terminals cause various failures (EMI: Electro-Magnetic Interference) such as malfunction of electronic devices and adverse effects on the human body. And an insulating layer structure (EMI shield). Since this EMI shield is conventionally performed by manually attaching to a metal plate, if the production time of the insulating layer can be shortened, the production time of the EMI shield will be shortened, and in terms of production cost and production speed. Become advantageous.

According to the production method of the present invention, a coating film is formed by the above-described printing technique (formation process) such as an inkjet method (inkjet printing method) or a dispenser, and the composition formed into a predetermined shape is irradiated with near infrared rays. By curing the composition (near-infrared curing step), the insulating layer of the cured film can be produced in a short time.
In the forming step, a known method capable of forming the composition into a predetermined shape can be used, but an inkjet method is preferable from the viewpoint of high efficiency.

By forming a composition with a predetermined shape in advance in the forming step, an insulating layer made of a cured product with a predetermined shape can be easily obtained by a near-infrared curing step in which the composition is irradiated with near-infrared rays.
If an inkjet method is used in the forming step, a predetermined shape can be easily formed with the composition discharged onto the substrate.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. Tetracarboxylic dianhydride used in the synthesis of epoxy compound (A), epoxy curing agent (B), pigment and dye as photothermal conversion agent (C), and polyester amic acid (D) used in Examples and Comparative Examples Names of (a1), diamine (a2), polyvalent hydroxy compound (a3), monohydric alcohol (a4), reaction solvent (a5), polyhydric acid anhydride (a6), solvent (E), and surfactant The abbreviations are also shown. This abbreviation is used in the following description.

<Tetracarboxylic dianhydride (a1)>
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride <Diamine (a2)>
DDS: 3,3′-diaminodiphenylsulfone <Polyvalent hydroxy compound (a3)>
BDOH: 1,4-butanediol <monohydric alcohol (a4)>
BzOH: benzyl alcohol <Reaction solvent (a5)>
MPM: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate EDM: diethylene glycol methyl ethyl ether <Acid anhydride (a6)>
SM: SMA1000 (trade name, manufactured by Kawa Crude Co., Ltd.)

<Epoxy compound (A)>
EG-200: OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
157S70: 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation)
S510: 3-Glycidoxypropyltrimethoxysilane (manufactured by JNC Corporation)
SQ: Compound represented by formula (1-1) synthesized by the method described in JP2009-167390A

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

<Photothermal conversion material (C)>
Marco 2004: Marco 2004 Black (trade name, manufactured by Tokiki Co., Ltd., solid content is 38.4% by weight of photothermal conversion agent (C), of which pigment solid content is 30.7% by weight DPMA of photothermal conversion agent (C) Dispersion)
Marco 2010: Marco 2010 Blue (trade name, manufactured by Tokushi Co., Ltd., solid content 22.3% by weight of photothermal conversion agent (C), of which pigment solid content is 15.9% by weight PGMEA of photothermal conversion agent (C) Dispersion)
Marco 2011: Marco 2011 Black (trade name, manufactured by Tokushi Co., Ltd., solid content: 37.3% by weight of photothermal conversion agent (C), of which pigment solid content is 29.8% by weight DPMA of photothermal conversion agent (C) Dispersion)
V3810: VALIFAST BLACK 3810 (trade name, manufactured by Orient Chemical Industry Co., Ltd., black dye)
O810: OIL BLACK 860 (trade name, manufactured by Orient Chemical Industry Co., Ltd., black dye)
V3320: VALIFAST RED 3320 (trade name, manufactured by Orient Chemical Co., Ltd., red dye)

<Other resins>
LTH: Tego Addbond LTH (trade name, manufactured by Evonik Japan Co., Ltd.)

<Solvent (E)>
EDM: Diethylene glycol methyl ethyl ether PGME: Propylene glycol monomethyl ether DPMA: Dipropylene glycol methyl ether acetate MTM: Triethylene glycol dimethyl ether

<Reaction accelerator>
SA-506: U-CAT SA506 (trade name, manufactured by San Apro Co., Ltd.)
<Antioxidant>
I1010: Irganox 1010 (trade name, manufactured by BASF)
<Surfactant>
BYK342: BYK342 (trade name, manufactured by Big Chemie Co., Ltd.)
RS-72K: Megafuck RS-72K (trade name, manufactured by DIC Corporation)

  First, polyester amic acid was synthesized as shown below (synthesis example). Table 1 summarizes the components and physical properties of the synthesis examples.

