JP6127908B2 - Thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition containing a specific amount of a polyamic acid having a specific structure, an epoxy resin, an epoxy curing agent, and a specific mixed solvent, and coating the resin composition on a support by an inkjet method. It relates to a cured film. More specifically, for example, the present invention relates to a thermosetting resin composition used for forming an insulating film layer in the production of electronic components, and a cured film formed by using this resin composition by an inkjet method, and an electronic material having the cured film. The present invention relates to a circuit board and an electronic component having the electronic material board.

  Patterned cured films are used in the field of electronic communication. Conventionally, such a patterned cured film has been formed by etching after forming a cured film using a photosensitive material or the like. However, the formation of a patterned cured film by this method requires a large amount of materials and chemicals such as a photoresist, a developing solution, an etching solution and a stripping solution, and a complicated process. For this reason, this method was inferior in productivity.

  Therefore, in recent years, a method of directly forming a desired patterned cured film by an ink jet method has been studied. Ink jet ink is used in this ink jet method. Various ink-jet inks have been proposed (Patent Documents 1 and 2). In this inkjet ink, various parameters such as ink viscosity, surface tension, and boiling point of the solvent must be optimized from the viewpoints of ejectability and printability.

In the field of electronic materials, since it is excellent in heat resistance and electrical insulation, an amic acid derivative or an imidized product thereof is widely used as the material (Patent Documents 3 to 6).
Various ink-jet inks for forming a polyimide film have been proposed (Patent Documents 7 to 15) such as an ink containing polyimide and an ink containing polyamic acid that becomes polyimide by heat treatment.

  In the inkjet ink for forming a cured film, it is important that the obtained cured film has predetermined functions and characteristics in addition to the necessary properties such as viscosity, surface tension, and boiling point of the solvent as described above. It is. For example, electrical characteristics such as volume resistivity, withstand voltage, dielectric constant and dielectric loss, mechanical properties such as bending test, elastic modulus and tensile elongation, chemical stability such as acid resistance, alkali resistance and plating resistance Various characteristics such as thermal characteristics such as thermal decomposition temperature, glass transition temperature and thermal linear expansion coefficient are required to be in a specific range. Furthermore, secondary characteristics such as adhesion to the substrate, warpage resistance due to shrinkage during film formation, and migration resistance are also required. The ink-jet ink is also required to have patternability and storage stability.

  Amic acid or imidized product thereof has been widely used for electronic materials as a film-forming resin having excellent electrical, mechanical, chemical and thermal properties. However, ink jet inks for forming cured films are prepared. However, there are various limitations, and it has not been easy to prepare an ink-jet ink having the required characteristics in a well-balanced manner. In particular, it has not been easy to prepare an inkjet ink that is excellent in ejection stability, pattern accuracy, and storage stability.

  For example, Patent Document 6 describes a resin composition containing a specific amide acid or the like and an organic solvent, and has good cured film properties such as transparency, heat resistance, and chemical resistance. On the other hand, there is no description regarding the solvent composition in Patent Document 6, and in the case of the solvent composition described in Example 5, there was a defect in ejection stability and pattern accuracy.

  For example, Patent Document 15 describes a composition containing a vinyl polymer and a specific organic solvent, and the ejection stability is good. On the other hand, when the solvent composition described in Example 1 of Patent Document 15 and the component (A) of the present invention were combined, defects occurred in ejection stability and pattern accuracy.

Conventionally, the solvent to be used is limited from the viewpoint of solubility of polyimide or polyamic acid to be dissolved. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, which is a good solvent for polyamic acid or polyimide, N , N-diethylacetamide, N, N-dimethylpropionamide, and dimethyl sulfoxide (DMSO) are generally used (Patent Documents 15 to 17).
On the other hand, an inkjet ink for forming a polyimide film using a single of these solvents is prepared with an excellent balance of the viscosity, surface tension, pattern accuracy and storage stability of the ink, and the required properties of the resulting polyimide film It was not easy to do.

JP 2003-213165 A JP 2006-131730 A JP 2000-039714 A JP 2003-238683 A JP 2004-094118 A JP 2005-105264 A JP 2009-35700 A International Publication No. 2008/123190 JP 2009-144138 A International Publication No. 2008/059986 JP 2009-203440 A JP 2009-221309 A JP 2009-12081A JP 2010-189631 A International Publication No. 2007-02804 Pamphlet JP-A-60-210630 JP 59-164328 A

  An object of the present invention is to provide a thermosetting resin composition that has good dischargeability and storage stability and can draw a desired pattern.

  Another object of the present invention is to provide a thermosetting resin composition capable of easily optimizing parameters such as viscosity, surface tension, and boiling point of a solvent so as to be an ink excellent in dischargeability and printability. .

  The present inventors diligently studied to solve the above problems. As a result, it was found that the above-mentioned problem can be solved by making the thermosetting resin composition a composition containing an amic acid derivative having a specific structure or an imidized product thereof and a specific mixed solvent having a specific quantitative ratio. The present invention has been completed. That is, the present invention is as follows.

