TWI445777B - Inkjet ink - Google Patents

Description

Inkjet ink

The present invention relates to an ink for inkjet, relating to a polylysine composition for forming an insulating film layer in the production of an electronic component, a polyimide film formed using the composition, and the like. A film substrate of a quinone imine film, and an electronic component having the film substrate.

Polyimine is a material which is excellent in heat resistance and electrical insulation and is widely used in the field of electronic communication (for example, refer to Patent Document 1, Patent Document 2, and Patent Document 3). When a polyimine is formed into a desired pattern film, it has been conventionally used to form an image by etching or photosensitive polyimide, but in recent years, inkjet is being used to form a desired pattern film. method.

Various inkjet inks have been proposed (for example, refer to Patent Document 4 and Patent Document 5). However, if a polyimide inkjet ink is to be prepared, the solvent contained in the ink composition is limited to N-methyl- A guanamine-based solvent such as 2-pyrrolidone causes a decrease in durability of an inkjet head or a decrease in precision of jetting. In particular, when a flexible substrate is used, the flexibility (the flexible substrate or the substrate is bent when the flexible substrate is erected and the both ends are alternately moved up and down) There is a case in which the characteristics of the cutting or the cutting property are also referred to as sliding properties. Therefore, a polyimide film having good flexibility is desired.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-039714

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-238683

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-094118

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-213165

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-131730

In the above case, a polyimide film having a good ink jet printability and a uniform film thickness can be obtained, and the obtained polyimide film has a strong mechanical strength, a crack is not generated, and a good bending property is obtained. Ink ink.

In view of the above, the present inventors have found an inkjet ink having the following constitution. The present invention has the following constitution.

[1] An inkjet ink comprising: polyglycine (A) having a weight average molecular weight of 50,000 to 500,000 and having a structural unit represented by the following formula (1), the polyglycine (A) It is obtained by using the compound (a1) having at least two or more acid anhydride groups and the diamine (a2); at least one selected from the group consisting of the proline acid compound (B1) and the proline acid compound (B2). In the above, the proline acid compound (B1) is obtained by using a compound (a3) having two or more acid anhydride groups and a monoamine (a5), and the above proline acid compound (B2) is a diamine (a4). And a compound (a6) having an acid anhydride group; and a solvent (C).

In the above formula (1), R ¹ and R ² each independently represent an organic group having 2 to 100 carbon atoms.

[2] The inkjet ink according to [1] above, wherein the inkjet ink contains 0.5% by weight (% by weight) to 20% by weight of polyacrylic acid (A), and the total amount is 5% by weight to 50% by weight. A proline (B1) and a proline (B2), 30% to 94.5 wt% of a solvent (C).

[3] The inkjet ink according to the above [1] or [2], wherein the compounds (a1) and (a3) having two or more acid anhydride groups are each independently selected from the following formula (2) And one or more of the group consisting of a copolymer of a tetracarboxylic dianhydride and a monomer having an acid anhydride group and another polymerizable monomer.

In the above formula (2), R is each independently an organic group having 2 to 100 carbon atoms.

[4] The inkjet ink according to any one of [1] to [3] wherein the diamines (a2) and (a4) are each independently a diamine represented by the following formula (3). .

In the above formula (3), R is each independently an organic group having 2 to 100 carbon atoms.

[5] The inkjet ink according to any one of [1] to [4] wherein the monoamine (a5) is an aminoguanidine compound represented by the following formula (4).

In the above formula (4), R ^{1 is} each independently hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and R ^{2 is} independently an organic group having 1 to 20 carbon atoms.

[6] The inkjet ink according to any one of the above [1] to [5] wherein the compound (a6) having one acid anhydride group is a hydrazine-containing carboxylic acid anhydride represented by the following formula (5).

In the above formula (5), R ^{1 is} each independently hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and R ² is an organic group having 1 to 20 carbon atoms.

[7] The ink for inkjet according to the above [3], wherein the tetracarboxylic dianhydride represented by the above formula (2) is selected from the group consisting of pyromellitic dianhydride, 3, 3', 4, 4'- Benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3 ',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylfluorene Formic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4 '-Diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(trimellitic anhydride), cyclobutane IV Formic acid dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic dianhydride and butane tetracarboxylic acid One or more of the groups consisting of anhydrides.

[8] The ink for inkjet according to the above [4], wherein the diamine represented by the above formula (3) is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and 4,4'-diamine. Diphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodi Phenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, M-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-amine Phenyloxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, bis[4-(4-amino) Benzyl)phenyl]methane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl] 4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl] 4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]methane, 1,3-bis(4-aminophenoxy)benzene, and the following formula ( One or more of the groups consisting of the compounds shown by XV).

In the above formula (XV), R ^{1 is} each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ^{2 is} independently a methylene group, a phenylene group or an alkyl group-substituted phenylene group, respectively. Independently, it is an integer of 1 to 6, and y is independently an integer of 1 to 70.

[9] The inkjet ink according to the above [5], wherein the aminoguanidine compound represented by the above formula (4) is selected from the group consisting of p-aminophenyltrimethoxydecane and p-aminophenyltriethoxylate. a group consisting of decane, m-aminophenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane and 3-aminopropyltriethoxydecane One or more of them.

[10] The ink for inkjet according to [6], wherein the hydrazine-containing carboxylic acid anhydride represented by the above formula (5) is selected from the group consisting of p-trimethoxydecyl phenyl succinic anhydride and p-triethoxy Phenylalkyl)phenylsuccinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, trimethoxydecyl propyl succinic anhydride, and triethoxy One or more of the group consisting of decylpropyl succinic anhydride.

[11] An ink for inkjet comprising: polyamic acid (A) having a weight average molecular weight of 50,000 to 500,000, and the polyamic acid (A) is a compound having two or more acid anhydride groups ( A1) and a diamine (a2) are obtained, and the compound (a1) having two or more acid anhydride groups is selected from 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 2,2 At least one of the group consisting of [bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, the diamine (a2) being selected from 2,2-bis[4-(4-aminobenzene) At least one of a group consisting of oxy)phenyl]propane and 1,3-bis(4-aminophenoxy)benzene; a proline compound (B2), the proline (B2) is used The diamine (a4) is obtained by a compound (a6) having an acid anhydride group, and the diamine (a4) is 2,2-bis[4-(4-aminophenoxy)phenyl]propane having an acid anhydride group. The compound (a6) is triethoxydecylpropyl succinic anhydride; and the solvent (C) selected from the group consisting of diethylene glycol methyl ether, N-methyl-2-pyrrolidone and γ- At least one of the groups consisting of butyrolactone.

[12] A polyimine film or a patterned polyimide film obtained by the inkjet ink according to any one of [1] to [11] above.

[13] A polyimine film or a patterned polyimide film obtained by the method of any one of the above [1] to [11], which is obtained by the inkjet method. The step of forming a polyamic acid film by inkjet ink and the step of treating the polyamic acid film to form a polyimide film.

[14] A film substrate obtained by forming the polyimide film according to [12] or [13] above on a substrate.

[15] An electronic component comprising the film substrate according to [14] above.

[Effect of the invention]

The inkjet ink of a preferred embodiment of the present invention is excellent in inkjet printability, for example, and a polyimide film having a uniform film thickness can be obtained. Further, when the inkjet ink of the preferred embodiment of the present invention is used, it is possible to form a polyimide film having high mechanical strength, no cracking, and good bendability.

The polyimide film formed of the inkjet ink of the present invention has high heat resistance and electrical insulating properties, and thus can improve the reliability and yield of electronic components.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

1 inkjet ink of the present invention

The inkjet ink of the present invention is an inkjet ink containing polyamic acid (A), a proline (B1 and/or B2), and a solvent (C). The ink for inkjet of the present invention may be colorless or colored.

The viscosity of the inkjet ink is not particularly limited, and when the viscosity is 1 mPa ‧ to 50 mPa ‧ at a normal temperature (25 ° C), the ejection accuracy of the inkjet coating method is improved. Further, the viscosity of the ink for inkjet at 25 ° C is more preferably 5 mPa ‧ to 30 mPa ‧ , more preferably 8 mPa ‧ to 20 mPa ‧ (25 ° C). When the ink jet head is heated and sprayed, the viscosity of the ink for inkjet at a heating temperature (preferably 40 ° C to 120 ° C) is preferably 1 mPa ‧ to 50 mPa ‧ , more preferably 5 mPa ‧ s ~ 30mPa‧s, particularly good is 8mPa‧s ~ 20mPa‧s.

Here, the viscosity of the ink for inkjet was measured at 25 ° C using an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI).

1.1 Polyaminic acid (A)

Polylysine (A) is a polylysine having a structural unit represented by the above formula (1). Hereinafter, the structural unit represented by the formula (1) will be described.

1.1.1 Structural unit shown by formula (1)

R ¹ in the above formula (1) is independently a tetravalent organic group having 2 to 100 carbon atoms in each structural unit, and R ² is independently a divalent carbon number 2 to each structural unit. 100 organic groups. The tetravalent or divalent "organic group having 2 to 100 carbon atoms" is preferably an organic group having 3 to 70 carbon atoms, more preferably an organic group having 4 to 50 carbon atoms.

Specific examples of the above-mentioned "organic group" include a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, an alkoxy group having 2 to 20 carbon atoms which may have a substituent, and a carbon number of 6 to 20 which may have a substituent. An aryloxy group, an amine group which may have a substituent, a decyl group which may have a substituent, an alkylthio group which may have a substituent (-SY ¹ , wherein Y ¹ represents a carbon number of 2 to 20 which may have a substituent An alkyl group, an arylthio group which may have a substituent (-SY ² , wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent), and an alkylsulfonyl group which may have a substituent (- SO ₂ Y ³ , wherein Y ³ represents a C 2-20 alkyl group which may have a substituent, and an arylsulfonyl group (-SO ₂ Y ⁴ which may have a substituent, wherein Y ⁴ represents A aryl group having 6 to 18 carbon atoms having a substituent.