[Synthesis Example 1]
A 200 ml separable flask equipped with a thermometer, stirring blade, raw material charging inlet and nitrogen gas inlet was charged with 44.70 g of dehydrated and purified MPM, 3.19 g of BDOH, 2.55 g of BzOH and 18.32 g of ODPA, and under a dry nitrogen stream Stir at 130 ° C. for 3 hours. Thereafter, the reaction liquid was cooled to 25 ° C., 2.93 g of DDS and 18.30 g of MPM were added, and the mixture was stirred at 20 to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour. Thereafter, by cooling to 30 ° C. or lower, a pale yellow transparent 30% by weight solution of polyester amic acid was obtained.
Here, the concentration of the polyester amide acid is a concentration as “solid content” which is a residue obtained by removing the solvent from the composition, that is, a concentration of the solid content excluding the reaction solvent in the obtained mixed solution. The same description in the following synthesis examples has the same meaning.

  The rotational viscosity of this solution was 28.2 mPa · s. Here, the rotational viscosity is a viscosity measured at 25 ° C. using an E-type viscometer (trade name; VISCONIC END, manufactured by Tokyo Keiki Co., Ltd.) (hereinafter the same).

Moreover, the weight average molecular weight of the obtained polyester amide acid was 4,100. The weight average molecular weight of the polyester amide acid was measured as follows.
The obtained polyester amic acid was diluted with N, N-dimethylformamide (DMF) so that the concentration of polyamic acid was about 1% by weight, and GPC apparatus: manufactured by JASCO Corporation, Chrom Nav (differential refractive index). Using a total of RI-2031 Plus), the diluted solution was measured by GPC method using a developing agent, and was calculated by polystyrene conversion. Three columns, GF-1G7B, GF-510HQ and GF-310HQ, manufactured by Showa Denko Co., Ltd., were connected in this order, and the column was measured under conditions of a column temperature of 40 ° C. and a flow rate of 0.5 ml / min. .

[Synthesis Example 2]
In a 300 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging inlet and a nitrogen gas inlet, PGMEA 134.4 g, ODPA 12.72 g, SM 38.7 g, BzOH 14.78 g, BDOH 2.46 g as reaction solvents, And EDM25.68g was prepared and it stirred at 125 degreeC under dry nitrogen stream for 2 hours. Thereafter, the reaction solution was cooled to 25 ° C., 3.39 g of DDS and 7.82 g of EDM were added, and the mixture was stirred at 20 to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour. Thereafter, by cooling to 30 ° C. or lower, a pale yellow transparent 30% by weight solution of polyester amic acid was obtained.

  The rotational viscosity of this solution was 38.0 mPa · s. Here, the rotational viscosity is a viscosity measured at 25 ° C. using an E-type viscometer (trade name; VISCONIC END, manufactured by Tokyo Keiki Co., Ltd.) (hereinafter the same).

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

[Example 1]
A 300 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and components other than the photothermal conversion agent (C) and the surfactant (i) were charged into the flask. Specifically, 9.33 g of the polyesteramic acid solution obtained in Synthesis Example 2, 11.20 g of EG-200, 0.45 g of S510, 0.56 g of TMA, and 52.77 g of dehydrated and purified DPMA were charged. Then, it stirred at room temperature for 1 hour and dissolved each component uniformly. Next, 28.57 g of Marco 2011 as the photothermal conversion agent (C) and 0.20 g of RS-72K as the surfactant (i) were added in this order, and after stirring for 1 hour at room temperature, the membrane filter (material: PTFE, pore size) : 5 μm) to obtain a filtrate (thermosetting resin composition).
The rotational viscosity of this composition was 8 mPa · s.

[Examples 2 to 9 and Comparative Example]
In Examples 2 to 9 and Comparative Example, thermosetting resin compositions were prepared in the same manner as in Example 1 except that the types and amounts of each component were changed as shown in Table 1.

  The “ratio of pigment solid content to resin solid content” shown in Table 2 is the ratio (wt%) of pigment solid content to 100 wt% resin solid content in the thermosetting resin composition. Here, the weight of the resin solid content in the thermosetting resin composition means the resin solid content other than the photothermal conversion agent (C) excluding the surfactant (i) and the solid content in the photothermal conversion agent (C). The weight of the solid content other than the solid content of the pigment in the thermosetting resin composition is the weight of the solid content of the pigment in the solid content of the photothermal conversion agent (C). It is.

