TWI532795B - Thermal curing ink composition and use thereof - Google Patents

Description

Thermosetting ink composition and use thereof

The present invention relates to a thermosetting ink composition and use thereof, and relates to an ink for forming an insulating film, for example, in the production of an electronic component, a coating method of the ink, and a polyfluorene formed using the ink. An imine film and a method for producing the same, comprising a film substrate of the above polyimide film, and an electronic component having the film substrate.

In recent years, miniaturization, weight reduction, and high performance of electronic devices are rapidly progressing, and these developments have been achieved by thinning or miniaturization of electronic components. Particularly in the field of printed wiring boards, foldable flexible wiring boards contribute greatly to miniaturization or weight reduction of electronic equipment.

Along with this, various requirements have been made for various physical properties of each member used in an electronic component. For example, the cured film used in electronic parts is required to have heat resistance, insulation properties, adhesion to a substrate, resistance to chemicals used in a process, low water absorption, and the like.

Polyimine is widely used in the above fields because of its excellent heat resistance and insulating properties. In recent years, a method of forming a cured film containing a desired polyimine by an inkjet method has been studied.

Patent Document 1 discloses an inkjet ink containing a polylysine having a specific structure. However, Patent Document 1 does not conduct any research on an inkjet ink which can form a cured film having adhesion to a copper substrate or copper plating, resistance to an alkaline aqueous solution, and low water absorbability. .

Patent Document 2 discloses a photosensitive resin composition containing a polyamine acid having a specific structure, a photopolymerizable compound, and a photopolymerization initiator. However, the above polyamic acid does not have a crosslinkable organic group at the molecular terminal, and the above polyamic acid monomer cannot obtain a cured film having sufficient resistance to an alkaline aqueous solution. Further, the above-mentioned composition is mainly applied by a dispensing method, a screen printing method, a press forming method, or the like, and the above composition cannot be used for the ink jet method from the viewpoint of viscosity design (1 Pa.s or more). .

Patent Document 3 and Patent Document 4 disclose a resin composition containing a polyimine of a specific structure. However, in Patent Document 3 and Patent Document 4, no inkjet ink which can form a cured film having good resistance to an alkaline aqueous solution and insulation properties has been studied.

Patent Document 5 discloses a polyimine precursor having a specific structure. However, in the exemplification of the diamine component constituting the polyimide precursor, the diamine derived from the dimer acid as described later is not mentioned. Further, in Patent Document 5, the use of a composition containing a polyimide precursor as a thermosetting ink composition has not been studied, and the use of an inkjet method including a design including concentration or viscosity is not mentioned.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-159402

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-256532

[Patent Document 3] US Patent No. 7157587B2

[Patent Document 4] US Patent No. 7208566B2

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-321924

An object of the present invention is to provide a good adhesion (for example, low dielectric constant), good adhesion to copper plating, etc., good resistance to an alkaline aqueous solution, and the like, and low water absorption. A thermosetting ink composition of a cured film and use thereof.

The inventors of the present invention have diligently studied in order to solve the above problems. In particular, in the amide acid which is preferably used as a component containing the ink, the lysine is obtained by reacting an acid dianhydride, a diamine and a terminal crosslinking agent, thereby performing various kinds of the above diamine. the study.

For example, the polylysine (3) used in Example 3 of Patent Document 1 has a 4,4'-[(isopropylidene)bis(p-phenoxy)diphthalic dianhydride and a repeating constituent unit formed of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and having a molecular terminal group formed of maleic anhydride. However, when an ink containing polyamic acid (3) is used, the obtained cured film has a water absorption rate of 3% and becomes high, and the adhesion to copper plating is also low, and resistance to an alkaline aqueous solution is obtained. It is also low (refer to Comparative Example 2 of the present specification).

Further, when diethylene glycol bis(3-aminopropyl)ether is used as the diamine, the water absorption of the obtained cured film is also increased to 3%, and the adhesion to copper plating is also low, and The tolerance to the alkaline aqueous solution was also low (refer to Comparative Example 1 of the present specification).

The present inventors believe that the ether bond in the diamine adversely affects water absorption, adhesion, and alkali resistance, and attempts have been made to use 1,8-diamino octyl having a long chain alkyl group between two amine groups. The above diamine was replaced by an alkane or 1,12-diaminododecane (refer to Comparative Example 8 to Comparative Example 11 of the present specification). But here In the case, it is difficult to dissolve the obtained polyamic acid in a solvent, and an ink usable for general use is not obtained.

The inventors of the present invention have been able to solve the above problems by studying the various diamines, and have found that the present invention has been accomplished by a thermosetting ink composition having the following constitution.

That is, the present invention relates to, for example, the following [1] to [17].

[1] A thermosetting ink composition comprising at least one proline acid (A) selected from the group consisting of proline acids: proline acid represented by formula (A1); represented by formula (A2) And a poly-proline which has a crosslinkable organic group at a molecular terminal, and is one or more kinds of diamines (a12) containing a diamine (a1) derived from a dimer acid, and has two The above acid anhydride group-containing compound (a3) is obtained by reacting one or two terminal crosslinking agents represented by the formula (T2) with a terminal crosslinking agent represented by the formula (T1).

[In the formula (A1) and the formula (A2), R ¹ is a residue of a diamine (a1) derived from a dimer acid, and R ² is a divalent crosslinkable organic group having a carbon number of 2 to 100]

R ³ -NH ₂ (T2)

[In the formula (T1), R ² is a divalent crosslinkable organic group having a carbon number of 2 to 100, and in the formula (T2), R ³ is a monovalent crosslinkable organic group having a carbon number of 2 to 100. ]

[2] The thermosetting ink composition according to [1] above, which is an ink for inkjet.

[3] The thermosetting ink composition according to [1] or [2] above, wherein the diamine (a1) derived from the dimer acid is a reduction of a dimer acid obtained from an unsaturated fatty acid. One or two or more kinds of diamines obtained by amination reaction, and the above unsaturated fatty acid is selected from the group consisting of crotonic acid, myristoleic acid, palmitolic acid, and oleic acid ( Oleic acid), elaidic acid, vaccenic acid, gadoleic acid, eicocosenoic acid, erucic acid, tetracosic acid Nervonic acid), linoleic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid ), eicosatrienoic acid, stearidonic acid, Arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, osbond acid, Clupanodonic acid, tetracosapentaenoic acid, docosahexaenoic acid, and nisinic acid.

[4] The thermosetting ink composition according to any one of [1] to [3] wherein the diamine (a12) contains, in addition to the diamine (a1) derived from the dimer acid, further contains At least one selected from the group consisting of 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3, 3'-Diaminodiphenylphosphonium, bis[3-(4-aminophenoxy)phenyl]anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane , 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, isophthalic acid Amine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-aminophenoxyl) Phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4-amine Benzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4- Aminobenzyl)phenyl]methane, 2,5-diaminomethylbicyclo[2.2.1]heptane, 2,6-diaminomethylbicyclo[2.2.1]heptane, 9,9- Bis(3-aminopropyl)anthracene, 9,9-bis(4-aminophenyl)anthracene, by formula (VI II) a compound represented by the formula (XIII), and a compound represented by the formula (i),

[In the formula (VIII), A ⁴ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -(CH ₂ ) _p -, -(CH ₂ ) _p -O- Or -O-(CH ₂ ) _p -, where p is an integer of 1 to 6; R ¹⁰ is a group having a steroid skeleton or a group having at least one ring structure selected from a cyclohexane ring and a benzene ring Wherein, when the positional relationship of the two amine groups bonded to the benzene ring is a para position, R ¹⁰ may be an alkyl group having a carbon number of 1 to 30, and when the above positional relationship is meta, R ¹⁰ may be An alkyl group or a phenyl group having 1 to 30 carbon atoms, and at least one -CH ₂ - of the above alkyl group may be selected from the group consisting of -CF ₂ -, -CHF-, -O-, -CH=CH-, and -C≡C - at least one of the substitutions, wherein at least one -CH _{3 of the} above alkyl group may be substituted with at least one selected from the group consisting of -CH ₂ F, -CHF ₂ and -CF ₃ and bonded to the ring-forming carbon of the above phenyl group The hydrogen on the surface may be substituted by at least one selected from the group consisting of -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ and -OCF ₃ ]

[In the formula (XIII), R ²⁸ and R ²⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ³⁰ is a methylene group, a phenyl group or at least one hydrogen having a carbon number of 1 to 10; Alkyl substituted phenyl, 2 x are each an integer from 1 to 6, and y is an integer from 1 to 70]

[In the formula (i), n is an integer of 1 to 50].

[5] The thermosetting ink composition according to any one of the above [1], wherein the compound (a3) having two or more acid anhydride groups is at least one selected from the group consisting of: Pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-diphenyl ketone tetracarboxylic dianhydride (2,2',3,3'-benzophenone tetracarboxylic dianhydride), 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride ( 2,3,3',4'-benzophenone tetracarboxylic dianhydride), 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride 2,2',3,3'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl 4,4'-dihydroxyphenyl sulfone tetratrile dianhydride, 4,4'-dihydroxyphenyl sulfone bistrimellitic dianhydride , 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether carboxylic acid 2,3',3,3'-diphenylether tetracarboxylic dianhydride, 2,3,3',4'-diphenylether tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethan tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxybenzene) ))] hexafluoropropane dianhydride, ethylene glycol bis (anhydro trimellitate), ring Cyclobutane tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1, 2, 4, 5-, 4-, 4-, 5-cyclohexane, tetracarboxylic dianhydride, ethan tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,3-Dihydro-1,3-di-oxy-5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1-(trifluoromethyl)ethylene]di-4 , 1-phenylene ester (1,3-dihydro-1,3-dioxy-5-isob Enzofuran carboxylic acid, [2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]di-4,1-phenylene ester), 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3 , 3',4,4'-tetracarboxylic dianhydride (2,2-bis(4-hydroxyphenyl)propanedibenzoate-3,3',4,4'-tetracarboxylic dianhydride), 1,3-dihydro-1, 3-dihydro-1,3-dioxy-5-isobenzofuran carboxylic acid oxy di-4,1 -phenylene ester), p-phenylenebis (trimellitic acid monoester anhydride), 4-(2,5-di-sided oxytetrahydrofuran-3-yl)-1 ,2,3,4-tetrahydronaphthalfuran-1,2-dicarboxylic acid anhydride (4-(2,5-dioxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride , 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid Diamine (3,3',4,4'-bicyclohexyl tetracarboxylic dianhydride), bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2,2,2 Octantane-2,3,5,6-tetracarboxylic dianhydride), 5-(2,5-di-sided oxytetrahydrofuranyl)-3- 5-(2,5-dioxytetrahydrofuryl-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride), 4,4'-[( Isopropyl) bis(p-phenyleneoxy)diphthalic acid dianhydride, ethylenediaminetetraacetic acid dianhydride (ethylenediamine tetraacetic acid dianhydride), 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (3,4-dicarboxy-1,2,3,4-tetrahydro-1 -naphthalene succinic acid dianhydride), and a compound represented by the following formula

[6] The thermosetting ink composition according to any one of [1] to [5] wherein the terminal crosslinking agent represented by the formula (T1) is selected from the group consisting of: Diacid anhydride, citraconic anhydride, allyl nadic acid anhydride, 5-northene-2,3-dicarboxylic anhydride, 4-ethynyl phthalic anhydride, 4- Phenyl ethynyl phthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride, and 3-(triethoxysilyl)propyl succinic acid anhydride At least one.

[7] The thermosetting ink composition according to any one of [1] to [6] wherein the terminal crosslinking agent represented by the formula (T2) is selected from the group consisting of 4-ethynylaniline, 3- Ethynyl aniline, propargylamine, 3-aminobutyne, 4-aminobutyne, 5-aminopentyne, 4-aminopentyne, allylamine, 7-aminoheptyne, M-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 3-aminophenylacetylene, 4-aminophenylacetylene, 3-aminopropyltriethoxydecane And at least one of 3-aminopropyltrimethoxydecane.

[8] The thermosetting ink composition according to any one of [1] to [7] above which further comprises a solvent (B).

