WO2018190346A1 - Thermosetting resin composition, cured film, substrate provided with cured film, electronic component, and ink jet ink - Google Patents

Abstract

A thermosetting resin composition according to the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, a coloring agent (D), and a thiol compound (E) having a plurality of thiol groups in the molecule, and is thus capable of forming a cured film having favorable adhesion to PET via low-temperature curing at 120°C or less while retaining favorable preservation stability prior to low-temperature curing. The thiol compound (E) content is preferably 0.1 to 20 parts by weight in 100 parts by weight of the solid content within the thermosetting resin composition (excluding the solvent from the full solution).

Description

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

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

In recent years, light shielding members and decorative members are often used in electronic devices such as smartphones. For example, in a liquid crystal display element, a light blocking member called a black matrix is required for a portion where light intrusion such as between pixels must be prevented. Moreover, in a smart phone, the light shielding member is required for the purpose of shielding the electrode part around a screen part in appearance. Furthermore, decoration members of various colors are used for decoration purposes in addition to light shielding applications around the screen part and the smartphone casing.
For touch panels and housing parts used in smartphones and the like, the use of plastic films such as PET is being studied for reasons such as reducing manufacturing costs. When using a PET film, a decorative member capable of low-temperature baking at 120 ° C. or lower is required in consideration of the heat resistance of the film. Moreover, since a decorating member contacts a PET film directly, the adhesiveness and reliability with respect to a PET film are requested | required.

As the light-shielding member and the decorative member, a composition in which a polymer material such as a resin and a colorant such as titanium compound particles are mixed is used in addition to a conventionally used metal material such as chromium. Various compositions have been studied.

For example, Patent Literature 1 and Patent Literature 2 disclose thermosetting resin compositions containing a polyester amide acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like. However, none of these patent documents discusses the adhesion of a cured film obtained from the composition to a PET film.
Patent Document 3 discloses a thermosetting resin composition containing a polyester amide acid having a specific structure, an epoxy compound having a fluorene skeleton, a curing agent, and a colorant. However, Patent Document 3 does not discuss any adhesiveness to the PET film after the high-temperature treatment of the cured film obtained from the composition.

JP 2005-105264 A JP 2008-156546 A WO2016 / 117579 pamphlet

An object of the present invention is to provide a thermosetting resin composition capable of low-temperature baking at 120 ° C. or lower in consideration of heat resistance of an optical film such as PET and further capable of forming a cured film having excellent adhesion to PET. It is to provide an object and its use.

The present inventors have intensively studied to solve the above problems.
As a result, by incorporating a thiol compound in the thermosetting resin composition, low temperature curing is improved while maintaining high storage stability before curing, and a cured film having good adhesion and reliability to a PET film. It was found that can be formed.

As a result of various studies, the present inventors have found that the above problems can be solved by a thermosetting resin composition having the following constitution, and have completed the present invention. The present invention relates to the following [1] to [13].

[1] Polyester amide acid (A), epoxy compound (B) having a fluorene skeleton, epoxy curing agent (C), colorant (D), thiol compound (E) having a plurality of thiol groups in the molecule and solvent ( A thermosetting resin composition comprising F).

[2] The thiol compound (E) is pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryl). Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropio) ), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and the following chemical formula (8 ) Selected from the group consisting of glycoluril derivatives 1 or 2 or more compounds, thermosetting resin composition according to [1].

[3] The content of the thiol compound (E) is 0.1 to 20 parts by weight in 100 parts by weight of the solid content (excluding the solvent from the whole solution) in the thermosetting resin composition. The thermosetting resin composition according to [1] or [2].

[4] The content of the colorant (D) is 0.1 in 100 parts by weight of solids (excluding the solvent from the whole solution) excluding the colorant (D) in the thermosetting resin composition. The thermosetting resin composition according to any one of [1] to [3], wherein the thermosetting resin composition is 70 parts by weight.

[5] The thermosetting resin composition according to any one of [1] to [4], wherein an epoxy equivalent of the epoxy compound (B) having a fluorene skeleton is 200 to 550 g / eq.

[6] Any of [1] to [5], wherein the content of the epoxy compound (B) having a fluorene skeleton is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amide acid (A). The thermosetting resin composition according to one item.

[7] The thermosetting resin composition according to any one of [1] to [6], wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 20,000.

[8] The thermosetting resin according to any one of [1] to [7], wherein the polyester amide acid (A) is a compound having a structural unit represented by formulas (3) and (4). Composition.

(Wherein R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is independently a divalent organic group having 1 to 40 carbon atoms, and R ³ is independently 1 carbon atom) A divalent organic group of ˜20.)

[9] A cured film obtained from the thermosetting resin composition according to any one of [1] to [8].
[10] The cured film according to [9], obtained by firing the thermosetting resin composition at 130 ° C. or lower.
[11] A substrate with a cured film having the cured film according to [9] or [10].
[12] An electronic component having the cured film according to [9] or [10] or the substrate with the cured film according to [11].
[13] An ink-jet ink comprising the thermosetting resin composition according to any one of [1] to [8].

Since the thermosetting resin composition of the present invention contains a thiol compound (E) and can be fired at a low temperature of 120 ° C. or lower, a cured film is formed on the surface of an optical film such as PET having low heat resistance. Can do. Furthermore, the cured film has good adhesion to optical films such as PET, and has improved reliability such as weather resistance and environmental tests over time. Thus, the cured film which is excellent in balance can be formed. Furthermore, the thermosetting resin composition also has good storage stability. For this reason, the thermosetting resin composition of the present invention is very practical, and can be used, for example, for decorating smartphone bezels and casings by an inkjet method.

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

1. Thermosetting resin composition The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, an epoxy curing agent (C), a colorant (D), a thiol compound (E), and Contains solvent (F). The composition of the present invention may contain additives in addition to the above components.
According to such a composition of the present invention, it is possible to perform low-temperature baking at 120 ° C. or less in consideration of heat resistance of an optical film such as PET, and also in a good balance in adhesion and reliability to an optical film such as PET. An excellent cured film can be formed. The composition of this invention can obtain the cured film from which a color differs by adjusting the kind and addition amount of a coloring agent. For this reason, according to the composition of this invention, it is possible to produce the decorating member etc. with which various colors are requested | required with sufficient productivity. Therefore, the composition of this invention can be used suitably for this use.

The composition of the present invention contains a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, an epoxy curing agent (C), a colorant (D), a thiol compound (E) and a solvent (F). Thereby, the cured film which is excellent in the said effect, especially excellent in adhesiveness with respect to PET etc. is obtained.
A conventional composition comprising a polyester amide acid or an epoxy compound having a fluorene skeleton, an epoxy curing agent and an epoxy curing accelerator could not provide a cured film having excellent adhesion to these substrates.
Therefore, the composition of the present invention is a composition having an effect which cannot be expected from the conventional composition, and is a composition containing polyester amic acid (A) and an epoxy compound (B) having a fluorene skeleton. In addition, by adding the colorant (D) and the thiol compound (E), an effect different from that of the conventional composition is obtained.