What formed the coating film on the following conditions using the said thermosetting resin composition was used as the sample board | substrate.
Substrate: SUS304 (thickness 500 μm, 4 cm square)
: Aluminum substrate (thickness 400μm, 4cm square)
: Glass substrate (trade name: EAGLE XG, manufactured by Corning, thickness 700 μm, 4 cm square)
Application method: inkjet printing Printer: DMP-2831 (manufactured by FUJIFILM Dimatix)
Head: DMC-11610 (manufactured by FUJIFILM Dimatix)
Printing conditions: Head temperature 30 ° C., voltage 18V, driving waveform Dimatix Model Fluid 2 (described in FIG. 1), driving frequency 1 kHz, inter-dot space 20 μm, single-sided two-layer printing Curing conditions: A cured film was obtained by infrared irradiation.
Near-infrared irradiation device: Conveyor type near-infrared irradiation device manufactured by Adphos, Inc. Output: 2.5 kW * 3, 100%
Board-lamp distance: 50mm
Irradiation area passage distance: 250mm
Conveyor speed: 7 m / min, 5 m / min, 3 m / min, 1 m / min (Near infrared irradiation time is 2.1 seconds, 3 seconds, 5 seconds, 15 seconds in order)

First, an evaluation of ink jet properties regarding ink jet discharge was performed. The evaluation method is shown below.
Next, inkjet coating was performed on the SUS304 substrate, and the near-infrared ray was irradiated at a conveyor speed of 7 m / min. When fluidity such as a liquid remained after irradiation with near infrared rays, this was discarded, and irradiation with near infrared rays was carried out at a conveyor speed of 5 m / min on a newly inkjet-coated one. In this way, the test is carried out in increments of 2 m / min up to a minimum of 1 m / mim, and the conveyor speed when fluidity does not remain is set as a curing condition, and various sample substrates (substrate 1 for SUS304 substrate, substrate 1 for aluminum substrate) Substrate 2 and substrate 3 in the case of glass substrate and substrate 4) in the case of chrome substrate were prepared. The following evaluations were performed using the obtained sample substrates.

[Evaluation method]
(I) Inkjet ejection stability Ink ejection was started from the inkjet head, and the ejection state was observed with a CCD camera attached to the printer. The time from the start of discharge to the time when a defective nozzle was found, such as non-discharge or an oblique discharge direction, was defined as the continuous discharge stabilization time. Next, the nozzles were cleaned, and the ink was re-ejected from the inkjet head in the order of 1 minute, 3 minutes, 5 minutes, 7 minutes, 9 minutes, and 10 minutes, and the presence or absence of the defective nozzle was observed. The longest standing time in which no discharge failure was found was taken as the stop holding time, and the re-discharge property was evaluated by the length of the stop holding time. The evaluation results are shown in Table 3.

(Ii) Appearance The appearance of the substrate 1 (SUS304 substrate) was visually observed for color unevenness, film surface roughness, and smoothness.

(Iii) Adhesiveness Substrates 1 to 3 (SUS304 substrate, aluminum substrate and glass substrate) are subjected to a gobang eye test (JIS-K-5400) by tape peeling of the cured film, and the remaining number is counted to obtain the substrate and the cured film. The adhesion with was evaluated. The grid spacing was 1 mm and the tape used was 3M # 600. The evaluation results are shown in Table 3 in terms of the remaining number after tape peeling (remaining number / 100) among 100 1 mm squares.

(Iv) Resistance to salt water The substrate 1 was immersed in a 5% by weight aqueous sodium chloride solution at 25 ° C. for 72 hours. Thereafter, the substrate was washed with pure water, and the moisture was wiped off with a non-woven fabric. Then, a Gobang eye test (JIS-K-5400) was conducted by peeling the cured film with tape, and the remaining number was counted to evaluate the salt water resistance. The grid spacing was 1 mm and the tape used was 3M # 600. The evaluation results are shown in Table 3 in terms of the remaining number after tape peeling (remaining number / 100) out of 100 1 mm squares.

