TWI432531B - Inkjet ink - Google Patents

Description

Inkjet ink

The present invention relates to an ink for inkjet, relating to an inkjet ink containing, for example, a ruthenium compound (A) and/or a ruthenium compound (A') for forming an insulating film layer in the production of an electronic component, using the inkjet A polyimide film formed of ink, a film substrate on which the polyimide film is formed, and an electronic component having the film substrate.

Polyimine is excellent in heat resistance and electrical insulation, and is therefore widely used in the field of electronic communication. For example, Japanese Patent Laid-Open No. 2000-039714, Japanese Patent Laid-Open No. 2003-238683, and Japanese Patent No. Japanese Patent Publication No. 2004-094118].

In the case where polyimine is used as a desired pattern film, it is conventionally to use etching or photosensitive polyimide to form a pattern, and in recent years, a need for formation by inkjet is being studied. The method of patterning a film.

A person skilled in the art has proposed various types of inkjet inks. For example, refer to Japanese Laid-Open Patent Publication No. 2003-213165, and Japanese Patent Laid-Open No. Hei. No. 2006-131730. The quinone imine ink is a relatively high-molecular ink. Therefore, in order to prepare an ink of the most suitable viscosity as the inkjet ink, it is necessary to increase the ratio of the solvent and reduce the polyamine content in the ink. In this case, there is a problem that the thickness of the film obtained by one ink ejection becomes thin.

On the other hand, it is known that if a proline acid compound (decane coupling agent) is used in combination with an epoxy resin or a phenol resin, it reacts with or forms a metal. In the case of the compound, the adhesion of the film is improved, and the solder crack resistance is improved [for example, refer to Japanese Laid-Open Patent Publication No. 2003-105059].

Under the above circumstances, an inkjet ink having a thick polyimine film (1 μm or more) can be formed by spraying (discharging) once.

In view of the above circumstances, the present inventors have found an inkjet ink containing at least one ruthenium compound (A) and/or at least one ruthenium compound (A'), and an inkjet ink containing the polymer compound (B), and further An inkjet ink containing an alkenyl group substituted with alkenyl-substituted nadimide (C) and an inkjet ink further containing a solvent (D).

The present invention provides an inkjet ink or the like as described below.

[1] An ink for inkjet comprising: an anthracene compound (A) obtained by using a compound (a1) having an acid anhydride group of 2 or more and a monoamine (a2), and using an acid anhydride group At least one of the hydrazone compound (A') obtained by the compound (a1') and the diamine (a2').

[2] The inkjet ink according to the above [1], wherein the compound (a1) having two or more acid anhydride groups is a tetracarboxylic dianhydride represented by the following formula (1), The amine (a2) is an aminoguanidine compound represented by the following formula (2).

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

[3] The inkjet ink according to [2] above, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-diphenyl ketone Carboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylfluorene Carboxylic 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 dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic acid One or more of the group consisting of acid dianhydride and butane tetracarboxylic dianhydride selected from the group consisting of p-aminophenyltrimethoxydecane and p-aminophenyltriethoxydecane , m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, aminopropyl trimethoxy One or more of the group consisting of decane and aminopropyltriethoxydecane.

[4] The inkjet ink according to the above [1], wherein the hydrazine compound (A) is a proline (A) represented by the following formula (3), [Chem. 17]

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

[5] The ink for inkjet according to the above [4], wherein the proline is a hydrazine represented by the following formula (4-1), (4-2) or (4-3) Proline,

(In the formula (4-1), (4-2) or (4-3), 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).

[6] The inkjet ink according to any one of [1] to [5] wherein the compound (a1) having two or more acid anhydride groups and the above monoamine (a2) The ratio is 1 mole: 0.5 mole to 8.0 mole.

[7] The inkjet ink according to any one of [1], wherein the compound (a1') having one acid anhydride group is represented by the following formula (1'). The carboxylic anhydride represented by the above diamine (a2') is a diamine represented by the following formula (2').

(In the formula (1'), R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, which may be the same or different, and Y' is an organic group having 1 to 20 carbon atoms, and the formula (2) In '), X' is a divalent organic group having a carbon number of 2 to 100).

[8] The ink for inkjet according to [7] above, wherein the carboxylic acid anhydride is selected from the group consisting of p-(trimethoxydecyl)phenyl succinic anhydride and p-(triethoxydecyl)phenyl amber. Anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, trimethoxy decyl propyl succinic anhydride, and triethoxy decyl propyl succinic anhydride One or more of the constituent groups, The above diamine is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenyl Ethylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-bis(4-aminophenyl)propane, bis(4-amino-3-methylphenyl) Methane, 1,2-bis-(4-amino-3-methylphenyl)ethane, bis(4-amino-2-methylphenyl)methane, 1,2-bis-(4- Amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl碸, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl-2,2'-propane, 1,4 -diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-bis[(4-aminophenyl)methyl]benzene, 1,4-bis(4-amino group) Phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-double [ 4-(4-Aminophenoxy)phenyl]fluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl Biphenyl, 1,3-double [4- (4-Aminobenzyl)phenyl]propane, 1,6-bis[4-(4-aminobenzyl)phenyl]hexane, 5-phenylmethyl-1,3-diaminobenzene , 5-[4-(4-Alkylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5-[4-(4-(4-alkylcyclohexyl)cyclohexyl)phenyl ]methyl-1,3-diaminobenzene, 5-[((alkylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 1,1-bis[4] -(4-Aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-alkylcyclohexane, 1,1- Bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-alkylcyclohexane, 1,3 One or more of the group consisting of bis(3-aminopropyl)-tetramethyldioxane.

[9] The inkjet ink according to any one of the above [1], wherein the oxime compound (A') is represented by the following formula (3'). Amino acid (A'),

(In the formula (3'), R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, which may be the same or different, Y' is an organic group having 1 to 20 carbon atoms, and X' is carbon Number 2~100 organic base).

[10] The inkjet ink according to [9] above, wherein the proline (A') is represented by the following formulas (4'-1), (4'-2), (4' -3), (4'-4) or (4'-5) represented by proline (A'), [Chem. 21]

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

[11] The inkjet ink according to any one of the above [1], wherein the compound (a1') having one acid anhydride group and the above two The ratio of amine (a2') is from 0.5 moles to 8.0 moles: 1 mole.

[12] The inkjet ink according to any one of [1], wherein the inkjet ink further contains a polymer compound (B).

[13] The inkjet ink according to [12], wherein the polymer compound (B) is at least one selected from the group consisting of polylysine and polyimine.

[14] The inkjet ink according to [12], wherein the polymer compound (B) has a weight average molecular weight of 1,000 to 5,000.

[15] The inkjet ink according to any one of [1] to [14] wherein the inkjet ink further contains an alkenyl group substituted with nadic acid yttrium imine (C).

[16] The inkjet ink according to [15] above, wherein the alkenyl-substituted nadic acid ylidene imine (C) is a monoamine, a diamine, a triamine or a tetraamine and the following formula (5) Alkenyl substituted nadic acid ylide imine substituted by alkenyl substituted nadic anhydride

In the formula (5'), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12; Any of an aryl group or a benzyl group.

[17] The inkjet ink according to the above [15], wherein the alkenyl-substituted nadic acid ylide (C) is a compound represented by the following formula (5) ,

In the formula (5), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12; Any of an aryl group or a benzyl group, n is an integer of 1 to 4, and when n=1, R ³ in the formula (5) is hydrogen, an alkyl group having 1 to 12 carbon atoms, and a hydroxyl group having 1 to 12 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, -{(C _q H _2q )O _t (C _r H _2r O) _u C _s H _2s X} ( Wherein, q, r, s are independently selected integers of 2 to 6, respectively, t is an integer of 0 or 1, u is an integer from 1 to 30, X is hydrogen or a hydroxyl group, and the polyoxyalkylene alkyl group is represented by -(R) _a -C ₆ H ₄ -R ⁴ (wherein a represents an integer of 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents hydrogen or an alkyl group having 1 to 4 carbon atoms) The group represented, -C ₆ H ₄ -T-C ₆ H ₅ {where T is -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -S- or -SO ₂ -} a group represented by the group or a group of one to three hydrogens directly bonded to the aromatic ring of the groups via a hydroxyl group, and when n=2, R ³ in the formula (5) is a carbon number of 2 ~20 of the alkylene group {any methylene group in the alkylene group which is not adjacent to each other may pass through - O- or -CH=CH-substitution, any hydrogen can be substituted by fluorine}, a cycloalkylene group having a carbon number of 5-8, -{(C _q H _2q O) _t (C _r H _2r O) _u C _s H _2s }- (wherein q, r, s are independently selected integers of 2 to 6, and t is an integer of 0 or 1, and u is an integer from 1 to 30). Polyoxyalkylene (polyoxyalkylene) , an arylene group having 6 to 12 carbon atoms, -(R) _a -C ₆ H ₄ -R ⁵ - (where a is an integer of 0 or 1, and R and R ⁵ are independently a carbon number of 1 to 4; a group represented by an alkyl group, consisting of -C ₆ H ₄ -T-C ₆ H ₄ -, -C ₆ H ₄ -T-C ₆ H ₄ -T-C ₆ H ₄ - or -C ₆ H ₄ -T'-C ₆ H ₄ -T-C ₆ H ₄ -T'-C ₆ H ₄ -{ wherein T is a single bond, an alkylene group having 1 to 6 carbon atoms, -C(CH ₃ ) ₂ - , -C(CF ₃ ) ₂ -, -CO-, -O-, -OC ₆ H ₄ C(CH ₃ ) ₂ C ₆ H ₄ O-, -S- or -SO ₂ -, T' is -CH ₂ - -O-}, or a group represented by the, or those on the aromatic group is directly bonded to the 1 to 3 hydrogen substituted hydroxy group, the formula (6-1) represented by the a group or a group represented by the following formula (6-2), in the formula (6-1), x is independently 1~ An integer of 6, y is an integer from 1 to 70,

When n=3, R ³ in the formula (5) is a group represented by the following formula (7-1) or a group represented by the following formula (7-2), [Chem. 25]

In the formula (7-1), R is hydrogen, fluorine, chlorine, -OH, -OCF ₃ , -OCF ₂ H, -CF ₃ , -CF ₂ H, -CFH ₂ , -OCF ₂ CF ₂ H, -OCF ₂ CFHCF ₃ or an alkyl group having 1 to 10 carbon atoms; in the formula (7-1) and the formula (7-2), R ⁴ , R ⁵ and R ⁶ are each independently a single bond or a trans-1,4-亚a cyclohexyl group, a 1,3-dioxane-2,5-diyl group, a 1,4-phenylene group, a hydrogen-substituted 1,4-phenylene group or a carbon number of 1 to 10 alkylene group. Any methylene group in the alkylene group which is not adjacent to each other may be substituted by -O- or -CH=CH-, and any hydrogen may be substituted by fluorine. When n=4, R ³ in the formula (5) is as follows (8) the group indicated,

In the formula (8), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, hydrogen 1,4-phenylene substituted by fluorine or alkylene having 1 to 10 carbon atoms; any methylene group in the alkylene group which is not adjacent to each other may be -O- or - CH=CH-substituted, any hydrogen can be substituted by fluorine.

[18] The ink for inkjet according to [17] above, wherein n is 2.

[19] The ink for inkjet according to [17] above, wherein n is 2, and R ³ in the formula (5) is an alkylene group having 2 to 15 carbon atoms; the alkylene groups are not adjacent to each other. Any methylene group may be substituted by -O- or -CH=CH-, any hydrogen may be substituted by fluorine}, -(R) _a -C ₆ H ₄ -R ⁵ - (where a is 0 or 1) a group represented by an integer, R and R ⁵ are each independently an alkylene group having 1 to 4 carbon atoms, and is represented by -C ₆ H ₄ -T-C ₆ H ₄ -, -C ₆ H ₄ -T-C ₆ H ₄ -T-C ₆ H ₄ - or -C ₆ H ₄ -T'-C ₆ H ₄ -T-C ₆ H ₄ -T'-C ₆ H ₄ -{ wherein T is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CO-, -O-, -OC ₆ H ₄ C(CH ₃ ) ₂ C ₆ H ₄ O-, -S- or -SO ₂ -, T 'is -CH ₂ - or -O-} group represented by the.

In the [20] of the first [17] As the above-described ink jet ink, wherein the formula (5) R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms of, n-2, the formula ( 5) wherein R ³ is an alkylene group having 2 to 15 carbon atoms. Any methylene group in the alkylene group which is not adjacent to each other may be substituted by -O- or -CH=CH-, and any hydrogen may be substituted by fluorine. }, a group represented by the formula (6-1), a group represented by the formula (6-2), a group represented by the formula (6-3), a group represented by the formula (6-4) or a group represented by the formula (6-5), [Chem. 27]

In the formula (6-1), x is independently an integer from 1 to 6, and y is an integer from 1 to 70. In the formula (6-3) and the formula (6-5), R is -CH ₂ -, -CH An organic group of ₂ CH ₂ -, -O-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, and in the formula (6-5), X is -CH ₂ - , -O-organic base.