[9] The thermosetting ink composition according to the above [8], wherein the solvent (B) is at least one selected from the group consisting of ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, and ethylene. Alcohol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethyl Diol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol Monomethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, anisole (anisole), methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-( 2-hydroxyethyl)-2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-ethylindol-2-pyrrolidone, N,N-diethyl Indoleamine, N,N-dimethylpropanamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone.

[10] The thermosetting ink composition according to [8] or [9] above which has a viscosity of 5 mPa at 25 ° C and 20 rpm. s~20mPa. s.

The thermosetting ink composition according to any one of the above [1], wherein the polypyridic acid has a polystyrene-reduced weight as measured by gel permeation chromatography. The average molecular weight is 500 to 10,000.

[12] The thermosetting ink composition according to any one of [1] to [11] wherein the content of the lysine (A) in the thermosetting ink composition is 15% by mass to 60% by mass. %.

[13] A method of forming a coating film, comprising the step of forming a coating film by applying the thermosetting ink composition according to any one of the above [1] to [12], by an inkjet coating method, And a step of hardening the above coating film.

[14] A method for producing a polyimide film, comprising: coating a thermosetting ink composition according to any one of the above [1] to [12] by an inkjet coating method to form a coating film And the step of hardening the above coating film to form a polyimide film.

[15] A polyimine film obtained by the method for producing a polyimide film according to [14] above.

[16] A film substrate comprising: a film; and a polyimide film formed on the film by the method for producing a polyimide film according to [14] above.

[17] An electronic component comprising the film substrate according to [16] above.

[instructions]

The terms used in the present specification will be described with specific examples.

The "diamine derived from a dimer acid" means a diamine having a structure in which a dimer acid removes two carboxyl groups. Although it also depends on the reductive amination reaction of the dimer acid, as the diamine derived from the dimer acid, for example, the substitution of two carboxyl groups (-COOH) of the dimer acid into an aminomethyl group (-CH _{2 )} a diamine of -NH ₂ ) or an amine group (-NH ₂ ).

The "residue of a diamine derived from a dimer acid" means a divalent group obtained by removing two amine groups from a diamine (H ₂ NR ¹ -NH ₂ ) derived from a dimer acid. , that is, a divalent group represented by -R ¹ -.

The term "crosslinkable organic group" refers to an organic group having crosslinkability, and examples thereof include a monovalent or divalent organic group having a carbon number of 2 to 100 having a crosslinkable unsaturated bond, and a formula ( The divalent organic group represented by α) and the monovalent organic group represented by the formula (β).

In the formula (α) and the formula (β), a plurality of R ^a are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Here, at least one of R ^a is the above alkoxy group. R ^b is a trivalent organic group having a carbon number of 1 to 20 (for example, an aliphatic group or an aromatic group). R ^c is a divalent organic group having a carbon number of 1 to 20 (for example, an alkyl group or an aryl group).

The "crosslinkable unsaturated bond" means, for example, a double bond or a triple bond. The number of crosslinkable unsaturated bonds in the crosslinkable organic group is preferably from 1 to 5, more preferably from one to three, and particularly preferably one.

The "monovalent organic group having 2 to 100 carbon atoms having a crosslinkable unsaturated bond" may, for example, be a carbon number of 2 to 20 (preferably 2 to 10, more preferably 2 to 6). Alkenyl group; alkynyl group having a carbon number of 2 to 20 (preferably 2 to 10, more preferably 2 to 6); carbon number of 4 to 20 (preferably 4 to 10, more preferably 4 to 6) An alkyldienyl group; a cycloalkenyl group having 3 to 20 (preferably 4 to 10) carbon atoms; -OR, -SR, -SO ₂ R (in the above formula, R is the above alkenyl group or the above alkynyl group) a group obtained by substituting one or more hydrogens having an aryl group having 6 to 30 (preferably 6 to 20, more preferably 6 to 12) to the alkenyl group or the alkynyl group; -OAr -SAr, -SO ₂ Ar (in the above formula, Ar is substituted with one or more hydrogens in an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms; An alkenyl group or a group of the above alkynyl groups).

The "divalent organic group having 2 to 100 carbon atoms having a crosslinkable unsaturated bond" may, for example, be a carbon number of 2 to 20 (preferably 2 to 10, more preferably 2 to 6). An alkenyl group or an alkynylene group; a cycloalkenyl group having a carbon number of 3 to 20 (preferably 4 to 10); -OR-, -SR-, -SO ₂ R- (in the above formula, R is the above An alkenyl group or an alkynyl group; and one or more hydrogens in an extended aryl group having a carbon number of 6 to 30 (preferably 6 to 20, more preferably 6 to 12) are substituted with the above alkenyl group, a group of an alkynyl group, an arylalkenyl group or an arylalkynyl group; -OAr-, -SAr-, -SO ₂ Ar- (in the above formula, Ar is a carbon number of 6 to 30, preferably 6 More preferably, it is a group in which one or more hydrogens of 6 to 12 are substituted with the above alkenyl group or the above alkynyl group; and a divalent group represented by the following formula.

In the formula, R is a hydrogen atom or an allyl group, and A is a methylene group or an oxygen atom.

In the description of each formula, the expression "at least one "A" may be replaced by "B"" means that when "A" is one, the position of "A" is arbitrary, and when the number of "A" is two or more. The positions of the "A"s can also be selected without limitation.

For example, "at least one "A" may be substituted by at least one selected from "B", "C", and "D"". The expression includes any case where "A" is replaced by "B", and arbitrary " The case where A" is replaced by "C", and the case where any "A" is replaced by "D", and further includes the case where a plurality of "A" are replaced by at least two of "B", "C", and "D". .

According to the present invention, it is possible to provide a thermosetting ink composition which can form a cured film which is free from solvent solubility of a component in the ink and which has low water absorption, and can be formed with A cured film having excellent insulating properties (for example, low dielectric constant), good adhesion to copper plating, and good resistance to an alkaline aqueous solution or the like.

Therefore, the polyimide film formed of the thermosetting ink composition of the present invention has a sufficiently low water absorption rate, high insulating property, excellent adhesion to a substrate, and excellent chemical resistance. Therefore, by using the ink, the reliability and yield of the electronic component can be improved.

Hereinafter, the thermosetting ink composition, the method of applying the ink, the polyimide film, the method for producing the same, the film substrate, and the electronic component of the present invention will be described in detail. The thermosetting ink composition of the present invention is also simply referred to as "the ink of the present invention".

Thermosetting ink composition

The thermosetting ink composition of the present invention contains a specific amic acid (A), and further preferably contains a solvent (B). The ink of the present invention may contain an additive in addition to the above components. The ink of the present invention may be either colored or colorless.

1.1 proline (A)

Examples of the valine acid (A) include the following compounds.

. The proline acid represented by the formula (A1) (hereinafter also referred to as "proline (A1)").

. The proline acid represented by the formula (A2) (hereinafter also referred to as "proline (A2)").

. Polylysine having a crosslinkable organic group at the molecular terminal (hereinafter also referred to as "polyglycine (A3)"), which is one or more kinds of diamines (a1) derived from dimer acid. a diamine (a12), a compound (a3) having two or more acid anhydride groups, and one or both kinds of terminal crosslinking agents represented by the formula (T1) and a terminal crosslinking agent represented by the formula (T2) The crosslinking agent is obtained by carrying out a reaction.

That is, in the present invention, the proline (A) as a component containing a thermosetting ink composition is selected from the group consisting of lysine (A1), proline (A2), and polyglycine (A3). At least one.

In the formula (A1) and the formula (A2), R ¹ is a residue of the diamine (a1) derived from a dimer acid. R ² is a divalent crosslinkable organic group having 2 to 100 carbon atoms, preferably a group derived from a terminal crosslinking agent represented by the formula (T1).

R ³ -NH ₂ (T2)

In the formula (T1), R ² is a divalent crosslinkable organic group having a carbon number of 2 to 100. In the formula (T2), R ³ is a monovalent crosslinkable organic group having a carbon number of 2 to 100.

The polystyrene-reduced acid (A3) has a polystyrene-equivalent weight average molecular weight of 500 to 10,000 as measured by Gel Permeation Chromatography (GPC method). In order to further enhance the solubility of the poly-proline (A3) for the solvent (B), and to make the ink low-viscosity, the weight average molecular weight of the poly-proline (A3) is more preferably 500 to 9,000, and more preferably 500 to 500. 8,000. Further, the proline (A1) and the proline (A2) are monomeric, but in the present invention, the molecular weights are also defined by the weight average molecular weight in terms of polystyrene measured by the GPC method. The weight average molecular weight of the proline (A1) and the proline (A2) is preferably from 500 to 10,000, more preferably from 500 to 9,000, and still more preferably from 500 to 8,000.

The (poly)proline which has a weight average molecular weight of at least the above lower limit value does not evaporate in the step of forming a polyimide film by heat treatment, and has chemical properties. Mechanical properties are stable. When the (poly)proline acid having a weight average molecular weight of at most the above upper limit is more soluble in the solvent (B), the polyamine can be used in a concentration of 15% by mass or more and suitable for spraying. The low viscosity of the ink printing coexists, so the ink ejection stability is improved, and Further, the film thickness of the obtained coating film can be increased.

The weight average molecular weight of the proline (A) can be determined by gel permeation chromatography (GPC method). Specifically, it can be determined by using N,N-dimethylformamide (DMF) to convert the obtained proline (A) to a concentration of lysine (A) of about 1% by mass. Diluted to form a dilution, and then two columns (GF-510HQ, GF-310HQ) manufactured by Showa Denko (share) were used in this order, at a column temperature of 40 ° C and a flow rate of 0.5 ml/min. Under the conditions, the above diluent was used as a developing solvent and measured by a GPC method, and then converted into polystyrene.

The above three kinds of valine acids (A) each have a diamine structure derived from a dimer acid. The proline acid (A) having the above structure greatly contributes to the low water absorption of the obtained cured film, or the resistance to chemicals (for example, an alkaline aqueous solution) and to a substrate (for example, copper plating). Increased adhesion. Further, since the solubility in the solvent (B) is also high, the preparation of an ink for general use such as an inkjet application is also easy.

Since all of the above three kinds of valine acids (A) have a crosslinkable organic group at the molecular terminal, a crosslinked structure derived from glutamic acid (A) is formed by heating the ink of the present invention. Therefore, in the present invention, a polyimine film having a sufficient mechanical strength can be obtained from a small molecular weight amic acid (A) having a weight average molecular weight of, for example, about 500 to 10,000.

The content of the proline (A) is usually 15% by mass to 60% by mass, preferably 15% by mass to 55% by mass, and more preferably 15% by mass to 50% by mass, based on the thermosetting ink composition of the present invention. If it is the concentration range, then When the ink of the present invention is used for inkjet applications, the viscosity is suitable for inkjet, and the thickness of the film obtained by one-time inkjet is optimized, and the ejection accuracy is high, which is preferable.

In the present specification, the diamine derived from the dimer acid is also referred to as "dimer acid type diamine (a1)", and the diamine other than the diamine derived from the dimer acid is also referred to as "other diamine. (a2)", one or more kinds of diamines containing a dimer acid type diamine (a1) and, if necessary, another diamine (a2) are also called "diamine (a12)", and also have two or more The acid anhydride group-based compound is referred to as "anhydride (a3)", and the terminal crosslinking agent represented by the formula (T1) is also referred to as "terminal crosslinking agent (T1)", and the terminal cross-linking represented by the formula (T2) is also referred to. The agent is called "terminal crosslinking agent (T2)".

Hereinafter, a dimer acid type diamine (a1), another diamine (a2), an acid anhydride (a3), a terminal crosslinking agent (T1), and a terminal crosslinking agent (T2) which can be used for obtaining a proline (A) Be explained.

1.1.1 Dimer acid type diamine (a1)

The dimer acid type diamine (a1) can be obtained, for example, by a reductive amination reaction of a dimer acid. The above reaction can be carried out, for example, by a known method such as a reduction method using ammonia or a catalyst (for example, Japanese Patent Laid-Open Publication No. Hei 9-12712).