The hydrocarbon of "hydrocarbon group having 2 to 20 carbon atoms" may be a saturated or unsaturated acyclic type, or may be a saturated or unsaturated ring type. When the hydrocarbon group having 2 to 20 carbon atoms is an acyclic type, it may be linear or branched. The "hydrocarbon group having 2 to 20 carbon atoms" includes an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 20 carbon atoms, and carbon. An aryl group having 6 to 18, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, and a cycloalkenyl group having 4 to 20 carbon atoms. .

The "alkyl group having 2 to 20 carbon atoms" is preferably an alkyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a dodecyl group.

The "alkenyl group having 2 to 20 carbon atoms" is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, a 2-methylallyl group, and a 2-butenyl group.

The "alkynyl group having 2 to 20 carbon atoms" is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 6 carbon atoms. Examples of the alkynyl group include an ethynyl group, a propynyl group, a butynyl group and the like.

The "alkanediyl group having 4 to 20 carbon atoms" is preferably an alkadienyl group having 4 to 10 carbon atoms, more preferably an alkadienyl group having 4 to 6 carbon atoms. Examples of the alkadienyl group include a 1,3-butadienyl group and the like.

The "aryl group having 6 to 18 carbon atoms" is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenyl, anthryl, and phenanthryl.

The "alkylaryl group having 7 to 20 carbon atoms" is preferably an alkylaryl group having 7 to 12 carbon atoms. Examples of the alkylaryl group include o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-dimethylphenyl, 2,5-di. Tolyl, o-cumenyl, m-isopropylphenyl, p-cumyl and 2,4,6-trimethyl (mesityl).

The "arylalkyl group having 7 to 20 carbon atoms" is preferably an arylalkyl group having 7 to 12 carbon atoms. Examples of the arylalkyl group include a benzyl group, a phenethyl group, a diphenylmethyl group, a triphenylmethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and a 2,2-di Phenylethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl, and the like.

The "cycloalkyl group having 4 to 20 carbon atoms" is preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.

The "cycloalkenyl group having 4 to 20 carbon atoms" is preferably a cycloalkenyl group having 4 to 10 carbon atoms. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

The "alkoxy group having 2 to 20 carbon atoms" is preferably an alkoxy group having 2 to 10 carbon atoms, more preferably an alkoxy group having 2 to 6 carbon atoms. Examples of the alkoxy group include an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and the like.

The "aryloxy group having 6 to 20 carbon atoms" is preferably an aryloxy group having 6 to 10 carbon atoms. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, a biphenyloxy group and the like.

"Alkylthio (-SY ¹ , wherein Y ¹ represents a C 2-20 alkyl group which may have a substituent)" and "alkyl sulfonyl (-SO ₂ Y ³ , wherein Y ³ represents In the alkyl group having 1 to 20 carbon atoms which may have a substituent, Y ¹ and Y ^{3 are} preferably an alkyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a dodecyl group.

"Arylthio (-SY ² , wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent)" and "aryl SO sulfonyl group (-SO ₂ Y ⁴ wherein Y ⁴ represents Among the aryl groups having 6 to 18 carbon atoms which may have a substituent, Y ² and Y ^{4 are} preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.

"Carbon group having 1 to 20 carbon atoms", "alkoxy group having 2 to 20 carbon atoms", "aryloxy group having 6 to 20 carbon atoms", "amine group", "decyl group" and "alkylthio group" Substituents may be introduced into the "arylthio group", "alkylsulfonyl group" and "arylsulfonyl group". Examples of the substituent include an ester group, a carboxyl group, a decylamino group, an alkynyl group, a trimethyldecyl group, an amine group, a phosphonyl group, a thio group, a carbonyl group, a nitro group, a sulfo group, an imido group, and the like. Halogen and alkoxy groups, etc.

In this case, the substituent may be introduced into one or more, up to the maximum number which can be substituted at the substitutable position, and it is preferred to introduce one to four. When the number of substituents is two or more, each substituent may be the same or different.

Examples of the "amino group which may have a substituent" include an amine group, a dimethylamino group, a methylamino group, a methylphenylamino group, and a phenylamino group.

Examples of the "decyl group which may have a substituent" include dimethyl decyl group, diethyl decyl group, trimethyl decyl group, triethyl decyl group, trimethoxy decyl group, and triethoxy decyl group. , diphenylmethyl decyl, triphenyl decyl, triphenyloxy decyl, dimethyl methoxy decyl, dimethyl phenoxy fluorenyl, methyl methoxy phenyl decyl, etc. .

In the above, the organic group is basically described by a specific example of monovalent, and in the specific example of the divalent organic group, the valence may be increased by one in the monovalent organic group described above. The group is explained. Similarly, as a specific example of the tetravalent organic group, a group in which the valence is increased by 3 in the monovalent organic group described above can be used. Further, the description of the organic group in the chemical formula represented by the above formula (1) can also be referred to as an explanation of the "organic group" in the chemical formula shown by another chemical formula.

The polyamic acid (A) can be obtained by using at least the compound (a1) having two or more acid anhydride groups and the diamine (a2), which are obtained by the following methods, but are not limited to those obtained by the method. Polylysine.

1.1.2 Reaction conditions for the synthesis of polyamic acid (A)

The polyamic acid (A) can be synthesized, for example, by reacting a compound (a1) having two or more acid anhydride groups with a diamine (a2). It is preferred to use 0.9 mol to 1.1 mol of the diamine (a2) with respect to 1 mol of the compound (a1) having two or more acid anhydride groups. More preferably, 0.95 mol to 1.05 mol of the diamine (a2) is used with respect to 1 mol of the compound (a1) having two or more acid anhydride groups. It is particularly preferred to use 1 mol (equal mole) of the diamine (a2) with respect to 1 mol of the compound (a1) having two or more acid anhydride groups.

1.1.3 reaction solvent

For example, a solvent for synthesizing poly-proline (A) by reacting a compound (a1) having two or more acid anhydride groups with a diamine (a2), as long as the poly-proline (A) can be synthesized In addition, it is not particularly limited, and examples thereof include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, and ethylene glycol single. Ethyl acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methyl-2- Pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. Since polylysine (A) has high solubility, among the above solvents, preferred are γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylformamide and N. , N-dimethylacetamide. These reaction solvents may be used singly or in combination of two or more kinds to prepare a mixed solvent. Further, in addition to the above reaction solvent, other solvents may be used in combination.

When 100 parts by weight or more of the reaction solvent is used in combination with 100 parts by weight of the compound (a1) and the diamine (a2) having two or more acid anhydride groups in total, the reaction proceeds smoothly, so that the reaction proceeds smoothly. better. The reaction is preferably carried out at 0 ° C to 100 ° C for 0.2 to 20 hours.

1.1.4 Order added to the reaction system

Further, the order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, any of the following methods and the like can be used: a compound (a1) having two or more acid anhydride groups and a diamine (a2) are simultaneously added to a reaction solvent; and the diamine (a2) is dissolved in the reaction. After the solvent, a compound (a1) having two or more acid anhydride groups is further added; after the compound (a1) having two or more acid anhydride groups is dissolved in the reaction solvent, a diamine (a2) is further added. .

1.1.5 Concentration of polyaminic acid (A)

The concentration of the polyamic acid (A) in the ink for inkjet is preferably from 0.5% by weight to 20% by weight, more preferably from 1% by weight to 10% by weight, still more preferably from 2% by weight to 4% by weight. If it is within this concentration range, the ink for inkjet can be adjusted to the inkjet printable viscosity range. Further, the coating film formed of the inkjet ink has strong mechanical strength and is excellent in heat resistance, chemical resistance, and flatness.

1.1.6 Weight average molecular weight of polyaminic acid (A)

The polyaminic acid (A) having a weight average molecular weight of 50,000 to 500,000 can obtain a polyimide film having a uniform film thickness, and the obtained polyimide film has strong mechanical strength, no cracking, and good bendability. An ink for inkjet is prepared. Polylysine (A) having a weight average molecular weight of 50,000 or more, since the obtained polyimine film has strong mechanical strength, does not cause cracking and has good bendability, and can obtain a polythene film having a uniform film thickness. The amine film is preferably used for preparing an ink for inkjet. On the other hand, polyamic acid (A) having a weight average molecular weight of 500,000 or less, can be stably ink-jet-printed. In order to further improve the ink jet printability of the inkjet ink and the mechanical strength of the obtained polyimide film, the polyamine acid (A) has a weight average molecular weight of 50,000 to 500,000, preferably 65,000 to 200,000, more preferably Good is 80,000 to 180,000.

The weight average molecular weight of the polyaminic acid (A) can be determined by a gel permeation chromatography (GPC) method. Specifically, the obtained polyglycolic acid (A) was diluted with N,N-dimethylformamide (DMF) so that the concentration of polyglycine was about 1% by weight, and then Tosoh was used. Columns G4000HXL, G3000HXL, G2500HXL, and G2000HXL manufactured by the company, which are measured by gel permeation chromatography (GPC) using DMF as a developing solvent, can be converted into polystyrene. Got it.

1.1.7 Compound having two or more acid anhydride groups (a1)

Specific examples of the compound (a1) having two or more acid anhydride groups for synthesizing polyamic acid (A) include styrene-maleic anhydride copolymer and methyl methacrylate-cis. A copolymer of a radical polymerizable monomer having an acid anhydride group such as a butenedi anhydride copolymer and another radical polymerizable monomer, or a tetracarboxylic dianhydride represented by the above formula (2).

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 2,2',3,3'-benzophenone IV. Formic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride, 2,2',3,3 '-Diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylstilbene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2 , 2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyl) Phenyl)]hexafluoropropane dianhydride, ethylene glycol bis(trimellitic anhydride), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1, Tetracarboxylate such as 2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, and a compound represented by the following formula (a1-1) to formula (a1-73) Acid dianhydride.