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.

1.1. Polyester amide acid (A)
The polyester amide acid (A) used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond, and a carboxyl group, and specifically represented by formulas (3) and (4). It is more preferable that the compound has a structural unit.
By using such a polyester amic acid (A) in combination with an epoxy compound (B) having a fluorene skeleton, an epoxy curing agent (C) and a thiol compound (E), it has excellent adhesion to a PET substrate or the like. Thus, a composition capable of forming a cured film having excellent chemical resistance can be obtained.
Polyester amide acid (A) 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.)

R ¹ is preferably independently a tetravalent organic group having 2 to 25 carbon atoms and 4 having 2 to 20 carbon atoms, since a compound having good compatibility with other components in the composition can be obtained. 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 alkyl group having 1 to 4 carbon atoms.)

R ² is a divalent organic compound having 2 to 35 carbon atoms from the standpoint that a compound having good compatibility with other components in the composition is obtained and a cured film having good adhesion to PET is obtained. It is preferably a group, more preferably a divalent organic group having 2 to 30 carbon atoms, and even more preferably a group represented by the formula (6).

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

R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, a group represented by the formula (7), —R ¹⁰ —NR ¹¹ —R ¹² — (R ¹⁰ and R ¹² are independently , 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 carbon atoms may be substituted with hydroxyl, and is more preferably a group optionally having —O—, and is a divalent group having 2 to 6 carbon atoms. More preferably, it is alkylene.

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

The polyester amic acid (A) is a compound obtained by reacting a component containing a tetracarboxylic dianhydride (a1), a component containing a diamine (a2) and a component containing a polyvalent hydroxy compound (a3). Preferably obtained by reacting a component containing tetracarboxylic dianhydride (a1), a component containing diamine (a2), a component containing polyvalent hydroxy compound (a3) and a component containing monohydric alcohol (a4). It is also preferable that it is a compound obtained.
That is, in formulas (3) and (4), R ¹ is independently a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue. Is preferred.
In this reaction, a reaction solvent (a5), an acid anhydride (a6) or the like may be used.
The component containing the tetracarboxylic dianhydride (a1) only needs to contain the tetracarboxylic dianhydride (a1), and may contain other compounds other than this compound. The same applies to the other components described above.
These (a1) to (a6) etc. may be used alone or in combination of two or more.

When the polyester amide acid (A) has an acid anhydride group at the molecular end, it is preferably a compound obtained by reacting a monohydric alcohol (a4) if necessary. The polyester amic acid (A) obtained using the monohydric alcohol (a4) comprises an epoxy compound (B) having an fluorene skeleton, an epoxy curing agent (C), a colorant (D), and a thiol compound (E). While there exists a tendency which becomes a compound excellent in compatibility, it exists in the tendency for the composition excellent in applicability | paintability to be obtained.

1.1.1. Tetracarboxylic dianhydride (a1)
The tetracarboxylic dianhydride (a1) is not particularly limited, but specific examples include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetra Carboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2 , 2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl) ] Aromatic tetracarboxylic dianhydrides such as fluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name: TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.); cyclobutanetetracarboxylic dianhydride Alicyclic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride and butanetetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides are listed.

Among these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid dicarboxylate is used in combination with an epoxy compound (B) having a fluorene skeleton to obtain a compound having good adhesion to a PET substrate. Anhydrides, 3,3 ', 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 preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4 4,4′-diphenylsulfonetetracarboxylic dianhydride is particularly preferred.

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

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

1.1.3. Polyvalent hydroxy compound (a3)
The polyvalent hydroxy compound (a3) is not particularly limited as long as it is a compound having two or more hydroxy groups. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol having a molecular weight of 1,000 or less. , Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2- Pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2 , 6- Xanthriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2 , 8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decane Examples include triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.

Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferable, and 1,4- Butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferable from the viewpoint of good solubility in the reaction solvent (a5).

1.1.4. Monohydric alcohol (a4)
The monohydric alcohol (a4) is not particularly limited as long as it is a compound having one hydroxy group. Specific examples include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol. Monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, Terpineol, dimethylbenzyl carbinol and 3-ethyl- - it includes hydroxymethyl oxetane.

Of these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyl oxetane are preferable. Compatibility of the resulting polyester amic acid (A) with the epoxy compound (B) and epoxy curing agent (C) having a fluorene skeleton, the colorant (D), and the thiol compound (E), and the resulting composition In consideration of applicability to PET, benzyl alcohol is more preferable as the monovalent alcohol (a4).

1.1.5. Reaction solvent (a5)
The reaction solvent (a5) is not particularly limited, but specific examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether. Acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

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

1.1.6. 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 Chemical Co., Ltd.), which is a styrene-maleic anhydride copolymer.

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

The order of adding each component during this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2), 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.

In the reaction, a synthetic reaction may be performed by adding a compound having 3 or more acid anhydride groups in order to increase the weight average molecular weight of the obtained polyesteramic acid (A). Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.

The polyester amide acid synthesized in this way contains the structural units represented by the above formulas (3) and (4), and the ends thereof are derived from the raw materials tetracarboxylic dianhydride, diamine or polyhydroxy compound, respectively. It is an acid anhydride group, an amino group or a hydroxy group, or a group derived from a component other than these compounds (for example, a monohydric alcohol residue).

When the amounts of tetracarboxylic dianhydride (a1), diamine (a2) and polyvalent hydroxy compound (a3) used in the reaction are X mol, Y mol and Z mol, respectively, X, Y and It is preferable that the relationship of Formula (1) and Formula (2) is established between Z. By using each component in such an amount, a polyester amide acid (A) having high solubility in the following solvent (F) can be obtained, a composition having excellent coatability can be obtained, and a cured film having excellent flatness can be obtained. Obtainable.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)

The relationship of the formula (1) is more preferably 0.7 ≦ Z / Y ≦ 7.0, and further preferably 1.3 ≦ Z / Y ≦ 7.0. The relationship of the formula (2) 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 and usage of polyester amide acid (A) >>
The weight average molecular weight of the polyester amic acid (A) measured by gel permeation chromatography (GPC) is the solubility in the solvent (F), especially in combination with the epoxy compound (B) and thiol compound (E) having a fluorene skeleton. In view of obtaining a cured film having a good balance between adhesion to PET and chemical resistance, it is preferably 2,000 to 30,000, and preferably 3,000 to 30,000. Is more preferable.
Specifically, this weight average molecular weight can be measured by the method described in the below-mentioned Examples.

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

The content of the polyester amic acid (A) is 100% by weight of the solid content of the composition of the present invention (residue from which the solvent is removed) from the viewpoint that a cured film having excellent chemical resistance is obtained. On the other hand, it is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, and still more preferably 5 to 50% by weight.