(1) Resin composition containing polyester amide acid, epoxy resin, epoxy curing agent, solvent (A) and solvent (B) obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential components The polyester amide acid is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compound so that the relationship of the following formulas (1) and (2) is established. Obtained by reacting at a certain ratio,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)
The epoxy resin is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid, the epoxy curing agent is 15 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin, and the solvent (A) is Thermal curing, which is triethylene glycol dimethyl ether, and the solvent (B) is at least one selected from diethylene glycol ethyl methyl ether, methyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether, and γ-butyrolactone Resin composition.

(2) The thermosetting resin composition according to item 1, wherein the polyesteramide acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound and monohydric alcohol as essential components. .

(3) The polyester amic acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, monohydric alcohol and silicon-containing monoamine as essential components, and the silicon-containing monoamine is 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amino Butylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, paminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltri The thermosetting resin composition according to claim 1 is at least one selected from Tokishishiran and m- aminophenyl methyl diethoxy silane.

(4) Item 2 or 3 wherein the monohydric alcohol is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane. Thermosetting resin composition.

(5) The thermosetting resin composition according to any one of Items 1 to 4, wherein the polyester amic acid is a polyester amic acid obtained by further reacting with a styrene-maleic anhydride copolymer.

ここで、Ｒ_１はテトラカルボン酸二無水物残基であり、Ｒ_２はジアミン残基であり、Ｒ_３は多価ヒドロキシ化合物残基である。 (6) The thermosetting resin composition according to any one of Items 1 to 5, wherein the polyester amide acid is a compound having structural units represented by the following formulas (3) and (4).

Here, R ₁ is a tetracarboxylic dianhydride residue, R ₂ is a diamine residue, and R ₃ is a polyvalent hydroxy compound residue.

(7) Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 Any one of Items 1 to 6, which is at least one compound selected from-(bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) The thermosetting resin composition according to item.

(8) The item 1-7, wherein the diamine is at least one compound selected from 3,3′-diaminodiphenylsulfone and bis (4- (3-aminophenoxy) phenyl) sulfone. Thermosetting resin composition.

(9) The polyvalent hydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol Item 9. The thermosetting resin composition according to any one of Items 1 to 8, which is at least one compound.

(10) The epoxy resin is polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer. Item 10. The thermosetting resin composition according to any one of Items 1 to 9, which is at least one compound selected from an epoxy group-containing polymer of a styrene-glycidyl methacrylate copolymer.

(11) The thermosetting resin composition according to any one of Items 1 to 9, wherein the epoxy resin is an alicyclic epoxy resin.

(12) The thermosetting resin composition according to any one of Items 1 to 11, wherein the epoxy curing agent is trimellitic anhydride.

(13) The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, the polyvalent hydroxy compound is 1, Item 1 or 4 which is 4-butanediol, the epoxy resin is an n-butyl methacrylate-glycidyl methacrylate copolymer, the epoxy curing agent is trimellitic anhydride, and the solvent (B) is methyl 3-methoxypropionate 2. The thermosetting resin composition according to 2.

(14) The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, the polyvalent hydroxy compound is 1, 4-butanediol, monohydric alcohol is benzyl alcohol, epoxy resin is n-butyl methacrylate-glycidyl methacrylate copolymer, epoxy curing agent is trimellitic anhydride, and solvent (B) is 3- Item 4. The thermosetting resin composition according to Item 2 or 3, which is methyl methoxypropionate.

(15) The thermosetting resin composition according to any one of Items 1 to 14, wherein the polyesteramidic acid has a weight average molecular weight of 2,000 to 200,000.

(16) The thermosetting resin composition according to any one of items 1 to 14, wherein the epoxy resin has a weight average molecular weight of 10,000 to 1,000,000.

(17) A cured film obtained by applying the thermosetting resin composition according to any one of Items 1 to 16 onto a support by an inkjet method to form a coating film, and heating the coating film .

(18) The cured film according to claim 17, which has a pattern shape.

(19) A substrate for electronic material having the cured film according to claim 17 or 18.

According to the present invention, it is possible to obtain an ink-jet ink that has good dischargeability and storage stability and can draw a desired pattern.
Moreover, if the inkjet ink of this invention is used, a pattern-shaped cured film can be formed by drawing only in a required part by the inkjet method. As a result, it is not necessary to use a photoresist, an etching solution, or the like, which has been used when forming a cured film having a conventional pattern, and the number of steps required for manufacturing can be reduced. A cured film can be easily produced.

  Specific examples of the tetracarboxylic dianhydride used in the present invention include 3,3 ′, 4,4′benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl Sulfonetetracarboxylic 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)] hexafluoroprop Dianhydrides and aromatic tetracarboxylic dianhydrides such as 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 Mention may be made of aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydrides.

  Among these, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride give resins having good transparency , 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.) 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are particularly preferred.

  Specific examples of the diamine used in the present invention include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, and bis [4- (4-aminophenoxy) 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, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, etc. Can be mentioned. Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that give a resin having good transparency are preferable, and 3,3′-diaminodiphenylsulfone is particularly preferable.

  Specific examples of the polyvalent hydroxy compound used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 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-pentane Diol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6 hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1,7 -F Tandiol, 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-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol Glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), 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 because of their good solubility in solvents.

  Specific examples of the monohydric alcohol used in the present invention 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 monoethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, 3-ethyl- And 3-hydroxymethyl oxetane .

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferable. In consideration of the compatibility when the polyester amide acid formed by using these, an epoxy resin and an epoxy curing agent are mixed, and the applicability on the color filter of the thermosetting resin composition as the final product, As the alcohol, benzyl alcohol is more preferably used.