[21] The ink for inkjet according to [17] above, wherein R ¹ and R ² in the formula (5) are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is 3, wherein 5) R ³ is the formula (7-1-1), formula (7-2-1), or formula (7-2-2), said

In the formula (7-1-1), R is an alkyl group having 1 to 10 carbon atoms or -OH, and in the formula (7-2-2), R ⁴ , R ⁵ and R ⁶ are each independently 1,2-Asia. Ethyl, 1,4-butylene.

Of the [22] As the first [17] An ink-jet ink, wherein in the formula (5) R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms of, is n-4, the formula ( 5) R ³ is represented by the following formula (8-1), [Chem. 29]

[23] The ink for inkjet according to the above [17], wherein the ink for inkjet contains an alkenyl group selected from the group consisting of an alkenyl group having n of 1 and a naphthyl imine (C) having n of 2 Substituting at least two of Nadick's yttrium imine (C), n's alkenyl substituted nadic ylidene imine (C), and n's 4 alkenyl substituted nadic ylidene imide (C) Alkenyl substituted nadic acid ylide (C).

[24] The inkjet ink according to [17] above, wherein the inkjet ink contains at least two alkenyl groups substituted with nadic acid ylide (C): R in the formula (5) ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ³ in the formula (5) is an alkyl group having 1 to 12 carbon atoms (n = 1) and an aryl group having 6 to 12 carbon atoms ( n=1), -(CH ₂ ) _{pair (} n=2, p is an integer of 6 to 12), a group represented by the formula (6-1-1), and a group represented by the formula (6-2) a group represented by the formula (6-3-1), a group represented by the formula (6-4), a group represented by the formula (6-5-1), and a formula (7-1-2). a group represented by the formula, a group represented by the formula (7-1-3), a group represented by the formula (7-2-1), a group represented by the formula (7-2-3), and a formula (8) -1) the group indicated, .

Further, the ink for inkjet of the present invention may be the following ink.

The inkjet ink according to the above [17], wherein the inkjet ink contains at least one alkenyl-substituted nadic acid ylide (C): n is 1, R in the formula (5) ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, -{(C _q H _2q )O _t (C _r H _2r O) _u C _s H _2s+1 } (wherein q, r, s are independently selected integers of 2-6, t is an integer of 0 or 1, u is an integer from 1 to 30), and the polyoxyalkylene alkyl group is represented by , -(R) _a -C ₆ H ₄ -R ⁴ (wherein a represents an integer of 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; a group represented by, or -C ₆ H ₄ -T-C ₆ H ₅ (wherein T is -CH ₂ -, -C(CH ₃ ) ₃ -, -CO-, -S- or SO ₂ - a group represented by the group; and at least one alkenyl group having n of 2 in place of the nadic acid ylide (C).

Further, the ink for inkjet of the present invention may be the following ink.

The inkjet ink according to the above item [171], wherein the inkjet ink contains at least one of the following alkenyl-substituted nadic acid ylides (C): R ¹ and R ² in the formula (5), respectively Independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 1, and R ³ in the formula (5) is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12 An aryl group, or a benzyl group; and at least one alkenyl group having n is 2 substituted with nadic acid ylide (C).

Further, the ink for inkjet of the present invention is the following ink.

The inkjet ink according to the above [17], wherein the inkjet ink contains at least one of the following alkenyl-substituted nadic acid ruthenium imides (C): R ¹ and R ² in the formula (5) Each of them is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 1, and R ³ in the formula (5) is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms; and at least one of the following Alkenyl substituted nadic acid ylide (C): R ¹ and R ² in the formula (5) are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 2, and R ³ in the formula (5) It is a group represented by -(CH ₂ ) ₆ -, the above formula (6-3-1) or a group represented by the above formula (6-4).

[25] The inkjet ink according to any one of [1], wherein the inkjet ink further contains a solvent (D).

[26] The inkjet ink according to [25] above, wherein the solvent (D) is selected from the group consisting of ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, and diethyl ether. Glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3 One or more of the group consisting of methyl methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, and γ-butyrolactone.

The inkjet ink according to any one of the above [1], wherein the ruthenium compound (A) and the ruthenium compound are the same as the ink for inkjet of 100 parts by weight. The total content of (A') is from 1 part by weight to 99 parts by weight.

The inkjet ink according to any one of the above [1], wherein the ruthenium compound (A) and the ruthenium compound are the same as the ink for inkjet of 100 parts by weight. The total content of (A') is from 10 parts by weight to 80 parts by weight.

The inkjet ink according to any one of the above-mentioned [11], wherein the ruthenium compound (A) and the ruthenium compound (the above-mentioned ruthenium compound) are used with respect to 100 parts by weight of the ink for inkjet. The total content of A') is from 22 parts by weight to 70 parts by weight.

[30] A polyimine film or a patterned polyimide film, the polyimide film or the patterned polyimide film is obtained by the following method: by the inkjet coating method, coating as described above After the coating film is formed by the inkjet ink according to any one of the items [1] to [29], the coating film is cured to form a polyimide film.

[31] A method for forming a polyimide film or a patterned polyimide film, the method comprising the following steps: coating by the inkjet coating method as in the above items [1] to [29] A process for forming a coating film by using the inkjet ink according to any one of the preceding claims; and a process of curing the coating film to form a polyimide film.

[32] A film substrate having a polyimide film or a patterned polyimide film, wherein the polyimide film or the patterned polyimide film is as described in the above [31] The method is formed on a substrate.

[33] An electronic component comprising the film substrate according to the above [32].

[Effect of the invention]

When the ink for inkjet according to the preferred embodiment of the present invention is used, a polyimide film having a relatively thick film thickness can be formed by spraying once. Moreover, the polyimide film formed by the inkjet ink of the preferred embodiment of the present invention has high heat resistance and electrical insulating properties, for example, and improves the reliability and yield of the electronic component.

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

The present invention provides an inkjet ink containing a ruthenium compound (A) and/or a ruthenium compound (A'), a method for forming a polyimide film using the ink, and the like. Further, the ink for inkjet of the present invention may be colorless or colored.

The inkjet ink is an inkjet ink containing at least one ruthenium compound (A) and/or at least one ruthenium compound (A'), and further contains an inkjet ink containing a polymer compound (B), and further contains an alkenyl group. An inkjet ink of nadicimide (C) and an inkjet ink further containing a solvent (D).

The hydrazine compound (A) can be obtained by using at least a compound (a1) having two or more acid anhydride groups and a monoamine (a2), for example, a product obtained by reacting (a1) with (a2). (Proline (A)), for example, a compound which can form a salt of (a1) and (a2), as long as it is a compound (a1) and a monoamine (a2) which have an acid anhydride group of 2 or more The ruthenium compound is not limited to the above examples.

Further, the oxime in the ruthenium compound (A) may be derived from the compound (a1) having two or more acid anhydride groups, may be derived from the monoamine (a2), or may be derived from both (a1) and (a2). . In the following detailed description, the ruthenium compound (A) is obtained by using a ruthenium derived from a monoamine (a2), and the compound (a1) having an acid anhydride group of 2 or more has an anthracene. For example, Japan is exemplified. Japanese Patent Laid-Open No. 61-205285, Japanese Patent Laid-Open The compound disclosed in Japanese Laid-Open Patent Publication No. Hei 5-- No. Hei.

Further, the hydrazine compound (A') can be obtained by using at least a compound (a1') having one acid anhydride group and a diamine (a2'), for example, by reacting (a1') with (a2'). The obtained product (proline (A')), for example, may be a compound in which (a1') forms a salt with (a2') as long as a compound (a1') having one anhydride group and a diamine are used. The ruthenium compound obtainable by (a2') is not limited to the above examples.

Further, the ruthenium compound (A') may be derived from a compound (a1') having one acid anhydride group, may be derived from a diamine (a2'), or may be derived from (a1') and (a2'). Both. In the following detailed description, the ruthenium compound (A') is obtained by using a ruthenium derived from the compound (a1') having one acid anhydride group, and the ruthenium (a2') has an oxime. For example, The azepine-based diamine represented by the formula (XV).

1 proline (A) and proline (A')

The lysine (A) contained in the inkjet ink of the present invention can be obtained by the following method using at least a compound (a1) and a monoamine (a2) having an acid anhydride group of 2 or more. However, it is not limited to the proline acid obtained by the production method. The guanamine (A) is a compound represented by the above formula (3), and preferably a compound represented by the above formula (4-1), (4-2) or (4-3).

Further, the lysine (A') contained in the inkjet ink of the present invention can be produced by using at least the compound (a1') having one anhydride group and the diamine (a2'). Obtained, but not limited to use The proline obtained by the process. The proline acid (A') may, for example, be a compound represented by the above formula (3'), preferably the above formula (4'-1), (4'-2), (4'-3) or (4'-4) the compound represented.

1.1 Reaction conditions for obtaining valine (A) and valine (A')

The valine acid (A) which can be used in the present invention is preferably a compound (a1) having an acid anhydride group of 2 or more with respect to 1 mol, and a monoamine of 0.5 mol to 8.0 mol (a2) ) obtained by reaction. Further, it is further preferably obtained by reacting a compound (a1) having 1 or more acid anhydride groups of 1 mol with 1.0 mol to 4.0 mol of the monoamine (a2). More preferably, it is obtained by reacting a compound (a1) having 1 or more acid anhydride groups of 1 mol with 1.5 mol to 2.5 mol of the monoamine (a2).

Further, the proline (A') which can be used in the present invention is preferably a compound having one acid anhydride group with respect to 1 mol of the diamine (a2') and 0.5 mol to 8.0 mol. A1') obtained by reaction. Further, it is preferably obtained by reacting with 1.0 mol% to 4.0 mol of the compound (a1') having one acid anhydride group per 1 mol of the diamine (a2'). More preferably, it is obtained by reacting with 1.5 mol to 2.5 mol of the compound (a1') having one acid anhydride group with respect to 1 mol of the diamine (a2').

1.1 (1) reaction solvent

The solvent for obtaining the proline (A) and the valine (A') of the present invention is not particularly limited as long as it can be synthesized, and examples thereof include diethylene glycol dimethyl ether and diethyl ether. Glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone , γ-butyrolactone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamide.

In the above solvent, if propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyl are used. The lactone is preferably prepared as an ink which is less damaged to the ink jet head.

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

When the reaction solvent is 100 parts by weight or more with respect to 100 parts by weight of the total of the compound (a1) and the monoamine (a2) having an acid anhydride group of 2 or more, or a compound having 1 anhydride group (a1') When 100 parts by weight or more of the total amount of the diamine (a2') is used, the reaction proceeds smoothly, which is preferable. Preferably, the reaction is carried out at 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).

1.1 (2) order added to the reaction system

Further, the order in which the reaction raw material is added to the reaction system is not particularly limited. That is, for the valine acid (A), any one of the following methods may be used: a compound (a1) having two or more acid anhydride groups and a monoamine (a2) are simultaneously added to the reaction solvent. Method; adding a monoamine (a2) to a reaction solvent and adding an acid anhydride group having two or more The method of the compound (a1); the method of adding a monoamine (a2) to the compound (a1) having an acid anhydride group of 2 or more.

Further, as the valine acid (A'), any one of the following methods may be used: a compound (a1') having one acid anhydride group and a diamine (a2') are simultaneously added to a reaction solvent. Method; a method of adding a compound (a1') having one acid anhydride group after dissolving a diamine (a2') in a reaction solvent; adding a diamine (a2') to a compound (a1') having one acid anhydride group Method etc.

1.2 Advantages of proline (A) and proline (A')

When phthalic acid (A) is used in combination with an epoxy resin or a phenol resin, it is known to act as a decane coupling agent, react with a metal or form a complex compound, thereby improving the adhesion of the film and preventing cracking. Sexual improvement. Further, the proline (A') is predictively used as a decane coupling agent when used in combination with an epoxy resin or a phenol resin, and reacts with a metal or forms a complex compound to form a dense film. Improved performance and improved weld resistance.

Further, as a result of intensive studies, the present inventors have found that proline (A) is a thermosetting property which can be hydrolyzed by heating, dehydrated and condensed, and becomes a solid product (polyimine) having a quinone bond. Compound. Further, it has been found that proline (A') is a thermosetting compound which can be hydrolyzed by heating, dehydrated and condensed to form a solid product (polyimine) having a quinone bond.