1.2. Epoxy compound having a fluorene skeleton (B)
The epoxy compound (B) having a fluorene skeleton used in the present invention is not particularly limited as long as it is an epoxy compound having a fluorene skeleton. The epoxy compound (B) having such a fluorene skeleton has a high decomposition temperature and is excellent in heat resistance stability. For this reason, the cured film which has these effects together can be obtained.
The epoxy compound (B) having a fluorene skeleton is usually an epoxy compound containing two or more oxirane rings or oxetane rings in the molecule.
Only one type of epoxy compound (B) having a fluorene skeleton may be used, or two or more types may be used.

The epoxy equivalent of the epoxy compound (B) having a fluorene skeleton is preferably 200 to 550 g / eq, more preferably 220 to 490 g / eq, and still more preferably, from the viewpoint of obtaining a cured film having excellent chemical resistance. Is 240 to 480 g / eq.
The epoxy equivalent of the epoxy compound (B) having a fluorene skeleton can be measured, for example, by the method described in JIS K7236.

The epoxy compound (B) having a fluorene skeleton may be obtained by synthesis or a commercially available product.
Examples of commercially available epoxy compounds (B) having a fluorene skeleton include OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent 259 g / eq), OGSOL CG-500 (trade name, Osaka Gas). Chemical Co., Ltd., epoxy equivalent 311 g / eq), OGSOL EG-200 (trade name, Osaka Gas Chemical Co., epoxy equivalent 290 g / eq), OGSOL EG-250 (trade name, 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 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent) 540 g / eq).

The content of the epoxy compound (B) having a fluorene skeleton is such that a cured film having excellent balance in heat resistance, chemical resistance and adhesion to PET can be obtained. The residue obtained by removing the solvent from the product) is preferably 1 to 90 parts by weight, more preferably 3 to 80 parts by weight, and still more preferably 5 to 70 parts by weight. The amount is preferably 10 to 400 parts by weight, more preferably 20 to 350 parts by weight, and still more preferably 30 to 300 parts by weight with respect to parts by weight.

1.3. Epoxy curing agent (C)
The composition of the present invention is blended with an epoxy curing agent (C), whereby a cured film having excellent heat resistance and chemical resistance is obtained.
The epoxy curing agent (C) is a compound different from the polyester amide acid (A), and specifically includes an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent. Although mentioned, an acid anhydride type hardening | curing agent is preferable from points, such as coloring resistance and heat resistance.
As the epoxy curing agent (C), only one 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 (F) and obtaining a cured film having excellent heat resistance.

The content of the epoxy curing agent (C) is such that a cured film having excellent balance in hardness, chemical resistance and adhesion to PET can be obtained, and the solid content of the composition of the present invention (the solvent is removed from the composition). The remaining amount is preferably from 1 to 300 parts by weight, more preferably from 3 to 200 parts by weight, and even more preferably from 5 to 100 parts by weight, based on 100 parts by weight, and a total of 100 epoxy compounds in the composition of the present invention. The amount is preferably 1 to 380 parts by weight, more preferably 3 to 350 parts by weight, and still more preferably 5 to 150 parts by weight with respect to parts by weight.
The total of the epoxy compounds in the composition of the present invention is the total of the epoxy compound (B) having a fluorene skeleton and the epoxy compound used as an additive.

The ratio of the epoxy compound (B) having a fluorene skeleton to be used and the epoxy curing agent (C) is such that a cured film having excellent heat resistance and chemical resistance can be obtained. The amount of the group capable of reacting with an epoxy group such as an acid anhydride group or a carboxyl group in the epoxy curing agent is preferably 0.2 to 2 times the amount of the epoxy group in B). It is more preferable that the amount is ˜1.5 times equivalent because the chemical resistance of the cured film obtained is further improved. At this time, for example, 1 equivalent of a compound having one epoxy group is used as the epoxy compound (B) having a fluorene skeleton, and 1 equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (C). When used, the amount of the epoxy curing agent (C) with respect to the epoxy compound (B) having a fluorene skeleton is assumed to be 2 times equivalent.

1.4. Colorant (D)
The composition of the present invention contains a colorant (D).
Examples of the colorant (D) include inorganic colorants and organic colorants. Since color inks are required to have high color purity, chemical resistance and heat resistance, organic dyes, organic pigments and inorganic pigments which are excellent in color purity, chemical resistance and heat resistance are preferred. When the cured film is used as a light shielding member, an inorganic pigment having a high light shielding property is preferable, and when it is used as a decorative member, an organic pigment having many kinds of colors is preferable.

Examples of inorganic pigments 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, copper phthalocyanine blue, 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, pigment yellow 185, C.I. I. Pigment violet 23, C.I. I. Pigment orange 43, C.I. I. Pigment black 1, C.I. I. And pigments having 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 the azo dye include “VALIFASTBLACK 3810”, “VALIFASTBLACK 3820”, “VALIFASTRED 3304”, “VALIFASTRED 3320”, “OIL BLACK 860” (trade names, manufactured by Orient Chemical Industry Co., Ltd.), spilon blue GNH (product) Name; Hodogaya Chemical Co., Ltd.).
Only one type of dye may be used, or two or more types may be mixed and used.

Commercially available products may be used as the colorant (D).

In the case where a titanium compound such as titanium black is blended as the colorant (D) in the composition of the present invention, the content of the titanium compound particles is preferably 10 to 25 parts by weight with respect to 100 parts by weight of the composition. By setting it as said range, a composition can be made into the viscosity with favorable jetting property.

The weight ratio of the titanate oxide to the titanate nitride in the titanium compound particles is preferably 0.5 to 0.9 parts by weight with respect to 1 part by weight of the titanate nitride. More preferably, the amount is from 5 to 0.8 parts by weight, and even more preferably from 0.5 to 0.7 parts by weight. By using the titanium compound particles having the above weight ratio, an effect that the light-shielding property of the thermosetting resin composition can be further improved is obtained.

When the cured film obtained by curing the composition of the present invention is used as a light shielding member, the OD value per 1 μm of the cured film can be provided with a light shielding property suitable for the cured film to be used as a light shielding member. Therefore, it is preferably 0.5 or more, and more preferably 0.7 or more.

The OD (Optical Density, optical density) value is the Y value calculated from the light transmittance (T) value using an ultraviolet-visible spectrophotometer V-670 (light source: D65) manufactured by JASCO Corporation. Was determined based on the following formula.
OD = −log (Y / 100) The Y value is Y of the tristimulus value of the object due to transmission in the XYZ color system.

When using a cured film obtained by curing the composition of the present invention as a decorative member, inorganic pigments, particularly titanium black, carbon black, C.I. I. Pigment red 209, C.I. I. Pigment red 177, C.I. I. Pigment Yellow 185 and copper phthalocyanine blue are preferable, and titanium black, C.I. I. Pigment red 209, C.I. I. Pigment red 177, C.I. I. Pigment yellow 185 and copper phthalocyanine blue are more preferable.