  Specific examples of the silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-amino. Butyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Examples thereof include methyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane are preferable, and 3-aminopropyltriethoxysilane is particularly preferable because of good acid resistance of the coating film.

In the method for producing the polyester amide acid used in the present invention, X mol of tetracarboxylic dianhydride, Y mol of diamine, and Z mol of polyvalent hydroxy compound are reacted in the above solvent. At this time, it is preferable that X, Y, and Z are set to such a ratio that the relationship of the following formulas (1) and (2) is established between them. If it is this range, the solubility to the solvent of a polyester amide acid is high, therefore the applicability | paintability of a composition improves, As a result, the cured film excellent in flatness can be obtained.
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)
The relationship of the formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. In addition, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) /X≦0.9, more preferably 0.7 ≦ (Y + Z) /X≦0.8.

  In consideration of the case where the polyester amide acid used in the present invention has an acid anhydride group at the molecular end, the above-described monohydric alcohol can be added and reacted. The polyester amide acid added with the monohydric alcohol is improved in compatibility with the epoxy resin and the epoxy curing agent, and the applicability of the thermosetting resin composition of the present invention containing them is improved.

  Moreover, when the silicon-containing monoamine described above is reacted with a polyester amide acid having an acid anhydride group at the molecular end, the acid resistance of the obtained coating film is improved. Furthermore, the monohydric alcohol and the silicon-containing monoamine can be reacted with the polyester amic acid at the same time.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, since the reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours. When the silicon-containing monoamine is reacted, after the reaction of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added. It is good to make it react at -40 degreeC for 0.1 to 6 hours. Further, the monohydric alcohol may be added at any point in the reaction.

  The order of adding the reaction raw materials to the reaction system is not particularly particular. That is, tetracarboxylic dianhydride and diamine and polyvalent hydroxy compound are simultaneously added to the reaction solvent, diamine and polyvalent hydroxy compound are dissolved in the reaction solvent, and then tetracarboxylic dianhydride is added, or tetra Any method can be used such as reacting carboxylic dianhydride and diamine in advance, and then adding a polyvalent hydroxy compound to the reaction product. The weight average molecular weight of the obtained polyester amide acid is preferably 2,000 to 200,000, and more preferably 3,000 to 150,000. This is because the chemical resistance is preferably as high as the molecular weight and the solubility in the solvent is as low as possible.

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

The polyester amide acid synthesized in this way contains the structural unit consisting of the above formulas (3) and (4), and the terminal thereof is an acid derived from tetracarboxylic dianhydride, diamine or polyvalent hydroxy compound as a raw material. It is an anhydride group, an amino group or a hydroxy group, or an additive other than these compounds constitutes the terminal. In Formulas 3 and 4, R ₁ is a tetracarboxylic dianhydride residue, preferably an organic group having 2 to 30 carbon atoms. R ₂ is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R ₃ is a polyvalent hydroxy compound residue, preferably an organic group having 2 to 20 carbon atoms.

  The epoxy resin used in the present invention is not particularly limited as long as it has good compatibility with the other components forming the thermosetting resin composition of the present invention, but is preferably a bisphenol A type epoxy resin or a glycidyl ester type. Examples thereof include an epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having an epoxy group, and a copolymer of a monomer having an epoxy group and another monomer.

  Specific examples of the epoxy resin include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (and above). Trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, Araldite CY184 (above trade name, manufactured by BASF), Celoxide 2021, EHPE-3150 (above trade name, manufactured by Daicel Chemical Industries, Ltd.), HP7200, HP7200H , HP7200HH (above trade name, manufactured by DIC Corporation), TEPIC-VL, TEPIC-B22 (above trade name, manufactured by Nissan Chemical Industries, Ltd.), MA-DGIC, DA-MGIC (above trade name, Shikoku Kasei Corporation )), EPPN 501H, EPPN-502H, EPPN-201, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names, Nippon Kayaku Co., Ltd.), JER 1032H60, JER 157S65, JER 157S70, JER 152, 154 (Trade name, manufactured by Mitsubishi Chemical Corporation), and TECHMORE VG3101L (trade name, manufactured by Printec Co., Ltd.). Two or more epoxy resins used in the present invention may be mixed and used. When an epoxy resin having a molecular weight of less than 10,000 and an epoxy resin having a molecular weight of 10,000 or more are mixed and used, the chemical resistance is good when the epoxy resin having a molecular weight of 10,000 or more is 5% by weight or more of the entire epoxy resin. Therefore, it is preferable.

  Among these, an alicyclic epoxy resin, a polymer of a monomer having an epoxy group, and a copolymer of a monomer having an epoxy group and another monomer are particularly preferable because of excellent transparency.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Among these, glycidyl methacrylate is preferable because it can provide a cured film having good chemical resistance.

  Specific examples of other monomers copolymerized with a monomer having an epoxy group include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2hydroxypropyl (meth) acrylate, styrene, methylstyrene , Chloromethylstyrene, and N-phenylmaleimide. Among these, methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl whose copolymer is excellent in compatibility with the polyester amide acid used in the present invention. More preferred are (meth) acrylates and styrene.