In the above specific examples of the tetracarboxylic dianhydride, the formula (a1-1), the formula (a1-2), the formula (a1-5), the formula (a1-6), the formula (a1-7), and the formula (a1) 8), formula (a1-9), formula (a1-14), formula (a1-15), formula (a1-16), formula (a1-17), formula (a1-18), and formula (a1-20) The compound shown is preferably soluble in a solvent and can be prepared by using an ink for inkjet. Further, it is necessary to have high insulation properties due to the use of the ink for inkjet. In this case, it is particularly preferable to use the formula (a1-14), the formula (a1-15), the formula (a1-16), and the formula (a1-17). A compound represented by the formula (a1-18) and the formula (a1-20).

In addition, the compound having an acid anhydride group described above may be used alone or in combination of two or more. Further, the formula (a1-1), the formula (a1-2), the formula (a1-5), the formula (a1-6), the formula (a1-7), the formula (a1-8), and the formula (a1) 9) The aromatic tetracarboxylic dianhydride shown by the formula (a1-14), the formula (a1-15), the formula (a1-16), the formula (a1-17), and the formula (a1-20) When the alicyclic tetracarboxylic dianhydride is used in combination, high solubility in a solvent and high insulating property of a polyimide film can be achieved at the same time, which is preferable. Particularly preferably, the pyromellitic dianhydride represented by the formula (a1-1) is used in combination with 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the formula (a1-14), or a formula 2,2',3,3'-biphenyltetracarboxylic dianhydride shown in (a1-2) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by formula (a1-14) .

1.1.8 diamine (a2)

In the present invention, the diamine (a2) used for the synthesis of the polyamic acid (A) is not particularly limited as long as it has two amine groups, and examples thereof include 3,3'-diaminodiphenyl.碸, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 1,3-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2 '-Diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-amino group Phenoxy)phenyl]-4-methylcyclohexane, bis[4-(4-aminobenzyl)phenyl]methane, 1,1-bis[4-(4-aminobenzyl)benzene Cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)benzene Cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-methylcyclohexane and 1,1-bis[4-(4-aminobenzyl) Phenyl]methane. Further, for example, a compound represented by the following formula (II) to formula (VIII) can be mentioned.

In the above formula (II), A ¹ is -(CH ₂ ) _m -, and m is an integer of 1 to 6.

In the above formula (IV) and formula (VI) to formula (VIII), A ¹ is a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -S-(CH ₂ ) _m -S - where m is an integer from 1 to 6; A ² is a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or a carbon number 1 to 3 alkylene groups.

In the above formulae (III) to (VIII), hydrogen bonded to a cyclohexane ring or a benzene ring may be substituted by -F or -CH ₃ .

Examples of the diamine represented by the above formula (II) include diamines represented by the following formulas (II-1) to (II-3).

Examples of the diamine represented by the above formula (III) include a diamine represented by the following formula (III-1) and formula (III-2).

Examples of the diamine represented by the above formula (IV) include diamines represented by the following formulas (IV-1) to (IV-3).

Examples of the diamine represented by the above formula (V) include diamines represented by the following formulas (V-1) to (V-5).

Examples of the diamine represented by the above formula (VI) include diamines represented by the following formulas (VI-1) to (VI-30).

Examples of the diamine represented by the above formula (VII) include a diamine represented by the following formula (VII-1) to formula (VII-6).

Examples of the diamine represented by the above formula (VIII) include diamines represented by the following formulas (VIII-1) to (VIII-11).

In the above specific examples of the diamine (a2) represented by the above formulas (II) to (VIII), preferred examples thereof include the formula (V-1) to the formula (V-5) and the formula (VI-1). -Formula VI-15), Formula (VI-26), Formula (VI-27), Formula (VII-1) - Formula (VII-6), Formula (VIII-1) - Formula (VIII-11) Aromatic diamine. More preferably, it is a diamine represented by Formula (V-1), Formula (VI-1), Formula (VI-7), Formula (VI-10), and Formula (VI-13).

The diamine (a2) used for the synthesis of the polyamic acid (A) may, for example, be a diamine represented by the following formula (IX).

In the above formula (IX), A ³ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _m - (wherein m is 1 to 6) Integer), R ⁶ is a group having a steroid skeleton, having one or more groups selected from the group consisting of a cyclohexane ring and a benzene ring, or two bonded to a benzene ring The positional relationship of the amine group is an alkyl group having 1 to 10 carbon atoms in the para position, or an alkyl group or a phenyl group having a carbon number of 1 to 10 in the positional position, and any -CH _{2 in the} alkyl group. - may be substituted by -CF ₂ -, -CHF-, -O-, -CH=CH- or -C≡C-, -CH ₃ may be substituted by -CH ₂ F, -CHF ₂ or -CF ₃ , bonded The hydrogen on the ring-forming carbon of the phenyl group may be substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ .

In the above formula (IX), the two amine groups are bonded to the benzene ring carbon, and it is preferred that the bonding position relationship of the two amine groups is meta or para. More preferably, when the bonding position of "R ⁶ A ³ -" is set to 1 position, the two amine groups are bonded to the 3 and 5 positions, respectively, or the 2 and 5 positions.

Examples of the diamine represented by the above formula (IX) include a diamine represented by the following formula (IX-1) to formula (IX-11).

In the above formula (IX-1), formula (IX-2), formula (IX-7) and formula (IX-8), R ¹⁸ is an organic group having 2 to 30 carbon atoms, and among these groups, Preferably, it is an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms, more preferably an alkyl group having 5 to 12 carbon atoms or an alkoxy group having 5 to 12 carbon atoms. Further, in the above formula (IX-3) to formula (IX-6) and formula (IX-9) to formula (IX-11), R ¹⁹ is an organic group of -H or a carbon number of 1 to 30, and these groups are these groups. Among the groups, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkyl group having 3 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms is more preferred.

The diamine represented by the above formula (IX) may, for example, be a diamine represented by the following formula (IX-12) to formula (IX-17).

In the above formula (IX-12) to formula (IX-15), R ²⁰ is -H or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, more preferably carbon. A number of 6 to 16 alkyl groups. In the formula (IX-16) and the formula (IX-17), R ²¹ is -H or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably a carbon number. 8 to 20 alkyl groups.

The diamine represented by the above formula (IX) may, for example, be a diamine represented by the following formula (IX-18) to formula (IX-38).

The above formula (IX-18), formula (IX-19), formula (IX-22), formula (IX-24), formula (IX-25), formula (IX-28), formula (IX-30), In the formula (IX-31), the formula (IX-36) and the formula (IX-37), R ²² is -H or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms. The alkoxy group having 1 to 12 carbon atoms is more preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. Further, the above formula (IX-20), formula (IX-21), formula (IX-23), formula (IX-26), formula (IX-27), formula (IX-29), and formula (IX-32) In the formulae (IX-35) and (IX-38), R ²³ is -H, -F, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF _{3 is} more preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. In the above formula (IX-33) and formula (IX-34), A ⁹ is an alkylene group having 1 to 12 carbon atoms.

Further, the diamine represented by the above formula (IX) may, for example, be a diamine represented by the following formula (IX-39) to formula (IX-48).

Among the diamines (a2) represented by the above formula (IX), a diamine represented by the formula (IX-1) to the formula (IX-11) is preferred, and a formula (IX-2) and a formula are more preferred. (IX-4), a diamine represented by the formula (IX-5) and the formula (IX-6).

The diamine (a2) used for the synthesis of the polyamic acid (A) may, for example, be a compound represented by the following formula (XI) to formula (XII).

In the above formula (XI) and formula (XII), R ¹⁰ is -H or -CH ₃ , and R ^{11 is} independently -H or an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, A ^{6 is} independently a single bond, -C(=O)- or -CH ₂ -, and R ¹³ and R ¹⁴ are each independently -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group.

In the above formula (XI), it is preferred that one of the two "NH ₂ -Ph-A ⁶ -O-" is bonded to the 3-position of the steroid core and the other is bonded to the 6-position. Further, the two amine groups are bonded to the benzene ring carbon, respectively, preferably to the bonding position of A ⁶ and to the meta or para position.

Examples of the diamine represented by the above formula (XI) include a diamine represented by the following formula (XI-1) to formula (XI-4).

In the above formula (XII), two "NH ₂ -(R ¹⁴ -)Ph-A ⁶ -O-" are bonded to the benzene ring carbon, respectively, preferably with respect to the carbon bonded to the steroid nucleus. Bonded to the meta or para carbon. Further, the two amine groups are bonded to the benzene ring carbon, respectively, preferably to the meta or para position relative to A ⁶ .

Examples of the diamine represented by the above formula (XII) include a diamine represented by the following formula (XII-1) to formula (XII-8).

The diamine (a2) used for the synthesis of the polyamic acid (A) may, for example, be a compound represented by the following formula (XIII) or (XIV).

In the above formula (XIII), R ¹⁵ is -H or an alkyl group having 1 to 20 carbon atoms, and any -CH ₂ - of the alkyl group having 2 to 20 carbon atoms in the alkyl group may be -O-, -CH=CH - or -C≡C-substituted, A ^{7 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and A ⁸ is a single bond or an alkylene group having 1 to 3 carbon atoms, and the ring T is 1, 4-phenylene or 1,4-cyclohexylene, h is 0 or 1.

In the above formula (XIV), R ¹⁶ is an alkyl group having 2 to 30 carbon atoms, and among these alkyl groups, an alkyl group having 6 to 20 carbon atoms is preferred. R ¹⁷ is -H or an alkyl group having 1 to 30 carbon atoms, and among these alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferred. A ^{7 is} independently -O- or an alkylene group having 1 to 6 carbon atoms.

In the above formula (XIII), the two amine groups are bonded to the benzene ring carbon, respectively, preferably to the meta or para position relative to A ⁷ .

Examples of the diamine represented by the above formula (XIII) include a diamine represented by the following formula (XIII-1) to formula (XIII-9).

In the above formula (XIII _- 1) to formula (XIII-3), R ^{24 is} preferably -H and an alkyl group having 1 to 20 carbon atoms, and in the above formula (XIII-4) to formula (XIII-9), More preferably, R ²⁵ is -H and an alkyl group having 1 to 10 carbon atoms.

In the above formula (XIV), the two amine groups are bonded to the benzene ring carbon, respectively, preferably to the meta or para position relative to A ⁷ .