The inorganic pigment or organic pigment is 0.1 to 70 parts by weight, more preferably 0.1 to 60 parts by weight, and still more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the solid content in the composition. is there. By setting it as said range, the cured film suitable for the use as a decorating member can be formed easily. When titanium black is used as the inorganic pigment, the cured film having good adhesion to the PET substrate is formed by adjusting the amount of titanium black to 14 parts by weight or less with respect to 100 parts by weight of the resin solid content in the composition of the present invention. be able to.
From the viewpoint of improving the adhesion with the PET film after the environmental test, when titanium black is used as the inorganic pigment, the compounding amount of titanium black with respect to 100 parts by weight of the resin solid content in the composition of the present invention is 8 parts by weight or less. Is preferable, and 7 parts by weight or less is more preferable.
As an organic pigment, C.I. I. Pigment red 209, C.I. I. Pigment red 177, C.I. I. When pigment yellow 185 and copper phthalocyanine blue are used, curing with good adhesion to the PET substrate is achieved by setting the blending amount of the organic pigment to 10 parts by weight or less with respect to 100 parts by weight of the resin solid content in the composition of the present invention. It can be a membrane.

1.5. Thiol compound (E)
In the composition of the present invention, the thiol compound (E) is blended, whereby the curing temperature of the composition of the present invention can be lowered, or the curing time can be shortened. Moreover, it is possible to obtain a cured film having good adhesion and reliability to the PET film.
The thiol compound (E) used in the present invention is not particularly limited as long as it has a plurality of thiol groups in the molecule, but preferably includes an oxygen atom in addition to the thiol group. By using the thiol compound (E) in combination with the polyester amide acid (A) having a specific structure, the epoxy compound (B) having a fluorene skeleton, and the colorant (D), low temperature curing at 120 ° C. or less and storage stability In addition, it is possible to obtain a cured film having good adhesion to the PET film and good reliability. Since the thiol compound (E) has both the action of reacting itself to cure the epoxy and the action of assisting the epoxy reaction without reacting itself, the epoxy curing agent (C ) And epoxy curing accelerator (i). Only 1 type may be used for a thiol compound (E), and 2 or more types may be used for it.

As the thiol compound (E), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and glycol of the following chemical formula (8) Examples include uril derivatives.

Among these, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane tris (3-mercaptobutyrate) are preferred because a composition having good storage stability can be obtained. Pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione, trimethylolpropane tris (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -Ethyl] -isocyanurate, trimethylolpropane tris (3-mercaptopropionate), and a glycolyl derivative represented by the formula (8) are preferable because a cured film having excellent heat resistance can be obtained.

Examples of commercially available thiol compounds (E) include “Karenz MT PE1,” “Karenzu MT BD1,” “Karenzu MT NR1,” “TPMB” (trade names, manufactured by Showa Denko KK), “DPMP”. , “PEMP”, “TEMPIC”, “TMMP” (trade name, manufactured by SC Organic Chemical Co., Ltd.) and “TS-G” (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.).

Only one type of thiol compound (E) may be used, or two or more types may be used.

The content of the thiol compound (E) is such that the solid content of the composition according to this embodiment (excluding the solvent is excluded from the composition) in terms of excellent balance in adhesion, reliability and storage stability to the PET film. (Remainder) Based on 100 parts by weight, 0.1 to 20 parts by weight is preferred, 0.1 to 18 parts by weight is more preferred, and 0.1 to 15 parts by weight is even more preferred. From the same point, the thiol compound (E) is preferably 0.1 to 35 parts by weight, more preferably 0.1 to 30 parts by weight, and 0.1 to 25 parts by weight with respect to 100 parts by weight of the total epoxy compound. Further preferred. Further, the amount is preferably 1 to 200 parts by weight, more preferably 3 to 180 parts by weight, and still more preferably 5 to 150 parts by weight with respect to 100 parts by weight of the epoxy curing agent (C).

1.6. Solvent (F)
In the composition of the present invention, for example, a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, an epoxy curing agent (C), a colorant (D), and a thiol compound (E) are used as a solvent (F). It can be obtained by dissolving. Therefore, the solvent (F) is a solvent capable of dissolving the polyester amide acid (A), the epoxy compound (B) having an fluorene skeleton and the epoxy curing agent (C), the colorant (D) and the thiol compound (E). It is preferable that Even if it is a solvent that does not dissolve the polyester amic acid (A), the epoxy compound (B) having an fluorene skeleton and the epoxy curing agent (C), the colorant (D) and the thiol compound (E) alone, It may become possible to use as a solvent (F) by mixing with a solvent.
Only 1 type may be used for a solvent (F) and 2 or more types may be used for it.

Examples of the solvent (F) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether. Acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate (DPMA), tetraethylene glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1 , 4-Geo Sun, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol Monobutyl ether (DB), ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol Divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, 2-methoxyethanol, 2-ethoxyethanol, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1 -Ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N -Diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, α-acetyl-γ-butyrolactone, ε-caprolactone, γ- Hexanolactone, δ-hexanolacto , Methyl ethyl sulfoxide, methyl 2-hydroxyisobutyrate (HBM), dimethyl sulfoxide and Idemitsu Kosan Co. Ekuamido (trade name).

Among these, the composition of the present invention in terms of solubility in the polyester amic acid (A), the epoxy compound (B) having a fluorene skeleton, the epoxy curing agent (C), the colorant (D) and the thiol compound (E). The products are ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, γ-butyrolactone, diethylene glycol Monobutyl ether (DB), methyl 2-hydroxyisobutyrate (HBM), dimethyl sulfoxide and Idemitsu Kosan Co., Ltd. At least one member selected from the group consisting of manufacturing Ekuamido (trade name), it is preferably contained as the solvent (F).

From the viewpoint of improving the adhesion to the substrate after the environmental test, it is preferable to contain propylene glycol monomethyl ether as the solvent (F). The content of propylene glycol monomethyl ether in 100 parts by weight of the solvent (F) is preferably 10 to 25 parts by weight, more preferably 12 to 22 parts by weight, and even more preferably 15 to 20 parts by weight. Further, when the solvent (F) contains propylene glycol monomethyl ether, it preferably further contains methyl 2-hydroxyisobutyrate. The content of methyl 2-hydroxyisobutyrate is preferably larger than that of propylene glycol monomethyl ether, and the content of methyl 2-hydroxyisobutyrate in 100 parts by weight of the solvent (F) is preferably 75 to 90 parts by weight, More preferred is 78 to 88 parts by weight, and still more preferred is 80 to 85 parts by weight.

The content of the solvent is preferably 45 to 90 parts by weight and more preferably 55 to 80 parts by weight with respect to 100 parts by weight of the composition from the viewpoint that the jetting property of the composition becomes good. preferable.