The dimer acid refers to a dibasic acid obtained by dimerization of an unsaturated fatty acid by an intermolecular polymerization reaction or the like. Although it depends on the synthesis conditions and the purification conditions, it usually contains a small amount of a monomeric acid or a trimer acid in addition to the dimer acid. After the above reaction, the double bond remains in the obtained molecule, but in the present invention, the double bond existing in the molecule is reduced by hydrogenation reaction. The formation of a saturated dibasic acid is also included in the dimer acid.

The dimer acid can be obtained, for example, by polymerizing an unsaturated fatty acid by using a Lewis acid and Bruce's acid as a catalyst. The dimer acid can be produced by a known method (for example, Japanese Patent Laid-Open Publication No. Hei 9-12712).

Examples of the unsaturated fatty acid include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, isooleic acid, oleic acid, eicosenoic acid, sinapic acid, and tetradecanoic acid. Linoleic acid, pine nut oleic acid, tung acid, honey acid, di- gamma-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, arachidonic acid, Adrenalic acid, octadecaphoenoic acid, docosapentaenoic acid, oleic acid, docosapentaenoic acid, docosahexaenoic acid, citric acid. The unsaturated fatty acid usually has a carbon number of 4 to 24, preferably 14 to 20.

For example, when linoleic acid is used to produce a dimer acid, the obtained mixture usually contains a dimer acid having a carbon number of 36 as a main component, but usually also contains a small amount of a monomeric acid having a carbon number of 18 and a carbon number of 54. The trimer acid serves as a by-component and contains various structures derived from the raw materials.

The dimer acid type diamine (a1) is, for example, one or a mixture of two or more kinds having a structure represented by the following formula (a) to the following formula (e). The dimer acid type diamine (a1) may also be hydrogenated, for example, having a structure represented by the following formula (c) or the following formula (e).

In the formulae (a) to (e), m, n, p, and q are each independently an integer of 0 to 15.

The commercially available product of the dimer acid type diamine (a1) is, for example, Versamine 551 (trade name, manufactured by Cognis Japan Co., Ltd.) and Primene 1074 (trade name, manufactured by Croda Japan Co., Ltd.). Dimerization The acid-type diamine (a1) also contains a compound obtained by hydrogenating a diamine obtained by a reductive amination reaction of a dimer acid, and as a commercial product, for example, Versamine 552 (trade name, manufactured by Cognis Japan Co., Ltd.) .

1.1.2 Other diamines (a2)

The details of the other diamine (a2) are described in "6. Examples of the compound" which will be described later.

1.1.3 Anhydride (a3)

The details of the acid anhydride (a3) are described in "6. Examples of the compound" which will be described later.

1.1.4 terminal crosslinker (T1)

The terminal crosslinking agent (T1) is represented by the formula (T1).

In the formula (T1), R ² is a divalent crosslinkable organic group having 2 to 100 carbon atoms, preferably a divalent organic group having 2 to 100 carbon atoms having a crosslinkable unsaturated bond, or A divalent organic group represented by the above formula (α).

Examples of the terminal crosslinking agent (T1) include maleic anhydride, citraconic anhydride, itaconic anhydride, allylic acid anhydride, 5-northene-2,3-dicarboxylic anhydride, and 4- Ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetra Hydrogen phthalic anhydride, allyl succinic anhydride, etc. a compound having a bond-unsaturated bond; p-(trimethoxyindenyl)phenylsuccinic anhydride, p-(triethoxyindenyl)phenylsuccinic anhydride, m-(trimethoxyindenyl)phenylsuccinic anhydride, m ( Triethoxyindenyl)phenylsuccinic anhydride, 3-(trimethoxyindenyl)propyl succinic anhydride, 3-(triethoxyindolyl)propyl succinic anhydride, etc. having the formula (α) A compound of a divalent organic group represented.

Among the terminal crosslinking agents (T1), maleic anhydride, citraconic anhydride, allyl-resistant anhydride, 5-northene are preferred from the viewpoint of excellent durability of the obtained film. -2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride and 3-(triethoxy) Mercapto) propyl succinic anhydride.

The terminal crosslinking agent (T1) may be used singly or in combination of two or more. From the viewpoint of uniformly controlling the crosslinking density, it is preferred to use only one type.

1.1.5 terminal crosslinker (T2)

The terminal crosslinking agent (T2) is represented by the formula (T2).

R ³ -NH ₂ (T2)

In the formula (T2), R ³ is a monovalent crosslinkable organic group having a carbon number of 2 to 100, preferably a monovalent organic group having a carbon number of 2 to 100 having a crosslinkable unsaturated bond, or A monovalent organic group represented by the above formula (β).

Examples of the terminal crosslinking agent (T2) include 4-ethynylaniline, 3-ethynylaniline, propargylamine, and 3-aminobutyne. 4-aminobutyne, 5-aminopentyne, 4-aminopentyne, allylamine, 7-aminoheptyne, m-aminostyrene, p-aminostyrene, m-amino-α a compound having a crosslinkable unsaturated bond such as methyl styrene, 3-aminophenylacetylene or 4-aminophenylacetylene; 3-aminopropyltrimethoxydecane, 3-aminopropyltri Ethoxy decane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyl Triethoxydecane, 4-aminobutylmethyldiethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxy矽 、, p-aminophenyl methyl diethoxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, m-aminophenyl dimethyl diethoxy decane, etc. A monovalent organic group compound represented by the formula (β).

Among the terminal crosslinking agents (T2), from the viewpoint of excellent durability of the obtained film, a compound having a crosslinkable unsaturated bond, 3-aminopropyltriethoxydecane, or the like, is preferred. 3-aminopropyltrimethoxydecane, more preferably 4-ethynylaniline, 3-ethynylaniline, m-aminostyrene, p-aminostyrene, 3-aminopropyltriethoxydecane, 3-Aminopropyltrimethoxydecane.

The terminal crosslinking agent (T2) may be used singly or in combination of two or more. From the viewpoint of uniformly controlling the crosslinking density, it is preferred to use only one type.

1.1.6 Synthesis conditions of proline (A)

Hereinafter, preferred synthesis conditions of the valine acid (A) will be described.

Synthesis of Proline (A1) and Proline (A2)

The proline (A1) and the proline (A2) can be synthesized, for example, by reacting one or two amine groups of the dimer acid type diamine (a1) with a terminal crosslinking agent (T1).

"Synthesis of Poly (A3)"

The polyaminic acid (A3) can be reacted with the terminal crosslinking agent (T1), for example, by reacting the diamine (a12) with the acid anhydride (a3), and/or The terminal acid anhydride group of the obtained reactant is reacted with a terminal crosslinking agent (T2) to synthesize.

For example, by reacting a diamine (a12) with an acid anhydride (a3), a constituent unit represented by the formula (A3-1) is formed, and a reaction of the terminal crosslinking agent (T1) with an amine group is formed. The molecular terminal group represented by the formula (T1') forms a terminal group of a molecule represented by the formula (T2') by a reaction of a terminal crosslinking agent (T2) with an acid anhydride group. The polyaminic acid (A3) has at least one of the above molecular terminal groups.

In the formula (A3-1), X is an organic group having a carbon number of 2 to 100, specifically, X is a residue of the acid anhydride (a3), and Y is a residue of a diamine (a12), wherein the constituent unit At least a portion of Y is a residue (-R ¹ -) of the dimer acid type diamine (a1).

In the formula (T1'), R ² is a divalent crosslinkable organic group having a carbon number of 2 to 100, and in the formula (T2'), R ³ is a monovalent crosslinkable organic having a carbon number of 2 to 100. base. The terminal group of the molecule represented by the formula (T1') is a residue of the terminal crosslinking agent (T1), and the terminal group of the molecule represented by the formula (T2') is a residue of the terminal crosslinking agent (T2).

The terminal group of the molecule represented by at least one selected from the above formula (T1') and the above formula (T2') is used as a terminal sealant of polyglycine, and thus is appropriately adjusted to be selected from a terminal crosslinking agent ( The amount of the terminal crosslinking agent used in at least one of T1) and the terminal crosslinking agent (T2) can be controlled so that the weight average molecular weight of the polyamic acid (A3) is 500 to 10,000.

For example, the polyamine acid (A3) is used to set the number of moles of the dimer acid type diamine (a1) used in the reaction to n1, the number of moles of the diamine (a12) to n2, and the acid anhydride (a3). When the number of moles is set to n3 and the number of moles of the terminal crosslinking agent (T1) is n4, it is preferable that each mole number becomes (1) 0.1 ≦ n1/n2 ≦ 1.0, and 2) The reaction molar ratio was adjusted in a manner of a relationship of 0.5 ≦ (n3 + 0.5 × n4) / n2 ≦ 1.3.

For example, the polyamine acid (A3) is used to set the number of moles of the dimer acid type diamine (a1) used in the reaction to n1, the number of moles of the diamine (a12) to n2, and the acid anhydride (a3). The number of moles is set to n3, and the terminal crosslinking agent (T2) When the number of moles is set to n5, it is preferable that each of the number of moles becomes (1') 0.1≦n1/n2≦1.0, and (2')0.3≦n3/(n2+0.5×n5)≦1.3 The way the relationship is adjusted is the response to the molar ratio.

By using polyglycine (A3) produced by the method of satisfying the formula (1) or the formula (1'), it is possible to obtain a polymer having excellent balance between heat resistance, adhesion, low dielectric constant and low water absorption.醯 imine film. When the ratio in the formula (2) is 0.5 or more, or the ratio in the formula (2') is 0.3 or more, the obtained polyimide film has improved alkali resistance and plating adhesion. By the above formula (2) and the formula (2'), the above ratio is 1.3 or less, and the solvent solubility of the obtained polylysine (A3) is improved.

Thus, by using polyamic acid (A3) which is manufactured in such a manner as to satisfy both the formula (1) and the formula (2) (or the formula (1') and the formula (2')), good insulation can be formed. Properties, low water absorption, good adhesion to copper plating, good resistance to alkaline aqueous solutions, and a balanced polyimide film.

Reaction solvent

Examples of the reaction solvent which can be used in the synthesis of the valine acid (A) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and B. Glycol monophenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether Acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, Diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol divinyl ether, three Propylene glycol monomethyl ether, tripropylene glycol dimethyl ether, butanediol monovinyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxane Heterocyclic pentane, 1,4-dioxane, anisole, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1 -ethyl-2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-ethylindenyl-2 - Pyrrolidone, N,N-diethylacetamide, N,N-dimethylpropionamide, Equamide (trade name) manufactured by Idemitsu Kosan Co., Ltd., N-methyl-ε-内Indoleamine, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone.

Among the reaction solvents, if selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ- At least one of the butyrolactones is preferably used as a reaction solvent to form an ink having less damage to the ink jet head.

These reaction solvents may be used alone or in combination of two or more. Further, in addition to the above reaction solvent, other solvents may be used in combination.

The amount of use of the reaction solvent is preferably 100 parts by mass or more, and more preferably 100 parts by mass to 600 parts by mass, per 100 parts by mass of the reaction raw material, from the viewpoint of the smooth progress of the reaction. The reaction conditions are preferably from 0 ° C to 100 ° C and the reaction time is from 0.2 to 20 hours. The reaction raw materials are the total amount of the diamine (a12), the acid anhydride (a3), the terminal crosslinking agent (T1), and the terminal crosslinking agent (T2).

"Additional order to the reaction system"

The order of addition of the reaction raw materials to the reaction system is not particularly limited.

For example, a method of simultaneously adding one or both terminal crosslinking agents of a diamine (a12), an acid anhydride (a3), and a terminal crosslinking agent (T1) and a terminal crosslinking agent (T2) to a reaction solvent can be mentioned; After the diamine (a12) and the acid anhydride (a3) are reacted in advance to synthesize a polymer, the polymer is subjected to one or both terminal crosslinking agents of the terminal crosslinking agent (T1) and the terminal crosslinking agent (T2). Method for reacting; after dissolving the diamine (a12) and the terminal crosslinking agent (T1) in the reaction solvent, adding an acid anhydride (a3) and an optional terminal crosslinking agent (T2); making the diamine (a12) After the terminal crosslinking agent (T2) is dissolved in the reaction solvent, a method of adding an acid anhydride (a3) and an optional terminal crosslinking agent (T1); and dissolving the acid anhydride (a3) and the terminal crosslinking agent (T2) in the reaction After the solvent, a method of adding a diamine (a12) and an optional terminal crosslinking agent (T1) is added.