The ruthenium compound can be obtained by stereocrosslinking, which is easier to process than the prior linear polyimine. Further, the ruthenium compound exhibits good heat resistance and has little occurrence of voids or cracks during curing, and thus is used as a molding material. Or a matrix resin of a build-up material has excellent properties.

1.3 Instructions for obtaining the components of proline (A) and proline (A')

Hereinafter, the compound (a1) and the monoamine (a2) having two or more acid anhydride groups which can be used to obtain the valine acid (A) will be described. Further, a compound (a1') having one acid anhydride group and a diamine (a2') which can be used to obtain valeric acid (A') will be described.

1.3(1) Compound having two or more acid anhydride groups (a1)

The compound (a1) having two or more acid anhydride groups used in the present invention may, for example, be a tetracarboxylic dianhydride represented by the above formula (1).

Specific examples of the compound (a1) having two or more acid anhydride groups used in the present invention include styrene-maleic anhydride copolymer and methyl methacrylate-maleic anhydride copolymer. A copolymer of a radical polymerizable monomer having an acid anhydride group and another radical polymerizable monomer, or a tetracarboxylic dianhydride or the like. Examples of the tetracarboxylic dianhydride include 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, and 2 , 2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-di Phenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis(trimellitic anhydride), ethane tetracarboxylic dianhydride, 4 -(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3- Specific examples of the methyl-3-cyclohexene-1,2-dicarboxylic anhydride include tetracarboxylic dianhydrides such as compounds represented by the following formulas (b1-1) to (b1-73).

[化32] [化34]

In the above specific examples of the compound having two or more acid anhydrides, the styrene-maleic anhydride copolymer, from the formula (b1-1), (b1-5), (b1-6), (b1) The compounds represented by -7), (b1-8), (b1-9), (b1-14), (b1-18), and (b1-20) have high solubility in a solvent, and can be prepared at a high concentration. Ink is therefore better. Further, depending on the use of the ink for inkjet, high transparency is sometimes required, and in this case, it is particularly preferable to use styrene-maleic acid. An anhydride copolymer, a compound represented by the formula (b1-6), (b1-7), (b1-8), (b1-9), (b1-14), (b1-18) or the like.

Further, the above-described compounds having two or more acid anhydride groups may be used singly or in combination of two or more kinds.

1.3(2) monoamine (a2)

The monoamine (a2) used in the present invention may, for example, be an aminoguanidine compound represented by the above formula (2).

The monoamine (a2) used in the present invention is not particularly limited, and specific examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropyl group. Methyl dimethoxy decane, 3-aminopropyl methyl diethoxy decane, 4-aminobutyl trimethoxy decane, 4-aminobutyl triethoxy decane, 4-aminobutyl group Diethoxy decane, p-aminophenyl trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane, p-aminophenyl methyl di Oxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, m-aminophenyl dimethyl diethoxy decane, and the like.

Among the above monoamines, in terms of excellent durability of the obtained film, preferred are p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxy. Particularly preferred are 3-aminopropyltriethoxylates, decanones, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, and 3-aminopropyltriethoxydecane. Base decane.

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

1.3(3) Compound having one anhydride group (a1')

The compound (a1') having one acid anhydride group used in the present invention may, for example, be a carboxylic acid anhydride represented by the above formula (1').

The compound (a1') having one acid anhydride group used in the present invention is not particularly limited, and specific examples thereof include trimethoxydecylpropyl succinic anhydride, triethoxydecylpropyl succinic anhydride, and methyl group. Dimethoxydecyl propyl succinic anhydride, methyl diethoxy decyl propyl succinic anhydride, trimethoxy decyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy Base alkyl butyl succinic anhydride, p-(trimethoxydecyl) phenyl succinic anhydride, p-(triethoxydecyl) phenyl succinic anhydride, p-(methyl dimethoxy decyl) phenyl succinic anhydride , p-(methyldiethoxydecyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, m (methyldiethyl) Oxonium alkyl) phenyl succinic anhydride or the like.

Among the above compounds, p-(trimethoxydecyl)phenylsuccinic anhydride, p-(triethoxydecyl)phenylsuccinic anhydride, and (preferably) are excellent in terms of durability of the obtained film. Particularly preferred is trimethoxydecyl)phenylsuccinic anhydride, m-(triethoxydecyl)phenylsuccinic anhydride, trimethoxydecylpropyl succinic anhydride, and triethoxydecylpropyl succinic anhydride. Triethoxydecyl propyl succinic anhydride.

These compounds having one acid anhydride group may be used alone or in combination of two or more.

1.3(4) diamine (a2')

The diamine (a2') used in the present invention may, for example, be a diamine represented by the above formula (2').

The diamine (a2') used in the present invention is not particularly limited as long as it has two amine groups, and examples thereof include p-phenylenediamine, m-phenylenediamine, p-xylenediamine, and 4,4'-. Diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-double (4-Aminophenyl)propane, bis(4-amino-3-methylphenyl)methane, 1,2-bis-(4-amino-3-methylphenyl)ethane, bis ( 4-amino-2-methylphenyl)methane, 1,2-bis-(4-amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone , 4,4'-diaminodiphenyl-2,2'-propane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-double [ (4-Aminophenyl)methyl]benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-double [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]fluoropropane, bis[4-(4-amino) Oxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]biphenyl, 1,3-bis[4-(4-aminobenzyl)phenyl]propane, 1, 6-bis[4-(4-aminobenzyl)phenyl]hexane, 5-phenylmethyl-1,3-diaminobenzene, 5-[4-(4-alkylcyclohexyl)benzene Methyl-1,3-diaminobenzene, 5-[4-(4-(4-alkylcyclohexyl)cyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5- [((Alkylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane Alkane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-alkylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl] Cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-alkylcyclohexane, 1,3-bis(3-aminopropyl)-tetramethyl The oxime may be a compound represented by the following general formulae (II) to (VIII).

[化37]

(In the formula (II), A ¹ is -(CH ₂ ) _m -, wherein m is an integer of 1 to 6, and in the formula (IV) and (VI) to (VIII), A ¹ is a single bond, - O-, -S-, -S-S-, -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-, wherein m is an integer from 1 to 6, and A ² is a single bond, -O-, - S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having 1 to 3 carbon atoms, which may be bonded to a cyclohexane ring or a benzene ring. -F, -CH ₃ replaced.)

The diamine represented by the formula (II) is, for example, a diamine represented by the following formulas (II-1) to (II-3).

The diamine represented by the formula (III) is, for example, a diamine represented by the following formulas (III-1) and (III-2).

The diamine represented by the formula (IV) is, for example, a diamine represented by the following formulas (IV-1) to (IV-3).

The diamine represented by the formula (V) is, for example, a diamine represented by the following formulas (V-1) to (V-5).

[化41]

The diamine represented by the formula (VI) is, for example, a diamine represented by the following formulas (VI-1) to (VI-30).

The diamine represented by the formula (VII) is, for example, a diamine represented by the following formulas (VII-1) to (VII-6).

[Chem. 46]

The diamine represented by the formula (VIII) is, for example, a diamine represented by the following formulas (VIII-1) to (VIII-11).

[化47]

In the above specific examples of the diamine (a2') represented by the general formulae (II) to (VIII), the formula (V-1) to (V-5) and the formula (VI-1) are more preferable. (VI-12), formula (VI-26), formula (VI-27), formula (VII-1), formula (VII) -2), the diamine represented by the formula (VII-6) and the formula (VIII-1) to (VIII-5), and further preferably, the formula (V-6), the formula (V-7), and the formula The diamine represented by (VI-1) to (VI-12).

The diamine (a2') used in the present invention may, for example, be a diamine represented by the following formula (IX).

(General formula (IX) in, A ³ is a single bond, -O -, - COO -, - OCO -, - CO -, - CONH- , or - (CH _{2) m} - (wherein, m is 1 to 6 In the integer), R ⁶ is a group having a steroid skeleton, a group represented by the following formula (X) or a positional relationship of two amine groups bonded to a benzene ring is a carbon number of 1 to a para position. An alkyl group of 30, or an alkyl group having a carbon number of 1 to 30 or a phenyl group in the positional relationship, wherein any -CH ₂ - may be via -CF ₂ -, -CHF-, -O -, -CH=CH- or -C≡C-substitution, -CH ₃ may be substituted by -CH ₂ F, -CHF ₂ or -CF ₃ 'hydrogen bonded to the ring carbon of the phenyl group may be - F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ substitution.)

[化49]

(In the formula (X), A ⁴ and A ⁵ are each independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH=CH- or an alkylene group having 1 to 12 carbon atoms. , R ⁷ and R ⁸ are each independently -F or -CH ₃ , and ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, Pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, R ⁹ is -H , -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , a and b respectively represent an integer of 0 to 4, and c, d and e each independently represent an integer of 0 to 3. When e is 2 or 3, a plurality of rings S may be the same group or different groups. f and g respectively represent an integer of 0~2, and c+d+e≧1.)

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

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

[化50]

In the above formulae (IX-1), (IX-2), (IX-7) and (IX-8), R ¹⁸ is hydrogen or an organic group having 1 to 30 carbon atoms, and among these, The alkyl group having 3 to 12 carbon atoms or the alkoxy group having 3 to 12 carbon atoms is preferably an alkyl group having 5 to 12 carbon atoms or an alkoxy group having 5 to 12 carbon atoms. Further, in the above formulae (IX-3) to (IX-6) and (IX-9) to (IX-11), R ¹⁹ is hydrogen or an organic group having 1 to 30 carbon atoms, which is preferably. The alkyl group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms is further preferably an alkyl group having 3 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms.

Further, examples of the diamine represented by the formula (IX) include diamines represented by the following formulae (IX-12) to (IX-17).

In the above formula (IX-12) to (IX-15), R ²⁰ is an organic group having 2 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, and more preferably a carbon number of 6 to 6 16 alkyl. In the formula (IX-16) and the formula (IX-17), R ²¹ is an organic group having 2 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and more preferably a carbon number of 8 to 8 20 alkyl.

The diamine represented by the formula (IX), for example, may be exemplified by the following formula The diamine represented by (IX-18)~(IX-38).

[54]

[化55]

In the above formula (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31) And (IX-36) and (IX-37), R ²² is hydrogen or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Further, it is preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. Further, in the above formula (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (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 , and further preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. In the above general formula (Ⅸ-33) and (Ⅸ-34) in, A ⁹ carbon atoms of the alkylene group having 1 to 12.

Further, examples of the diamine represented by the formula (IX) include a diamine represented by the following formulas (IX-39) to (IX-48).

[化57]

Among the diamines (a2') represented by the formula (IX), preferred are the diamines represented by the formulae (IX-1) to (IX-11), and further preferably by the formula (IX-). 2), the diamines represented by (IX-4), (IX-5), and (IX-6).

The diamine (a2') used in the present invention may furthermore be a compound represented by the following formula (XI) and (XII).

[化58]

(In the general formulae (XI) and (XII), R ¹⁰ and R ¹¹ are each independently -H or an alkyl or alkenyl group having 1 to 20 carbon atoms, and A ^{6 is} independently a single bond, -C(=O)- Or -CH ₂ -, 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 two "NH ₂ -Ph-A ⁶ -O-" (wherein Ph represents a phenylene group) is bonded to the steroid core at the 3 position, and One key is in 6 digits. Further, the two amine groups are bonded to the benzene ring carbon, respectively, and it is preferably bonded to the meta or para position relative to the bonding position of A ⁶ .

The diamine represented by the formula (XI) is, for example, a diamine represented by the following formulas (XI-1) to (XI-4).

[化59]

In the formula (XII), two "NH ₂ -(R ¹⁴ -)Ph-A ⁶ -O-" (wherein Ph represents a phenylene group) are bonded to the benzene ring carbon, preferably The bond is bonded to the carbon of the meta or para position relative to the carbon to which the steroid nucleus is bonded. Further, the two amine groups are bonded to the benzene ring carbon, respectively, and it is preferably bonded to the meta or para position with respect to A ⁶ .

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

[60]

The diamine (a2') used in the present invention may, for example, be a compound represented by the following formula (XIII) or (XIV).

(In the 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, A ⁸ is a single bond or an alkylene group having 1 to 3 carbon atoms, and ring T is 1 , 4-phenylene or 1,4-cyclohexylene, h is 0 or 1.)

(In the formula (XIV), R ¹⁶ is an alkyl group having 6 to 22 carbon atoms, R ¹⁷ is -H or an alkyl group having 1 to 22 carbon atoms, and A ^{7 is} independently -O- or a carbon number of 1 to 6 Alkylene.)

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

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

[化65]

In the above formula (XIII-1) to (XIII-3), R ^{24 is} preferably -H, an alkyl group having 1 to 20 carbon atoms, and (XIII-4) to (XIII-9), R. Further preferably, 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, and it is preferably bonded to the meta or para position with respect to A ⁷ .