1.7. Additives The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, an epoxy curing agent (C), a colorant (D), a thiol compound ( You may contain additives other than E) and a solvent (F). Examples of the additive include an epoxy compound containing two or more oxirane rings or oxetane rings in the molecule, a polyimide resin, a polymerizable monomer, an antistatic agent, a coupling agent, a pH adjusting agent, a rust preventive agent, an antiseptic agent, and an anticorrosive agent. Examples include glazes, antioxidants, surfactants, epoxy curing 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.

1.7.1. Epoxy Compound In the present invention, the epoxy compound used as an additive refers to an epoxy compound other than the epoxy compound (B) having a fluorene skeleton.
As the epoxy compound, a compound having two or more oxirane rings is preferably used. Only one type of epoxy compound may be used, or two or more types may be used.

Examples of the epoxy compound include a bisphenol A type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound, a polymer of a monomer having an oxirane ring, and a copolymer of a monomer having an oxirane ring and another monomer. It is done.

Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and compounds represented by the following structure.
In the 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, and a copolymer of (3-ethyl-3-oxetanyl) methyl methacrylate and glycidyl methacrylate. Examples thereof include a polymer and a copolymer of styrene and glycidyl methacrylate. 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 “jER807”, “jER815”, “jER825”, “jER825”, “jER828”, “jER828EL”, “jER871”, “jER872”, “jER190P”, “jER191P”, “jER1001”. ”,“ JER1004 ”,“ jER1004AF ”,“ jER1007 ”,“ jER1256 ”,“ jER157S70 ”,“ jER1032H60 ”(above, manufactured by Mitsubishi Chemical Corporation),“ Araldite CY177 ”,“ Araldite CY184 ” Name, manufactured by Huntsman Japan Co., Ltd.), “Celoxide 2021P”, “Celoxide 3000”, “Celoxide 8000”, “EHPE-3150” (trade name, manufactured by Daicel Corporation), “TECHMORE V 3101L "(trade name, manufactured by Printec Co., Ltd.)," HP7200 "," HP7200H "," HP7200HH "(trade name, manufactured by DIC Corporation)," NC-3000 "," NC-3000H "," EPPN-501H ”,“ EOCN-102S ”,“ EOCN-103S ”,“ EOCN-104S ”,“ EPPN-501H ”,“ EPPN-501HY ”,“ EPPN-502H ”,“ EPPN-201-L ”(and above) Trade name, manufactured by Nippon Kayaku Co., Ltd.), “TEP-G” (trade name, manufactured by Asahi Organic Materials Co., Ltd.), “MA-DGIC”, “Me-DGIC”, “TG-G” (and above) Trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), “TEPIC-VL” (trade name, manufactured by Nissan Chemical Industries, Ltd.), N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 3- Scan (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', -4,4'- N'- tetraglycidyl diaminodiphenylmethane and the like. Among these, a composition containing the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “TECHMORE VG3101L”, and the trade name “828” can obtain a cured film with particularly good flatness. preferable.

The concentration of the epoxy compound used as an additive in the composition of the present invention is not particularly limited, but from the standpoint of obtaining a cured film with excellent balance in heat resistance and adhesion to PET, the composition of the present invention The solid content (residue obtained by removing the solvent from the composition) is preferably contained in an amount of 0 to 50% by weight, and more preferably 0 to 40% by weight.

1.7.2. 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 (A) is mentioned, for example. Examples of the diamine include diamine (a2) that can be used for the synthesis of polyester amic acid (A).

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

1.7.3. 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.

When the composition of the present invention contains a polymerizable monomer, the concentration of the polymerizable monomer in the composition of the present invention is not particularly limited, but a cured film having a better chemical resistance and surface hardness can be obtained. Therefore, the solid content of the composition of the present invention (the residue obtained by removing the solvent from the composition) is preferably 10 to 80% by weight, 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-propanedi Ruji (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol di (meth) acrylate.

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

1.7.4. The antistatic agent can be used to prevent the composition of the present invention from being charged. When the composition of the present invention contains an antistatic agent, 0.01 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.

1.7.5. 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 PET. 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-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylme Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-amino Propyltrimethoxysilane, N-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Propylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanate Inert propyl methyl diethoxy silane, include γ- isocyanato propyl triethoxysilane.

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

1.7.6. Antioxidant (i)
When the composition of the present invention contains an antioxidant, it is possible to prevent deterioration when the cured film obtained from the composition is exposed to high temperature or light. When the composition of the present invention contains an antioxidant, 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 up to 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), Adeka Stub AO-20, Adeka Stub AO-40, Ade 40 A-40 Adeka Stub AO-60, Adeka Stub AO-80, Adeka Stub AO-330 (trade name, manufactured by ADEKA Corporation) and the like.

1.7.7. Surfactant (j)
When the composition of the present invention contains a surfactant, it is possible to obtain a composition with improved wettability, leveling property and coating property 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, the product names MegaFuck F-171, MegaFuck F-177, MegaFuck F-410, MegaFuck F-430, and the like can be applied from the viewpoint that the coating property of the composition of the present invention can be improved. Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F-553, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Megafuck F-558, Megafuck F-559, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 (all trade names; DIC Corporation), trade names “BYK-300”, “BYK-” 06 ”,“ BYK-335 ”,“ BYK-310 ”,“ BYK-341 ”,“ BYK-342 ”,“ BYK-344 ”,“ BYK-370 ”(above, manufactured by Big Chemie Japan Co., Ltd.), Silicon surfactants such as “KP-112”, “KP-326”, “KP-341” (manufactured by Shin-Etsu Chemical Co., Ltd.); trade names “BYK-354”, “BYK-358”, Acrylic surfactants such as “BYK-361” (manufactured by Big Chemie Japan); trade names “DFX-18”, “Furgent 250”, “Furgent 251” (Neos Co., Ltd.) Fluorine-based surfactants such as

1.7.8. Epoxy curing accelerator (k)
The epoxy curing accelerator (k) of the present invention refers to an agent that accelerates the epoxy curing reaction without reacting itself. In the present invention, the thiol compound (E) is not included in the epoxy curing accelerator (k).
As the epoxy curing accelerator, “DBU”, “DBN”, “U-CAT”, “U” can be used because the curing temperature of the composition of the present invention can be lowered or the curing time can be shortened. -CAT SA1 "," U-CAT SA102 "," U-CAT SA506 "," U-CAT SA603 "," U-CAT SA810 "," U-CAT 5002 "," U-CAT 5003 "," U- "CAT 18X", "U-CAT SA841 / 851", "U-CAT SA881", "U-CAT 891" (trade name, manufactured by San Apro Co., Ltd.), "CP-001", "NV-203-R4" (The 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 further preferably 30 to 150% by weight with respect to 100% by weight of the epoxy curing agent (C).