1.2 Solvent (B)

The thermosetting ink composition of the present invention can be obtained, for example, by dissolving valeric acid (A) in a solvent (B). Therefore, the solvent (B) contained in the ink of the present invention is not particularly limited as long as it is a solvent capable of dissolving the lysine (A). Further, even a solvent which does not dissolve the lysine (A) when used alone can be used as the solvent (B) by mixing with other solvents.

Examples of the solvent (B) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, and ethylene glycol monomethyl. Ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single Dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Alcohol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol Monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, butanediol monovinyl ether, Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, anisole, benzoic acid Ester, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-(2-hydroxyethyl)- 2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-ethenyl-2-pyrrolidone, N,N-diethylacetamide, N,N- Equamide (trade name), N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazole, manufactured by dimethyl propyl amide, Idemitsu Kosan Co., Ltd. , Γ- butyrolactone.

Among the solvents (B), for example, from the viewpoint of improving the durability of the ink jet head, the ink composition of the present invention preferably contains a solvent selected from the group consisting of ethyl lactate, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. At least one of acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and γ-butyrolactone As solvent (B).

Further, among the solvents exemplified above, when the durability of the ink jet head is a problem, it is also preferable to reduce the use of the amide-based solvent. In this case, the content of the guanamine-based solvent is preferably 80% by mass or less, more preferably less than 60% by mass based on the total amount of the solvent (B).

Examples of the guanamine-based solvent include 1-vinyl-2-pyrrolidine. Ketone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, 2-pyrrolidone, N-methyl -2-pyrrolidone, 1-ethylindol-2-pyrrolidone, N,N-diethylacetamide, N,N-dimethylpropanamide, Equamide manufactured by Idemitsu Kosan Co., Ltd. (trade name), N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone.

The solvent (B) may be used alone or in combination of two or more.

The solvent (B) is preferably used in an amount of 15% by mass to 80% by mass, particularly 20% by mass to 80% by mass, based on the solid content of the ink of the present invention. In the present invention, the solid content concentration means the total concentration of all components other than the solvent (B). When the content of the solvent (B) is at least the above lower limit value, the viscosity of the ink does not become excessively large, and the ejection characteristics are excellent. When the content of the solvent (B) is at most the above upper limit value, the polyimide film formed by one shot can be prevented from becoming too thin. Thus, the ink of the present invention can be preferably used for ink jet applications.

1.3 additives

The thermosetting ink composition of the present invention may contain an additive in accordance with the intended properties. Examples of the additive include an epoxy resin, a polyimide resin, a polymerizable monomer, a surfactant, an antistatic agent, a coupling agent, an epoxy curing agent, a pH adjuster, a rust preventive, a preservative, and an anti-corrosion agent. A mold, an antioxidant, a reduction inhibitor, an evaporation promoter, a chelating agent, a water-soluble polymer, a pigment, or a dye. The additive may be used alone or in combination of two or more.

1.3.1 Epoxy resin

In the present invention, there will be more than one oxirane ring (oxirane) The compound of the ring or oxetane ring is called an epoxy resin. In the present invention, a compound having two or more oxirane rings can be preferably used as the epoxy resin.

The concentration of the epoxy resin in the ink of the present invention is not particularly limited, but is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass. If it is this concentration range, the heat resistance, chemical resistance, and flatness of the coating film formed from the ink of this invention are favorable.

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

Examples of the monomer having an oxirane ring include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate. .

Examples of other monomers copolymerizable with the monomer having an oxirane ring include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, styrene, methyl styrene, chloromethyl styrene, (meth)acrylic acid (3-ethyl-3-oxalate) Cyclobutyl)methyl ester, N-cyclohexylmethyleneimine, N-phenyl maleimide.

Preferred examples of the copolymer of a monomer having an oxirane ring and a copolymer of a monomer having an oxirane ring and another monomer may be listed. For example: polyglycidyl methacrylate, copolymer of methyl methacrylate and glycidyl methacrylate, copolymer of benzyl methacrylate and glycidyl methacrylate, n-butyl methacrylate and Copolymer of glycidyl acrylate, copolymer of 2-hydroxyethyl methacrylate and glycidyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate and methyl A copolymer of glycidyl acrylate, a copolymer of styrene and glycidyl methacrylate. When the ink of the present invention contains these epoxy resins, the heat resistance of the coating film formed of the ink is good, which is preferable.

Specific examples of the epoxy resin include epoxy resin "807", epoxy resin "815", epoxy resin "825", epoxy resin "827", epoxy resin "828", and epoxy resin. 190P", epoxy resin "191P", epoxy resin "1004", epoxy resin "1256" (above, Mitsubishi Chemical, and these epoxy resins were once used as Epikote (trade name) by Japan Epoxy Resins (sales) sales, the trade name "Araldite CY177", the trade name "Araldite CY184" (manufactured by BASF), the trade name "Celloxide2021P", "Celloxide3000", "EHPE-3150" (Daicel Chemical Industry Co., Ltd.), products "Techmore VG3101L" (manufactured by Mitsui Chemicals Co., Ltd.), N, N, N', N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylamine) Methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane. Among these, the product name "Araldite CY184", the trade name "Celloxide 2021P", the trade name "Techmore VG3101L", and the epoxy resin "828" are particularly excellent in the flatness of the obtained polyimide film. Preferably.

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

1.3.2 Polyimine resin

The polyimine resin is not particularly limited as long as it has a quinone imine group. Further, the polyimide resin may also contain a structure derived from a dimer acid.

The concentration of the polyimine resin in the ink of the present invention is not particularly limited, but is preferably 0.1% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass. If it is this concentration range, the coating film formed from the ink of this invention is favorable in the heat resistance, chemical resistance, and folding resistance.

The polyimine resin can be obtained, for example, by imidization of a proline which is obtained by reacting an acid dianhydride with a diamine. The acid dianhydride includes, for example, a compound having two acid anhydride groups which can be used in the synthetic acid anhydride (a3) of methionine (A). Examples of the diamine include a dimer acid type diamine (a1) and another diamine (a2) which can be used for the synthesis of amic acid (A).

The polyimine resin may be used alone or in combination of two or more.

1.3.3 Polymerizable monomer

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

The concentration of the polymerizable monomer in the ink of the present invention is not particularly limited, but is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass. the amount%. If it is this concentration range, the heat resistance, chemical resistance, and flatness of the coating film formed from the ink of this invention are favorable.

Examples of the monofunctional polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 4-cyclohexanedimethanol mono(meth)acrylate. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexane dimethanol monoacrylate are preferable from the viewpoint of making the formed film soft.

Examples of the monofunctional polymerizable monomer having no hydroxyl group include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and butyl (meth)acrylate. Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Anthracene ester, dicyclopentenyloxyethyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decyl methacrylate, glycerol mono(meth)acrylate, (meth)acrylic acid 5 - (tetra) decyloxycarbonyl pentyl ester, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, (A 3,4-epoxycyclohexyl acrylate, 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl) propylene oxime Oxymethyloxetane, 3-methyl-3-(methyl)propenyloxyethyloxetane, 3-ethyl-3-(methyl)propenyloxyethyl Oxetane, p-vinylphenyl-3-ethyloxetan-3-ylmethyl ether, 2-phenyl-3-( Acryloxymethyloxetane, 2-trifluoromethyl-3-(methyl)propenyloxymethyloxetane, 4-trifluoromethyl-2-(A) Acryloxymethyloxetane, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, Vinyl toluene, N-cyclohexylmethyleneimine, N-phenyl maleimide, (meth)acrylamide, N-propenylmorpholine, polystyrene Body, polymethyl methacrylate macromonomer, (meth)acrylic acid, crotonic acid, alpha-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, Sinocanic acid, ω-carboxypolycaprolactone mono(meth)acrylate, succinic acid mono[2-(methyl)propenyloxyethyl ester], maleic acid mono[2-(A Base) propylene methoxyethyl ester], cyclohexene-3,4-dicarboxylic acid mono[2-(methyl) propylene methoxyethyl ester].

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 diacrylate , trimethylolpropane diacrylate, dipentaerythritol diacrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate and ethylene oxide-modified trimethylolpropane tri(meth)acrylic acid. 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 modification Dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Lactone modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified tris(meth) acrylate, tris[(methyl) propylene oxyethyl]isocyanate, The lactone is modified with tris((meth)acryloxyethyl)isocyanate or (meth)acrylic acid urethane.

The polymerizable monomer may be used alone or in combination of two or more.

1.3.4 surfactant

The surfactant can be used to improve the wettability, leveling property, or coatability of the ink of the present invention with respect to the base substrate. In the ink of the present invention, the interface is preferably used in an amount of 0.01% by mass to 1% by mass. Active agent.

As a surfactant, the viewpoint of improving the coatability of the ink of the present invention includes, for example, the trade names "Byk-300", "Byk-306", "Byk-335", and "Byk-310". , "Byk-341", "Byk-344", "Byk-370" (BYK-Chemie (manufactured by the company)) and other surfactants; trade names "Byk-354", "ByK-358", "Byk -361" (acrylic surfactant such as BYK-Chemie); a fluorine-based surfactant such as "DFX-18", "Ftergent 250", "Ftergent 251" (manufactured by Neos).

The surfactant may be used alone or in combination of two or more.

1.3.5 Antistatic agent

The antistatic agent can be used to prevent the ink of the present invention from being charged. In the ink of the present invention, it is preferable to use antistatic in an amount of 0.01% by mass to 1% by mass. Electric agent.

As the antistatic agent, a 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; a quaternary ammonium salt.

The antistatic agent may be used alone or in combination of two or more.

1.3.6 coupling agent

The coupling agent is not particularly limited, and a known coupling agent such as a decane coupling agent can be used. In the ink of the present invention, the coupling agent is preferably used in an amount of from 0.01% by mass to 3% by mass.

Examples of the decane coupling agent include a trialkoxy decane compound and a dialkoxy decane compound. For example, preferred is γ-vinylpropyltrimethoxydecane, γ-vinylpropyltriethoxydecane, γ-acryloylpropylmethyldimethoxydecane, γ-acrylallylpropyltrimethyl Oxy decane, γ-propylene propyl propyl methyl diethoxy decane, γ-propylene decyl propyl triethoxy decane, γ-methyl propylene propyl propyl methyl dimethoxy decane, γ -Methacrylylmercaptopropyltrimethoxydecane, γ-methylpropenylpropylmethyldiethoxydecane, γ-methylpropenylpropyltriethoxydecane, γ-glycidyloxy Propyl propyl dimethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl methyl diethoxy decane, γ-glycidoxy propyl triethyl Oxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltri Ethoxy decane, N-aminoethyl-γ-iminopropylmethyldimethoxydecane, N-aminoethyl-γ-aminopropyltrimethoxydecane, N-amino B --γ-aminopropyl diethoxy decane, N -phenyl-γ-amino group Propyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropylmethyldimethoxydecane, N-phenyl-γ- Aminopropylmethyldiethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-mercaptopropylmethyldiethoxydecane, γ - mercaptopropyltriethoxydecane, gamma-isocyanatopropylmethyldiethoxydecane, gamma-isocyanatopropyltriethoxydecane.

Among them, particularly preferred are γ-vinylpropyltrimethoxydecane, γ-acrylonitrilepropyltrimethoxydecane, γ-methylpropenylpropyltrimethoxydecane, and γ-isocyanate. Propyltriethoxydecane.

The coupling agent may be used alone or in combination of two or more.

1.3.7 epoxy hardener

The epoxy curing agent is not particularly limited, and a known epoxy curing agent can be used. In the ink of the present invention, it is preferred to use an epoxy curing agent in an amount of 0.2% by mass to 5% by mass.