(V) Thermal shock resistance The substrate 1 was subjected to 15 cycles of −40 ° C. for 12 hours and 80 ° C. for 2 hours. Thereafter, moisture adhering to the substrate was wiped off with a non-woven fabric, and then a gobang eye test (JIS-K-5400) by tape peeling of the cured film was performed, and the remaining number was counted to evaluate thermal shock resistance. The grid spacing was 1 mm and the tape used was 3M # 600. The evaluation results are shown in Table 3 in terms of the remaining number after tape peeling (remaining number / 100) out of 100 1 mm squares.

(Vi) Heat dissipation characteristics For the substrate 2, a metal surface side and a ceramic heater (Micro Ceramic Heater MS-3 manufactured by Sakaguchi Electric Heat Co., Ltd.) are attached to a double-sided tape (Sumitomo 3M Co., Ltd. thermally conductive adhesive transfer tape No. 9885). Were bonded together. A K thermocouple (ST-50 manufactured by Rika Kogyo Co., Ltd.) was attached to the surface opposite to the surface of the ceramic heater bonded to the substrate 2, and the temperature was observed. The ceramic heater to which the substrate 2 is attached is left in the center of a constant temperature bath set at 40 ° C. After confirming that the temperature of the ceramic heater is constant at 40 ° C., a DC stabilized power source is used for the ceramic heater. 1.22V was applied. And the temperature of the ceramic heater surface 30 minutes after starting voltage application was measured. Since the ceramic heater generates a certain amount of heat, if the measured temperature of the ceramic heater is observed to be low, it can be said that the heat dissipation effect of the substrate 2 is high. As a reference example, as a result of measuring an aluminum substrate (thickness 400 μm, 4 cm square) on which no cured film was formed, the surface temperature of the ceramic heater 30 minutes after voltage application was 97 ° C.

(Vii) Insulation Regarding the substrate 4, aluminum was vapor-deposited on the cured film to form an electrode having a diameter of 5 mm. The volume resistivity was measured using this substrate, and the insulation property was evaluated. For the measurement of insulation, a digital super insulation / microammeter DSM-8104 (manufactured by Hioki Electric Co., Ltd.) was used.

  In the results shown in Table 3, the portion marked as brown unevenness indicates a state in which the ink that was originally transparent after irradiation with near-infrared light has turned brown as if it was partially burned and carbonized.

  In the results shown in Table 3, the portion marked as unevaluated is one in which the evaluation of adhesion was stopped because fluidity remained after irradiation with near infrared rays.

  As is clear from the results shown in Table 3, the cured films formed by near infrared irradiation from the thermosetting resin compositions obtained in Examples 1 to 9 were excellent in salt water resistance and thermal shock resistance. .

  In all of Examples 1 to 9, the ceramic heater temperature after 30 minutes of voltage application was lower than those of Comparative Examples 1 and 2. In particular, Example 4 containing the photothermal conversion agent (C) in the composition was 88 ° C., whereas Comparative Example 1 not containing the photothermal conversion agent (C) was 94 ° C. From these results, it was found that by using the photothermal conversion agent (C), a cured film formed by near-infrared irradiation becomes a cured film having not only the above characteristics but also good heat dissipation characteristics.

  In comparison with Examples 6 and 7 and Comparative Example 2, which differ in whether or not the composition contains a photothermal conversion agent (C), by using the photothermal conversion agent (C), by near infrared irradiation The formed cured film was found to be a cured film having not only the above properties but also good heat dissipation properties.

In Examples 1 to 9, the curing rate (1 m / min) of Comparative Examples 1 and 2 was about 3 to 7 times. From this, it can be seen that by blending the photothermal conversion agent (C), the thermosetting speed of the composition is increased, the production efficiency of the cured product is improved, and a cured film or the like can be produced efficiently.
Examples 1 to 5 using a pigment as the photothermal conversion agent (C) were able to increase the conveyor speed used in thermosetting than Examples 6 to 9 using a dye. From these comparisons, it was found that the curing time by near infrared irradiation can be shortened by using a pigment as the photothermal conversion agent (C). From the results of Examples 1 to 5, by using a pigment as the photothermal conversion agent (C), not only can the curing time be shortened, but in addition to SUS304 and an aluminum substrate, the glass substrate is also cured by near infrared irradiation, It was found that a cured film with good adhesion can be formed.

  As described above, the cured film obtained by thermally curing a composition containing an epoxy resin, an epoxy curing agent, and a photothermal conversion agent by irradiation with near infrared rays can satisfy all desired characteristics.