2. Preparation method of thermosetting resin composition The composition of the present invention comprises a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton, an epoxy curing agent (C), a colorant (D), and a thiol compound ( E) can be prepared by mixing the solvent (F) and other additives as necessary.
Moreover, the composition of this invention is the epoxy compound (B) which has a fluorene skeleton, an epoxy hardening | curing agent (C), as needed, with the reaction liquid and mixed liquid which were obtained at the time of the synthesis | combination of the polyester amide acid (A) as it is. It can also be prepared by mixing with the solvent (F) used or other additives.

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

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

For example, when forming a decorative member using the composition of the present invention, the amount of ink used is overwhelmingly less than conventional coating methods, and it is not necessary to use a photomask or the like. An ink jet 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 forming a decorative member from the composition of the present invention using an inkjet method, a step of coating a substrate by applying the inkjet method to form a coating film (coating film forming step), and heat-treating the coating film A method having a step of forming a cured film (heating step) can be used. In this method, before the composition of the present invention is applied on the substrate, a surface treatment step (surface treatment step) is provided, and the composition of the present invention is applied onto the surface-treated substrate. It is preferable to form a film.

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.

The cured film produced in this way 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, a cured film having excellent adhesion with the 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 board, paper phenol board, paper epoxy board, green epoxy board, BT (bismaleimide triazine) resin board; copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, stainless steel, etc. A substrate made of any of these metals (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 silicic 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 spojumen Substrates made of inorganic substances (may be substrates having a layer containing these inorganic substances on the surface); PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene) Tele Talate), 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) (above, ( ) Registered trademark of Tayca), such gel sheet; and the like.
The composition of the present invention is preferably applied onto a PET substrate or a resin film substrate.

3.2. Curing method of thermosetting resin composition After applying the composition of the present invention, a cured film can be obtained by heating the composition applied on the substrate. As a method for forming a cured film in this manner, preferably, after applying the composition of the present invention, the solvent is removed by heating (drying treatment) by heating with a hot plate or an oven, etc. Further, a method of further heating (curing treatment) is used.

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

After forming the coating film, a curing treatment is usually performed at 70 to 300 ° C., preferably 80 to 300 ° C., more preferably 90 to 200 ° C. At this time, a cured film can be obtained by heat treatment usually for 10 to 120 minutes when using an oven, and usually 5 to 30 minutes when using a hot plate.
The curing treatment is not limited to heat treatment, and may be treatment such as ultraviolet ray, near infrared ray, far infrared ray, ion beam, electron beam or gamma ray irradiation.
For example, when irradiating near infrared rays, the near infrared rays used are in the 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 is in the range of 750 to 1200 nm, which is suitable for the production method of the present invention. Can be used for
Since the composition of the present invention contains the polyester amide acid (A), the epoxy compound (B) having a fluorene skeleton, and the thiol compound (E), the low temperature curability is good. For this reason, the cured film which is excellent in adhesiveness with a PET film, etc. can be formed by low-temperature baking at 120 ° C. or lower. Further, by using the colorant (D) and the thiol compound (E) in combination, it is possible to form a cured film having high adhesion to the PET film and better reliability than before.

4). Substrate with cured film The substrate with a cured film of the present invention is not particularly limited as long as it has the cured film of the present invention, but at least one substrate selected from the group consisting of the substrate, in particular, a PET substrate and a resin film substrate. It is preferable to have the above-mentioned cured film on it.
Such a substrate with a cured film, for example, on the substrate of glass, ITO, PET, PEN, etc., the composition of the present invention is applied to the entire surface or a predetermined pattern (line shape, etc.) by the coating method, Then, it can form by passing through the drying process and hardening process which were demonstrated above.

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

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. Epoxy compound (B) having a fluorene skeleton, other epoxy compounds, epoxy curing agent (C), colorant (D), thiol compound (E), solvent (F), reaction accelerator, antioxidant used in Examples Agent, surfactant (i), tetracarboxylic dianhydride (a1), diamine (a2), polyvalent hydroxy compound (a3), monohydric alcohol (a4) used for the synthesis of the polyester amic acid (A), The names and abbreviations of the reaction solvent (a5) and the polyhydric acid anhydride (a6) are shown. This abbreviation is used in the following description.

<Polyester amide acid (A)>
<Tetracarboxylic dianhydride (a1)>
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride <Diamine (a2)>
DDS: 3,3′-diaminodiphenylsulfone <Polyvalent hydroxy compound (a3)>
BDOH: 1,4-butanediol <monohydric alcohol (a4)>
BzOH: benzyl alcohol <Reaction solvent (a5)>
MPM: methyl 3-methoxypropionate

<Epoxy compound having a fluorene skeleton (B)>
EG-200: OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.) (epoxy equivalent 290, weight average molecular weight 2,000 or less)

<Other epoxy compounds>
C620: NANOPOX C620 (trade name, manufactured by EVONIK), epoxy resin containing 40% nanosilica EP4088S: Adeka Resin EP-4088S (trade name, manufactured by ADEKA Corporation)
S510: 3-Glycidoxypropyltrimethoxysilane (trade name: Sila Ace S510, manufactured by JNC Corporation)

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

<Colorant (D)>
Red 1: JN-8603 (trade name, manufactured by Tokushi Co., Ltd., solid content is 23.5% by weight of colorant (D), of which pigment solid content is 15% by weight of colorant (D) diethylene glycol ethyl methyl ether ( EDM) dispersion)
Yellow 1: JN-8602 (trade name, manufactured by Tokushi Co., Ltd., solid content is 23.5% by weight of colorant (D), of which pigment solid content is 15% by weight of colorant (D) EDM dispersion)
Blue 1: JN8561 BLUE (trade name, manufactured by Tokushi Co., Ltd., solid content is 23% by weight of colorant (D), of which solid content is 15% by weight of colorant (D) EDM dispersion)
Blue 2: JN8562 BLUE (trade name, manufactured by Tokushi Co., Ltd., solid content is 23% by weight of colorant (D), of which pigment solid content is 15% by weight of colorant (D) EDM dispersion)
Black 1: Marco 2011 Black (trade name, manufactured by Tokushi Co., Ltd., solid content is 37.5% by weight of colorant (D), of which pigment solid carbon black is 30% by weight of colorant (D) dipropylene glycol Methyl ether acetate (DPMA) dispersion)
Black 2: Marco 2004 Black (trade name, manufactured by Tokushi Co., Ltd., solid content 37.5% by weight of colorant (D), of which pigment solid content titanium black is 30% by weight of colorant (D) DPMA dispersion )

<Thiol compound (E)>
PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT PE1, manufactured by Showa Denko KK)
BD1: 1,4-bis (3-mercaptobutyryloxy) butane (trade name Karenz MT BD1, manufactured by Showa Denko KK)
NR1: 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name Karenz MT NR1, Showa Denko) (Made by Co., Ltd.)
TPMB: Trimethylolpropane tris (3-mercaptobutyrate)
DPMP: Dipentaerythritol Hexakis (3-mercaptopropionate)
Pemp: pentaerythritol tetrakis (3-mercaptopropionate)
TEMPIC: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate TMMP: Trimethylolpropane tris (3-mercaptopropionate)
TSG: Glycoluril derivative represented by the following chemical formula (8) (trade name TS-G, manufactured by Shikoku Kasei Kogyo Co., Ltd.)