Examples of the epoxy curing agent include diterpene compounds of organic acids, imidazoles and derivatives thereof, dicyandiamides, aromatic amines, polycarboxylic acids, and polycarboxylic anhydrides. More specifically, an organic acid diterpene compound such as diammonium adipate or 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin; 2,4-di Amino-6-[2'-ethylimidazolyl-(1')]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl An imidazole derivative such as 5-hydroxymethylimidazole; a dicyandiamide such as dicyanodiamide; a polycarboxylic acid such as trimellitic acid; phthalic anhydride, trimellitic anhydride, 1, 2, A polycarboxylic acid anhydride such as 4-cyclohexanetricarboxylic acid-1,2-anhydride. Among these, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are preferred.

The epoxy curing agent may be used alone or in combination of two or more.

1.3.8 pigments, or dyes

Examples of the pigment include a group selected from the group consisting of boron nitride, aluminum nitride, tantalum carbide, aluminum oxide, magnesium oxide, cerium oxide, rutile titanium oxide, zinc oxide, low-valent titanium oxide, and graphite. One or more. The rutile-type titanium oxide means white titanium oxide represented by TiO ₂ . The low-valent titanium oxide refers to black titanium oxide such as Ti ₃ O ₅ , Ti ₂ O ₃ or TiO. For example, a commercially available product of low-priced titanium oxide (black) which is known as titanium black is Tilack D (trade name) manufactured by Ako Chemical Co., Ltd. Examples of the dye include an azo dye, a methylimine dye, a dibenzopyran dye, and an anthraquinone dye.

1.4 Physical properties of the thermosetting ink composition of the present invention

The thermosetting ink composition of the present invention has good storage stability under normal temperature storage. Further, by using the ink, a polyimide film having a low water absorption property, a good insulating property, chemical resistance, and substrate adhesion can be formed and balanced.

In particular, in the present invention, the high concentration of the solid content concentration of 15% by mass or more and the low viscosity suitable for inkjet printing can be coherent, so that the discharge stability of the ink is improved, and the obtained coating film can be enlarged. Film thickness. The ink of the present invention having such characteristics is particularly suitable for use as an ink for inkjet.

1.4.1 Viscosity

When the thermosetting ink composition of the present invention is used for ink jet applications, the viscosity of the ink composition at 25 ° C, 20 rpm is usually 1 mPa. s~50mPa. s, preferably 5 mPa. s~30mPa. s, more preferably 5mPa. s~20mPa. s, and more preferably 8mPa. s~20mPa. s. If the viscosity is 25 ° C Within the above range, the ejection accuracy of the inkjet coating method is improved. When the viscosity at 25 ° C is at most the above upper limit value, inkjet ejection failure is less likely to occur.

When the inkjet head is heated and then sprayed, the viscosity of the ink composition at a heating temperature (discharge temperature; preferably 30 ° C to 120 ° C) at 20 rpm is usually 1 mPa. s~50mPa. s, preferably 5 mPa. s~30mPa. s, more preferably 8mPa. s~20mPa. s, and more preferably 5mPa. s~15mPa. s. If the viscosity is within the above range, the ejection accuracy of the inkjet coating method is improved. When the viscosity is at most the above upper limit value, inkjet ejection failure is less likely to occur.

Further, the viscosity was measured using an E-type viscometer.

1.4.2 Surface tension

The surface tension of the thermosetting ink composition of the present invention at 25 ° C is usually from 20 mN/m to 70 mN/m, preferably from 20 mN/m to 40 mN/m. If the surface tension is within the above range, good droplets can be formed by spraying, and a meniscus can be formed.

2. Method for applying ink and method for producing polyimine film

The method of applying the ink of the present invention comprises: (1) a step of applying the ink of the present invention onto a substrate by an inkjet coating method to form a coating film (coating film forming step), and (2) performing the coating film. The step of hardening treatment (hardening treatment step). The method for producing a polyimide film of the present invention is a method for forming a polyimide film using the above coating method.

When the inkjet ink is printed in a pattern (for example, a linear shape or a square shape), a patterned polyimide film is formed. In this specification, as long as Unless otherwise specified, the polyimide film contains a patterned polyimide film.

2.1 coating film formation steps

As the inkjet coating method, there are various types depending on the method of discharging the ink. Examples of the discharge method include a piezoelectric element type, a foam jet (registered trademark) type, a continuous ejection type, and an electrostatic induction type.

A preferred method of ejecting when applying the ink of the present invention is a piezoelectric element type. The piezoelectric element type inkjet head is a drop-on-demand inkjet coating head including a nozzle forming substrate having a plurality of nozzles, and a pressure comprising a piezoelectric material and a conductive material disposed opposite to the nozzle The generating element and the ink filling the periphery of the pressure generating element are displaced by applying a voltage to cause small droplets of ink to be ejected from the nozzle.

The inkjet coating device is not limited to a configuration in which the coating head is separated from the ink containing portion, and a configuration in which the coating head and the ink containing portion cannot be separated from each other can be used. Further, the ink accommodating portion is integrated with the ink jet head so as to be separable or inseparable, and may be mounted on the holder, or may be provided at a fixed portion of the device, and may be supplied to the device via an ink supply member, for example, a tube. The form in which the coating head supplies ink.

Further, when a configuration for allowing a preferable negative pressure to act on the coating head is provided in the ink cartridge, an embodiment in which the absorber is disposed in the ink containing portion of the ink cartridge or a flexible ink housing bag may be employed. And a biasing force in a direction in which the internal volume of the ink containing bag is expanded is applied to the form of the spring portion of the coating head. In addition to the continuous coating method, the coating device may also employ a coating member over a range corresponding to the total width of the coating medium. A device in the form of a line printer.

Further, when the viscosity of the ink of the present invention is high, the ink jet head may be heated at preferably 30 ° C to 80 ° C to heat the ink to lower the viscosity of the ink, and then apply the coating.

The ink of the present invention is applied onto a substrate by an inkjet coating method, and then dried (solvent removal) by a hot plate or an oven to form a coating film. By the above drying, a coating film which can maintain the shape is formed on the substrate.

The drying conditions vary depending on the type of the ink-containing components and the blending ratio. When an oven is used, it is usually dried at 70 ° C to 120 ° C for 5 minutes to 15 minutes. When a hot plate is used, it is usually dried at 70 ° C to 120 ° C. 1 minute to 15 minutes.

2.2 hardening treatment steps

In order to obtain heat resistance, chemical resistance, and flatness of the coating film, and to obtain sufficient mechanical strength, the curing treatment is performed by, for example, a hot plate or an oven, thereby forming a full-surface polyimide film or a predetermined one. A polyimine film having a pattern (for example, a linear shape or a square shape).

The hardening treatment is carried out usually at 180 ° C to 350 ° C, preferably 200 ° C to 300 ° C. The hardening treatment time (heating time) is, for example, 30 minutes to 90 minutes in the case of using an oven, and 5 minutes to 30 minutes in the case of using a hot plate. Further, the curing treatment is not limited to the heat treatment, and may be an ultraviolet (Ultraviolet) treatment or an irradiation such as an ion beam, an electron beam, or a gamma ray. A polyimide film was formed in the above manner.

When a patterned polyimide film is produced, in the present invention, a spray is used. Ink printing only ejects (depicts) ink to a desired portion, so the amount of material used is absolutely small compared to other methods such as etching in photolithography used to form a polyimide film, and there is no need to use a mask. . Therefore, in the present invention, mass production of a plurality of types of polyimide membranes can be realized, and the number of steps required for production can be reduced.

3. Polyimine film

The polyimide film of the present invention is obtained from the above thermosetting ink composition. For example, after the thermosetting ink composition of the present invention is applied onto a substrate by an inkjet coating method to form a coating film, the coating film is subjected to a curing treatment to obtain a polyimide film of the present invention.

In the ink of the present invention, the solid content concentration can be set as high as described above. Therefore, in the present invention, a polyimide film having a thickness of usually 2 μm or more, preferably 2 μm to 10 μm, which is obtained from a previous ink, can be obtained by one-time ink jetting. The film thickness of the amine film is large. For example, when a thick insulating film of about 10 μm is formed, by using the ink of the present invention, the number of times of repeated coating can be reduced as compared with the prior ink, and the manufacturing process of the insulating film can be shortened.

The insulating film containing the polyimide film of the present invention has low water absorbability, for example, and exhibits good adhesion to a substrate in a printed wiring board application (particularly, a flexible wiring board use), and exhibits good resistance to chemicals. It has high heat resistance and electrical insulation, has sufficient mechanical strength, and can improve the reliability or yield of electronic parts.

4. Film substrate

The film substrate of the present invention includes a film and the above-described film formed on the film Polyimine film. The film substrate can be produced, for example, by forming a polyimide film on a film (for example, a polyimide film) on which a wiring is formed according to the method for producing a polyimide film.

The polyimide film of the present invention is preferably formed on a film such as a polyimide film, but is not particularly limited thereto and can be formed on a known substrate.

Examples of the substrate that can be applied to the present invention include glass epoxy substrates, glass composite substrates, and phenolic paper substrates suitable for various specifications such as FR-1, FR-3, FR-4, CEM-3, and E668. An epoxy paper substrate, a green epoxy substrate, and a Bismaleimide Triazine (BT) resin substrate.

Examples of other substrates that can be applied to the present invention include substrates including metals such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, and stainless steel. Some metal substrates); alumina, aluminum nitride, zirconia, zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate, titanic acid Lead (PT), lead zirconate titanate (PZT), lead zirconate titanate (PLZT), lithium niobate, lithium niobate, cadmium sulfide, molybdenum sulfide, beryllium strontium, cerium oxide (cerium oxide) ), silicon carbide, silicon nitride, boron nitride, zinc oxide, mullite, ferrite, stataite, magnesium a ceramic substrate such as forsterite, spinel or spodumene (may also be a substrate having such ceramics on the surface); comprising PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (poly(1,4-cyclohexanedimethylene terephthalate)) Resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyether sulfimine a substrate of a resin such as a resin, a polyimide, an epoxy resin, an acrylic resin, a Teflon (registered trademark), a thermoplastic elastomer, or a liquid crystal polymer (may also be a substrate having such a resin on the surface); a semiconductor substrate such as bismuth or gallium arsenide; a glass substrate; a substrate on which an electrode material such as tin oxide, zinc oxide, ITO (indium tin oxide) or ATO (yttrium tin oxide) is formed; αGEL (α gel), βGEL ( A gel sheet such as β gel), θGEL (θ gel), or γGEL (γ gel) (above, registered trademark of Taica Co., Ltd.).

5. Electronic parts

The electronic component of the present invention is an electronic component having the above film substrate. Thus, with the film substrate of the present invention, a flexible electronic component can be obtained. As an example of the usage of the present invention, an insulating film for flexible wiring and an electronic component using the same can be cited.

6. An illustration of a compound

Hereinafter, other diamines (a2) and acid anhydrides (a3) which can be used for the synthesis of arginine (A) in the present invention will also be described in detail with reference to preferred examples.

6.1 Other diamines (a2)

The other diamine (a2) is not particularly limited as long as it has two amine groups and the diamine derived from the dimer acid is removed, and examples thereof include m-xylylenediamine and p-xylylenediamine. , 2,5-diaminomethylbicyclo[2.2.1]heptane, 2,6-diaminomethylbicyclo[2.2.1]heptane, from formula (I) to formula (VII) The compound represented by the formula and the compound represented by the formula (i) to the formula (iii).

H ₂ NA ¹ -NH ₂ (I)

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

In formula (III), formula (V) and formula (VII), A ² is a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -NHCO- , -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _n -, -O-(CH ₂ ) _n -O- or -S-(CH ₂ ) _n -S- Here, n is an integer from 1 to 6.

In the formulae (VI) and (VII), two of A ³ are independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ). ₂ - or an alkylene group having a carbon number of 1 to 3.

In the formulae (I) to (VII), at least one hydrogen possessed by the cyclohexane ring or the benzene ring may be substituted with at least one selected from the group consisting of -F and -CH ₃ .