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

[化66]

In the above formula (XIV-1) to (XIV-3), R ²⁶ is an organic group having 2 to 30 carbon atoms, and among these, an alkyl group having 6 to 20 carbon atoms and R ²⁷ being a carbon number are preferred. Further, an organic group of 2 to 30, and more preferably a -H or an alkyl group having 1 to 10 carbon atoms.

As described above, the diamine (a2') used in the present invention may be, for example, a diamine represented by the formulae (II) to (XIV), but a diamine other than the diamine may be used. For example, a naphthalene type diamine having a naphthalene structure, an anthracene diamine having a fluorene structure, or a decane group diamine having a decane bond may be used alone or in combination with other diamines.

The oxirane-based diamine is not particularly limited, and the oxirane-based diamine represented by the following formula (XV) can be preferably used in the present invention.

(In the above formula (XV), R ³ and R ^{4 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ^{5 is} independently a methylene group, a phenylene group or a phenylene group substituted by an alkyl group, x Independently an integer from 1 to 6, and y is an integer from 1 to 70. Among them, it is better that y is an integer from 1 to 15.)

Further, the diamine (a2') used in the present invention may be a diamine represented by the following formula (XVI-1) to (XVI-8).

(In the above formula (XVI-1) to (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 in the present invention is not limited to the diamine of the present specification, and other various forms of diamine can be used within the range in which the object of the present invention is achieved.

Further, the diamine (a2') which can be used in the present invention may be used alone or in combination of two or more. That is, a combination of two or more kinds of diamines may be used: a combination of the above diamines, the above diamine and A combination of his diamines or a combination of diamines other than the above diamines.

Further, depending on the use of the ink for inkjet, high transparency is sometimes required. In this case, it is particularly preferable to use 3,3'-diaminodiphenylanthracene and y=1 in the above formula (XV). A diamine of an integer of ~15.

2 polymer compound (B)

The polymer compound (B) which can be further contained in the inkjet ink of the present invention is polyacrylic acid, soluble polyimine, polyamide, polyamidamine, polyphthalate, polyester A polymer compound such as an acrylic polymer, an acrylate polymer, polyvinyl alcohol or polyoxyethylene, but is not limited to the compound. A polyimine-based polymer compound such as a polyaminic acid or a soluble polyimine is preferable, and for example, the poly-proline which is disclosed in Japanese Patent Application No. 2006-235336, or the poly-proline is preferably used. The imidized polymer is, but not limited to, the compound.

The polyamic acid can be obtained by using at least a compound (b1) having two or more acid anhydride groups and a diamine (b2) and a monoamine (b3), but is not limited to the polyfluorene obtained by the process. Amino acid.

Hereinafter, the compound (b1) and the diamine (b2) and the monoamine (b3) having two or more acid anhydride groups which can be used for obtaining the polymer compound (B) will be described.

2.1 Compound having two or more acid anhydride groups (b1)

As a specific example of the compound (b1) having two or more acid anhydride groups used in the present invention, a compound having the acid anhydride group of 2 or more which can be used for obtaining the valine acid (A) can be used (a1). ) the same compound.

The compound (b1) having two or more acid anhydride groups may be the same as or different from the compound (a1) having two or more acid anhydride groups. Further, the compound having an acid anhydride group disclosed above may be used alone or in combination of two or more.

2.2 diamine (b2)

As a specific example of the diamine (b2) used in the present invention, the same diamine as the above-mentioned diamine (a2') which can be used for obtaining valine acid (A') can be used.

The diamine (b2) and the diamine (a2') may be the same or different. Further, the diamines disclosed above may be used alone or in combination of two or more.

2.3 monoamine (b3)

As a specific example of the monoamine (b3) used in the present invention, the same monoamine as the above-mentioned monoamine (a2) which can be used for obtaining valine acid (A) can be used. The monoamine (b3) may be the same as or different from the monoamine (a2). Further, the monoamines disclosed above may be used alone or in combination of two or more.

2.4 Polyampinic acid reaction conditions

The polyamic acid which can be used in the present invention is preferably a compound (b1) having an acid anhydride group of 2 or more with respect to 1 mole, and 0.05 to 0.8 mole of diamine (b2), 0.4. Obtained by the reaction of moles to 1.9 moles of monoamine (b3). Further, further preferably, it is a compound (b1) having an acid anhydride group of 2 or more with respect to 1 mol, and a diamine (b2) of 0.1 mol to 0.6 mol, and a molar of 1.8 mol to 1.8 mol. The amine (b3) is obtained by a reaction. More preferably, it has an acid anhydride group of 2 or more with respect to 1 mole.

The compound (b1) is obtained by reacting with 0.15 moles to 0.35 moles of diamine (b2) and 1.3 moles to 1.7 moles of monoamine (b3).

2.4(1) Reaction solvent

As the solvent for obtaining polylysine which can be used in the present invention, the same solvent as the above-mentioned solvent which can be used for obtaining glutamic acid (A) or lysine (A') can be used. The reaction solvent may be used singly or as a mixed solvent of two or more kinds. Further, in addition to the above reaction solvent, other solvents may be used in combination.

When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the compound (b1), the diamine (b2) and the monoamine (b3) having two or more acid anhydride groups, the reaction proceeds smoothly, so that the reaction proceeds smoothly. it is good. Preferably, the reaction is carried out at 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).

2.4(2) Sequence added to the reaction system

Further, the order in which the reaction raw material is added to the reaction system is not particularly limited. That is, any one of the following methods may be used: a method of simultaneously adding a compound (b1) having two or more acid anhydride groups and a diamine (b2) and a monoamine (b3) to a reaction solvent; (b2) a method of adding a compound (b1) having two or more acid anhydride groups after dissolving in a reaction solvent with a monoamine (b3); first, a compound (b1) having an acid anhydride group of 2 or more and a monoamine (b3) a method of adding a diamine (b2) after the reaction; after reacting a compound (b1) having two or more acid anhydride groups with a diamine (b2) to synthesize a copolymer, a monoamine is added to the copolymer ( Method of b3), etc.

2.5 Weight average molecular weight of the polymer compound (B)

The polymer compound (B) having a weight average molecular weight of 1,000 to 20,000 is particularly excellent in solubility in a solvent, and is preferably used as an ink for inkjet. In the present invention, in order to further enhance the "solubility" of the polymer compound (B) with respect to the solvent, it is preferred that the polymer compound (B) has a weight average molecular weight of 1,000 to 10,000, more preferably 1,000 to 7,500. Good is 1,000~5,000, especially good is 1,000~3,500.

The reason is that the polymer compound (B) having a weight average molecular weight of 1,000 or more is not evaporated by heat treatment, and is chemical. The polymer compound (B) having a weight average molecular weight of 20,000 or less is stable in terms of mechanical properties, and the solubility in a solvent can be improved. Therefore, the film thickness of the obtained coating film can be increased, and it can be suitably used as an ink for inkjet.

The weight average molecular weight of the polymer compound (B) can be measured by a gel permeation chromatography (GPC) method. Specifically, it can be obtained by diluting the concentration of the obtained polymer compound (B) to about 1 weight percent (wt%) with tetrahydrofuran (THF) or the like, using a column manufactured by Tosoh Co., Ltd. (column) G4000HXL, G3000HXL, G2500HXL, and G2000HXL were measured by gel permeation chromatography (GPC) using THF as a developing solvent, and converted to polystyrene.

3-alkenyl substituted nadic acid ylide imine compound (C)

The alkenyl-substituted nadic ylidene imide compound (C) contained in the inkjet ink of the present invention is a compound having at least one alkenyl-substituted nadic acid ylidene imine structure in the molecule, and it is preferred to The monoamine, diamine, triamine or tetraamine is reacted with an alkenyl-substituted nadic anhydride represented by the above formula (5')

The alkenyl group obtained by substituting the naphthyl group is more preferably an alkenyl group substituted with a nadic acid ylide compound represented by the above formula (5), but is not limited to the compound.

Alkenyl-substituted nadic acid ylidene imine compound (C): n-substituted alkenyl-substituted nadic acid ylidene imine compound (c1: hereinafter, sometimes only referred to as "alkenyl-substituted nadic acid ylide" "), and n is an alkenyl group substituted with a nadic acid ylide compound (c2: hereinafter, sometimes referred to simply as "dienyl substituted nadic acid ylide"), n is an alkenyl substituted sodium of 3 Dick acid imine compound (c3: hereinafter, sometimes referred to simply as "trienyl substituted nadic acid ylide"), n is an alkenyl-substituted nadic acid ylide compound (c4: below, It is only referred to as "tetraalkenyl substituted nadic acid ylide").

3.1 alkenyl substituted nadic acid ylide (c1)

Specific examples of the alkenyl-substituted nadic acid ruthenium imine compound in which n is 1 used in the present invention include, for example, the following compounds.

There may be mentioned allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-di Carboxylimine, methallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, methallylmethyl bicyclo [2.2.1] hept-5-ene -2,3-dicarboxy quinone imine, N-hydroxy-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-hydroxy-allyl methyl bicyclic [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-hydroxy-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene amine, N-Hydroxy-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-methyl-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methyl- Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, and the like Oligomers, etc.

Further, N-(2-ethylhexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-allyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene amine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl bicyclo [2.2.1] g-5 -ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl- Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-phenyl-allyl bicyclo [2.2.1] hept-5-ene-2,3 - Dicarboxy quinone imine, and oligomers thereof and the like.

Further, N-phenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-benzyl-allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- Benzyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(2'-hydroxyethyl)-allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxyindolimine, N-(2'-hydroxyethyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(2'-hydroxyethyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, and oligomers thereof .

Further, N-(2',2'-dimethyl-3'-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2',2'-dimethyl-3'-hydroxypropyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N- (2',3'-Dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2',3'-dihydroxypropyl ())-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3'-hydroxy-1'-propenyl)-allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4'-hydroxy-cyclohexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, and oligomers thereof.

Further, N-(4'-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(4'-hydroxyphenyl) -allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4'-hydroxyphenyl)-methylallylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine, N-(4'-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-(3'-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3'-hydroxybenzene Base)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-{2'-(2'-hydroxyl Ethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and oligomers thereof and the like.

Further, N-{2'-(2'-hydroxyethoxy)ethyl}-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarlimine, N-{2'-(2'-hydroxyethoxy)ethyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-{2 '-(2'-Hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2'- {2'-(2"-Hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2 '-{2'-(2"-Hydroxyethoxy)ethoxy}ethyl]-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-[2'-{2'-(2"-Hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine , N-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4'-(4'-hydroxyl Phenyl isopropyl) phenyl} - methallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (PEI) And such oligomers and the like.

Further, the alkenyl-substituted nadic acid ylidene imide (c1) may be used singly or as a mixture of these.

Preferred examples of the above alkenyl-substituted nadic acid ylidene imide (c1) include N-methyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-methyl-methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (2-Ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine.

Further, N-(2-ethylhexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-allyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Base imine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl bicyclo [2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-phenyl-allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, and the like.

Further, N-phenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-benzyl-allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- Benzyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and the like.

More preferably, the alkenyl-substituted nadic acid ylide (c1) is N-methyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N- Methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-methyl-methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-ethylhexyl)-allylbicyclo[2.2 .1] Hept-5-ene-2,3-dicarboxy quinone imine, and the like.

Further, N-(2-ethylhexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-allyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-isopropenyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and the like.

3.2 Dienyl substituted nadic acid ylide (c2)

Further, specific examples of the alkenyl-substituted nadic acid ruthenium imine compound in which n is 2 used in the present invention include, for example, the following compounds.

Mention may be made of N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'- Trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N,N'-docamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-docamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-cyclohexylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), and oligomers thereof and the like.

Also exemplified by 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, 1,2- Double {3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, 1,2-double {3'-( Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy}ethane, Bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{ 3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, 1,4-double {3'-( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy}butane, 1,4-double {3'-(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine)propoxy}butane, and oligomers thereof and the like.

Also exemplified are: N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-m-xylylene - bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), and Oligomers and the like.

Further, exemplified by 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenoxy}phenyl] Propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenoxy}phenyl] Propane, 2,2-bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl] Propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxyinimide)phenyl}methane, and oligomers thereof.

Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine) phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl} Ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine) phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole, double {4-(allyl Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, and oligomers thereof and the like.

Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)phenyl}anthracene, 1,6-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-3-hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) Propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)-2-hydroxy-benzene, And such oligomers and the like.

Further, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)-2,5-dihydroxy-benzene, N,N '-p-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-pair (2- Hydroxy) benzenedimethyl-bis(allylmethylcyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-p-(2,3-dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine), and oligomers and the like.