<Solvent (F)>
HBM: Methyl 2-hydroxyisobutyrate MTM: Triethylene glycol dimethyl ether (trade name Highsolve MTM, manufactured by Toho Chemical Industry Co., Ltd.)
DB: Diethylene glycol monobutyl ether PGME: Propylene glycol monomethyl ether

<Antioxidant>
I1010: Irganox 1010 (trade name, manufactured by BASF)
<Surfactant>
RS-72K: Fluorine-based liquid repellent (trade name: Mega-Fac RS-72K, manufactured by DIC Corporation)
BYK-342: Silicon-based surface conditioner (trade name BYK-342, manufactured by Big Chemie Japan Co., Ltd.)

<Epoxy resin curing agent>
SA506: p-toluenesulfonate of diazabicycloundecene (DBU) (trade name U-CAT SA506, manufactured by San Apro Co., Ltd.)

<Polyester amide acid (A)>
First, polyester amic acid was synthesized as shown below (Synthesis Example 1).
[Synthesis Example 1]
A 1000 ml separable flask equipped with a thermometer, a stirring blade, a raw material charging inlet and a nitrogen gas inlet was charged with 46.96 g of dehydrated and purified MP31.93 g of BDOH, 25.54 g of BzOH and 183.20 g of ODPA under a dry nitrogen stream. Stir at 130 ° C. for 3 hours. Thereafter, the reaction solution was cooled to 25 ° C., 29.33 g of DDS and 183.04 g of MPM were added, and stirred at 20 to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour. Thereafter, by cooling to 30 ° C. or lower, a pale yellow transparent 30% by weight solution of polyester amic acid was obtained.

The rotational viscosity of this solution was 28.2 mPa · s. Here, the rotational viscosity is a value measured at 25 ° C. using an E-type viscometer (trade name; TVE-22LT, manufactured by Toki Sangyo Co., Ltd.) (hereinafter the same).

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

[Example 1]
A 50 ml three-necked flask equipped with a stirring blade was purged with nitrogen, and 3 g of the polyester amic acid (A) solution obtained in Synthesis Example 1 (the amount of the polyester amic acid (A) in the solution was 0.9 g) , 1.80 g of EG-200 (the amount of the epoxy compound (B) having a fluorene skeleton is 1.80 g), 0.27 g of TMA, 8.97 g of HBM, 1.80 g of DB, and 0.80 of RS-72K. 03 g was charged. Then, it stirred at 25 degreeC (room temperature) for 1 hour, and dissolved each component uniformly. Next, 0.31 g of Red 1 was added and stirred at 25 ° C. for 1 hour, followed by filtration with a membrane filter (material: nylon, pore size: 5 μm) to obtain a thermosetting resin-containing composition as a filtrate.

[Examples 2 to 26]
In Examples 2 to 26, curable resin compositions were prepared in the same manner as in Example 1 except that the types and amounts of each component were changed as shown in Tables 2, 3 and 4. In addition, the preparation amount of each component in the table indicates weight (g) (the same applies to the following tables).

[Comparative Examples 1 to 8]
In Comparative Examples 1 to 8, curable resin compositions were prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 5. In Comparative Example 1, the thiol compound (E) was blended without blending the colorant (D). In Comparative Examples 2 to 7, the colorant (D) was blended and the thiol compound (E) was not blended.

[Evaluation]
About an Example and a comparative example, application | coating was implemented on the following conditions on the board | substrate by inkjet printing.
Substrate: PET substrate (thickness: 50 μm) Brand name: Lumirror T60, manufactured by Toray Industries, Inc.
The PET film was subjected to UV ozone ashing using an optical surface treatment apparatus (light source: PL2003N-12, power source: UE2003N-8) manufactured by Sen Special Light Source Co., Ltd. before the cured film was produced.
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 19-20V (set to discharge speed 10m / s), drive waveform Dimatix Model Fluid2, drive frequency 5kHz, dot spacing 15-20μm, single-sided single layer printing

First, the jetting characteristics relating to inkjet ejection were evaluated, and then the applied sample was dried under the following conditions, followed by firing to cure the thermosetting resin composition and form a cured film on the substrate. The obtained sample substrate was obtained.
Curing conditions Main baking process Clean oven DT-610 manufactured by Yamato Scientific Co., Ltd.
Temperature setting: 120 ° C., 10 minutes In Examples 23-1 and 23-2 described later, curing was performed under the following conditions.
Example 23-1
Main firing process Yamato Science Co., Ltd. clean oven DT-610
Temperature setting: 75 ° C., 10 minutes Example 23-2
Curing Step After ink jet printing, near-infrared irradiation was performed with the following near-infrared irradiation device, followed by heating with an oven to obtain a cured film.
Near-infrared irradiation device: Conveyor type near-infrared irradiation device manufactured by Adphos Output: 2.5 kW * 3, 40%
Board-lamp distance: 150mm
Irradiation time: 6 seconds The cured film thus obtained was evaluated for OD value and adhesion with a PET (polyethylene terephthalate) film.

[Jetting characteristics]
(I) Evaluation of inkjet discharge stability (continuous discharge stabilization time)
Ink (thermosetting resin composition) was started to be ejected 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.
In Tables 6 to 9, the numbers in the column of continuous discharge stabilization time indicate the time (minutes) when a defective nozzle is generated, and “10 or more” indicates that a defective nozzle is not generated after 10 minutes. Means that.

(Ii) Re-ejectability After 1 minute has elapsed from the stop of ink ejection, ink was ejected again, and the ejection state was observed. In the case where no discharge failure was found, after 3 minutes had elapsed after stopping the discharge, the discharge was performed again and the discharge state was observed. Similarly, after 5 minutes, 7 minutes, and 10 minutes, the re-ejectability was evaluated and the elapsed time until a discharge failure was found was measured. In Tables 6 to 9, the numbers shown in the re-ejection property column indicate the elapsed time when ejection failure was found.

[color]
A sample substrate obtained using the curable resin composition according to each of the above samples was placed on a white calibration plate (“CR-A43” manufactured by Konica Minolta Co., Ltd.), and a spectrocolorimeter (Konica Minolta Co., Ltd.). Using “CM-600d”), reflected light measurement (regular reflection light field of view: 2 degrees, light source: D65) is performed from the PET substrate side, and color coordinates of L * a * b * color system (SCI method) I got the data.