In the formula (i), n is an integer of 1 to 50. As a commercial item of the compound represented by the formula (i), for example, Jeffamine D-230 (trade name, manufactured by Huntsman Co., Ltd.) and Jeffamine D-400 (trade name, manufactured by Huntsman Co., Ltd.) as a mixture of these compounds are mentioned. .

In the formula (ii), Y is an integer of 1 to 40, and X + Z is an integer of 1 to 6. As a commercial item of the compound represented by the formula (ii), for example, Jeffamine HK-511 (trade name, manufactured by Huntsman Co., Ltd.) and Jeffamine ED-600 (trade name, manufactured by Huntsman Co., Ltd.) are used as a mixture of these compounds. , Jeffamine ED-900 (trade name, manufactured by Huntsman Co., Ltd.), Jeffamine ED-2003 (trade name, manufactured by Huntsman Co., Ltd.).

In the formula (iii), n is an integer of 1 to 10, and X is an integer of 1 to 10. As a commercial item of the compound represented by the formula (iii), for example, Jeffamine EDR-148 (trade name, manufactured by Huntsman Co., Ltd.), Jeffamine EDR-176 (trade name, manufactured by Huntsman Co., Ltd.), n is 2 and X is exemplified. Diethylene glycol bis(3-aminopropyl)ether (manufactured by Aldrich Co., Ltd.) of 3.

The compound represented by the formula (I) includes, for example, a compound represented by the formula (I-1) to the formula (I-3). The compound represented by the formula (II) includes, for example, a compound represented by the formula (II-1) to the formula (II-2). The compound represented by the formula (III) includes, for example, a compound represented by the formula (III-1) to the formula (III-3). The compound represented by the formula (IV) is, for example, a compound represented by the formula (IV-1) to the formula (IV-5). Examples of the compound represented by the formula (V) include compounds represented by the formula (V-1) to the formula (V-30). The compound represented by the formula (VI) includes, for example, a compound represented by the formula (VI-1) to the formula (VI-6). The compound represented by the formula (VII) includes, for example, a compound represented by the formula (VII-1) to the formula (VII-12).

Among other diamines (a2), preferred are 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-Diaminodiphenylphosphonium, bis[3-(4-aminophenoxy)phenyl]anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, Phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-amino group Phenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4 -aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-methylcyclohexane, 1,1-bis[4-( 4-aminobenzyl)phenyl]methane, 2,5-diaminomethylbicyclo[2.2.1]heptane, 2,6-diaminomethylbicyclo[2.2.1]heptane.

As the other diamine (a2), a compound represented by the formula (VIII) can also be mentioned.

In the formula (VIII), A ⁴ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -(CH ₂ ) _p -, -(CH ₂ ) _p -O- or -O-(CH ₂ ) _p -, where p is an integer from 1 to 6. R ¹⁰ is a group having a steroid skeleton or a group having at least one ring structure selected from a cyclohexane ring and a benzene ring; wherein, when the positional relationship of the two amine groups bonded to the benzene ring is a para position When R ¹⁰ is an alkyl group having 1 to 30 carbon atoms, when the above positional relationship is meta, R ¹⁰ may be an alkyl group having 1 to 30 carbon atoms or a phenyl group.

The alkyl group having 1 to 30 carbon atoms in R ¹⁰ may be linear or branched. At least one -CH ₂ - of the alkyl groups may be substituted with at least one selected from the group consisting of -CF ₂ -, -CHF-, -O-, -CH=CH-, and -C≡C-, the alkyl groups At least one -CH ₃ may be substituted with at least one selected from the group consisting of -CH ₂ F, -CHF ₂ and -CF ₃ .

The hydrogen bonded to the ring-forming carbon of the above phenyl group in R ¹⁰ may be substituted with at least one selected from the group consisting of -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ and -OCF ₃ .

In the formula (VIII), two amine groups are bonded to the benzene ring carbon, but the bonding position relationship of the two amine groups is preferably a meta or para position. Further, when the bonding position of "R ¹⁰ -A ⁴ -" to the benzene ring is set to 1 position, the two amine groups are preferably bonded to the 3 position and the 5 position, or the 2 position and the 5 position, respectively.

The compound represented by the formula (VIII) includes, for example, a compound represented by the formula (VIII-1) to the formula (VIII-11).

In the formula (VIII-1), the formula (VIII-2), the formula (VIII-7) and the formula (VIII-8), R ¹¹ is an organic group having a carbon number of 1 to 30, preferably a carbon number of 3 to 3. The alkyl group of 12 or an alkoxy group having 3 to 12 carbon atoms is more preferably an alkyl group having 5 to 12 carbon atoms or an alkoxy group having 5 to 12 carbon atoms.

In the formula (VIII-3) to the formula (VIII-6) and the formula (VIII-9) to the formula (VIII-11), R ¹² is an organic group having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms. The alkyl group of 10 or the alkoxy group having 1 to 10 carbon atoms is more preferably an alkyl group having 3 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms.

The compound represented by the formula (VIII) may, for example, be a compound represented by the formula (VIII-12) to the formula (VIII-17).

In the formula (VIII-12) to the formula (VIII-15), R ¹³ is an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, more preferably 6 to 16 carbon atoms. Alkyl.

In the formula (VIII-16) and the formula (VIII-17), R ¹⁴ is an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably 8 to 20 carbon atoms. Alkyl.

The compound represented by the formula (VIII) may, for example, be a compound represented by the formula (VIII-18) to the formula (VIII-38).

Formula (VIII-18), Formula (VIII-19), Formula (VIII-22), Formula (VIII-24), Formula (VIII-25), Formula (VIII-28), Formula (VIII-30), Formula In (VIII-31), formula (VIII-36) and formula (VIII-37), R ¹⁵ is an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms or a carbon number of The alkoxy group of 1 to 12 is more preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms.

Formula (VIII-20), Formula (VIII-21), Formula (VIII-23), Formula (VIII-26), Formula (VIII-27), Formula (VIII-29), Formula (VIII-32)~ In (VIII-35) and (VIII-38), R ¹⁶ is hydrogen, -F, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, -CN, -OCH ₂ F And -OCHF ₂ or -OCF ₃ , preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms.

In the formula (VIII-33) and the formula (VIII-34), A ⁵ is an alkylene group having 1 to 12 carbon atoms.

The compound represented by the formula (VIII) may, for example, be a compound represented by the formula (VIII-39) to the formula (VIII-48).

Among the compounds represented by the formula (VIII), a compound represented by the formula (VIII-1) to the formula (VIII-11) is preferred, and more preferably a compound of the formula (VIII-2) or the formula (VIII-4). a compound represented by the formula (VIII-5) and the formula (VIII-6).

Examples of the other diamine (a2) include compounds represented by the formulae (IX) to (X).

In the formulae (IX) and (X), R ¹⁷ is hydrogen or -CH ₃ , and two of R ¹⁸ are independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. There are two A ⁶ which are each independently a single bond, -C(=O)- or -CH ₂ -. In the formula (X), R ¹⁹ and R ²⁰ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms or a phenyl group.

In the formula (IX), two "NH ₂ -Ph-A ⁶ -O-" (-Ph- represents a phenylene group) bonded to the B ring of the steroid nucleus is preferably a bond to the steroid nucleus 3 In the bit, the other key is connected to 6 bits. Further, the two amine groups are bonded to the benzene ring carbon, respectively, but are preferably bonded to the meta or para position relative to the bonding position of A ⁶ on the benzene ring.

In formula (X), two "NH ₂ -(R ²⁰ -)Ph-A ⁶ -O-" (-Ph- represents a phenylene group) are bonded to the benzene ring carbon, respectively, but when considering the steroid core and When NH ₂ -(R ²⁰ -)Ph-A ⁶ -O-" is bonded to the benzene ring, the positional relationship between the steroid nucleus and "NH ₂ -(R ²⁰ -)Ph-A ⁶ -O-" is preferred. For the meta or alignment. Further, the two amine groups are bonded to the benzene ring carbon, respectively, but are preferably bonded to the meta or para position with respect to A ⁶ .

Examples of the compound represented by the formula (IX) include a formula (IX-1)~ A compound represented by the formula (IX-4).

The compound represented by the formula (X) includes, for example, a compound represented by the formula (X-1) to the formula (X-8).

Examples of the other diamine (a2) include a compound represented by the formula (XI) and a compound represented by the formula (XII).

In the formula (XI), R ²¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one of -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-. There are two A ⁷ independently of -O- or an alkylene group having a carbon number of 1 to 6, and A ⁸ is a single bond or an alkylene group having a carbon number of 1 to 3, and the ring T is a 1,4-stretch. Phenyl or 1,4-cyclohexylene, h is 0 or 1.

In the formula (XII), R ²² is an alkyl group having 2 to 30 carbon atoms, and among these, an alkyl group having 6 to 20 carbon atoms is preferable. R ²³ is hydrogen or an alkyl group having 1 to 30 carbon atoms, and among these, an alkyl group having 1 to 10 carbon atoms is preferred. There are two A ⁹ groups independently of -O- or an alkylene group having a carbon number of 1 to 6.

In the formula (XI), two amine groups are bonded to the benzene ring carbon, respectively, but it is preferably bonded to the meta or para position with respect to A ⁷ . Further, in the formula (XII), two amine groups are bonded to the benzene ring carbon, respectively, but it is preferably bonded to the meta or para position with respect to A ⁹ .

Examples of the compound represented by the formula (XI) include 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane and 1,1-bis[4-(4- Aminophenoxy)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-( A compound represented by the formula (XI-1) to the formula (XI-9), such as 4-aminobenzyl)phenyl]-4-methylcyclohexane.

In the formula (XI-1) to the formula (XI-3), R ²⁴ is hydrogen or an alkyl group having 1 to 20 carbon atoms.

In the formula (XI-4) to the formula (XI-9), R ²⁵ is hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably hydrogen or an alkyl group having 1 to 10 carbon atoms.

The compound represented by the formula (XII) includes, for example, a compound represented by the formula (XII-1) to the formula (XII-3).

In the formula (XII-1) to the formula (XII-3), R ²⁶ is an alkyl group having 2 to 30 carbon atoms, and among these, an alkyl group having 6 to 20 carbon atoms is preferable, and R ²⁷ is hydrogen. Or an alkyl group having 1 to 30 carbon atoms, and among these, hydrogen or an alkyl group having 1 to 10 carbon atoms is preferred.

As described above, as the other diamine (a2), for example, m-xylylenediamine, p-xylylenediamine, 2,5-diaminomethylbicyclo[2.2.1]heptane, 2,6 can be used. - bisaminomethylbicyclo[2.2.1]heptane, which is represented by the above formula (I) to formula (XII) At least one of the compound represented by the above formula (i) and formula (iii) may be used, but a diamine other than these compounds may also be used. For example, a naphthalene-based diamine having a naphthalene structure, an anthracene-based diamine having a fluorene structure, a decane-based diamine having a decane bond, or the like may be used alone or in combination with the above formula (I) to formula (XII). The compound represented by the above-mentioned diamine is used in combination.

The oxirane-based diamine is, for example, a compound represented by the formula (XIII).

In the formula (XIII), R ²⁸ and R ²⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ³⁰ is a methylene group, a phenyl group or at least one hydrogen group having a carbon number of 1 to 10. The alkyl-substituted phenyl group, 2 x are each independently an integer of 1 to 6, and y is an integer of 1 to 70. High transparency is required depending on the use of the thermosetting ink composition. In this case, y is particularly preferably an integer of 1 to 15. A plurality of R ²⁸ , R ²⁹ and R ³⁰ may be the same or different from each other.

Examples of the oxime diamine include 9,9-bis(3-aminopropyl)anthracene and 9,9-bis(4-aminophenyl)anthracene.

Examples of the other diamine (a2) include compounds represented by the formulae (11) to (18).

In the formulae (11) to (18), R ³¹ and R ³² each independently represent an alkyl group having 3 to 20 carbon atoms.

The other diamine (a2) which can be used for synthesizing the valine acid (A) is not limited to the above-exemplified diamine, and other various forms of diamine can be used within the scope of achieving the object of the present invention.