Also exemplified is: 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinylimine)-2'-hydroxy-benzene Oxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)-2-hydroxy-phenyl}methane, Double {3-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-4-hydroxy-phenyl}ether, double {3-(methallyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4'-(allylmethylbicyclic [2.2.1]hept-5-ene-2,3-dicarboxy quinazomine)}phenoxymethylpropane, N,N',N"-tris(ethylene allylenylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxyinimide) a trimeric isocyanate, and oligomers thereof.

Further, it may also be an asymmetric alkylene group. The following compounds of phenylene.

[化69]

Further, these dienyl substituted nadic acid ylides (c2) may be used singly or as a mixture of these.

The above dienyl substituted nadic acid ylide (c2) is preferably exemplified by N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine), N,N'-ethylidene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N' -ethylidene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-trimethylene-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-dicarboxynonimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-double ( Allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, N'-docamethylene-bis(allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N'- Cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) and the like.

Also exemplified are: N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylmethylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine) phenoxy} phenyl] propane, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) benzene Methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane, and the like.

Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine) phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl} ether, Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, bis{4-(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine) phenyl} oxime and the like.

Further, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}anthracene or the like can be mentioned.

More preferred examples of the dienyl substituted nadic acid ylide (c2) are: N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'- Ethylene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-trimethylene-bis(allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-dodecamethylene-double (allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine) and the like.

Also exemplified are: N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-m-xylylene - bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxy quinone imine) and the like.

Also exemplified is: 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenoxy} phenyl] propane, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) Phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane, and the like.

Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}methane, and the like.

3.3 trienyl substituted nadic acid ylide (c3)

The synthesis of a 3, 3-alkenyl substituted nadic acid ylidene imine compound used in the present invention can be carried out by mixing 3.0 moles to 5.0 moles of alkenyl substitution with respect to 1.0 mole of triamine. Nadickic anhydride, dissolved at room temperature, for example, benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin, chloroform, trichloroethylene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran , hexamethylene ether, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, N, N-dimethylformamide, dimethyl hydrazine, etc. The solvent may be stirred in a solvent or in a mixture of two or more solvents for 0.5 to 30 hours. The solvent was removed by drying under reduced pressure at 20 ° C to 80 ° C to obtain valine acid. Will be above The proline is refluxed in the above solvent at a boiling point of the solvent for 0.5 hours to 30 hours, or the compound itself is heated at 160 ° C to 200 ° C to cause dehydration ring closure, and the solvent is dried under reduced pressure to obtain a target. Compound. It can be confirmed as a target compound by nuclear magnetic resonance (NMR) or infrared (IR).

Specific examples of the n-alkenyl-substituted nadic ylidene imide compound used in the present invention are, for example, the following compounds.

Tris{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)triethyl}amine (TrisANITAEA), tris{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)triphenyl}methane (TrisANITrisAM), tris{4-(allylbicyclo[2.2.1]hept-5-ene-2, The IR spectrum of TrisANI PARAR, "TrisANITAEA" and the ¹ H-NMR spectrum (400 MHz) are shown in Fig. 1 and Fig. 2, respectively.

In the IR spectrum, it belongs to the olefin C-H stretching: 3070 cm ^-1 , 2966 cm ^-1 ; the aromatic C-H expansion: 2966 cm ^-1 ; the alkane C-H expansion: 2938 cm ^-1 ;醯 醯 imine C=O stretching: 1762 cm ^-1 , 1690 cm ^-1 ; belonging to C=C stretching: 1640 cm ^-1 ; belonging to -CH ₂ -N-methylene scissor vibration: 1448 cm ^-1 ; belongs to the quinone imine C-N expansion: 1382 cm ^-1 and so on.

[化70]

¹ H-NMR spectrum, belonging to a, b, e, f, g, i, l proton (30H): 2.50 pm ~ 3.49 pm peak; belonging to j, k, m, n proton (12H): 5.01 Peak of ppm~6.27 ppm; attributed to h proton (6H): peak of 1.25 ppm~1.76 ppm.

The IR spectrum and ¹ H-NMR spectrum (400 MHz) of "TrisANI Tris AM" are shown in Fig. 3 and Fig. 4, respectively.

In the IR spectrum, it belongs to the olefin C-H stretching: 3056 cm ^-1 , 2970 cm ^-1 ; the aromatic C-H expansion: 2970 cm ^-1 ; the alkane C-H expansion: 2936 cm ^-1 ;醯 醯 imine C=O stretching: 1772 cm ^-1 , 1706 cm ^-1 ; belonging to C=C stretching: 1638 cm ^-1 ; belonging to yttrium C-N stretching: 1402 cm ^-1 and so on.

[71]

¹ H-NMR spectrum, belonging to a proton to d proton (12H): 6.50 ppm ~ 7.59 ppm peak; belonging to e, f, g, i, l proton (18H): 2.25 ppm ~ 3.73 ppm peak; Attributable to h proton (6H): 1.25 ppm~1.81 ppm; attributed to j, k, m, n protons (12H): 5.01 ppm~5.14 ppm, 5.74 ppm~6.34 ppm peak; attributed to o proton (1H): 5.30 ppm to 5.60 ppm peak.

The IR spectrum and ¹ H-NMR spectrum (400 MHz) of "TrisANIPARARO" are shown in Fig. 5 and Fig. 6, respectively.

In the IR spectrum, it belongs to the olefin C-H stretching: 3056 cm ^-1 , 2972 cm ^-1 ; the aromatic C-H expansion: 2972 cm ^-1 ; the alkane C-H expansion: 2936 cm ^-1 ;醯 醯 imine C=O stretching: 1776 cm ^-1 , 1706 cm ^-1 ; belonging to C=C stretching: 1636 cm ^-1 ; belonging to yttrium imine C-N stretching: 1402 cm ^-1 and so on.

¹ H-NMR spectrum, belonging to a proton to d proton (12H): 6.98 ppm ~ 7.53 ppm peak; belonging to e, f, g, i, l proton (18H): 2.27 ppm ~ 3.60 ppm peak; Attributable to h proton (6H): peak from 1.47 ppm to 1.81 ppm; attributed to j, k, m, n protons (12H): peaks from 5.01 ppm to 6.24 ppm.

3.4 Tetraalkenyl Substituted Nadidic Acid Imine (c4)

The synthesis of a 4 tetraalkenyl substituted nadic acid ruthenium imine compound using n in the present invention can be carried out by mixing 4.0 moles to 6.0 moles of alkenyl substitution with respect to 1.0 mole of tetraamine. Nadic anhydride, dissolved at room temperature such as benzene, toluene, xylene, mesitylene, methyl naphthalene, tetrahydronaphthalene, chloroform, trichloroethylene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran, six Methyl ether, anisole, acetone, methyl ethyl ketone, methyl Any solvent such as isobutyl ketone, acetophenone, N,N-dimethylformamide, dimethyl hydrazine, or a mixture of two or more solvents, and stirred as a solution for 0.5 hour to 30 hours. Carry out the reaction. The solvent was removed by drying under reduced pressure at 20 ° C to 80 ° C to obtain valine acid. The above proline is refluxed in the above solvent at a boiling point of the solvent for 0.5 to 30 hours, or the compound itself is heated at 160 to 200 ° C to dehydrate the ring, and the solvent is dried under reduced pressure. The target compound is obtained. It can be confirmed as a target compound by NMR or IR.

Specific examples of the n-alkenyl-substituted nadic ylidene imide compound to be used in the present invention include, for example, the following compounds.

Tetra{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)tetraphenyl}methane (TetrakisANITAM)

The IR spectrum and ¹ H-NMR spectrum (400 MHz) of "Tetrakis ANITAM" are shown in Fig. 7 and Fig. 8, respectively.

In the IR spectrum, it is attributed to olefin C-H stretching: 3060 cm ^-1 , 2972 cm ^-1 ; attributed to aromatic C-H stretching: 2972 cm ^-1 ; attributable to alkane C-H stretching: 2936 cm ^-1 ;醯 醯 imine C=O stretching: 1776 cm ^-1 , 1706 cm ^-1 ; belonging to C=C stretching: 1638 cm ^-1 ; belonging to yttrium imine C-N stretching: 1404 cm ^-1 and so on.

[化73]

¹ H-NMR spectrum attributed to a proton ~ d protons (16H): 6.80 ppm ~ 7.59 Peak ppm of; attributed to e, f, g, i, l protons (24H): 2.25 ppm ~ 3.60 ppm of the peak; Attributable to j, k, m, n protons (16H): peaks from 5.04 ppm to 6.50 ppm; attributable to h protons (8H): peaks from 1.25 ppm to 1.75 ppm.

The preferred alkenyl-substituted nadic acid ylidene imine compound (C) of the present invention is a low molecular weight quinone imine monomer having a bulky structure, and thus is soluble in most organic solvents, even if stored in a solution state for a long period of time. It can be used stably without precipitation or gelation of crystals. Further, the polyimine which forms a three-dimensional crosslinked structure by heating exhibits good heat resistance, mechanical properties, electrical properties, and chemical resistance.

4 solvent (D)

The inkjet ink of the present invention may, for example, be a proline (A) and/or a proline (A'), and if necessary, a polymer compound (B) or an alkenyl group, may be substituted with a nadic acid ylide compound. (C) is obtained by dissolving in a solvent (D). Therefore, the solvent contained in the inkjet ink of the present invention can dissolve the polymer compound (B) and the alkenyl group if necessary, as long as it can dissolve the lysine (A) and/or the proline (A'). The nadic acid imide compound (C) is not particularly limited. Further, even a solvent which cannot dissolve valine acid (A), valine acid (A'), and if necessary, a polymer compound (B) or an alkenyl group substituted with a nadic acid ylide compound (C) It can also be used as a solvent (D) contained in the ink for inkjet by mixing with other solvents.

Specific examples of the solvent (D) contained in the inkjet ink include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, and N-methylpropionamidine. Amine, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ- Butyrolactone, ethyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethanol, 2-propanol, dioxane, ethylene glycol, and the like.

As described above, the solvent contained in the inkjet ink of the present invention is not particularly limited, but depending on the specifications of the inkjet head of the inkjet printer, the bonding member or the internal filter material may be used depending on the use. Corrosion or expansion due to the type of solvent. Or, a solvent that dries faster will make the head Blockage or the like is generated, so the choice of the solvent (D) is very important.

As a result of intensive studies, the present inventors have found that ethyl lactate, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether acetate are used in terms of improving the durability of the ink jet head or the nozzle clogging and ink ejection properties. Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and γ-butyrolactone are particularly preferred as the solvent (D).

Further, since the surface tension of the ink has a large influence on the coatability of the ink for inkjet, it is preferred to adjust the surface tension of the ink to 20 mN/m to 45 mN/m, more preferably 27 mN/m. ~42 mN/m, and preferably 30 mN/m~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 discharge port becomes stable, and the ink is ejected well.

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

Further, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethyl Ethyl amide, diethyl acetamide, N-methyl propyl amide, N, N, N', N'-tetramethyl urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε- The amide-based solvents such as caprolactam, N-methyl caprolactam, and carbamate are lysine (A) and proline (A'). Further, since the polymer compound (B) or the alkenyl group is a good solvent for the nadic acid ylidene imide compound (C), it can be preferably used. However, these solvents affect the durability of the ink jet head, and therefore, note.

It is preferred that the solvent (D) contained in the inkjet ink of the present invention contains no guanamine-based solvent at all, or at most 20% by weight or less based on the total weight of the solvent (D).

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

5 Concentration of lysine (A), proline (A'), polymer compound (B) and alkenyl substituted nadic acid ylide compound (C) in the inkjet ink of the present invention

In the present invention, the total concentration of the lysine (A) and the lysine (A') in the ink for inkjet is not particularly limited, and is preferably from 1 wt% to 99 wt%, more preferably 10 wt% to 80 wt%, and further preferably 22 wt% to 70 wt%. In the case of the above concentration range, the film thickness obtained by one ejection of ink is most suitable, and the ejection precision is high, which is preferable.

In the present invention, the concentration of the polymer compound (B) in the ink for inkjet is not particularly limited, but is preferably 0 wt% to 50 wt%, more preferably 0 wt% to 25 wt%. If it is the said concentration range, since it can provide favorable characteristics as an insulating film, it is preferable.

In the present invention, the concentration of the alkenyl-substituted nadic acid ylidene imine compound (C) in the ink for inkjet is not particularly limited, and is preferably 0 wt% to 50 wt%, more preferably 0 wt%. 25 wt%. If it is the said concentration range, since it can provide favorable characteristics as an insulating film, it is preferable.

For use as an inkjet ink, valeric acid (A) and/or proline (A'), polymer compound (B) and alkenyl substituted nadic acid ylide compound (C) The higher the concentration, the thicker the film thickness of the obtained polyimide film, but the viscosity tends to be higher. Therefore, there is a problem that the inkjet printer cannot be ejected. As a result of intensive studies, the present inventors have found that, particularly in the above concentration range, it can be suitably used as an inkjet ink which can form a polyimide film having a thick film thickness.