Examples of the diamine represented by the above formula (XIV) include diamines represented by the following formulas (XIV-1) to (XIV-3).

In the above formula (XIV-1) to formula (XIV-3), R ²⁶ is an alkyl group having 2 to 30 carbon atoms, and among these alkyl groups, an alkyl group having 6 to 20 carbon atoms and R ^{27 are} preferable. It is -H or an alkyl group having 1 to 30 carbon atoms, and among these groups, -H or an alkyl group having 1 to 10 carbon atoms is preferred.

As described above, as the diamine (a2) for synthesizing the polyamic acid (A), for example, a diamine represented by the above formula (II) to formula (XIV) may be used, and two other than these diamines may be used. amine. For example, a naphthalene type diamine having a naphthalene structure, an anthracene diamine having a fluorene structure, or a fluorene-based diamine having a siloxane bond may be used alone or in combination with other diamines. .

The oxoxane-based diamine is not particularly limited, and a decane-based diamine represented by the following formula (XV) can be preferably used.

In the above formula (XV), R ^{1 is} each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ^{2 is} independently a methylene group, a phenylene group or an alkyl group-substituted phenylene group, respectively. Independently, it is an integer of 1 to 6, and y is independently an integer of 1 to 70. Here, a more preferable y is an integer of 1 to 15.

Further, as the diamine (a2) for synthesizing the polyamic acid (A), a diamine represented by the following formula (XVI-1) to formula (XVI-8) can be used.

In the above formula (XVI-1) to formula (XVI-8), R ³⁰ and R ^{31 are} independently an alkyl group having 3 to 20 carbon atoms.

Further, the diamine (a2) which can be used for the synthesis of the polyamic acid (A) is not limited to the diamine described in the present specification, and other various forms of the diamine can be used within the scope of achieving the object of the present invention.

Further, the diamine (a2) which can be used for the synthesis of the polyamic acid (A) may be used alone or in combination of two or more. That is, a combination of two or more kinds of the above diamines, a combination of the above diamines and other diamines, or a combination of diamines other than the above diamines may be used.

Further, in order to make the mechanical strength of the polyimide film obtained by the ink for inkjet strong, it is particularly preferable that an aromatic diamine having two amine groups bonded to the para position of the benzene ring or two anilines An aromatic diamine of a structure in which four (aniline) are linked by a divalent organic group.

Specific examples of the aromatic diamine having two amine groups bonded to the phenyl ring in the para position include the formula (V-1) and the formula (V-3) to the formula (V-5). Aromatic diamine. Specific examples of the aromatic diamine having a structure in which four aniline groups are bonded by a divalent organic group include the above formula (VI-1), formula (VI-7), and formula (VI-10). ～Formula (VI-13), Formula (VI-27), Formula (VII-1) to Formula (VII-6), Formula (VIII-1) to Formula (VIII-11), Formula ( -1), formula ( -2), formula (XII-1), formula (XII-2), formula (XII-5), formula (XII-7), formula (XII-8), formula (XIII-1) to formula (XIII-) 9) An aromatic diamine represented by the formula (XIV-1) to the formula (XIV-3). Particularly preferably, it is a formula (V-1), a formula (V-3) to a formula (V-5), a formula (VI-1), a formula (VI-7), and a formula (VI-10). (VI-13) and an aromatic diamine represented by the formula (VI-27).

1.2 proline compounds (B1 and B2)

The proline acid compound (B1) can be obtained by using at least a compound (a3) having two or more acid anhydride groups and a monoamine (a5), and for example, a product obtained by reacting these compounds, for example, these can also be used. The compound which forms a salt of the compound is not limited to the above-described proline acid compound, if it is a proline acid compound which can be obtained by using the compound (a3) and the monoamine (a5) which have two or more acid anhydride groups.

Further, when the proline acid compound (B1) has a hydrazine, the hydrazine may be derived from the compound (a3) having two or more acid anhydride groups, may be derived from the monoamine (a5), or may be derived from both. In the following detailed description, a hydrazine compound having a hydrazine is obtained by using hydrazine derived from a monoamine (a5), and as a compound (a3) having two or more acid anhydride groups, an oxime is exemplified, and for example, The compound described in JP-A-61-205285, JP-A-H05-271245, and JP-A No. 5-320172.

The guanamine compound (B1) is a compound represented by the following formula (6), and is preferably a compound represented by the following formula (6-1), formula (6-2) or formula (6-3). .

In the above formula (6), X is a tetravalent organic group having 2 to 100 carbon atoms, and R ¹ , R ² and R ³ are hydrogen, a halogen or a monovalent organic group, and these groups may be the same or different, Y It is an organic group having 1 to 20 carbon atoms.

In the above formula (6-1), formula (6-2) or (6-3), at least one of R ¹ , R ² and R ³ contains an alkoxy group having 1 to 20 carbon atoms, and a is 1 to 20 The integer.

Further, the proline acid compound (B2) can be obtained by using at least a diamine (a4) and a compound (a6) having an acid anhydride group, and for example, a product obtained by reacting these compounds, for example, a salt can be formed for these compounds. The compound which is obtained by using the diamine (a4) and the compound (a6) having one acid anhydride group is not limited to the above proline acid compound.

Further, when the proline acid compound (B2) has a hydrazine, the hydrazine may be derived from the diamine (a4), or may be derived from the compound (a6) having one acid anhydride group, or may be derived from both. In the following detailed description, a hydrazine compound having a hydrazine is obtained by using hydrazine derived from the compound (a6) having one acid anhydride group, and examples of the hydrazine compound having a hydrazine as the diamine (a4) include, for example, the above formula (XV). The alkoxysilane shown is a diamine or the like.

The proline acid compound (B2) may, for example, be a compound represented by the following formula (7), and is preferably the following formula (7-1), formula (7-2), formula (7-3), and formula (7). -4) or a compound represented by formula (7-5).

In the above formula (7), R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, and these groups may be the same or different, and Y' is an organic group having 1 to 20 carbon atoms, X' It is an organic group having 2 to 100 carbon atoms.

In the above formula (7-1), formula (7-2), formula (7-3), formula (7-4) or formula (7-5), at least one of R ¹ , R ² and R ³ contains An alkoxy group having 1 to 20 carbon atoms, R in the formula (7-3) is an organic group having 2 to 30 carbon atoms, and R in the formula (7-4) is hydrogen or an alkyl group having 1 to 20 carbon atoms. , a is an integer from 1 to 20.

1.2.1 Reaction conditions for obtaining proline compounds (B1 and B2)

The proline acid compound (B1) is preferably obtained by reacting 0.5 mol to 8.0 mol of the monoamine (a5) with respect to 1 mol of the compound (a3) having two or more acid anhydride groups. . Further, the proline compound (B1) is more preferably a reaction of 1.0 mol to 4.0 mol of the monoamine (a5) with respect to 1 mol of the compound (a3) having two or more acid anhydride groups. And get. The proline acid compound (B1) is particularly preferably obtained by reacting 1.5 mol to 2.5 mol of the monoamine (a5) with respect to 1 mol of the compound (a3) having two or more acid anhydride groups. .

The proline compound (B2) is preferably obtained by reacting 0.5 mol to 8.0 mol of the compound (a6) having an acid anhydride group with respect to 1 mol of the diamine (a4). Further, the proline acid compound (B2) is more preferably obtained by reacting 1.0 mol to 4.0 mol of the compound (a6) having one acid anhydride group with respect to 1 mol of the diamine (a4). The proline compound (B2) is particularly preferably obtained by reacting 1.5 mol to 2.5 mol of the compound (a6) having an acid anhydride group with respect to 1 mol of the diamine (a4).

1.2.2 Reaction solvent

The solvent for obtaining the valeric acid compound (B1 and B2) is not particularly limited as long as it can synthesize the guanamine compound, and for example, the same solvent as that used for the synthesis of the above polyamic acid (A) can be used. Solvent. Specific examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl Ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone and N,N-dimethyl Ethylamine and the like.

If propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ether, diethylene glycol dimethyl ether and γ-butyrolactone are used in these solvents, Further, it is preferable to produce an ink having less damage to the ink jet head.

These reaction solvents may be used singly or in combination of two or more kinds to prepare a mixed solvent. Further, in addition to the above reaction solvent, other solvents may be used in combination.

100 parts by weight or more of the reaction solvent or 100 parts by weight relative to the total of 100 parts by weight of the compound (a3) having two or more acid anhydride groups and the monoamine (a5). When the diamine (a4) and the compound (a6) having one acid anhydride group are used in an amount of 100 parts by weight or more, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at a temperature of from 0 ° C to 100 ° C (preferably from 8 ° C to 70 ° C) for from 0.2 hours to 20 hours (preferably from 2 hours to 10 hours).

1.2.3 Order added to the reaction system

Further, the order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, for the proline acid compound (B1), any one of the following methods may be used: a compound (a3) having two or more acid anhydride groups and a monoamine (a5) are simultaneously added to a reaction solvent; After dissolving the monoamine (a5) in the reaction solvent, a compound (a3) having two or more acid anhydride groups is further added; and a monoamine (a3) is added to the compound (a3) having two or more acid anhydride groups ( A5).

Further, as the proline acid compound (B2), any one of the following methods may be used: a diamine (a4) and a compound (a6) having an acid anhydride group are simultaneously added to a reaction solvent; a diamine (a4) After dissolving in the reaction solvent, a compound (a6) having one acid anhydride group is further added; and a diamine (a4) is added to the compound (a6) having one acid anhydride group.

1.2.4 Concentration of proline compounds (B1 and B2)

The total concentration of the lysine compounds (B1 and B2) in the ink for inkjet is preferably from 5% by weight to 50% by weight, more preferably from 10% by weight to 45% by weight, still more preferably from 15% by weight to 40% by weight. . If it is within this concentration range, the ink for inkjet can be adjusted to a viscosity range in which inkjet printing can be performed.