  In the production method of the present invention, a cured film can be formed in a short time by applying near infrared rays after the composition is applied using, for example, an ink jet method. In addition, the resulting cured film has no poor appearance, has excellent adhesion to SUS304, aluminum, glass substrate, etc., and has good saltwater resistance and thermal shock resistance, so it can be used to produce EMI shields and light shielding members with high productivity. Is possible. Moreover, since the heat dissipation characteristic is also good, it can contribute to the rationalization of productivity, such as being able to apply at once to the location where insulation is required and the location where heat dissipation is required by an inkjet process.

Claims (20)

  The manufacturing method of hardened | cured material provided with the near-infrared hardening process which irradiates near infrared rays to the composition containing an epoxy compound (A), an epoxy hardening agent (B), and a photothermal conversion agent (C), and hardens a composition.   The said epoxy compound (A) is a manufacturing method of the hardened | cured material of Claim 1 containing the epoxy compound which has a fluorene skeleton.   The method for producing a cured product according to claim 2, wherein an epoxy equivalent of the epoxy compound having a fluorene skeleton is 200 to 550 g / eq.   The said composition contains 1-50 weight part of said epoxy hardening | curing agents (B) with respect to 100 weight part of said epoxy compounds (A), The manufacture of the hardened | cured material of any one of Claims 1-3. Method.   The said composition is a manufacturing method of the hardened | cured material of any one of Claims 1-4 containing the photothermal conversion material (C) in which an absorption wavelength area | region exists in 750-1500 nm.   The said composition is a manufacturing method of the hardened | cured material of any one of Claims 1-5 which further contains polyester amide acid (D).   The said composition is a manufacturing method of the hardened | cured material of Claim 6 which contains the said polyester amide acid (D) 1 to 60 weight% in solid content of 100 weight%.   The said polyester amic acid (D) is a manufacturing method of the hardened | cured material of Claim 6 or 7 whose weight average molecular weights are 2,000-30,000. The method for producing a cured product according to claim 6, 7 or 8, wherein the polyester amic acid (D) is a compound having a structural unit represented by formula (1) or (2).
(In the formula, R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is 2 having 1 to 20 carbon atoms. Valent organic group.)   The polyester amic acid (D) is a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and polyvalent hydroxy compound (a3) as essential components. The manufacturing method of hardened | cured material of any one of these.   The polyester amic acid (D) is a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3) and monohydric alcohol (a4) as essential components. The manufacturing method of the hardened | cured material of any one of Claims 6-10 which exists. The polyester amic acid (D) is prepared by converting X mol of tetracarboxylic dianhydride (a1), Y mol of diamine (a2) and Z mol of polyvalent hydroxy compound (a3) into the formulas (3) and (4). The manufacturing method of the hardened | cured material of any one of Claims 6-11 which is a compound obtained by making it react by the ratio in which the relationship of () is materialized.
0.2 ≦ Z / Y ≦ 8.0 (3)
0.2 ≦ (Y + Z) /X≦1.5 (4)   The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2 , 2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and one or more compounds selected from the group consisting of ethylene glycol bis (anhydrotrimellitate). The manufacturing method of hardened | cured material of any one of -12.   The diamine (a2) is one or more compounds selected from the group consisting of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. The manufacturing method of hardened | cured material of any one.   The polyvalent hydroxy compound (a3) is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol. The manufacturing method of the hardened | cured material of any one of Claims 10-14 which is 1 or more types of compounds selected from the group which consists of.   The monohydric alcohol (a4) is at least one compound selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. The manufacturing method of the hardened | cured material of Claim 11.   The tetracarboxylic dianhydride (a1) is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine (a2) is 3,3′-diaminodiphenylsulfone, The method for producing a cured product according to any one of claims 10 to 16, wherein the monovalent hydroxy compound (a3) is 1,4-butanediol and the epoxy curing agent (B) is trimellitic anhydride.   The method for producing a cured product according to any one of claims 1 to 17, wherein the composition further contains a solvent (E).   The manufacturing method of the board | substrate with hardened | cured material which forms hardened | cured material with the manufacturing method of hardened | cured material of any one of Claims 1-18.   The manufacturing method of an electronic component which has a board | substrate with hardened | cured material which forms hardened | cured material with the manufacturing method of hardened | cured material of any one of Claims 1-18.