6 Additives added to the inkjet ink of the present invention

The inkjet ink of the present invention is obtained by mixing a proline (A) and/or a proline (A'), and if necessary, a polymer compound (B), an alkenyl group, and a naphthyl imide. The compound (C) is obtained by mixing the solvent (D) as necessary.

Further, according to the desired characteristics, the inkjet ink of the present invention can be obtained by adding an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, a trimellitic acid or the like as needed. Oxygen curing agent, amine hydrazine compound, pH adjuster, rust inhibitor, preservative, mold inhibitor, antioxidant, reduction inhibitor, evaporation promoter, chelating agent, water soluble polymer, pigment, dye, etc. Additives, which are uniformly mixed and dissolved.

6(1) epoxy resin

The inkjet ink of the present invention may further contain an epoxy resin. The epoxy resin contained in the inkjet ink of the present invention is not particularly limited as long as it has oxirane or oxetane, and preferably has two or more epoxy acrylates. a compound of an alkane.

In the present invention, the concentration of the epoxy resin in the ink for inkjet is not particularly limited, but is preferably 0.1 wt% to 20 wt%, more preferably 1 wt% to 10 wt%. When it is the said concentration range, the coating film formed from the inkjet ink is favorable 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 having a monomer of ethylene oxide, and a single having ethylene oxide. a copolymer of a body and 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.

Preferred examples of the polymer of the monomer having ethylene oxide and the copolymer of the monomer having ethylene oxide and other monomers 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 acrylate copolymer, methacryl Acid (3-ethyl-3-epoxypropyl)methyl ester-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer. When the inkjet ink of the present invention 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 which can be contained in the inkjet ink of the present invention include "Epikote 807", "Epikote 815", "Epikote 825", "Epikote 827", "Epikote 828", and "Epikote 190P". "Epikote 191P" (above, manufactured by Yuka Shell Epoxy Co., Ltd.), trade name "Epikote 1004", "Epikote 1256" (above, manufactured by Nippon Epoxy Co., Ltd.), "Araldite CY177", trade name "Araldite CY184" (manufactured by Ciba-Geigy Co., Ltd.), trade name "Celloxide 2021P", "Celloxide 3000", "EHPE-3150" (Daicel Chemistry) Manufactured by Industrial Co., Ltd., trade name "Techmore VG3101L" (manufactured by Mitsui Chemicals, Inc.), N, N, N', N'-tetraglycidyl-m-xylenediamine, 1,3-double (N) , N-diglycidylamine methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

In the above, when the trade name "Araldite CY184", the trade name "Celloxide 2021P", the trade name "Techmore VG3101L", and the trade name "Epikote 828" are used, the flatness of the obtained polyimide film is particularly good, so that it is good.

The epoxy resin may be used singly or in combination of two or more.

6(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 acrylonitrile group or a methacrylium group.

The concentration of the acrylic resin in the inkjet ink is not particularly limited, but is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight. When it is the said concentration range, the coating film formed from the inkjet ink is favorable 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 polyfunctional (meth)acrylic acid or more. Ester and the like.

Specific examples of the monofunctional polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or 1,4-cyclohexanedimethanol mono(meth)acrylate or the like. Among them, 4-hydroxybutyl acrylate and 1,4-cyclohexane dimethanol monoacrylate are particularly preferable in terms of flexibility of the formed film.

Specific examples of the monofunctional polymerizable monomer having no hydroxyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate. Ester, 3-methyl-3-(methyl)propenyloxymethyl propylene oxide, 3-ethyl-3-(methyl) propylene methoxymethyl propylene oxide, 3-methyl-3 -(Methyl)acryloxyethyl propylene oxide, 3-ethyl-3-(methyl) propylene oxiranyl ethyl propylene oxide, p-vinyl phenyl-3-ethyl epoxide - 3-methyl methyl ether, 2-phenyl-3-(methyl) propylene methoxymethyl propylene oxide, 2-trichloromethyl-3-(methyl) propylene methoxymethyl propylene oxide, 4-trichloromethyl-2-(methyl)propenyloxymethyl propylene oxide, (meth)acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate Isopropyl ester, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, styrene , methyl styrene, chloromethyl styrene, (meth)acrylic acid (3- Ethyl-3-epoxypropyl)methyl ester, N-cyclohexylmethyleneimine, N-phenyl maleimide, vinyl toluene, (meth) acrylamide, ( Methyl)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decyl ester, dicyclopentenyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, phenyl (meth)acrylate, glycerol (Meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, N-propylene hydrazinomorph, (meth)acrylic acid 5-tetrahydrofurfuryloxycarbonyloxypentoxide, lauryl alcohol (meth) acrylate, (meth) acrylate, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, ethylene oxide adducts, Methyl maleic acid, methyl fumaric acid, ω-carboxy polycaprolactone mono (meth) acrylate, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, Maleic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, or cyclohexene-3,4-dicarboxylic acid mono [2-(methyl) propylene methoxyethyl] ester Wait.

Specific examples of the difunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, and isomeric cyanuric acid ethylene oxide. Modified diacrylate, polyethylene 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 dipropylene An acid ester, trimethylolpropane diacrylate, or dipentaerythritol diacrylate.

Specific examples of the trifunctional polyfunctional (meth) acrylate are: trimethylolpropane tri(meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate Ester, propylene oxide modified trimethylolpropane tri(meth) acrylate, epichlorohydrin modified trimethylolpropane tri(meth) acrylate, di-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, trimeric isocyanide Tris[(methyl)propenyloxyethyl]ester, caprolactone modified trimeric isocyanate tris[(methyl)propene oxime An oxyethyl] ester, or a urethane (meth) acrylate or the like.

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

6(3) surfactant

When it is desired to improve the coatability of the ink for inkjet, a surfactant which achieves the object can be added. Specific examples of the surfactant added to the inkjet ink of the present invention include "Byk-300", "Byk-306", "Byk-335", "Byk-310", and "Byk-". 341", "Byk-344", "Byk-370" An anthraquinone surfactant such as BYK Chemie Co., Ltd.; an acrylic surfactant such as "Byk-354", "Byk-358", "Byk-361" (manufactured by BYK Chemie Co., Ltd.); 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 is preferably used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the inkjet ink.

6 (4) antistatic agent

The antistatic agent to be added to the inkjet ink of the present invention is not particularly limited, and a well-known antistatic agent can be used. Specifically, it can be mentioned: tin oxide, tin oxide. Cerium oxide composite oxide, tin oxide. A metal oxide such as an indium oxide composite oxide or a quaternary ammonium salt.

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

The antistatic agent is for preventing static electricity, and is preferably used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the ink for inkjet.

6(5) coupling agent

The coupling agent to be added to the inkjet ink of the present invention is not particularly limited, and a well-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-vinylpropyl is exemplified: Trimethoxy decane, γ-vinyl propyl triethoxy decane, γ-propylene propyl propyl methyl dimethoxy decane, γ-acryl propyl propyl trimethoxy decane, γ-propylene decyl propyl Methyldiethoxy decane, γ-propylene propyl propyl triethoxy decane, γ-methyl propylene propyl propyl methyl dimethoxy decane, γ-methyl propylene propyl propyl trimethoxide Base decane, γ-methyl propylene propyl propyl methyl diethoxy decane, γ-methyl propylene propyl propyl triethoxy decane, γ-glycidoxy propyl methyl dimethoxy decane , γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-aminopropyl Methyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltriethoxydecane, N-Amino B Base-γ-iminopropylmethyldimethoxydecane, N-aminoethyl-γ-aminopropyltrimethoxydecane, N-aminoethyl-γ-aminopropyldi Ethoxy decane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropylmethyl Dimethoxy decane, N-phenyl-γ-aminopropylmethyldiethoxy decane, γ-mercaptopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, Γ-mercaptopropylmethyldiethoxydecane, γ-mercaptopropyltriethoxydecane, γ-isocyanate propylmethyldiethoxydecane, γ-isocyanatepropyltriethoxydecane, and the like. Among these, γ-vinylpropyltrimethoxydecane, γ-acrylonitrilepropyltrimethoxydecane, γ-methylpropenylpropyltrimethoxydecane, and γ-isocyanatepropyltriethyl can be cited. Oxydecane, etc.

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

The coupling agent is preferably used in an amount of 0.01 part by weight to 3 parts by weight based on 100 parts by weight of the ink for inkjet.

6(6) epoxy curing agent

The epoxy curing agent to be added to the inkjet ink of the present invention is not particularly limited, and a known epoxy curing agent can be used. Specific examples thereof include diterpene compounds of organic acids, derivatives of imidazoles and imidazoles, dicyandiamides, aromatic amines, polycarboxylic acids, polycarboxylic anhydrides, and the like. More specifically, dicyandiamides such as dicyandiamide, diammonium adipate, and 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin (1,3-) Bis(hydrazino carboethyl)-5-isopropyl hydantoin), such as diterpene, 2,4-diamino-6-[2'-ethylimidazolyl-(1')]-ethyltriazine, 2- Imidazole derivatives such as phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, trimellitic anhydride, 1,2 An acid anhydride such as 4-cyclohexanetricarboxylic acid-1,2-anhydride or the like.

Among them, preferred are trimellitic acid having good transparency and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride.

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

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

6(7)Aminoguanidine compound

An amine sulfonium compound can be added to the inkjet ink of the present invention. The amine ruthenium compound may, for example, be p-aminophenyltrimethoxydecane or p-aminophenyl. Triethoxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, aminopropyl trimethoxy decane, aminopropyl triethoxy decane, and the like.

These amine-based ruthenium compounds may be used alone or in combination of two or more.

The amine ruthenium compound is used to improve the adhesion to the substrate, and is preferably added in an amount of 0.05 part by weight to 2 parts by weight based on 100 parts by weight of the ink for inkjet.

7 inkjet ink viscosity

In the present invention, the viscosity of the ink for inkjet is not particularly limited, and when it is sprayed at a normal temperature, the ejection accuracy by the inkjet coating method is improved, preferably 1 mPa. s~50 mPa. s (25 ° C), more preferably 5 mPa. s~30 mPa. s (25 ° C), and thus good is 8 mPa. s~20 mPa. s (25 ° C).

In the case of heating the ink jet head for spraying, it is 1 mPa at a heating temperature (temperature at which valerine does not cure, preferably 40 ° C to 120 ° C). s~50 mPa. s, preferably 5 mPa. s~30 mPa. s, better is 8 mPa. s~20 mPa. s.

8 polyimine film

The inkjet ink of the present invention is applied onto the surface of the substrate by inkjet, and is heat-treated by a hot plate or an oven to form a polyimide film having a whole surface or a predetermined pattern (linear shape, etc.). Further, the formation of the polyimide film of the present invention is not limited to the heat treatment, and may be an ultraviolet (UV) treatment or an ion beam, an electron beam, a gamma ray or the like.

Previously, in the case of forming a patterned polyimide film, photolithography has been used, and this technique requires the use of various chemicals such as photoresist materials, developing liquids, etching liquids, and stripping liquids, and requires cumbersome Process. On the other hand, the patterned polyimide film formed using the inkjet ink of the present invention is characterized in that the amount of material used is absolutely small because it is drawn only by a portion required by inkjet printing. Moreover, the reticle is not used, so that it can be mass-produced in a variety of varieties, and the number of processes required for manufacturing is small.

8.1 Coating of inkjet ink by inkjet method

There are various types of inkjet coating methods depending on the ink ejection method. For example, a piezoelectric element type, a bubble jet (registered trademark) type, a continuous injection type, a static induction type, and the like can be cited. By appropriately selecting the respective components contained in the ink, the ink of the present invention can be ejected by various methods, and the ink for inkjet can be applied to a predetermined pattern.

A better ejection method for coating using the ink of the present invention is a piezoelectric element type. The piezoelectric element type head is an on-demand inkjet coating head having a nozzle forming substrate having a plurality of nozzles, a piezoelectric material disposed opposite the nozzle, and a pressure of a conductive material. The generating element, the ink filled around the pressure generating element, is displaced by the application of a voltage, so that small droplets of ink are ejected from the nozzle.

The inkjet coating device is not limited to a device in which the coating head and the ink containing portion are separated, and an integrated device in which the two are inseparable may be used. Further, the ink accommodating portion is not only integrated with the head so as to be separable or inseparable from the coating head, but is also mounted on the bracket, and is also provided. The ink is supplied to the coating head via an ink supply member such as a tube at a fixed portion of the device.