1.2.5 Advantages of proline compounds (B1 and B2)

It is known that a proline acid compound (B1) having a ruthenium, when used in combination with an epoxy resin or a phenol resin, can function as a decane coupling agent and react with a metal or form a complex compound, so that the adhesion of the film is increased. , solder crack resistance is improved. In addition, it is predicted that the proline acid compound (B2) having a ruthenium can act as a decane coupling agent when used in combination with an epoxy resin or a phenol resin, and react with a metal or form a complex compound, so that the film is adhered. Increased, solder crack resistance improved.

Further, the inventors of the present invention have diligently studied and found that the proline acid compound (B1) having a hydrazine is hydrolyzed by condensation, dehydration condensation, to form a solid product (polyimine) having a quinone bond. Thermosetting compound. Further, it has been found that the hydrazine acid compound (B2) having a hydrazine is also a thermosetting compound which can be hydrolyzed by heating, dehydrated and condensed to form a solid product (polyimine) having a quinone imine bond.

The proline acid compound having a hydrazine can obtain a film by stereo cross-linking of a hydrazine compound, and thus processing is easier than the previous linear polyimine. Further, since it exhibits good heat resistance and few voids or cracks are formed during hardening, the guanamine compound having a ruthenium has excellent properties as a matrix resin of a molding material or a laminate material.

1.2.6 Compounds having two or more anhydride groups (a3)

As the compound (a3) having two or more acid anhydride groups for synthesizing the proline acid compound (B1), the same compound as the above compound (a1) having two or more acid anhydride groups can be used.

1.2.7 Diamine (a4)

As the diamine (a4) for synthesizing the proline acid compound (B2), the same diamine as the above diamine (a2) can be used.

1.2.8 monoamine (a5)

The monoamine (a5) for synthesizing the proline acid compound (B1) is not particularly limited as long as it has one amine group, and examples thereof include an amine sulfonium compound represented by the above formula (4). Specific examples of such an amine sulfonium compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldimethoxydecane. 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylmethyldiethoxydecane, Aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxydecane, p-aminophenylmethyldiethoxydecane, m-aminobenzene Trimethoxy decane, m-aminophenyl triethoxy decane, m-aminophenyl dimethyl diethoxy decane, and the like. Further, examples thereof include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, monoethanolamine, n-butylamine, and aniline.

Among these monoamines, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and p-aminophenyl are preferred in terms of excellent durability of the obtained film. Trimethoxy decane is particularly preferred as 3-aminopropyltriethoxydecane. These monoamines may be used alone or in combination of two or more.

1.2.9 Compound with an anhydride group (a6)

The compound (a6) having one acid anhydride group for synthesizing the proline acid compound (B2) is not particularly limited as long as it has one acid anhydride group, and examples thereof include a hydrazine-containing carboxylic acid anhydride represented by the above formula (5). And a hydrazine-containing carboxylic acid anhydride represented by the following formula (5').

In the above formula (5'), R ¹ is an organic group having 2 to 100 carbon atoms containing Si, R ² is an organic group having 2 to 100 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring. .

Among such hydrazine-containing carboxylic anhydrides, preferred are p-(trimethoxydecyl)phenyl succinic anhydride, p-(triethoxydecyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl. Succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, trimethoxydecyl propyl succinic anhydride, triethoxy decyl propyl succinic anhydride, methyl dimethoxy decyl propyl succinic anhydride , methyl diethoxy decyl propyl succinic anhydride, trimethoxy decyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy decyl butyl succinic anhydride, Methyldimethoxydecylalkyl)phenylsuccinic anhydride, p-(methyldiethoxydecyl)phenyl succinic anhydride, m-(methyldiethoxydecyl)phenyl succinic anhydride, the following formula The compound shown by 5-1) and the compound represented by the following formula (5-2).

The compound represented by the above formula (5-1) can be obtained, for example, by reacting 5-norbornene-2,3-dicarboxylic acid anhydride with trimethoxydecane. Further, the compound represented by the above formula (5-2) can be obtained, for example, by reacting allylic acid anhydride with trimethoxydecane.

1.3 Solvent (C)

The inkjet ink can be obtained, for example, by dissolving polyamic acid (A) and a proline acid compound (B1 and/or B2) in a solvent (C). Therefore, the solvent contained in the inkjet ink is not particularly limited as long as it is a solvent capable of dissolving polyglycolic acid (A) and a proline acid compound (B1 and/or B2). Further, even a solvent which cannot dissolve the polyamic acid (A) and the proline (B1 and/or B2) alone can be used as a solvent contained in the ink for inkjet by mixing with other solvents. (C).

Specific examples of the solvent (C) contained in the inkjet ink include N-methyl-2-pyrrolidone, dimethyl imidazolidinone, and N-methyl caprolactam (N- Methyl caprolactam), N-methylpropionamide, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, Diethylacetamide, γ-butyrolactone, ethyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl Ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, triethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl Ether acetate, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethanol, 2-propanol, dioxane ), ethylene glycol, and the like.

Among these solvents, for example, in terms of improvement in durability of the ink jet head, it is preferred to contain ethyl lactate, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol diethylene glycol. Ether, diethylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and γ-butyrolactone were used as the solvent (C).

Further, it is preferred to contain 20% by weight or less of the amide-based solvent, and more preferably no amide-based solvent, based on the total weight of the solvent (C). Here, examples of the guanamine-based solvent include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylidene. Indoleamine, N,N-dimethylacetamide, diethylacetamide, N-methylpropionamide, N,N,N',N'-tetramethylurea, 2-pyrrolidone, N- Methyl-2-pyrrolidone, ε-caprolactam, N-methyl caprolactam, urethane, and the like. These solvents may be used alone or in combination of two or more. Further, the solvent is preferably added so that the solid content concentration of the inkjet ink is 10% by weight to 50% by weight.

Further, since the surface tension of the ink greatly affects the coatability of the ink for inkjet, the surface tension of the ink is preferably adjusted to be 20 mN/m to 45 mN/m, more preferably 27 mN/m. 42 mN/m, more preferably 30 mN/m to 40 mN/m. When the surface tension is in the range of 20 mN/m to 45 mN/m, the ink meniscus of the ink ejection port is relatively stable, and the ejection of the ink becomes good.

In order to adjust the surface tension to a range of 20 mN/m to 45 mN/m, it is important to select a solvent. A solvent having a surface tension in the range of 20 mN/m to 45 mN/m can be used, if a solvent having a large surface tension (for example, γ-butyrolactone: 43 mN/m) and a solvent having a small surface tension (for example, two When a mixture of diol methyl ether: 24 mN/m or ethylene glycol monobutyl ether: 32 mN/m is used, the solvent composition can be used to finely adjust the surface tension, which is preferable.

The total concentration of the solvent (C) in the ink for inkjet is preferably from 30% by weight to 94.5% by weight, more preferably from 35% by weight to 90% by weight, still more preferably from 40% by weight to 80% by weight. If it is within this concentration range, it can be adjusted to the viscosity range in which inkjet printing can be performed.

1.4 The water content of the ink for inkjet

The amount of water in the ink for inkjet is not particularly limited, but is preferably 10,000 ppm or less, more preferably 5,000 ppm or less. In the case of the above-described moisture content, the inkjet ink has a small change in viscosity and excellent storage stability, which is preferable.

1.5 Additives added to inkjet inks

According to the characteristics of the ink, the ink for inkjet can be obtained by adding an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, an epoxy hardener such as trimellitic acid, or the like, as needed. Additives such as conditioners, rust inhibitors, preservatives, mildew inhibitors, antioxidants, anti-reducing agents, evaporation accelerators, chelating agents, water-soluble polymers, pigments, dyes, etc., and uniformly mix these additives Dissolved.

1.5.1 Epoxy resin

The ink for inkjet may further contain an epoxy resin. The epoxy resin contained in the inkjet ink is not particularly limited as long as it has oxirane or oxetane, and preferably has two or more ethylene oxides. compound of.

The concentration of the epoxy resin in the ink for inkjet is not particularly limited, but is preferably from 0.1% by weight to 20% by weight, more preferably from 1% by weight to 10% by weight. When it is in this concentration range, the coating film formed from the inkjet ink is excellent in heat resistance, chemical resistance, and flatness.

Examples of the epoxy resin include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having ethylene oxide, and a monomer having ethylene oxide. Copolymers with other monomers, and the like.

Specific examples of the monomer having ethylene oxide include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate. .

Further, specific examples of the other monomer copolymerized with the monomer having ethylene oxide include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). Isopropyl 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, chloromethylstyrene, (meth)acrylic acid (3-ethyl-3- Epoxypropyl)methyl ester, N-cyclohexylmethyleneimine, and N-phenyl maleimide.

Preferable examples of the copolymer of the monomer having ethylene oxide and the copolymer of the monomer having ethylene oxide and another monomer include polyglycidyl methacrylate and methyl methacrylate- Glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate- A glycidyl methacrylate copolymer, a (3-ethyl-3-epoxypropyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer. When the inkjet ink contains these epoxy resins, the coating film formed of the inkjet ink is excellent in heat resistance, which is preferable.

Specific examples of the epoxy resin include the trade names "EPIKOTE 807", "EPIKOTE 815", "EPIKOTE 825", "EPIKOTE 827", "EPIKOTE 828", "EPIKOTE 190P", and "EPIKOTE 191P" (all of which are Oiled Shell Epoxy Co., Ltd., manufactured under the trade names "EPIKOTE 1004" and "EPIKOTE 1256" (above, all by Japan Epoxy Resins Co.) , Ltd.), trade name "Araldite CY177", trade name "Araldite CY184" (both manufactured by Ciba-geigy Corporation), trade name "CELLOXIDE 2021P", "CELLOXIDE 3000" , "EHPE-3150" (manufactured by Diacel Chemical Industries), trade name "TECHMORE VG3101L" (manufactured by Mitsui Chemicals, Inc.), N, N, N', N'-four shrinkage Glyceryl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4 '-Diaminodiphenylmethane and the like.

Among these epoxy resins, the trade name "Araldite CY184", the trade name "CELLOXIDE 2021P", the trade name "TECHMORE VG3101L", and the trade name "EPIKOTE 828" are particularly preferable because the flatness of the obtained polyimide film is particularly good. .