[OD value (Optical Density)]
For the thermosetting resin compositions of Examples and Comparative Examples, a cured film having a thickness of 4 μm was formed on a PET substrate, and the Y value was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation. It was measured. The OD value was calculated from the Y value according to the following formula.
OD = -log (Y / 100)
By dividing this value by the thickness of the cured film, the OD value per unit μm, that is, per 1 μm film thickness of the cured film was calculated.

[Adhesion with PET film]
For PET film (thickness: 50 μm, brand name: Lumirror T60, manufactured by Toray Industries, Inc.), an optical surface treatment device (light source: PL2003N-12, power source: UE2003N-8) manufactured by Sen Special Light Source Co., Ltd. was used before producing a cured film. Then, UV ozone ashing treatment was performed. A square (3 cm × 3 cm) cured film was formed on each PET film, and the adhesion of the cured film to the PET film was evaluated using a cross-cut method. Evaluation of adhesion was performed on a cured film immediately after production (initial adhesion evaluation) and a cured film (adhesion evaluation after treatment) after storage for 120 hours under conditions of a temperature of 85 ° C. and a humidity of 85%. For Examples 23-1 and 23-2 described later, a cured film obtained by immersing in a 5 wt% sodium chloride aqueous solution at 25 ° C. for 72 hours, and then cleaning the substrate with pure water and wiping the moisture with a nonwoven fabric, or −40 Cured film that was subjected to 30 cycles of 1 hour at 85 ° C. and 1 hour at 85 ° C., or a xenon weathering tester (manufactured by Suga Test Instruments Co., Ltd., trade name: SX-75, irradiance 180 W / m ² , black The adhesion of the cured film after testing at a panel temperature of 63 ° C. and 50% RH for 72 hours was also evaluated. The result of the adhesion evaluation after the treatment indicates the reliability of the cured film.
In the cross-cut method, a line of 1 mm intervals is drawn with a cutter 11 by 11 in length and width, and after producing 100 grids, the ratio of the cured film peeled off from the substrate surface is applied to ASTM D3359 by applying tape and peeling. Based on the evaluation.
As the tape for peeling, Scotch # 610, manufactured by 3M: 402 N / 100 mm (longitudinal direction) was used.
Evaluation criteria based on ASTM D3359 are as follows.
0B: 65% or more 1B: 35% or more, 65% or less 2B: 15% or more, 35% or less 3B: 5% or more, 15% or less 4B: 5% or less 5B: No peeling

[Storage stability (viscosity)]
The compositions of Examples and Comparative Examples were stored for 7 days at room temperature (25 ° C.), and then the viscosity was measured after 14 days and 21 days.
When the viscosity increase value after 7 days or 21 days with respect to the initial viscosity (0 days) was 0.8 mPa · s or more, Δ was evaluated, and when it was less than 0.8 mPa · s, ○ was evaluated.

As shown in Tables 6 to 8, all the cured products formed from the compositions of Examples 1 to 26 using the colorant (D) and the thiol compound (E) in combination with the initial PET film The adhesion was good (5B). On the other hand, as shown in Table 9, all of Comparative Examples 2 to 7 containing only the colorant (D) had slightly poor initial adhesion (4B). Moreover, in the comparative example 1 which mix | blended only the thiol compound (E), the initial adhesiveness was 1B. Moreover, the cured film of an Example showed the tendency which the adhesiveness (reliability) after a 120-hour preservation | save on conditions of temperature 85 degreeC and humidity 85% improves compared with the cured film of a comparative example. From these results, a cured film having good adhesion and reliability with a PET film can be formed by low-temperature baking at 120 ° C. or less by blending with the colorant (D), the thiol compound (E) and the composition. You can see that

From the test results of the cured products formed from the compositions of Examples 23 to 26, in order to improve the adhesion to the PET film after the environmental test, PGME (propylene glycol monomethyl ether) was used as the solvent (F). It has been found preferable to include.

Further, from the results of Comparative Examples 2 to 7, the composition containing the colorant (D) had a problem that the storage stability was poor (Δ). In contrast, many of the compositions of Examples 1 to 22 containing the colorant (D) and the thiol compound (E) have good storage stability (◯). From this result, it was found that the storage stability was improved by adding the thiol compound (E) to the composition containing the colorant (D).

[Reference Examples 1 to 11]
In Reference Examples 1 to 11, curable resin compositions were prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 10.
[Storage stability (viscosity)]
About each reference example, the viscosity was measured after preserve | saving for 7 days, 14 days, and 30 days on 45 degreeC conditions. The ratio (%) to the initial viscosity of 100 was calculated by the following formula using the viscosity after the storage stability test and the initial viscosity.
Ratio (%) with initial viscosity 100 = (viscosity after storage stability test / initial viscosity) × 100

As shown in Table 10, all of the compositions of Reference Examples 1 to 11 containing the thiol compound (E) had good storage stability under high temperature conditions.

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

Claims (13)

1. Polyester amide acid (A), epoxy compound (B) having fluorene skeleton, epoxy curing agent (C), colorant (D), thiol compound (E) having a plurality of thiol groups in the molecule and solvent (F) A thermosetting resin composition.
2. The thiol compound (E) is pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and glycol of the following chemical formula (8) 1 selected from the group consisting of uril derivatives Others are two or more compounds, the thermosetting resin composition of claim 1.
   

   
3. The content of the thiol compound (E) is 0.1 to 20 parts by weight in 100 parts by weight of the solid content (excluding the solvent from the total solution) in the thermosetting resin composition. The thermosetting resin composition according to claim 1 or 2.
4. The content of the colorant (D) is 0.1 to 70% by weight in 100 parts by weight of the solid content excluding the colorant (D) in the thermosetting resin composition (excluding the solvent from the whole solution). The thermosetting resin composition according to any one of claims 1 to 3, wherein the thermosetting resin composition is a part.
5. The thermosetting resin composition according to any one of claims 1 to 4, wherein an epoxy equivalent of the epoxy compound (B) having a fluorene skeleton is 200 to 550 g / eq.
6. The content of the epoxy compound (B) having the fluorene skeleton is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid (A). Thermosetting resin composition.
7. The thermosetting resin composition according to any one of claims 1 to 6, wherein the polyester amic acid (A) has a weight average molecular weight of 2,000 to 20,000.
8. The thermosetting resin composition according to any one of claims 1 to 7, wherein the polyester amic acid (A) is a compound having a structural unit represented by formulas (3) and (4).
   

   

   (Wherein R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is independently a divalent organic group having 1 to 40 carbon atoms, and R ³ is independently 1 carbon atom) A divalent organic group of ˜20.)
9. A cured film obtained from the thermosetting resin composition according to any one of claims 1 to 8.
10. The cured film according to claim 9, obtained by firing the thermosetting resin composition at 130 ° C. or lower.
11. A substrate with a cured film, comprising the cured film according to claim 9 or 10.
12. An electronic component having the cured film according to claim 9 or 10, or the substrate with the cured film according to claim 11.
13. An inkjet ink comprising the thermosetting resin composition according to any one of 1 to 8.