  Preferable specific examples of a polymer of a monomer having an epoxy group and a copolymer of a monomer having an epoxy group and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, and benzyl methacrylate-glycidyl methacrylate copolymer. Examples of the polymer include n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

  The proportion of the copolymer of the monomer having an epoxy group and another monomer is preferably 30% by mole or more of the monomer having an epoxy group because the chemical resistance is excellent. More preferably, the monomer having an epoxy group is 50 mol% or more. The molecular weight of the polymer of the monomer having an epoxy group or the copolymer of a monomer having an epoxy group and another monomer is preferably 10,000 to 1,000,000 in terms of weight average molecular weight, and preferably 50,000 to 500, 000 is more preferable. This is because the chemical resistance is better as the molecular weight is higher, and the solubility in the solvent is better as the molecular weight is lower.

  In order to improve heat resistance and chemical resistance, it is effective to add an epoxy curing agent to the thermosetting resin composition of the present invention. Examples of the epoxy curing agent include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst curing agent, and an acid anhydride curing agent is preferable from the viewpoint of coloring and heat resistance.

  Specific examples of the acid anhydride-based curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and aliphatic dicarboxylic anhydrides such as methylhexahydrophthalic anhydride, phthalic anhydride, and trimellitic anhydride. And aromatic polycarboxylic acid anhydrides such as styrene-maleic anhydride copolymer. Among these, trimellitic anhydride is particularly preferable from the viewpoint of the balance between heat resistance and solubility in a solvent.

  The thermosetting resin composition of this invention is 20-400 weight part of epoxy resins with respect to 100 weight part of polyester amic acid. When the epoxy resin is within this range, the balance of flatness, heat resistance, chemical resistance and adhesion is good. The epoxy resin is more preferably in the range of 50 to 200 parts by weight.

  When the epoxy curing agent is added for the purpose of improving heat resistance and chemical resistance, the ratio of the epoxy resin and the epoxy curing agent is 0 for the carboxylic anhydride group or carboxylic acid group as the epoxy curing agent with respect to the epoxy group. It is preferable to add in an amount equivalent to 2 to 2 times. At this time, the carboxylic acid anhydride group is calculated as divalent. Addition of the carboxylic acid anhydride group or the carboxylic acid group in an amount of 0.5 to 1.5 times equivalent is more preferable because the chemical resistance is further improved.

  The solvent used in the present invention is such that the solvent (A) is triethylene glycol dimethyl ether (MTM), the solvent (B) is diethylene glycol ethyl methyl ether (EDM), methyl 3-methoxypropionate (MMP), 2-hydroxy It is not particularly limited as long as it is at least one solvent selected from methyl isobutyrate (HBM), propylene glycol monomethyl ether (PGME), and γ-butyrolactone (GBL), and good storage stability can be obtained by mixing with these solvents. Ink can be obtained, and the pattern accuracy can be improved.

  Since the mixed solvent of the solvent (A) and the solvent (B) can easily dissolve the polyester amide acid and the epoxy resin, it can be preferably used as a solvent for the inkjet ink.

  In the ink of the present invention, the total amount of the solvent (A) and the solvent (B) is preferably 65 to 100 with respect to 100% by weight of the total of the solvent (A), the solvent (B) and the other solvent (C). It is contained in an amount of wt%, more preferably 70 to 100 wt%, and still more preferably 75 to 100 wt%. Further, the amount of the solvent (A) is 10 to 95% by weight, more preferably 15 to 90% by weight, still more preferably 20 to 90% by weight with respect to the total of 100% by weight of the solvent (A) and the solvent (B). Contains. When the total amount of the solvent (A) and the solvent (B) and the mixing ratio of the solvent (A) and the solvent (B) are within the above ranges, the ink has good storage stability, dischargeability and patternability. Ink that is unlikely to cause deterioration of the inkjet head or the like can be obtained. In addition, since components other than the materials can be easily dissolved, components other than the solvent are not clogged in the ink jet head, and components other than the solvent do not precipitate during ink storage.

  If the solvent (C) is a compound other than the solvent (A) and the solvent (B) and can dissolve components other than the solvent by mixing with the solvent (A) and the solvent (B), There is no particular limitation.

The solvent (C) is preferably a solvent having a boiling point in the range of preferably 80 to 300 ° C, more preferably 100 to 270 ° C.
Furthermore, as the solvent (C), those having low toxicity are preferred. In the present invention, toxicity means comprehensively acute toxicity, mutagenicity, skin irritation, eye irritation, carcinogenicity and the like.

  Specific examples of the solvent (C) include ethanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol Methyl ether, triethylene glycol divinyl ether, propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, dipropylene Glycol monomethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, α-acetyl-γ-butyrolactone, ε-caprolactone, γ-hexanolactone, δ-hexanolactone, methyl ethyl sulfoxide and diethyl sulfoxide Is mentioned.

  As for the said solvent (C), only 1 type may be used and 2 or more types may be mixed and used for it.

The thermosetting resin composition according to the present invention may contain other components other than the above, if necessary, as long as the object of the present invention is not impaired. Examples of such other components include a coupling agent and a surfactant.
The coupling agent is used to improve the adhesion to the substrate, and is 100 parts by weight of the solid content of the thermosetting resin composition (the remaining component excluding the solvent from the resin composition). It is used by adding 10 parts by weight or less.