Epoxy resins may be used alone or in combination of two or more.

1.5.2 Acrylic resin

The ink for inkjet may further contain an acrylic resin. The acrylic resin contained in the inkjet ink is not particularly limited as long as it has an acryl group or a methacryl group.

The concentration of the acrylic resin in the inkjet ink is not particularly limited, but is preferably from 0.1% by weight to 20% by weight, more preferably from 1% by weight to 10% by weight. When it is in this concentration range, the coating film formed from the inkjet ink is excellent in heat resistance, chemical resistance, and flatness.

Examples of the acrylic resin include a monofunctional polymerizable monomer having a hydroxyl group, a monofunctional polymerizable monomer having no hydroxyl group, a difunctional (meth)acrylate, and a trifunctional or trifunctional or higher polyfunctional (methyl) group. Acrylate and the like.

Specific examples of the monofunctional polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Ester or 1,4-cyclohexanedimethanol mono(meth)acrylate or the like. Among these monomers, particularly preferred is a 4-hydroxybutyl acrylate or a 1,4-cyclohexane dimethanol monoacrylate in terms of a film which is soft.

Specific examples of the monofunctional polymerizable monomer having no hydroxyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl shrinkage of (meth)acrylic acid. Glyceride, 3-methyl-3-(methyl)propene oxime methyl propylene oxide, 3-ethyl-3-(methyl) propylene oxime methyl propylene oxide, 3-methyl-3- (Meth) propylene oxiranyl ethyl propylene oxide, 3-ethyl-3-(methyl) propylene oxiranoxy propylene oxide, p-vinyl phenyl-3-ethyl propylene oxide-3-yl Methyl ether, 2-phenyl-3-(methyl)propene oxime methyl propylene oxide, 2-trifluoromethyl-3-(methyl) propylene oxime methyl propylene oxide, 4-trifluoromethyl 2-(methyl)propene oxime methyl propylene oxide, (meth)acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (a Butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, styrene, methyl styrene, Chloromethylstyrene, (3-ethyl-3-epoxypropyl)methyl (meth)acrylate, N-cyclohexylmethyleneimine, N-benzene a cis-butenylene imine, a vinyl toluene, a (meth) acrylamide, a tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, a dicyclopentene oxy (meth) acrylate Ester, isobornyl (meth)acrylate, phenyl (meth)acrylate, glycerol mono(meth)acrylate, macromonomer, polymethyl methacrylate macro, N- (meth) acrylate, methacrylic acid, crotonic acid, propylene decylmorpholine, (meth)acrylic acid-5-tetrahydroindole oxycarbonyl pentyl ester, lauryl alcohol ethylene oxide adduct, --chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, methyl fumarate Mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2-(methyl) propylene oxime], maleic acid mono [2-(methyl) ) propylene oxime ethyl ester] or cyclohexene-3,4-dicarboxylic acid mono [2-(methyl) propylene oxirane].

Specific examples of the difunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isomeric cyanuric acid ethylene modified diacrylate, and poly Ethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, trimethylolpropane II Acrylate or dipentaerythritol diacrylate, and the like.

Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylic acid. Ester, propylene oxide modified trimethylolpropane tri(meth) acrylate, epichlorohydrin modified trimethylolpropane tri(meth) acrylate, bis(trimethylolpropane) tetra(methyl) Acrylate, glycerol tri(meth) acrylate, epichlorohydrin modified glycerol tri(meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl) Acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol III ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified tris(meth) acrylate, tris[(methyl) Propylene oxiranyl ethyl) isomeric isocyanate, caprolactone modified tris[(methyl) propylene methoxy ethoxylate ] Iso-cyanuric acid esters or (meth) acrylate, urethane and the like.

These acrylic resins may be used alone or in combination of two or more.

1.5.3 surfactant

When it is desired to improve the coatability of the inkjet ink, a surfactant suitable for this purpose can be added. Specific examples of the surfactant include: "Byk-300", "Byk-306", "Byk-335", "Byk-310", "Byk-341", "Byk-344", "Byk". -370" (manufactured by BYK-Chemie Co., Ltd.) and other surfactants; acrylic acid such as "Byk-354", "ByK-358", "Byk-361" (by BYK-Chemie Co., Ltd.) Surfactant; a fluorine-based surfactant such as "DFX-18", "FTERGENT 250", or "FTERGENT 251" (manufactured by Neos Co., Ltd.).

These surfactants may be used alone or in combination of two or more.

The surfactant is used to improve the wettability, leveling property, or coatability of the base substrate, and it is preferably added in an amount of 0.01 part by weight to 1 weight per 100 parts by weight of the inkjet ink. Part of the surfactant.

1.5.4 Antistatic agent

The antistatic agent is not particularly limited, and a known antistatic agent can be used. Specific examples thereof include metal oxides such as tin dioxide, tin dioxide, and antimony trioxide composite oxide, and a metal oxide or a quaternary ammonium salt such as a tin oxide or a tri-doped indium oxide composite oxide.

These antistatic agents may be used alone or in combination of two or more.

The antistatic agent is used to prevent static electricity, and it is preferred to use 0.01 to 1 part by weight of an antistatic agent per 100 parts by weight of the inkjet ink.

1.5.5 coupling agent

The coupling agent is not particularly limited, and a known coupling agent can be used. The coupling agent to be added is preferably a decane coupling agent, and specific examples thereof include a trialkoxy decane compound or a dialkoxy decane compound. Preferably, for example, γ-vinylpropyltrimethoxydecane, γ-vinylpropyltriethoxydecane, γ-acrylenylpropylmethyldimethoxydecane, γ-acrylofluorene can be exemplified. Propyltrimethoxydecane, γ-acrylamidopropylmethyldiethoxydecane, γ-acrylenylpropyltriethoxydecane, γ-methylpropenylpropylmethyldimethoxy Baseline, γ-methylpropenylpropyltrimethoxydecane, γ-methylpropenylpropylmethyldiethoxydecane, γ-methylpropenylpropyltriethoxydecane, γ - glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidyloxy Propyltriethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-amine Propyl triethoxy decane, N-aminoethyl-γ-iminopropylmethyldimethoxydecane, N-aminoethyl-γ-aminopropyltrimethoxydecane, N -aminoethyl-γ-aminopropyltriethyl Baseline, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropylmethyldi Methoxydecane, N-phenyl-γ-aminopropylmethyldiethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ- Mercaptopropylmethyldiethoxydecane, γ-mercaptopropyltriethoxydecane, γ-isocyanatepropylmethyldiethoxydecane, γ-isocyanatepropyltriethoxydecane, and the like. Among these decanes, preferred are γ-vinylpropyltrimethoxydecane, γ-acrylonitrilepropyltrimethoxydecane, γ-methylpropenylpropyltrimethoxydecane, and γ. - Isocyanatopropyltriethoxydecane, and the like.

These coupling agents may be used alone or in combination of two or more.

The coupling agent is preferably added in an amount of from 0.01 part by weight to 3 parts by weight per 100 parts by weight of the ink for inkjet.

1.5.6 epoxy hardener

The epoxy curing agent is not particularly limited, and a known epoxy curing agent can be used. Specific examples thereof include an organic acid dihydrazide compound, imidazole and a derivative thereof, dicyanodiamine, an aromatic amine, a polyvalent carboxylic acid, and a polycarboxylic acid anhydride. More specifically, dicyanoguanamine such as dicyanodiamine, diammonium adipate, and 1,3-bis(decylcarboethyl)-5-isopropylethyl An organic acid such as guanidine or the like, 2,4-diamino-6-[2'-ethylimidazolyl-(1')]-ethyltriazine, 2-phenylimidazole, 2-phenyl- Imidazole derivatives such as 4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid- An acid anhydride such as 1,2-anhydride.

Among the above epoxy curing agents, trimellitic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are preferred.

These epoxy hardeners may be used alone or in combination of two or more.

The epoxy curing agent is preferably used in an amount of from 0.2 part by weight to 5 parts by weight per 100 parts by weight of the inkjet ink.

2 Polyimine film of the invention

The inkjet ink is applied onto the surface of the substrate by inkjet, and is heat-treated by a hot plate or an oven to form a full-surface or a specific pattern (for example, a linear) polyimide film. . Further, the formation of the polyimide film is not limited to the heat treatment, and treatment with an ultraviolet (UV) treatment, an ion beam, an electron beam, a gamma ray or the like may be employed.

2.1 Coating of ink for inkjet by an inkjet method

The inkjet coating method has various types depending on the method of discharging the ink. Examples of the discharge method include a piezoelectric element type, a bubble-jet (registered trademark) type, a continuous injection type, and a static induction type. The inkjet ink can be ejected by various methods by appropriately selecting the components contained in the ink, and the inkjet ink can be applied in a predetermined pattern.

A preferred discharge method for coating using inkjet ink is a piezoelectric element type. The piezoelectric element type head is an on-demand inkjet coating head comprising: a nozzle forming substrate having a plurality of nozzles, configured to face the nozzle The pressure generating element formed by the piezoelectric material and the conductive material fills the ink around the pressure generating element, and the nozzle causes the pressure generating element to be displaced by applying a voltage to cause small droplets of the ink to be ejected from the nozzle.

The inkjet coating device is not limited to an inkjet coating device in which the coating head is different from the ink containing portion, and may be an inkjet coating device in which the coating head and the ink containing portion are integral. Further, in addition to the inkjet coating device that is attached to the carriage in which the ink container is detachably or inseparably integrated, the ink accommodating portion may be provided at a fixed portion of the device and may be provided via an ink supply member. For example, a tube is used to supply ink to an inkjet coating device in the form of a coating head.

Further, when a configuration for allowing a preferable negative pressure to act on the coating head is provided in an ink tank, a form in which an absorber is disposed in an ink containing portion of the ink tank or a configuration may be employed; In the form of a flexible ink containing bag and a spring portion, the spring portion applies a force to the flexible ink containing bag to expand the inner volume of the flexible ink containing bag. In addition to the coating apparatus using a serial coating method as described above, the coating apparatus may employ a lining printer formed by arranging coating elements in a range corresponding to the total width of the coating medium ( Line printer) form.