The other diamine (a2) which can be used for the synthesis of the valine acid (A) may be used alone or in combination of two or more. In other words, the diamines exemplified above, the diamines other than the above-exemplified diamines, and the diamines other than the above-exemplified diamines may be mentioned. In particular, it is preferably selected from the group consisting of m-xylylenediamine, p-xylylenediamine, 2,5-diaminomethylbicyclo[2.2.1]heptane, and 2,6-diaminomethylbicyclo[2.2. 1] heptane, a compound represented by formula (I) to formula (VII), a compound represented by formula (VIII), and formula (i) At least one of the compound represented, the oxane-based diamine, and the quinone-based diamine.

6.2 Anhydride (a3)

Examples of the acid anhydride (a3) include a tetracarboxylic dianhydride; a copolymer of maleic anhydride and styrene; a copolymer of maleic anhydride and methyl methacrylate; and a radical polymerization having an acid anhydride group. A copolymer of a monomer and another radical polymerizable monomer.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, and 2,2',3,3'-diphenyl. Ketotetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (DSDA) , 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-dihydroxyphenyl Bis-trimellitic dianhydride (BPS-TME), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 2,2',3,3'-diphenyl ether Carboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2-[double (3,4-dicarboxyphenyl)]hexafluoropropane dianhydride (6FDA), ethylene glycol bis(hydroper trimellitate), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic acid Dihydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,3-two Hydrogen-1,3-di-oxo-5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]di-4,1-phenylene Ester, 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride (TMBPA), 1,3-dihydro-1,3 -two Sideoxy-5-isobenzofurancarboxylic acid oxydi-4-,1-phenylene ester, p-phenylene bis(trimellitic acid monoester anhydride) (TMHQ), 4-(2,5-di Side oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3, 3',4,4'-double ring Tetracarboxylic dianhydride (BPDA-H), bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-di-tertiary tetrahydrofuranyl -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4,4'-[(isopropylidene)bis(p-phenoxy)diphthalic dianhydride ( BSAA), ethylenediaminetetraacetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and are represented by the following formula 1-1 to formula 1-57 The compound represented.

By using the tetracarboxylic dianhydride in the above specific examples, pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4, 4' - diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2-[Bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, cyclobutane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane Alkane tetracarboxylic dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Bicyclohexyltetracarboxylic dianhydride, 4,4'-[(isopropylidene)bis(p-phenoxy)diphthalic dianhydride, BPS-TME, TMBPA, OPPBP-TME, The methionine (A) having a high solubility in the solvent (B) is preferred because it can prepare a high concentration of ink.

Further, high transparency is required depending on the use of the ink for inkjet, and in this case, a copolymer of maleic anhydride and styrene, 3,3',4,4'-diphenyl ketone is particularly preferred. Tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[ Bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, cyclobutane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 4,4'-[(isopropylidene) bis ( P-phenoxy)]diphthalic dianhydride, BPS-TME, TMBPA, OPPBP-TME.

The acid anhydride (a3) may be used alone or in combination of two or more.

[Example]

Hereinafter, the present invention will be described by way of examples and comparative examples, but the invention is not limited to the examples. The dimer acid type diamine (a1), other diamine (a2), acid anhydride (a3), and terminal used in the examples and the comparative examples are indicated by the abbreviations. The names of the crosslinking agent (T1), the terminal crosslinking agent (T2), and the solvent (B). This abbreviation is used in the following description.

Dimer acid diamine (a1)

P-1074: Primene 1074 (trade name, manufactured by Croda Japan (stock))

Other diamines (a2)

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

BAPS-M: bis[3-(4-aminophenoxy)phenyl]indole

BAPPF: 9,9-bis(3-aminopropyl)indole (Compound 1 below)

BAPF: 9,9-bis(4-aminophenyl)anthracene (Compound 2 below)

D-400: Jeffamine D-400 (product name, manufactured by Huntsman) (Compound 3 below)

Where n is a mixture of 6.1 on average

NBDA: a mixture of 2,5-diaminomethylbicyclo[2.2.1]heptane and 2,6-diaminomethylbicyclo[2.2.1]heptane (Compound 4 below)

3o2o2o3DA: diethylene glycol bis(3-aminopropyl) ether

DDE: 4,4'-diaminodiphenyl ether

DA8: 1,8-diaminooctane

DA12: 1,12-diaminododecane

Anhydride (a3)

BSAA: 4,4'-[(isopropylidene) bis(p-phenoxy)diphthalic dianhydride

BPS-TME: 4,4'-dihydroxyphenyl hydrazine trimellitic acid dianhydride (Compound 5 below)

TMHQ: p-phenylene bis(trimellitic acid monoester anhydride) (compound 6 below)

TMBPA: 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride (Compound 7 below)

DSDA: 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride

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

OPPBP-TME: the following compound 8

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

BPDA-H: 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride

Terminal crosslinker (T1)

MA: maleic anhydride

TESA: 3-(triethoxyindenyl)propyl succinic anhydride

ANA: allylic acid anhydride

4-EPA: 4-phenylethynyl phthalic anhydride

Terminal crosslinker (T2)

APSE: 3-Aminopropyltriethoxydecane

Solvent (B) (reaction solvent)

EDM: diethylene glycol methyl ethyl ether

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

[Measurement of physical properties]

The viscosity of the thermosetting ink composition (solution) at 25 ° C and 20 rpm was measured using an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI).

The weight average molecular weight of the proline (A) can be determined by using the N,N-dimethylformamide (DMF) to obtain the proline (A) concentration of the proline (A). Diluted to about 1% by mass to form a diluent, and then used a GPC apparatus: JASCO GULLIVER 1500 (Smart Differential Refractive Index RI-1530) manufactured by JASCO Corporation (share), using the above diluent as a developing solvent and The GPC method was used to measure and then converted to polystyrene. The column is connected by using two columns (GF-510HQ, GF-310HQ) manufactured by Showa Denko (share) in this order, and is carried out under the conditions of a column temperature of 40 ° C and a flow rate of 0.5 ml/min. Determination.

[Example 1]

Addition of EDM as solvent (B) to a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet port 31.50 g, NMP 31.50 g, as a dimer acid type diamine (a1), P-1074, 27.12 g, and then, while stirring under a dry nitrogen gas stream, added 9.88 g of MA as a terminal crosslinking agent (T1), and Stir at 40 ° C for 5 hours. As a result, a 37% by mass solution (ink) of pale yellow transparent proline (A) was obtained. The viscosity of the ink is 14.8mPa. s (25 ° C), the weight average molecular weight of the proline (A) was 800.

[Example 2]

To a 300-ml four-necked flask equipped with a thermometer, a stirrer, a raw material supply port, and a nitrogen gas inlet, 39.50 g of EDM as a solvent (B) and 39.50 g of NMP were added as a P-dimer acid diamine (a1). 1074 12.60 g, then 2.30 g of MA as a terminal crosslinking agent (T1) was added while stirring under a stream of dry nitrogen gas, and stirred at 40 ° C for 1 hour. Then, 6.10 g of BSAA as an acid anhydride (a3) was added thereto, and stirred at 40 ° C for 5 hours. As a result, a 21% by mass solution (ink) of yellow transparent lysine (A) was obtained. The viscosity of the ink is 16.1mPa. The weight average molecular weight of the proline (A) was 6,000 at s (25 ° C).

[Example 3 to Example 5, Example 7 to Example 10]

In Example 2, the raw materials were added as shown in Table 1, except for the same input sequence as in Example 2. A solution (ink) of valine acid (A) was prepared under the reaction conditions, and the weight average molecular weight of the obtained valine acid (A) and the viscosity of the ink at 25 ° C were measured.

[Example 6]

Addition of EDM as solvent (B) to a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet port 41.50 g, NMP 41.50 g, as P-1274 9.99 g of the dimer acid type diamine (a1), and then stirred with a dry nitrogen gas stream, and added 1.66 g of MA as a terminal crosslinking agent (T1), and Stir at 40 ° C for 1 hour. Then, 3.03 g of BPS-TME and 2.32 g of TMHQ as an acid anhydride (a3) were simultaneously added thereto, and stirred at 40 ° C for 5 hours. As a result, a 17% by mass solution (ink) of yellow transparent lysine (A) was obtained. The viscosity of the ink is 14.0mPa. The weight average molecular weight of the proline (A) was 7,500 at s (25 ° C).

[Example 11]

To a 300-ml four-necked flask equipped with a thermometer, a stirrer, a raw material supply port, and a nitrogen gas inlet, 39.00 g of EDM as a solvent (B) and 39.00 g of NMP were added as a P-dimer acid diamine (a1). 1074 7.28 g, 3.71 g of BAPP as the other diamine (a2), and then stirred under a dry nitrogen gas stream, while adding 2.21 g of MA as a terminal crosslinking agent (T1), and stirring at 40 ° C for 1 hour. Then, 8.80 g of BSAA as an acid anhydride (a3) was added thereto, and stirred at 40 ° C for 5 hours. As a result, a 22% by mass solution (ink) of yellow transparent proline (A) was obtained. The viscosity of the ink is 14.5mPa. s (25 ° C), the weight average molecular weight of the proline (A) was 5,000.

[Example 12 to Example 17, Example 21 to Example 23]

In Example 11, the materials were added as shown in Table 2, except that in the same order as in Example 11. A solution (ink) of valine acid (A) was prepared under the reaction conditions, and the weight average molecular weight of the obtained valine acid (A) and the viscosity of the ink at 25 ° C were measured.

[Example 18]

To a 300-ml four-necked flask equipped with a thermometer, a stirrer, a raw material supply port, and a nitrogen gas inlet, 39.00 g of EDM as a solvent (B) and 39.00 g of NMP were added as a P-dimer acid diamine (a1). 1074 11.61 g of 4.78 g of APSE as a terminal crosslinking agent (T2), followed by stirring under a dry nitrogen gas stream, while adding 5.61 g of BSAA as an acid anhydride (a3), and stirring at 40 ° C for 5 hours. As a result, a 22% by mass solution (ink) of yellow transparent proline (A) was obtained. The viscosity of the ink is 14.1mPa. The weight average molecular weight of the proline (A) was 1,800 at s (25 ° C).

[Example 19 to Example 20]

In Example 18, the raw materials were added as shown in Table 2, except that in the same order as in Example 18. A solution (ink) of valine acid (A) was prepared under the reaction conditions, and the weight average molecular weight of the obtained valine acid (A) and the viscosity of the ink at 25 ° C were measured.

[Comparative Example 1 to Comparative Example 11]

In Example 11, the materials were added as shown in Table 3, except that in the same order as in Example 11. Reaction conditions A proline solution (ink) was prepared, and the weight average molecular weight of the obtained limin acid and the viscosity of the ink at 25 ° C were measured. However, in Comparative Examples 8 to 11, there were precipitates, and it was not possible to prepare a solubilized uniform ink.

The details of each condition and physical properties of the examples and comparative examples are shown in Tables 1 to 4.

N2: molar number of diamine (a12)

N3: molar number of anhydride (a3)

N4: Molar number of terminal crosslinking agent (T1)

N5: Molar number of terminal crosslinking agent (T2)

The evaluation methods of the inks obtained in the examples and the comparative examples are described below.

[Ink characteristics]

(i) Evaluation of stable discharge time

The inks obtained in the examples and the comparative examples were injected into an ink jet cartridge, and then mounted in an ink jet apparatus (DMP-2800 manufactured by FUJIFILM Dimatix Co., Ltd.) using an ink jet head for 10 pl at a discharge voltage (pressure The discharge state was observed under the conditions of an electric voltage of 16 V, an ink jet head temperature of 30 ° C, and a driving frequency of 5 kHz. During the ejection process, the ink is ejected in the vertical direction, and the state in which the following phenomenon does not occur is set as a normal ejection, which is a phenomenon in which droplets are generated in addition to the ink droplets originally contributing to image recording from the nozzle when the ink is dropped. (that is, a phenomenon called satellite which is not ejected exactly as a drop), and observes the time during which the ejection is normally continued from the start of the ejection. The observation was carried out for 20 minutes from the start of the injection, and the maximum value of the stable discharge time was set to 20 minutes.