As the coupling agent, silane-based, aluminum-based and titanate-based compounds can be used.
Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane, and aluminum such as acetoalkoxyaluminum diisopropylate And titanate systems such as tetraisopropyl bis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

  The surfactant is used to improve the wettability, leveling property, or coating property to the base substrate, and is added in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the thermosetting resin composition. Used. As the surfactant, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used. Specifically, silicon systems such as Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (above trade names, manufactured by BYK Chemie Co., Ltd.) , Byk-354, ByK-358, and Byk-361 (above trade names, manufactured by Big Chemie Co., Ltd.) and the like, DFX-18, Aftergent 250, and Aftergent 251 (above trade names, Neos ( Product)).

Viscosity of ink The viscosity of the ink of the present invention at the temperature (ejection temperature) when ejected from an inkjet coating apparatus is preferably 1 to 50 mPa · s, more preferably 3 to 20 mPa · s, and further preferably 4 to 15 mPa · s. s. When the viscosity is within the above range, an ink having excellent ejection accuracy can be obtained. When the viscosity is lower than 50 mPa · s, ejection failure is unlikely to occur.

  For example, it is preferable that the viscosity of the ink after being stored at a predetermined temperature for 7 days is also in the above range. The change in ink viscosity at the time of ink preparation and after standing for 7 days is preferably within 15%. If it exceeds 15%, it is often necessary to change the ejection conditions, and there is a possibility that ejection becomes impossible.

  The viscosity of the ink can be adjusted by appropriately selecting the type and amount of the solvent used according to the component (A) used.

  In many cases, the ink is ejected at room temperature (25 ° C.). Therefore, the viscosity of the ink of the present invention at 25 ° C. is preferably in the same range as the preferred viscosity range at the ejection temperature.

Ink surface tension The surface tension of the ink of the present invention is preferably 20 to 70 mN / m, more preferably 20 to 45 mN / m. It is preferable that the surface tension is within the above-mentioned range because droplets having a desired size and shape can be easily formed at the time of discharge, and ink having good discharge properties can be obtained.
The surface tension of the ink can be adjusted by appropriately selecting the type and the amount of the solvent used and, if necessary, using a surfactant according to the component (A) to be used.

Cured film The cured film of the present invention is formed from the ink of the present invention.
The cured film is excellent in heat resistance and electrical insulation, and can improve the reliability and yield of electronic components.

Forming method of cured film (manufacturing method)
The cured film is preferably a step of applying the ink of the present invention on a support by an inkjet method to form a coating film (hereinafter also referred to as “coating film forming step”) and a step of curing the coating film. (Hereinafter also referred to as “curing step”). Further, a cured film having a predetermined pattern (for example, a line) can be formed by the same method. When the ink of the present invention is ejected in a pattern, a patterned cured film can be formed. In the present specification, unless otherwise specified, the cured film includes a patterned cured film.

Coating film forming step The coating film forming step can be performed by an ink jet method using an ink jet coating apparatus.
Examples of the ejection method in the inkjet method include a piezoelectric element type, a bubble jet (registered trademark) type, a continuous ejection type, and an electrostatic induction type ejection method, and a piezoelectric element type ejection method is preferable.
The ink of the present invention can be ejected by various methods by appropriately selecting each component contained, and can be applied in a predetermined pattern.

  The inkjet coating apparatus is not limited to a configuration in which the inkjet head and the ink storage unit are separated from each other, and may have a configuration in which they are integrated so as not to be separated. Further, the ink storage unit may be integrated with the inkjet head so as to be separable or non-separable and mounted on the carriage, or may be provided at a fixed portion of the apparatus. In the latter case, the ink may be supplied to the coating head through an ink supply member, for example, a tube.

  Further, in the case where the ink tank is provided with a configuration for applying a preferable negative pressure to the ink jet head, a configuration in which an absorber is disposed in the ink storage portion of the ink tank, or a flexible ink storage bag, On the other hand, the form etc. which have the spring part which applies the force of the direction which expands the internal volume are employable.

  The coating device may be a serial printer or a line printer in which coating elements are aligned over a range corresponding to the entire width of the coating medium.

  The discharge temperature at the time of discharging the ink of the present invention may be appropriately adjusted depending on the viscosity of the ink to be used, but is preferably 10 to 50 ° C, more preferably 15 to 40 ° C.

  Examples of the support include a glass epoxy support, a glass composite support, and a paper phenol support that meet various standards for printed circuit boards such as FR-1, FR-3, FR-4, CEM-3, or E668. Paper epoxy support, green epoxy support and BT resin support.

  Further, for example, a support made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or stainless steel (a support having a layer made of these metals on the surface. Aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate, lead titanate (PT), titanium Lead zirconate (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), A support made of an inorganic substance such as boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spodumene (may be a support having a layer made of these inorganic substances on the surface) PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylenedimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyimide resin, polyamide resin, Polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic A support made of a resin such as a lastomer or a liquid crystal polymer (may be a support having a layer made of these resins on its surface); a semiconductor support made of silicon, germanium, gallium arsenide, or the like (eg, a silicon wafer); glass Support: a support on which an electrode material (wiring) such as tin oxide, zinc oxide, ITO (indium tin oxide) or ATO (antimony tin oxide) is formed; αGEL (alpha gel), βGEL (beta gel), θGEL (Theta gel) or γGEL (gamma gel) (registered trademark of Tyca Co., Ltd.).