2.2 Formation of poly-proline membrane

The inkjet ink is applied onto the substrate by inkjet coating, and then heated by a hot plate or an oven to remove the solvent by vaporization or the like, thereby drying. Proline membrane. The heating conditions vary depending on the type of each component and the blending ratio. Usually, the polyamic acid film is formed at 70 ° C to 120 ° C for 5 minutes to 15 minutes when using an oven, and 1 minute to 5 hours when using a hot plate. The polyamine membrane was formed in minutes.

2.3 Formation of polyimine film

After the polyperuric acid film is formed, in order to carry out the hydrazine imidization, the heat treatment is carried out for 30 minutes to 90 minutes at 180 to 350 ° C, preferably 200 to 300 ° C in an oven. The heat treatment is performed by heating the plate for 5 minutes to 30 minutes, whereby a polyimide film can be obtained. When the polyproline film is formed into a pattern, a patterned polyimide film is formed. In the present specification, the polyimide film includes a patterned polyimide film, unless otherwise specified.

3 film substrate of the invention

The film substrate of the present invention is obtained by, for example, coating the inkjet ink by a inkjet coating method on a substrate such as a polyimide film having wiring formed by a method such as inkjet. The entire surface or a specific pattern (linear shape, etc.) is formed, and then the substrate is dried, and further heat treatment or the like is performed to form a polyimide film.

The polyimide film which can be used in the present invention is excellent in flexibility, and is preferably formed on a substrate such as the above polyimide film. However, the polyimide film is not particularly limited thereto, and may be formed on a known substrate. .

Examples of the substrate that can be used in the present invention include glass epoxy substrates and glass composite substrates of various specifications such as FR-1, FR-3, FR-4, CEM-3, and E668. Printed wiring board such as paper phenol substrate, paper epoxy substrate, green epoxy substrate or bismaleimide-triazine resin (BT resin) substrate .

In addition, other substrates applicable in the present invention may be exemplified by metals such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or stainless steel. Substrate (may also be a substrate having the surface of these metals); from alumina, aluminum nitride, zirconia, zirconium silicate (zircon, zircon), magnesium oxide (magnesia), Aluminum titanate, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, tannic acid Lithium, cadmium sulfide, molybdenum sulfide, beryllia, silica, silicon carbide, silicon nitride, boron nitride, zinc oxide, mullite a substrate formed of ceramics such as (mullite), ferrite, stataite, forsterite, spinel or spodumene (may also have The surface of these ceramics); by polyethylene terephthalate (PET) Polybutylene terephthalate (PBT) resin, polycyclohexylene dimethylene terephthalate (PCT) resin, polyphenyl sulfide (PPS) resin, Polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyether oxime imide resin, polyamidoximine resin, ring a substrate formed of a resin such as an oxygen resin, an acrylic resin, a teflon (registered trademark), a thermoplastic elastomer (elastomer), or a liquid crystal polymer (may also be a substrate having a surface of these resins); Or a semiconductor substrate such as gallium arsenide; a glass substrate; or a substrate having an electrode material such as tin oxide, zinc oxide, indium tin oxide (ITO) or antimony tin oxide (ATO) formed on the surface; or αGEL, A gel sheet such as βGEL, θGEL or γGEL (all of which are registered trademarks of Taica Co., Ltd.).

4 electronic parts of the invention

For example, the inkjet ink is applied onto a film substrate such as a polyimide film having a wiring formed in advance by an inkjet coating method, and then the film substrate is dried and further heated. A flexible electronic component covered with an insulating polyimide film.

[Examples]

Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

The compounds (a1) and (a3), diamines (a2) and (a4) having two or more acid anhydride groups used in the synthesis examples and the examples or the comparative examples are indicated by the abbreviations, and have an acid anhydride group. The name of the compound (a6) and the solvent (C). This abbreviation is used in the following description.

Compounds (a1) and (a3) having two or more acid anhydride groups

ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

6FDA: 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride

Diamines (a2) and (a4)

BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

TPE-R: 1,3-bis(4-aminophenoxy)benzene

a compound having one or more anhydride groups (a6)

TESA: triethoxydecyl propyl succinic anhydride

Solvent (C)

EDM: Diethylene glycol methyl ether

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

[Synthesis Example 1] Synthesis of Polylysine (A-1) Solution

The raw material shown below was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and then stirred at 25 ° C for 5 hours under a stream of dry nitrogen gas to obtain a pale yellow transparent polymer. A 12 wt% solution of valine. The viscosity of this solution was 5100 mPa ‧ (25 ° C). The weight average molecular weight measured by GPC was 117,000. This solution was used as a solution of polyamic acid (A-1).

The viscosity of the solution was measured using an E-type viscometer (manufactured by TOKYO KEIKI, VISCONIC ELD). Further, the weight average molecular weight of polylysine is determined by diluting the obtained polyglycolic acid with tetrahydrofuran (THF) so that the polyaminic acid concentration becomes about 1% by weight, followed by using GPC. Device: JASCO GULLIVER 1500 (Intelligent Differential Refractometer RI-1530) manufactured by JASCO Corporation was measured by the GPC method using the above diluent as a developing solvent, and then converted into polystyrene. The pipe string was used by sequentially connecting the four columns of G1000HXL, G3000HXL, G2500HXL, and G2000HXL manufactured by Tosoh Corporation, and the measurement was carried out under the conditions of a column temperature of 40 ° C and a flow rate of 1.0 ml/min.

ODPA 1.03g

BAPP 1.37g

GBL 17.60g

[Synthesis Examples 2 to 3] Polylysine (A-2) to (A-3) solution

A polyamine solution was prepared under the same conditions as in Synthesis Example 1 except that the raw materials shown in Table 1 were charged, and used as a solution of poly-proline (A-2) to (A-3).

The weight average molecular weight of the obtained polyaminic acid (A-2) to (A-3) solution and the viscosity at 25 ° C were measured under the same conditions as in Example 1. The results of these measurements are shown in Table 1.

[Synthesis Example 4] Synthesis of proline acid compound (B2) solution

The raw material shown below was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and then stirred at 25 ° C for 5 hours under a nitrogen stream to obtain a 40 wt% solution of the proline compound. . The viscosity of this solution was 30.4 mPa ‧ (25 ° C). This solution was used as a solution of the proline (B2) solution.

BAPP 4.83g

TESA 7.17g

EDM 12.6g

GBL 5.4g

[Example 1] Inkjet ink (1)

The polylysine (A-1) solution of Synthesis Example 1, the proline acid compound (B2) solution of Synthesis Example 4, and EDM were mixed as shown below, and then stirred for 2 hours to obtain a 24 wt% solution. . The viscosity of this solution was 13.3 mPa ‧ (25 ° C). This solution was directly used as an ink for inkjet (1).

Polylysine (A-1) solution 4.0g

Proline (B2) solution 6.0g

EDM 2.0g

The composition of the inkjet ink (1) is as follows.

Polylysine (A-1) 0.48g

Proline (B2) 2.40g

Solvent (C)

GBL 3.52g

EDM 5.60g

[Example 2] Inkjet ink (2)

The polylysine (A-2) solution of Synthesis Example 2, the proline acid compound (B2) solution of Synthesis Example 4, and EDM were mixed as shown below, and then stirred for 2 hours to obtain 23 wt%. Solution. The viscosity of this solution was 14.0 mPa ‧ (25 ° C). This solution was directly used as an ink for inkjet (2).

Polylysine (A-2) solution 3.0g

Proline (B2) solution 6.0g

EDM 3.0g

The composition of the inkjet ink (2) is as follows.

Polylysine (A-2) 0.36g

Proline (B2) 2.40g

Solvent (C)

GBL 3.72g

EDM 5.52g

[Example 3] Inkjet ink (3)

The polylysine (A-3) solution of Synthesis Example 3, the proline acid compound (B2) solution of Synthesis Example 4, and EDM were mixed as shown below, and then stirred for 2 hours to obtain 22% by weight. Solution. The viscosity of this solution was 10.8 mPa ‧ (25 ° C). This solution was directly used as an ink for inkjet (3).

Polylysine (A-3) solution 2.0g

Proline (B2) solution 5.0g

EDM 3.0g

The composition of the inkjet ink (3) is as follows.

Polylysine (A-3) 0.2g

Proline (B2) 2.0g

Solvent (C)

NMP 0.9g

GBL 0.9g

EDM 6.0g

[Comparative Example 1] Inkjet ink (E1)

The solution of the proline acid compound (B2) of Synthesis Example 4 was diluted with the following composition so as to have a viscosity of 20 mPa ‧ s or 20 mPa ‧ s or less to prepare an inkjet ink (E1). The ink had a viscosity of 14.4 mPa ‧ and a concentration of 30% by weight.

Proline (B2) solution 15g

EDM 5g

The composition of the inkjet ink (E1) is as follows.

Proline (B2) solution 6.0g

Solvent (C)

GBL 2.7g

EDM 11.3g

[Comparative Example 2] Inkjet ink (E2)

The polyacrylic acid (A-1) solution of Synthesis Example 1 was diluted with a composition such that the viscosity became 20 mPa ‧ s or 20 mPa ‧ s or less to prepare an inkjet ink (E2). The ink had a viscosity of 10.8 mPa‧s and a concentration of 4.0% by weight.

Polylysine (A-1) solution 5g

EDM 10g

The composition of the inkjet ink (E2) is as follows.

Polylysine (A-1) 0.60g

Solvent (C)

GBL 4.4g

EDM 10.0g

[Example 4]

Formation and Flexibility Evaluation of Polyimine Film Using Inkjet Ink (1)

(1) Formation of linear polyimide film by inkjet printing

Using the inkjet ink (1) prepared in Example 1 as an inkjet ink, using an inkjet coating device DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd., on a 1.5 mm thick glass epoxy resin double-sided copper foil plate, The line coating having a length of 5 cm was carried out by setting a dot pitch of 40 μm and 20 μm at a 1-point width. The heater of the ink jet head was set to 30 ° C, the piezo voltage was set to 16 V, and the driving frequency was set to 5 kHz. Next, the substrate was dried on a hot plate at 80 ° C for 5 minutes, and then heated in an oven at 230 ° C for 30 minutes to obtain a polyimide film formed into a linear shape.