[Formation of hardened film]

The inks obtained in the examples and the comparative examples were injected into an ink jet cartridge, and then mounted in an ink jet apparatus (DMP-2811 manufactured by FUJIFILM Dimatix Co., Ltd.) using an ink jet head for 10 pl at a discharge voltage (pressure The electric voltage is 16 V; the head temperature is 30 ° C, the driving frequency is 5 kHz, and the number of times of application of the phthalic acid concentration of less than 20% by mass is 4 times, and the concentration of valine is 20% by mass or more, 25 The number of times of application of the ink having a mass % or less is three times, and the number of times of application of the ink having a lysine concentration of more than 25% by mass is two times, and the copper foil (thickness: 12.5 μm) is laminated on the polyfluorene. Substrate on the substrate [(Mitsui Chemical Co., Ltd.) Neoflex A square pattern of 40 mm × 40 mm was formed on the copper foil surface of NEX-13FE (trade name). Thereafter, the film was dried on a hot plate at 80 ° C for 10 minutes, and further fired at each temperature condition shown in Table 5 using an oven to obtain a cured film having a film thickness of 8 μm to 11 μm.

(ii) Alkaline aqueous solution tolerance

The cured film obtained above was immersed in a 2 (2N) aqueous NaOH solution for 15 minutes at room temperature, washed with water, and dried at 60 ° C for 30 minutes. The interface between the cured film and the copper foil was observed with an optical microscope, and the alkali aqueous solution resistance was evaluated by the following evaluation criteria.

. AA: No penetration occurred at the interface between the cured film and the copper foil, and no abnormality such as peeling was observed.

. CC: Penetration occurred at the interface between the cured film and the copper foil, and some abnormalities such as peeling were observed.

(iii) plating test

The electroless copper plating obtained by the above-mentioned hardened film was subjected to electroless copper plating using the electroless copper plating liquid PEA manufactured by Uemura Industrial Co., Ltd., and the adhesion of copper plating was observed by the following evaluation criteria.

. AA: Copper plating is attached to the cured film.

. CC: The hardened film is dissolved, and copper plating is not attached.

Then, a copper plating layer having a thickness of 20 μm was formed using an electrolytic copper plating solution EPL manufactured by Uemura Industrial Co., Ltd. for the cured film after electroless copper plating. A slit of 2 mm × 30 mm was formed on the copper plating layer by a cutter, and then the interface between the copper plating layer at the end of the slit and the cured film was peeled off to prepare a sample for peeling test. The sample was set up at Shimadzu Corporation (shares) The peel strength was measured in a tensile tester EZGraph.

(iv) Determination of water absorption

A cured film was produced in the same manner as the above [formation of the cured film], except that the substrate to be formed was changed to an aluminum foil, and then the aluminum foil was peeled off to obtain a separate film. The film was immersed in ultrapure water at room temperature for 24 hours, and then water droplets adhering to the surface of the film were wiped off with a non-woven fabric, and the weight change of the film was observed by a scale. Water absorption rate (%) = (weight change portion of film before and after water absorption × 100) / (weight of film before water absorption).

(v) Dielectric constant measurement

The inks obtained in the examples and the comparative examples were injected into an ink jet cartridge, and then mounted in an ink jet apparatus (DMP-2811 manufactured by FUJIFILM Dimatix Co., Ltd.) using an ink jet head for 10 pl at a discharge voltage (pressure An ink having an electric voltage of 16 V, an ink jet head temperature of 30 ° C, a driving frequency of 5 kHz, and an ink having a lysine concentration of 25% by mass or less and a coating having a valeric acid concentration of 25% by mass or more Under the discharge conditions of one application, a square pattern of 70 mm × 50 mm was formed on the chromium substrate. Thereafter, the film was dried on a hot plate at 80 ° C for 10 minutes, and further fired at each temperature condition shown in Table 5 using an oven to obtain a cured film having a film thickness of 2 μm to 4 μm. Thereafter, aluminum was vapor-deposited on the cured film to form an electrode. The dielectric constant was measured using a precision LCR meter E4980A (manufactured by Agilent Technologies, Inc.).

The above evaluation results are shown in Table 5 for the examples and comparative examples.

When the thermosetting ink composition of the present invention is used as an ink for inkjet, the ink is excellent in ejection stability from an inkjet head, and further, from the ink. The cured film obtained by water has excellent resistance to an alkaline aqueous solution and adhesion to a copper plating layer, and has a low dielectric constant and water absorption, and exhibits excellent results as an insulating film.

Claims (17)

A thermosetting ink composition comprising at least one proline acid (A) selected from the group consisting of liminic acid: a proline acid represented by the formula (A1); a guanamine represented by the formula (A2) And a poly-proline which has a crosslinkable organic group at the molecular terminal, and is one or more kinds of diamines (a12) containing a diamine (a1) derived from a dimer acid, and has two or more acid anhydride groups. The compound (a3), which is obtained by reacting one or two terminal crosslinking agents represented by the formula (T2) with a terminal crosslinking agent represented by the formula (T1); [In the formula (A1) and the formula (A2), R ¹ is a residue of a diamine (a1) derived from a dimer acid, and R ² is a divalent crosslinkable organic group having a carbon number of 2 to 100] R ³ -NH ₂ (T2) [In the formula (T1), R ² is a divalent crosslinkable organic group having a carbon number of 2 to 100, and in the formula (T2), R ³ is a carbon number of 2 to 100. A monovalent crosslinkable organic group]. The thermosetting ink composition according to claim 1, which is an ink for inkjet. The thermosetting ink composition according to claim 1 or 2, wherein the diamine (a1) derived from the dimer acid is a reduced amine of a dimer acid obtained from an unsaturated fatty acid. One or two or more kinds of diamines obtained by the reaction, and the above unsaturated fatty acid is selected from the group consisting of crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, isooleic acid, oleic acid, and Decenoic acid, sinapic acid, tetracosic acid, linoleic acid, pine nut oleic acid, tung acid, honey acid, di- gamma-linolenic acid, eicosatrienoic acid, stearidonic acid , arachidonic acid, arachidonic acid, adrenal acid, octadecaphoenoic acid, docosapentaenoic acid, oleic acid, docosapentaenoic acid, docosahexaenoic acid And tannic acid. The thermosetting ink composition according to claim 1 or 2, wherein the diamine (a12) contains, in addition to the diamine (a1) derived from the dimer acid, further contains a compound selected from the group consisting of the following compounds At least one of: 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diamine Diphenyl hydrazine, bis[3-(4-aminophenoxy)phenyl]anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, m-phenylenediamine, p-phenylene Amine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-aminophenoxy)phenyl] Cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)benzene Cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl) Phenyl]methane, 2,5-diaminomethylbicyclo[2.2.1]heptane, 2,6-diaminomethylbicyclo[2.2.1]heptane, 9,9-bis(3-amine Propyl, 9,9-bis(4-aminophenyl)anthracene a compound represented by the formula (VIII), a compound represented by the formula (XIII), and a compound represented by the formula (i), [In the formula (VIII), A ⁴ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -(CH ₂ ) _p -, -(CH ₂ ) _p -O- Or -O-(CH2) _p -, wherein p is an integer of 1 to 6; R ¹⁰ is a group having a steroid skeleton, or a group having at least one ring structure selected from a cyclohexane ring and a benzene ring; Wherein, when the positional relationship of the two amine groups bonded to the benzene ring is a para position, R ¹⁰ may be an alkyl group having a carbon number of 1 to 30, and when the above positional relationship is meta, R ¹⁰ may be carbon. a number of 1 to 30 alkyl groups or phenyl groups, at least one of -CH ₂ - of the above alkyl groups may be selected from the group consisting of -CF ₂ -, -CHF-, -O-, -CH=CH-, and -C≡C - at least one of the substitutions, wherein at least one of -CH _{3 of the} above alkyl group may be substituted with at least one selected from the group consisting of -CH ₂ F, -CHF ₂ and -CF ₃ , and bonded to the phenyl group The hydrogen on the carbon may be substituted with at least one selected from the group consisting of -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ and -OCF ₃ ] [In the formula (XIII), R ²⁸ and R ²⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ³⁰ is a methylene group, a phenyl group or at least one hydrogen having a carbon number of 1 to 10; Alkyl substituted phenyl, 2 x are each an integer from 1 to 6, and y is an integer from 1 to 70] [In the formula (i), n is an integer of 1 to 50]. The thermosetting ink composition according to claim 1 or 2, wherein the compound (a3) having two or more acid anhydride groups is at least one selected from the group consisting of pyromellitic dianhydride. , 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl fluorene tetracarboxylic dianhydride, 2,2',3,3'-diphenyl fluorene tetracarboxylic dianhydride , 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-dihydroxyphenyl fluorenyl trimellitic dianhydride, 3,3',4,4'- Phenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3' , 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(hydrogen trimellitate) ), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,3-dihydro-1,3-di- oxy-5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1 -(Trifluoromethyl)ethylidene]di-4,1-phenylene ester , 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride, 1,3-dihydro-1,3-dihydrogen 5--5-isobenzofurancarboxylic acid oxydi-4,1-phenylene ester, p-phenylene bis(trimellitic acid monoester anhydride), 4-(2,5-di-tertiary oxytetrahydrofuran- 3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-biscyclohexyltetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-di-oxytetrahydrofuranyl) 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4,4'-[(isopropylidene)bis(p-phenoxy)diphthalic dianhydride, B Diamine tetraacetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and a compound represented by the following formula The thermosetting ink as described in claim 1 or 2 of the patent application a water composition wherein the terminal crosslinking agent represented by the formula (T1) is selected from the group consisting of maleic anhydride, citraconic anhydride, allyl ceric anhydride, 5-northene-2,3-dicarboxylic anhydride 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride and 3-(triethoxyindolyl)propyl succinic anhydride At least one of them. The thermosetting ink composition according to claim 1 or 2, wherein the terminal crosslinking agent represented by the formula (T2) is selected from the group consisting of 4-ethynylaniline, 3-ethynylaniline, and alkyne. Propylamine, 3-aminobutyne, 4-aminobutyne, 5-aminopentyne, 4-aminopentyne, allylamine, 7-aminoheptyne, m-aminostyrene, p-amine Styrene, m-amino-α-methylstyrene, 3-aminophenylacetylene, 4-aminophenylacetylene, 3-aminopropyltriethoxydecane and 3-aminopropyltrimethyl At least one of oxydecanes. The thermosetting ink composition according to claim 1 or 2, further comprising a solvent (B). The thermosetting ink composition according to claim 8, wherein the solvent (B) is at least one selected from the group consisting of ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, and ethylene glycol. Monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol II Ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol Methyl ether, dipropylene glycol monomethyl ether, Triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, butanediol monovinyl ether, 3-methoxy Methyl propyl propionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, anisole, methyl benzoate, benzoic acid Ethyl ester, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidine Ketone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-ethenyl-2-pyrrolidone, N,N-diethylacetamide, N,N-dimethylpropane Indoleamine, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone. The thermosetting ink composition according to claim 8 is characterized in that the viscosity at 25 ° C and 20 rpm is 5 mPa. s~20mPa. s. The thermosetting ink composition according to claim 1 or 2, wherein the polyacrylic acid has a polystyrene-equivalent weight average molecular weight of 500 Å as measured by gel permeation chromatography. 10,000. The thermosetting ink composition according to the first or second aspect of the invention, wherein the content of the lysine (A) in the thermosetting ink composition is 15% by mass to 60% by mass. A method of coating an ink, comprising: a step of forming a coating film by coating a thermosetting ink composition according to any one of claims 1 to 12, by an inkjet coating method, and The step of hardening the above coating film. A method for producing a polyimide film, comprising: coating a thermosetting ink composition according to any one of claims 1 to 12 to form a coating film by an inkjet coating method. Steps and the above The coating film is subjected to a hardening treatment to form a polyimide film. A polyimine film obtained by the method for producing a polyimide film according to item 14 of the patent application. A film substrate comprising: a film, and a polyimide film formed on the film by a method for producing a polyimide film according to claim 14 of the patent application. An electronic component comprising the film substrate of claim 16 of the patent application.