  The polyimide film is preferably formed on a support made of the above-described polyimide resin, particularly a film-like support made of a polyimide resin, and a silicon wafer.

  In the coating film forming step, after the ink of the present invention is applied onto a support by an inkjet method, the support in ink is heated using a hot plate or an oven to evaporate the solvent in the ink. It is preferable to include the process of removing and drying. This heating condition varies depending on the type and mixing ratio of each component contained in the ink, but is usually 70 to 150 ° C., 5 to 15 minutes when using an oven, and 1 to 5 minutes when using a hot plate.

  The thickness of the obtained coating film may be appropriately adjusted according to the desired application, but is preferably 1 to 20 μm, and more preferably 1 to 10 μm.

Curing Step In the curing step, the coating film obtained in the coating film forming step is cured.
This curing step may be performed by heat-treating the coating film, and when the component (A) is substantially composed only of the imidized product (A2), it is not limited to the heat treatment, and ultraviolet rays, You may carry out by irradiating an ion beam, an electron beam, or a gamma ray.

  The heat treatment is preferably performed at 100 to 250 ° C., more preferably 120 to 230 ° C., in order to obtain a cured film having excellent heat resistance, chemical resistance and flatness, and sufficient mechanical strength. When using a hot plate, it is performed for 30 to 90 minutes, and when using a hot plate, it is performed for 5 to 30 minutes.

  The thickness of the cured film thus obtained may be appropriately adjusted according to the desired application, but is usually 2 μm or more, preferably 2 to 5 μm. Since the ink of the present invention can contain the component (A) at a high concentration, it is possible to easily form a cured film having a thickness larger than that of the conventional ink.

  Thus, according to the ink of the present invention, a thick cured film can be obtained by one discharge. For this reason, when forming a thick cured film of about 10 μm, for example, the number of overcoating can be reduced as compared with the conventional inkjet ink, and the manufacturing process of the cured film can be shortened.

Electronic Material Substrate The electronic material substrate of the present invention has the cured film described above. Examples of the electronic material substrate of the present invention include a film substrate and a semiconductor wafer substrate.
As the film substrate, for example, the ink of the present invention is formed on the entire surface or a predetermined pattern (line shape or the like) by an ink jet method on a film-like support such as a polyimide film in which wiring is formed in advance by the ink jet method or the like. The board | substrate obtained by apply | coating and forming a coating film and drying and heating the said coating film after that is mentioned.

  The cured film thus obtained has a high molecular weight when heated, 1) the polyamic acid portion of the polyester amic acid is dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid reacts with the epoxy resin. And 3) Since the epoxy resin is cured and has a high molecular weight, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance.

  Next, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples. A polyester amic acid solution comprising a reaction product of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound was synthesized as shown below.

Synthesis example 1
A 500 ml flask equipped with a thermometer and a stirring blade was purged with nitrogen, and then charged with 13.3 g of 3,3′-diaminodiphenylsulfone (DDS) and 14.19 g of 1,4-butanediol, followed by dehydration purification 3 -280 g of methyl methoxypropionate (MMP) was charged and stirred at room temperature to dissolve DDS and 1,4-butanediol. Thereafter, 81.42 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 11.35 g of benzyl alcohol were added. The mixture was heated to 130 ° C. in an oil bath, stirred for 4 hours, and then cooled. A 30% by weight solution of a pale yellow transparent ester group-containing polyamic acid was obtained. The rotational viscosity of this solution was 20.5 mPa · s. The weight average molecular weight measured by gel permeation chromatography (GPC) was 4,500. In addition, the weight average molecular weight is obtained by diluting the obtained polyamic acid solution with tetrahydrofuran (THF) so that the polyamic acid concentration is about 1% by weight, and using columns G4000HXL, G3000HXL, G2500HXL and G2000HXL manufactured by Tosoh Corporation. , Measured by GPC method using THF as a developing agent, and converted to polystyrene (standard substance).

Example 1
A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 50 g of an MMP solution of the polyester amic acid obtained in Synthesis Example 1 and a butyl methacrylate / glycidyl methacrylate copolymer (molar ratio 20:80, weight) were placed in the flask. 15 g of an average molecular weight of 80,000), 3 g of trimellitic anhydride, 1.5 g of 3-glycidoxypropyltrimethoxysilane and 279 g of dehydrated and purified triethylene glycol dimethyl ether (MTM) were added and stirred at room temperature for 5 hours. It was dissolved uniformly. Next, 0.38 g of Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution.

(Example 2)
A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 57.5 g of the polyester amic acid MMP solution obtained in Synthesis Example 1 was added to the flask, 17.3 g of VG-3101L, and 17.3 g of HP7200H. , 5.2 g of trimellitic anhydride, 2.8 g of 3-glycidoxypropyltrimethoxysilane, 0.29 g of Irganox 1010 (trade name, manufactured by BASF), and 199.6 g of dehydrated and purified MTM at room temperature For 5 hours to dissolve uniformly. Next, 0.15 g of KP-341 (trade name; manufactured by DIC Corporation) was added, stirred for 1 hour at room temperature, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution.