Further, in the case where a configuration for providing a negative pressure to the coating head is provided in the ink cartridge, the ink container may be disposed in the ink containing portion of the ink cartridge, or may have a flexible ink containing bag, and This storage bag acts to expand the shape of the spring portion of the pushing force in the direction in which the internal volume is accumulated. The coating device may adopt a serial coating method as described above, and other line printers may be used in which the coating elements are arranged over the entire range of the corresponding coating medium. Shape.

8.2 Solvent drying

After the inkjet ink of the present invention is applied onto a substrate by inkjet coating by the above-described inkjet coating method, the solvent (D) is vaporized by heating using a hot plate or an oven or the like, for example, to obtain a solvent (D). The film is removed by drying, whereby a film of proline (A) and/or amic acid (A') can be formed. When the inkjet ink further contains a polymer compound (B) or an alkenyl group substituted with a nadic acid ruthenium imine compound (C), proline (A) and/or proline (A' can be formed. A polymer compound (B) and an alkenyl group-substituted composite film of the nadic acid ylide compound (C).

The heating conditions vary depending on the type of each component and the blending ratio, and it is preferred that the temperature at which the valine acid (A) and the proline (A') are not cured is usually 70 ° C to 120 ° C. When an oven is used, a dried film is formed at 5 minutes to 15 minutes, and when a hot plate is used, a dried film is formed at 1 minute to 5 minutes.

8.3 Formation of polyimine film

Forming a membrane of proline (A) and/or proline (A'), or proline (A) and/or proline (A'), polymer (B) and alkenyl After the composite film of the Nadick acid ylidene imine compound (C) is substituted, in order to imidize the valine (A) and/or valine (A'). The curing of the crucible portion is preferably carried out at 150 ° C to 350 ° C, more preferably at 200 ° C to 300 ° C, whereby a polyimide film can be obtained (for 30 minutes in the case of using an oven) 90 minutes, 5 minutes to 30 minutes when using a hot plate). Further, when the polymer compound (B) is a polyglycolic acid or a polyglycolate or the like, the oxime imidization reaction by heat treatment is simultaneously performed.

When the film is formed into a pattern, a patterned polyimide film is formed. In the present specification, the polyimine film is considered to include a patterned polyimide film unless otherwise specified.

The polyimide film obtained in this way is an insulating film excellent in heat resistance and electrical insulation. In addition, when the inkjet ink of the raw material contains an epoxy resin, it is preferable because it is an insulating film which is excellent in toughness, chemical resistance, flatness, adhesion, and sputter resistance.

9 film substrate

The film substrate of the present invention is obtained, for example, on a substrate such as a polyimide film having a wiring formed by an inkjet method or the like, and is formed in a whole surface or a predetermined pattern by an inkjet coating method (linear The inkjet ink of the present invention is applied, and then the substrate is dried and further heated to form a polyimide film.

10 electronic parts

For example, the inkjet ink of the present invention 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 to form a film. 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 invention is not limited to the examples.

The compound (a1) having two or more acid anhydride groups used in the examples and the comparative examples, the monoamine (a2), the compound (a1') having one acid anhydride group, and the diamine (a2') have a larger than The name of the compound (b1), the diamine (b2), the monoamine (b3), the alkenyl-substituted nadic acid ylide (C), and the solvent (D) equal to two acid anhydride groups are designated as the abbreviations. This abbreviation is used in the following description.

Compounds (a1) and (b1) having an acid anhydride group of 2 or more

ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BTDA: 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride 6FDA: 4,4'-six Fluorinated bisphthalic dianhydride

Monoamine (a2), (b3)

APSE: 3-Aminopropyltriethoxydecane

Compound having one anhydride group (a1')

TESA: triethoxydecyl propyl succinic anhydride

Diamine (a2'), (b2)

DDS: 3,3'-diaminodiphenylphosphonium PDA: p-phenylenediamine

7HHP: 5-[((n-heptylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene 7HB: 1,1-bis[4-(4-aminobenzyl) Phenyl]-4-n-heptylcyclohexane BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

Alkenyl substituted nadic acid ylide (c1)

ANIM: N-methyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine

Dienyl substituted nadic acid ylide (c2)

BANIM: bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane

Trienyl substituted nadic acid ylide (c3)

TrisANITAEA: tris{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)triethyl}amine TrisANITrisAM: tris{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)triphenyl}methane TrisANIPARARO: tris{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} hydroxymethane

Tetraalkenyl substituted nadic acid ylide (c4)

TetrakisANITAM: Tetra{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)tetraphenyl}methane

Solvent (D)

EDM: Diethylene glycol methyl ethyl ether GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone

[Example 1] Inkjet ink (1)

The raw material as described below was supplied to a 200 ml three-necked flask equipped with a stirrer and a raw material supply port, and stirred under a nitrogen stream at room temperature for 3 hr to obtain a transparent lysine (A) 30 wt% solution. This solution was directly used as an ink for inkjet (1).

The viscosity of the solution is 10.8 mPa. s (25 ° C), surface tension (25 ° C) is 33 mN / m. The viscosity of the solution was measured by an E-type viscosity meter (VISCONIC ELD manufactured by TOKYO KEIKI). The surface tension was measured by a hanging drop method using an interfacial tensiometer (Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd.).

[Example 2] Inkjet ink (2)

In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material supply port, and a nitrogen inlet, the following materials were supplied, and the mixture was stirred under a dry nitrogen stream at 40 ° C for 5 hr to obtain a pale yellow transparent polyamine. 50 wt% solution of acid (B).

The viscosity of the solution is 586 mPa. s. The weight average molecular weight measured by GPC was 2,100. The weight average molecular weight of polylysine is determined by diluting the obtained polyglycine in tetrahydrofuran (THF) in such a manner that the concentration of polyglycine becomes about 1 wt%, using a GPC apparatus: Japan Specimen Limited Made by the company, JASCO GULLIVER 1500 (smart An intelligent differential refractometer (RI-1530) was measured by a GPC method using the above diluent as a developing solvent, and converted into polystyrene. The pipe string is connected by using four columns of columns G4000HXL, G3000HXL, G2500HXL, and G2000HXL manufactured by Tosoh Co., Ltd. in this order, and is measured at a column temperature of 40 ° C and a flow rate of 1.0 ml/min. .

The solution of the proline (A) solution of Example 1 and the solution of the polyaminic acid (B) were supplied as follows, and stirred for 2 hr to obtain a solution having a solid concentration of 30 wt%. This solution was used as an ink for inkjet (2). The viscosity of the solution is 12.9 mPa. s (25 ° C), surface tension (25 ° C) was 31.7 mN / m.

[Example 3] Inkjet ink (3)

The solution of the proline (A) solution of Example 1 and the alkenyl group substituted with the nadic acid ylide (C) were supplied as follows, and the mixture was stirred until the solid component was completely dissolved to obtain a proline (A)/alkenyl substituted sodium. A 40 wt% solution of dick acid imine (C). This solution was used as an ink for inkjet (3). The viscosity of the solution is 18.1 mPa. s (25 ° C), surface tension (25 ° C) was 31.8 mN / m.

[Example 4]

The inkjet ink (1) prepared in Example 1 was used as an inkjet ink, and was set on a 1.5 mm thick glass epoxy double-sided copper plate by an inkjet coating device DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd. A line length of 5 cm was applied to a width of 1 point and a pitch of 40 micrometers. The heater of the ink jet head was set to 30 ° C, the piezoelectric voltage was 16 V, and the driving frequency was 5 kHz. 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 an insulating film of a polyimine formed into a linear shape.

The line width of the obtained polyimide film and the uniformity of the line width were observed with an optical microscope, and the film thickness was measured. The film thickness was measured by using a stylus type film thickness meter α-step 200 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of the measured values at three places was taken as the film thickness. The results are shown in Table 1. The wire has sufficient thickness.

[Example 5]

The inkjet ink (2) prepared in Example 2 was used as an inkjet ink, and an insulating film of polyimide was obtained under the same conditions as in Example 4.

The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The wire has sufficient thickness.

[Embodiment 6]

The inkjet ink (3) prepared in Example 3 was used as an inkjet ink, An insulating film of polyimine was obtained under the same conditions as in Example 4 except that the dot pitch was set to 20 μm.

The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The wire has sufficient thickness.

[Comparative Example 1] Inkjet ink (4)

The polyamine acid (B) 50% solution of Example 2 was supplied as follows, and stirred under a nitrogen stream at room temperature to obtain a 25 wt% solution of pale yellow transparent polyamine (B). This solution was used as an ink for inkjet (4). The viscosity of the solution is 12.3 mPa. s, surface tension (25 ° C) is 33.2 mN / m.

[Comparative Example 2]

An insulating film of polyimine was obtained under the same conditions as in Example 4 except that the inkjet ink (4) prepared in Comparative Example 1 was used as an inkjet ink.

The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The wire does not have a thickness of more than 1 micron.

[Example 7] Preparation of inkjet ink (5) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

Further, a polyimide film was formed in accordance with the method of Example 4.

[Example 8] Preparation of inkjet ink (6) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

Further, a polyimide film was formed in accordance with the method of Example 4.

[Example 9] Preparation of inkjet ink (7) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

Further, a polyimide film was formed in accordance with the method of Example 4.

[Example 10] Preparation of inkjet ink (8) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

Further, a polyimide film was formed in accordance with the method of Example 4.

[Example 11] Preparation of inkjet ink (9) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

Further, a polyimide film was formed in accordance with the method of Example 4.

[Example 12] Preparation of inkjet ink (10) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

Further, a polyimide film was formed in accordance with the method of Example 4.

[Example 13] Preparation of inkjet ink (11) and formation of polyimide film

The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.

The obtained polyimine membranes were evaluated under the same conditions as in Example 4 for Examples 7 to 13. The results are shown in Table 2. The wire has sufficient thickness.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope is subject to the definition of the scope of the patent application attached.

[Industrial availability]

Examples of the active use of the present invention include an insulating film for a flexible wiring board and an electronic component using the insulating film.

Figure 1 shows the IR spectrum of "TrisANITAEA".

Fig. 2 is a ¹ H-NMR spectrum of "TrisANITAEA".

Figure 3 shows the IR spectrum of "TrisANITrisAM".

Fig. 4 is a ¹ H-NMR spectrum of "TrisANITrisAM".

Figure 5 shows the IR spectrum of "TrisANIPARARO".

Fig. 6 is a ¹ H-NMR spectrum of "TrisANIPARARO".

Figure 7 shows the IR spectrum of "Tetrakis ANITAM".

Fig. 8 is a ¹ H-NMR spectrum of "Tetrakis ANITAM".

Claims (33)