The line width and the line width uniformity of the obtained polyimide film were observed using an optical microscope, and the film thickness was measured. The film thickness was measured by a stylus type film thickness meter α-STEP 200 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of the three measured values was taken as the film thickness. A film having a thickness of the obtained polyimide film and a uniform film having a line width of 1.25 μm and 120 μm, respectively, was obtained.

(2) Flexibility of the polyimide film (folding resistance)

The inkjet ink (1) synthesized in Example 1 was applied onto a substrate (Kapton 200H (thickness: 50 μm) manufactured by DUPONT-TORAY Co., Ltd.) using an applicator. Next, using a hot plate, drying at 50 ° C for 30 minutes, and then heating in an oven at 230 ° C for 30 minutes to form a film on one side of the substrate. Then, the test piece was prepared by cutting into a width of 1.5 cm and a length of 13 cm so that the TD direction (transverse direction) of the base material became the longitudinal direction of the test sample.

Using a folding resistance tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., MIT-DA), the curvature radius of the bending surface was set to 0.38 mm, the bending angle was 135°, and the tension was 4.9 N. The test sample was bent at a secondary speed, and cracks were observed when the bending was repeated for a specific number of times. As a result, no crack was generated when the number of times of bending was 1000, and it was evaluated as ◎.

The results of the bendability were evaluated in the following manner.

◎: No cracking occurred when bending 1000 times

○: No crack occurred when the bending was performed 500 times, but cracks were observed when the bending was performed 1000 times.

△: No crack occurred when the bending was performed 100 times, but cracks were observed when the bending was performed 500 times.

The ink for inkjet which was bent to ○ or more was judged to have good bendability.

[Examples 5 to 6]

Formation of polyimine film using inkjet inks (2) to (3) and evaluation of flexibility

An insulating polyimide film formed into a linear shape was obtained under the same conditions as in Example 4 except that the ink for inkjet shown in Table 2 was used. Further, a folding test specimen was prepared under the same conditions as in Example 4, and bent, and the presence or absence of cracking was observed when the bending was repeated a certain number of times. The results are shown in Table 3.

[Comparative Example 3]

Formation of polyimine film using inkjet ink (E1) and evaluation of bendability

(1) Formation of linear polyimide film by inkjet printing

An insulating polyimide film formed into a linear shape was obtained under the same conditions as in Example 4 except that the inkjet ink (E1) synthesized in Comparative Example 1 was used as the inkjet ink.

The obtained polyimide film was evaluated under the same conditions as in Example 4. As a result, the linear width of the polyimide film was 230 μm, which was wider than the width at the time of coating. The obtained polyimide film had a line thickness of 1.43 μm, and a uniform film was obtained.

(2) Flexibility of the polyimide film (folding resistance)

A folding test specimen was produced under the same conditions as in Example 4 except that the inkjet ink (E1) synthesized in Comparative Example 1 was used.

The test specimen was bent under the same conditions as in Example 4, and cracks were observed when the bending was repeated for a specific number of times. As a result, cracks were not generated when the number of times of bending was 100, but 500 times when bending was performed. Cracks were observed and evaluated as Δ.

[Comparative Example 4]

Formation of polyimine film using inkjet ink (E2) and evaluation of bendability

(1) Formation of linear polyimide film by inkjet printing

A linear insulating polyimide film was formed under the same conditions as in Example 4 except that the inkjet ink (E2) synthesized in Comparative Example 2 was used. As a result, since the inkjet ink is a component having a high molecular weight component as a main component, stringiness occurs due to elongation of the polymer chain, and the ink droplet formation process is greatly affected, so that uniformity cannot be formed. Polyimine film.

(2) Flexibility of the polyimide film (folding resistance)

A folding test specimen was produced under the same conditions as in Example 4 except that the inkjet ink (E2) synthesized in Comparative Example 2 was used.

The test sample was bent under the same conditions as in Example 4, and the presence or absence of cracking was observed when the bending was repeated for a specific number of times. As a result, no crack was generated when the number of times of bending was 1000, and it was evaluated as ◎.

[Industrial availability]

The effective use of the present invention is, for example, an insulating film for a flexible wiring board or an electronic component using the insulating film for a flexible wiring board.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (15)

An ink for inkjet comprising: a polylysine (A) having a weight average molecular weight of 50,000 to 500,000 and having a structural unit represented by the following formula (1), the polyamic acid (A) being used at least Obtained by two or more acid anhydride group-containing compounds (a1) and diamines (a2); at least one selected from the group consisting of a proline acid compound (B1) and a proline acid compound (B2), the above-mentioned hydrazine The amino acid compound (B1) is obtained by using a compound (a3) having two or more acid anhydride groups and a monoamine (a5) which is a diamine (a4) and has an acid anhydride. Obtained as a compound (a16); and solvent (C), In the above formula (1), R ¹ and R ² are each independently an organic group having 2 to 100 carbon atoms, and the ink content of the inkjet ink is 10,000 ppm or less. The inkjet ink according to the first aspect of the invention, wherein the inkjet ink contains 0.5 wt% to 20 wt% of polyamic acid (A), and a total of 5 wt% to 50 wt% of a proline compound ( B1) and a proline (B2), 30% by weight to 94.5 wt% of a solvent (C). The ink for inkjet according to claim 1, wherein the compounds (a1) and (a3) having two or more acid anhydride groups are each independently selected from the group consisting of the following formula (2) One or more of a group consisting of a copolymer of a carboxylic acid dianhydride and a monomer having an acid anhydride group and another polymerizable monomer, In the above formula (2), R is each independently an organic group having 2 to 100 carbon atoms. The inkjet ink according to the first aspect of the invention, wherein the diamines (a2) and (a4) are each independently a diamine represented by the following formula (3), H ₂ NR-NH ₂ (3) In the above formula (3), R is each independently an organic group having 2 to 100 carbon atoms. The ink for inkjet according to claim 1, wherein the monoamine (a5) is an amine ruthenium compound represented by the following formula (4). In the above formula (4), R ^{1 is} each independently hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and R ^{2 is} independently an organic group having 1 to 20 carbon atoms. The ink for inkjet according to claim 1, wherein the compound (a6) having an acid anhydride group is a hydrazine-containing carboxylic acid anhydride represented by the following formula (5). In the above formula (5), R ^{1 is} each independently hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and R ² is an organic group having 1 to 20 carbon atoms. The ink for inkjet according to Item 3, wherein the tetracarboxylic dianhydride represented by the above formula (2) is selected from the group consisting of pyromellitic dianhydride, 3,3', 4, 4'-two. Benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3' , 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-diphenylstilbene tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic acid Dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(trimellitic anhydride), cyclobutane tetracarboxylic acid Dihydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic dianhydride, and butane tetracarboxylic dianhydride One or more of the group consisting of. The ink for inkjet according to Item 4, wherein the diamine represented by the above formula (3) is selected from 3,3'-diaminodiphenylanthracene and 4,4'-diaminodiamine. Phenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, isophthalic acid Diamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-aminobenzene) Oxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, bis[4-(4-aminobenzyl) Phenyl]methane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]4- Methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4 -methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]methane, 1,3-bis(4-aminophenoxy)benzene, and the following formula (XV) One or more of the groups consisting of the compounds shown, In the above formula (XV), R ^{1 is} each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ^{2 is} independently a methylene group, a phenylene group or an alkyl group-substituted phenylene group, respectively. Independently an integer from 1 to 6, y is independently an integer from 1 to 70. The ink for inkjet according to claim 5, wherein the amine sulfonium compound represented by the above formula (4) is selected from the group consisting of p-aminophenyltrimethoxydecane and p-aminophenyltriethoxylate. a group consisting of decane, m-aminophenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, and 3-aminopropyltriethoxydecane One or more of them. The inkjet ink according to Item 6, wherein the hydrazine-containing carboxylic acid anhydride represented by the above formula (5) is selected from the group consisting of p-trimethoxydecyl phenyl succinic anhydride and p-triethoxy.矽alkyl)phenylsuccinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, trimethoxydecyl propyl succinic anhydride, and triethoxy decane One or more of the group consisting of propyl succinic anhydride. An ink for inkjet comprising: polyamic acid (A) having a weight average molecular weight of 50,000 to 500,000, and the polyamic acid (A) is a compound (a1) having two or more acid anhydride groups and two Obtained from the amine (a2), wherein the compound (a1) having two or more acid anhydride groups is selected from the group consisting of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 2,2-[double At least one of the group consisting of (3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, the diamine (a2) being selected from 2,2-bis[4-(4-aminophenoxy) At least one of a group consisting of phenyl]propane and 1,3-bis(4-aminophenoxy)benzene; a proline compound (B2), which is used to use two The amine (a4) and the compound (a6) having an acid anhydride group, wherein the diamine (a4) is 2,2-bis[4-(4-aminophenoxy)phenyl]propane, having an acid anhydride group The compound (a6) is triethoxydecylpropyl succinic anhydride; and the solvent (C) which is selected from the group consisting of diethylene glycol methyl ether, N-methyl-2-pyrrolidone and γ- At least one of the groups consisting of butyrolactone, the ink of the inkjet ink having a moisture content of 10,000 ppm or 10,00 0ppm the following. A polyimine film obtained in the form of a whole surface or a pattern, and obtained by the ink for inkjet according to any one of the items 1 to 11. A polyimine film which is in the form of a whole surface or a pattern, and which is obtained by the following steps: coating the spray according to any one of the first to eleventh aspects of the patent application by the inkjet method The step of forming a polyamic acid film by ink, and the step of forming a polyimide film by treating the polyamic acid film. A film substrate obtained by forming a polyimide film according to claim 12 or 13 on a substrate. An electronic component having the film substrate as described in claim 14 of the patent application.