(Example 3)
A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 51.1 g of an MMP solution of the polyester amic acid obtained in Synthesis Example 1 was added to the flask, 19.1 g of EHPE-3150, and 11.5 g of HP7200H. 13.8 g of trimellitic anhydride, 0.26 g of Irganox 1010 (trade name, manufactured by BASF), 84.0 g of dehydrated and purified MTM, and 120.3 g of propylene glycol monomethyl ether (PGME), Stir for hours to dissolve uniformly. Next, 0.15 g of KP-341 (trade name; manufactured by DIC Corporation) was added, stirred for 1 hour at room temperature, and filtered through a membrane filter having a pore size of 0.2 μm to prepare a coating solution.

(Comparative Example 1)
A coating solution was prepared in the same manner as in Example 1 except that the MTM in Example 1 was changed to MMP.

(Comparative Example 2)
A coating solution was prepared in the same manner as in Example 2 except that the MTM in Example 2 was changed to MMP.

(Comparative Example 3)
A coating solution was prepared in the same manner as in Example 3 except that MTM and PGME in Example 3 were changed to MMP.

[Evaluation method]
Evaluation methods used in Examples and Comparative Examples are shown below.
〔Evaluation method〕
Ink evaluation (1) Viscosity (mPa · s)
The viscosity of the ink was measured at 25 ° C. using an E-type viscometer (VISCONIC EHD manufactured by TOKYO KEIKI).
(2) Surface tension (mN / m)
The surface tension of the ink was measured with DM500 (manufactured by Kyowa Interface Science Co., Ltd.). A thermostatic bath set at 25 ° C. was prepared, and the surface tension of the ink was measured by a pendant drop method in an atmosphere at 25 ° C. Measurement was performed at least 5 times, and the average value was calculated as the surface tension.
(3) Storage stability The low temperature storage stability of the ink was evaluated. The ink was placed in a freezer at −20 ° C. or at a room temperature of 25 ° C., and the state after 7 days was observed for the formation of insoluble matter and the change in viscosity. When an insoluble matter was not generated, the case where the viscosity change was less than 10% was evaluated as ◯, and the others were evaluated as x.
(4) Inkjet ejection stability Using an inkjet device (XY100, PU100, BP100, EB100) manufactured by Konica Minolta, a 14 pL inkjet head (KM512MH manufactured by Konica Minolta), a discharge voltage (piezo voltage) of 16 V, a head temperature of 30 ° C. The state of discharge was confirmed under the drive frequency of 700 Hz. Ink was ejected from 512 nozzles, a straight line was drawn at a resolution of 360 dpi, and the ejection performance was judged by whether or not printing was performed. When printing was carried out after nozzle cleaning and no chipping was found in the printing, the initial ejection property was marked with ◯, and when chipping was confirmed with printing, the marking was marked with x.
Subsequently, after discharging was stopped for 1 minute, it was discharged again and observed in the same manner as the initial discharge property. Further, the same observation was made when re-ejection was performed after the ejection was stopped for 5 minutes and 10 minutes, respectively.
(5) Pattern dimensional accuracy Pattern application (5 cm long lines, 150 μm intervals) was performed on a 0.7 mm thick glass substrate under the above discharge conditions. In addition, the frequency | count of application | coating was 2 times.
After applying the ink, the obtained substrate with ink was placed on a hot plate at 80 ° C., and the ink was dried for 5 minutes. Thereafter, the dried substrate with ink was heated in an oven at 120 ° C. for 60 minutes to obtain a line-shaped cured film.
Evaluation of Cured Film (6) Transparency In the obtained glass substrate with a cured film, a spectrophotometer (trade name: MICRO COLOR ANALYZER TC-1800M, manufactured by Tokyo Denshoku Technical Center) can transmit only the light of the cured film. The transmittance at a wavelength of 400 nm was measured. The case where the transmittance was 99% or more was rated as ◯, and the case where the transmittance was less than 99% was rated as ×.
(7) Heat resistance After the obtained cured film moon glass substrate was reheated at 250 degrees for 1 hour, the remaining film ratio after heating with respect to the film thickness before heating and the transmittance at 400 nm after heating were measured. A case where the remaining film ratio after heating was 95% or more and the transmittance at 400 nm after heating was 99% or more was evaluated as ◯. The case where the residual film rate after heating was less than 95% or the transmittance at 400 nm after heating was less than 99% was evaluated as x.
(8) Chemical resistance The obtained cured film-coated glass substrate is immersed in a 5% by weight aqueous sodium hydroxide solution at 30 ° C. for 30 minutes (hereinafter abbreviated as NaOH treatment), 36% hydrochloric acid / 60% nitric acid / water. = Immersion treatment at 50 ° C. for 15 minutes (hereinafter abbreviated as mixed acid treatment) and immersion treatment at 40 ° C. for 30 minutes in a mixed solution (weight ratio) comprising 40/20/40 (hereinafter abbreviated as mixed acid treatment) (Hereinafter abbreviated as “NMP treatment”), the remaining film rate after each treatment relative to the film thickness before each treatment and the transmittance before and after each treatment were measured. A case where the remaining film rate after each treatment was 95% or more and the transmittance at 400 nm after each treatment was 99% or more was evaluated as ◯. The case where the residual film rate after each treatment was less than 95% or the transmittance after each treatment was less than 99% was evaluated as x.
(9) Adhesiveness The obtained cured film-coated glass substrate was subjected to a pressure cooker test (hereinafter abbreviated as PCT treatment) for 24 hours under the conditions of 120 ° C., 100%, and 0.2 MPa. The Goban eye test (JIS-K-5400) by tape peeling was performed and the remaining number was counted. The case where the remaining number / 100 was 100/100 was evaluated as ◯, and the case where it was 99/100 or less was evaluated as ×.