An inkjet ink comprising: an anthracene compound (A) selected from the group consisting of a compound (a1) having an acid anhydride group of 2 or more and a monoamine (a2), and a compound having one acid anhydride group ( A1') at least one of the hydrazine compound (A') obtained with the diamine (a2'). The inkjet ink according to the first aspect of the invention, wherein the compound (a1) having two or more acid anhydride groups is a tetracarboxylic dianhydride represented by the following formula (1), a monoamine (a2) ) is an amine sulfonium compound represented by the following formula (2), (In the formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms, and in the formula (2), R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, and these may be the same Or different, Y is an organic group having 1 to 20 carbon atoms). The ink for inkjet according to claim 2, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-diphenyl ketone tetracarboxylic acid Anhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4 '-Diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic acid Anhydride, 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 Tetracarboxylate Acid dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic dianhydride, and butyl One or more of the group consisting of alkanetetracarboxylic dianhydride selected from the group consisting of p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminobenzene One or more of the group consisting of trimethoxy decane, m-aminophenyl triethoxy decane, aminopropyl trimethoxy decane, and aminopropyl triethoxy decane. The inkjet ink according to the first aspect of the invention, wherein the hydrazine compound (A) is a proline (A) represented by the following formula (3), (In the formula (3), X is a tetravalent organic group having 2 to 100 carbon atoms, and R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, and these may be the same or different, and Y is a carbon number. 1 to 20 organic base). The inkjet ink according to Item 4, wherein the proline is a proline represented by the following formula (4-1), (4-2) or (4-3) , [Chemical 3] (In the formula (4-1), (4-2) or (4-3), 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). The inkjet ink according to any one of the items 1 to 5, wherein the ratio of the compound (a1) having two or more acid anhydride groups to the monoamine (a2) is 1 mol. Ear: 0.5 moles ~ 8.0 moles. The inkjet ink according to any one of the items 1 to 5, wherein the compound (a1') having one acid anhydride group is a carboxylic anhydride represented by the following formula (1'). The diamine (a2') is a diamine represented by the following formula (2'), [Chemical 4] (In the formula (1'), R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, which may be the same or different, and Y' is an organic group having 1 to 20 carbon atoms, and the formula (2) In '), X' is a divalent organic group having a carbon number of 2 to 100). The inkjet ink according to Item 7, wherein the carboxylic anhydride is selected from the group consisting of p-trimethoxydecylphenyl succinic anhydride and p-triethoxydecyl phenyl succinic anhydride. a group consisting of (trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, trimethoxydecyl propyl succinic anhydride, and triethoxy decyl propyl succinic anhydride One or more of the above diamines are selected from the group consisting of p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diamino group. -1,2-diphenylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-bis(4-aminophenyl)propane, bis(4-amino group -3-methylphenyl)methane, 1,2-bis-(4-amino-3-methylphenyl)ethane, bis(4-amino-2-methylphenyl)methane, 1, 2-bis-(4-amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4' -diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl -2,2'-propane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-bis[(4-aminophenyl)methyl]benzene , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Fluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]biphenyl, 1,3-bis[4-(4 -aminobenzyl)phenyl]propane, 1,6-bis[4-(4-aminobenzyl)phenyl]hexane, 5-phenylmethyl-1,3-diaminobenzene, 5 -[4-(4-Alkylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5-[4-(4-(4-alkylcyclohexyl)cyclohexyl)phenyl]- -1,3-diaminobenzene, 5-[((alkylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 1,1-bis[4-( 4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-alkylcyclohexane, 1,1-double [ 4-(4-Aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-alkylcyclohexane, 1,3-double One or more of the groups consisting of (3-aminopropyl)-tetramethyldioxane. The inkjet ink according to any one of the items 1 to 5, wherein the oxime compound (A') is a proline (A' represented by the following formula (3'). ), (In the formula (3'), R ¹ , R ² and R ³ are hydrogen, halogen or a monovalent organic group, which may be the same or different, Y' is an organic group having 1 to 20 carbon atoms, and X' is carbon Number 2~100 organic base). The ink for inkjet according to claim 9, wherein the proline (A') is represented by the following formulas (4'-1), (4'-2), (4'-3) , (4'-4) or (4'-5) represents a proline (A'), [Chem. 6] (in the general formula (4'-1), (4'-2), (4'-3), (4'-4) or (4'-5), at least one of R ¹ , R ² and R ³ An alkoxy group having 1 to 20 carbon atoms, R of the formula (4'-3) is an organic group having 2 to 30 carbon atoms, and R of the formula (4'-4) is hydrogen or a carbon number of 1 to 20 The alkyl group, a is an integer from 1 to 20). Spray as described in any one of claims 1 to 5 The ink for ink, wherein the ratio of the above compound (a1') having one acid anhydride group to the above diamine (a2') is from 0.5 mol to 8.0 mol: 1 mol. The inkjet ink according to any one of the items 1 to 5, wherein the inkjet ink further contains a polymer compound (B). The inkjet ink according to Item 12, wherein the polymer compound (B) is at least one selected from the group consisting of polylysine and polyimine. The inkjet ink according to Item 12, wherein the polymer compound (B) has a weight average molecular weight of 1,000 to 5,000. The inkjet ink according to any one of the items 1 to 5, wherein the inkjet ink further contains an alkenyl group substituted alkenyl-substituted nadimide (C). The ink for inkjet according to claim 15, wherein the alkenyl-substituted nadic acid ylide (C) is a monoamine, a diamine, a triamine or a tetraamine and the following formula (5') An alkenyl-substituted nadic acid ylide imine formed by reacting an alkenyl group with a nadic anhydride In the formula (5'), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12; Any of an aryl group or a benzyl group. The inkjet ink according to Item 15, wherein the alkenyl-substituted nadic acid ylide (C) is a compound represented by the following formula (5), In the formula (5), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12; Any of an aryl group or a benzyl group, n is an integer of 1 to 4, and when n=1, R ³ in the formula (5) is hydrogen, an alkyl group having 1 to 12 carbon atoms, and a hydroxyl group having 1 to 12 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, -{(C _q H _2q )O _t (C _r H _2r O) _u C _s H _2s X} ( Wherein, q, r, s are independently selected integers of 2 to 6, respectively, t is an integer of 0 or 1, u is an integer from 1 to 30, X is hydrogen or a hydroxyl group, and the polyoxyalkylene alkyl group is represented by -(R) _a -C ₆ H ₄ -R ⁴ (wherein a represents an integer of 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents hydrogen or an alkyl group having 1 to 4 carbon atoms) the group _{represented, -C 6 H 4 -T-C} 6 H 5 { wherein, T is _{-CH 2 -, - C (CH} 3) 2 -, - CO -, - S- or -SO ₂ -} a group represented by the group or a group of one to three hydrogens directly bonded to the aromatic ring of the groups via a hydroxyl group, and when n=2, R ³ in the formula (5) is a carbon number of 2 ~20 of the alkylene group {any methylene group in the alkylene group which is not adjacent to each other may pass through - O- or -CH=CH-substitution, any hydrogen can be substituted by fluorine}, a cycloalkylene group having a carbon number of 5-8, -{(C _q H _2q O) _t (C _r H _2r O) _u C _s H _2s }- (wherein q, r, s are independently selected integers of 2 to 6, and t is an integer of 0 or 1, and u is an integer from 1 to 30), and the number of carbon atoms is represented by carbon number. 6 to 12 arylene, -(R) _a -C ₆ H ₄ -R ⁵ - (wherein a is an integer of 0 or 1, and R and R ⁵ are each independently an alkylene group having 1 to 4 carbon atoms) a group represented by -C ₆ H ₄ -T-C ₆ H ₄ -, -C ₆ H ₄ -T-C ₆ H ₄ -T-C ₆ H ₄ - or -C ₆ H ₄ -T' -C ₆ H ₄ -T-C ₆ H ₄ -T'-C ₆ H ₄ -{ wherein T is a single bond, an alkylene group having 1 to 6 carbon atoms, -C(CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CO-, -O-, -OC ₆ H ₄ C(CH ₃ ) ₂ C ₆ H ₄ O-, -S- or -SO ₂ -, T' is -CH ₂ - or a group represented by -O-}, or a group in which one to three hydrogens are directly bonded to an aromatic ring of the groups, or a group represented by the following formula (6-1) or In the formula (6-1), x is independently an integer from 1 to 6, and y is a group represented by the following formula (6-2). An integer from 1 to 70, When n=3, R ³ in the formula (5) is a group represented by the following formula (7-1) or a group represented by the following formula (7-2), [Chemical 10] In the formula (7-1), R is hydrogen, fluorine, chlorine, -OH, -OCF ₃ , -OCF ₂ H, -CF ₃ , -CF ₂ H, -CFH ₂ , -OCF ₂ CF ₂ H, -OCF in ₂ CFHCF _3, or an alkyl group having 1 to 10 carbon atoms, the formula (7-1) and formula ^{(7-2), R 4, R} 5, R 6 are independently a single bond, trans-1,4- a cyclohexyl group, a 1,3-dioxane-2,5-diyl group, a 1,4-phenylene group, a hydrogen-substituted 1,4-phenylene group or a carbon number of 1 to 10 alkylene group. Any methylene group in the alkylene group which is not adjacent to each other may be substituted by -O- or -CH=CH-, and any hydrogen may be substituted by fluorine. When n=4, R ³ in the formula (5) is as follows (8) the group indicated, In the formula (8), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, hydrogen 1,4-phenylene substituted by fluorine or alkylene having 1 to 10 carbon atoms; any methylene group in the alkylene group which is not adjacent to each other may be -O- or - CH=CH-substituted, any hydrogen can be substituted by fluorine. The ink for inkjet according to Item 17, wherein n is 2. The ink for inkjet according to Item 17, wherein n is 2, and R ³ in the formula (5) is an alkylene group having 2 to 15 carbon atoms; any of the alkylene groups which are not adjacent to each other The methyl group may be substituted by -O- or -CH=CH-, and any hydrogen may be substituted by fluorine}, -(R) _a -C ₆ H ₄ -R ⁵ - (where a is an integer of 0 or 1, R And a group represented by R ⁵ each independently being an alkylene group having 1 to 4 carbon atoms, and consisting of -C ₆ H ₄ -T-C ₆ H ₄ -, -C ₆ H ₄ -T-C ₆ H ₄ - T-C ₆ H ₄ - or -C ₆ H ₄ -T'-C ₆ H ₄ -T-C ₆ H ₄ -T'-C ₆ H ₄ -{ wherein T is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CO-, -O-, -OC ₆ H ₄ C(CH ₃ ) ₂ C ₆ H ₄ O-, -S- or -SO ₂ -, T' is a group represented by -CH ₂ - or -O-}. The ink for inkjet according to claim 17, wherein R ¹ and R ² in the formula (5) are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is 2, in the formula (5) the carbon number of R ³ is an alkylene group having 2 to 15 {the alkylene group of mutually non-adjacent any methylene group may be substituted by -O- or = CH- -CH, arbitrary hydrogen may be replaced by fluorine} formula (6-1) a group represented by the formula, a group represented by the formula (6-2), a group represented by the formula (6-3), a group represented by the formula (6-4) or a formula (6) -5) the group represented, [Chem. 12] In the formula (6-1), x is independently an integer from 1 to 6, and y is an integer from 1 to 70. In the formula (6-3) and the formula (6-5), R is -CH ₂ -, -CH An organic group of ₂ CH ₂ -, -O-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, and in the formula (6-5), X is -CH ₂ - , -O-organic base. The patentable scope of the application of paragraph 17 inkjet ink, wherein in the formula (5) R & lt ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms of, n is 3, the formula (5) R ³ is represented by the formula (7-1-1), the formula (7-2-1) or the formula (7-2-2). In the formula (7-1-1), R is an alkyl group having 1 to 10 carbon atoms or -OH, and in the formula (7-2-2), R ⁴ , R ⁵ and R ⁶ are each independently 1,2-Asia. Ethyl, 1,4-butylene. The ink for inkjet according to claim 17, wherein R ¹ and R ² in the formula (5) are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is 4, in the formula (5) R ³ is represented by the following formula (8-1), [Chem. 14] The ink for inkjet according to claim 17, wherein the ink for inkjet contains an alkenyl-substituted nadic acid imine (C) selected from n being n, and an alkenyl-substituted nadick having n being 2 At least two alkenyl substitutions of the acid quinone imine (C), n-substituted alkenyl substituted nadic ylidene imine (C), and n-alkenyl substituted nadic acid yttrium imine (C) Nadick acid imine (C). The inkjet ink according to Item 17, wherein the inkjet ink contains at least two alkenyl groups substituted with nadic acid ylide (C): R ¹ and R in the formula (5) ^{2 is} independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ³ in the formula (5) is an alkyl group having 1 to 12 carbon atoms (n=1) and an aryl group having 6 to 12 carbon atoms (n=1). ), -(CH ₂ ) _p (n=2, p is an integer of 6 to 12), a group represented by the formula (6-1-1), a group represented by the formula (6-2), and a formula ( 6-3-1) a group represented by the formula, a group represented by the formula (6-4), a group represented by the formula (6-5-1), and a group represented by the formula (7-1-2) a group represented by the formula (7-1-3), a group represented by the formula (7-2-1), a group represented by the formula (7-2-3), and a formula (8-1) The group indicated, . The inkjet ink according to any one of the items 1 to 5, wherein the inkjet ink further contains a solvent (D). The ink for inkjet according to claim 25, wherein the solvent (D) is selected from the group consisting of ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, and diethylene glycol. Ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxy One or more of the group consisting of methyl propyl propionate, ethyl 3-ethoxypropionate, cyclohexanone, and γ-butyrolactone. The inkjet ink according to any one of the preceding claims, wherein the ruthenium compound (A) and the ruthenium compound (A') are the same with respect to 100 parts by weight of the ink for inkjet. The total content is from 1 part by weight to 99 parts by weight. The inkjet ink according to any one of the preceding claims, wherein the ruthenium compound (A) and the ruthenium compound (A') are the same with respect to 100 parts by weight of the ink for inkjet. The total content is from 10 parts by weight to 80 parts by weight. The inkjet ink according to any one of the preceding claims, wherein the ruthenium compound (A) and the ruthenium compound (A') are the same with respect to 100 parts by weight of the ink for inkjet. The total content is from 22 parts by weight to 70 parts by weight. A polyimine film or a patterned polyimide film, the polyimide film or the patterned polyimide film is obtained by the following method: by inkjet In the coating method, a coating film is formed by applying the inkjet ink according to any one of the first to the twenty-ninth aspects of the invention, and the coating film is cured to form a polyimide film. A method for forming a polyimide film or a patterned polyimide film, the method comprising the following steps: coating by any one of the first to the 29th claims of the patent application by an inkjet coating method a process for forming a coating film by using inkjet ink; and a process of curing the coating film to form a polyimide film. A film substrate having a polyimide film or a patterned polyimide film formed by the method of claim 31 On the substrate. An electronic component having the film substrate as described in claim 32 of the patent application.