Table 1 shows the evaluation results of the examples and comparative examples.

  As is clear from the results shown in Table 1, the inks of Examples 1 to 3 were particularly excellent in inkjet discharge stability and pattern dimensional accuracy. Moreover, the cured film obtained in Examples 1-3 was balanced in all points of transparency, heat resistance, chemical resistance, and adhesion. On the other hand, the inks containing no MTM in Comparative Examples 1 to 3 are inferior in terms of inkjet ejection stability and pattern dimensional accuracy, and yields when used as protective film materials for electronic components, for example, electrode insulation films for touch panels. Is expected to decline.

  Since the thermosetting resin composition of the present invention has good ejection properties during ink jet printing and excellent storage stability, it is possible to produce a cured film with a high yield. In addition, the cured film obtained by the ink jet method is excellent in properties as an optical material such as sputtering resistance and transparency, so that a protective film such as a color filter, various optical materials such as an LED light emitting element and a light receiving element, In addition, it can be used as a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (19)

A resin composition comprising a polyester amide acid, an epoxy resin, an epoxy curing agent, a solvent (A) and a solvent (B) obtained by reacting tetracarboxylic dianhydride, diamine and a polyvalent hydroxy compound as essential components. Thus, the polyester amic acid is used in such a ratio that X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compounds satisfy the relationship of the following formulas (1) and (2). Obtained by reacting,
0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦1.5 (2)
The epoxy resin is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester amic acid, the epoxy curing agent is 15 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin, and the solvent (A) is triethylene glycol dimethyl ether. A thermosetting resin composition wherein the solvent (B) is at least one selected from diethylene glycol ethyl methyl ether, methyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether, and γ-butyrolactone.   The thermosetting resin composition according to claim 1, wherein the polyester amic acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound and monohydric alcohol as essential components.   Polyester amide acid is a reaction product obtained by reacting tetracarboxylic dianhydride, diamine, polyhydric hydroxy compound, monohydric alcohol and silicon-containing monoamine as essential components, and the silicon-containing monoamine is 3-aminopropyltriamine. Methoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldi Ethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, paminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxy Run and thermosetting resin composition according to claim 1 is at least one selected from m- aminophenyl methyl diethoxy silane.   The thermosetting according to claim 2 or 3, wherein the monohydric alcohol is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3 ethyl-3-hydroxymethyl oxetane. Resin composition.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the polyester amic acid is a polyester amic acid obtained by further reacting with a styrene-maleic anhydride copolymer. The thermosetting resin composition according to any one of claims 1 to 5, wherein the polyester amide acid is a compound having structural units represented by the following formulas (3) and (4).

Here, R ₁ is a tetracarboxylic dianhydride residue, R ₂ is a diamine residue, and R ₃ is a polyvalent hydroxy compound residue.   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis The compound according to any one of claims 1 to 6, which is at least one compound selected from (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate). The thermosetting resin composition as described.   The heat according to any one of claims 1 to 7, wherein the diamine is at least one compound selected from 3,3'-diaminodiphenylsulfone and bis (4- (3-aminophenoxy) phenyl) sulfone. Curable resin composition.   At least the polyvalent hydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol; The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is one or more compounds.   The epoxy resin is polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer and styrene- The thermosetting resin composition according to any one of claims 1 to 9, which is at least one compound selected from epoxy group-containing polymers of a glycidyl methacrylate copolymer.   The thermosetting resin composition according to any one of claims 1 to 9, wherein the epoxy resin is an alicyclic epoxy resin.   The thermosetting resin composition according to claim 1, wherein the epoxy curing agent is trimellitic anhydride.   The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, and the polyvalent hydroxy compound is 1,4-butane. The diol, the epoxy resin is an n-butyl methacrylate-glycidyl methacrylate copolymer, the epoxy curing agent is trimellitic anhydride, and the solvent (B) is methyl 3-methoxypropionate. The thermosetting resin composition as described.   The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the diamine is 3,3′-diaminodiphenyl sulfone, and the polyvalent hydroxy compound is 1,4-butane. Diol, monohydric alcohol is benzyl alcohol, epoxy resin is n-butyl methacrylate-glycidyl methacrylate copolymer, epoxy curing agent is trimellitic anhydride, and solvent (B) is 3-methoxypropionic acid The thermosetting resin composition according to claim 2, which is methyl.   The thermosetting resin composition according to claim 1, wherein the polyester amic acid has a weight average molecular weight of 2,000 to 200,000.   The thermosetting resin composition according to any one of claims 1 to 14, wherein the epoxy resin has a weight average molecular weight of 10,000 to 1,000,000.   The cured film obtained by apply | coating the thermosetting resin composition of any one of Claims 1-16 on a support body by the inkjet method, forming a coating film, and heating this coating film.   The cured film according to claim 17, which has a pattern shape.   The board | substrate for electronic materials which has the cured film of Claim 17 or 18.