KR101984017B1 - Thermosetting ink composition and use thereof - Google Patents

Abstract

...식(A1) 및 식(A2)
[상기 식(A1) 및 식(A2)에서, R¹은 다이머산에서 유도되는 디아민(a1)의 잔기이며, R²는 탄소수 2 내지 100인 2가의 가교성 유기기이다.]A thermosetting ink composition capable of forming a cured film having excellent insulating properties, good adhesion to plated copper, good resistance to an aqueous alkali solution, and low water absorption. (A) containing at least one amide acid selected from an amide acid represented by the following formula (A1), an amide acid represented by the following formula (A2), and a specific polyamic acid having a crosslinkable organic group at the molecular terminal , Thermosetting ink composition.

... (A1) and (A2)
[In the formulas (A1) and (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 2 to 100 carbon atoms.]

Description

THERMOSETTING INK COMPOSITION AND USE THEREOF FIELD OF THE INVENTION [0001]

The present invention relates to a thermosetting ink composition and its use, for example, an ink for forming an insulating film in the production of electronic parts, a method of applying the ink, a polyimide film formed using the ink, A film substrate having the polyimide film, and an electronic component having the film substrate.

2. Description of the Related Art In recent years, miniaturization, light weight, and high performance of electronic devices have been progressing rapidly, and these power generations have been achieved by slimming or miniaturizing electronic components. Particularly in the field of printed wiring boards, foldable flexible wiring boards contribute greatly to miniaturization and weight reduction of electronic devices.

As a result, various physical properties of each member used as an electronic component have been demanded of various colors. For example, a cured film used in electronic parts is required to have heat resistance, insulation, adhesiveness to a substrate, resistance to chemicals used in the process, low water absorption, and the like.

Polyimides are widely used in the above-mentioned fields because they are excellent in heat resistance and insulating properties. In recent years, a method of forming a cured film of a desired polyimide by an inkjet method has been studied.

Patent Document 1 discloses an inkjet ink containing a polyamic acid having a specific structure. However, in Patent Document 1, no inkjet ink capable of forming a cured film having both adhesiveness to a copper substrate or plated copper, resistance to an aqueous alkaline solution, and low water absorption property has been studied.

Patent Document 2 discloses a photosensitive resin composition containing a polyamic acid having a specific structure, a photopolymerizable compound and a photopolymerization initiator. However, the polyamic acid does not have a crosslinkable organic group at the molecular end, and in the case of the polyamic acid alone, a cured film having sufficient resistance to an aqueous alkali solution can not be obtained. In addition, the composition is applied mainly by dispensing, screen printing, stamping, etc., and the composition can not be used in the ink-jet method because of its viscosity design (1 Pa · s or more).

Patent Documents 3 and 4 disclose a resin composition containing a polyimide having a specific structure. However, in Patent Documents 3 and 4, no inkjet ink capable of forming a cured film having good resistance to an aqueous alkali solution and insulating properties has been studied.

Patent Document 5 discloses a polyimide precursor having a specific structure. However, as an example of the diamine component constituting the polyimide precursor, there is no mention of a diamine derived from a dimer acid as described later. In addition, Patent Document 5 does not disclose the use of a composition containing a polyimide precursor as a thermosetting ink composition, and does not mention the use of an inkjet method including the design of a concentration or viscosity.

Prior art literature

Patent Document 1: JP-A-2010-159402

Patent Document 2: JP-A-2010-256532

Patent Document 3: U.S. Patent No. 7157587 B2

Patent Document 4: U.S. Patent No. 7208566 B2

Patent Document 5: Japanese Patent Application Laid-Open No. 2006-321924

The present invention provides a thermosetting ink composition capable of forming a cured film having excellent insulating properties (e.g., low dielectric constant), good adhesion to plated copper, good resistance to an aqueous alkali solution, and low water absorption, and its use It is on.

The inventors of the present invention have conducted extensive studies in order to solve the above problems. Particularly, various diamines have been studied in amide acids which can be obtained by reacting an acid dianhydride, a diamine and a terminal cross-linking agent, which can be preferably used as an ink containing component.

For example, the polyamic acid (3) used in Example 3 of Patent Document 1 is obtained by reacting 4,4 '- [(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid with anhydride, Has repeating structural units formed of 2-bis [4- (4-aminophenoxy) phenyl] propane, and has a molecular end group formed of maleic anhydride. However, when the ink containing the polyamic acid (3) was used, the cured film obtained had a water absorption rate as high as 3%, a low adhesion to plated copper, and a low resistance to an aqueous alkali solution (Comparative Example 2 Reference).

Also, when diethylene glycol bis (3-aminopropyl) ether was used as the diamine, the cured film obtained had a water absorption rate as high as 3%, a low adhesion to plated copper, and a low resistance to an aqueous alkali solution Of Comparative Example 1).

The inventors of the present invention have found that 1,1-diaminooctane having a long-chain alkylene group between two amino groups and 1, 2-diaminohexane having a long-chain alkylene group between the two amino groups can be used in place of the diamine in view of the fact that the ether bond in the diamine adversely affects the water absorption, , And 12-diaminododecane (see Comparative Examples 8 to 11 of this specification). However, in this case, it was difficult to dissolve the obtained polyamic acid in a solvent, so that an ink which can be used for a general purpose could not be obtained.

The inventors of the present invention have studied diamines in various other manners on the basis of the above knowledge and found that the above problems can be solved by a thermosetting ink composition having the following constitution and have completed the present invention.

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

[1] A process for producing an amide compound represented by the following formula (1), comprising reacting at least one diamine (a12) containing an amide acid represented by the following formula (A1), an amide acid represented by the following formula (A2) A crosslinking organic group obtained by reacting a compound (a3) having two or more groups with a terminal crosslinking agent of one or both of the terminal crosslinking agent represented by the following formula (T1) and the terminal crosslinking agent represented by the following formula (T2) And at least one amide acid (A) selected from the group consisting of a polyamide acid and a polyamide acid.

[In the formulas (A1) and (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 2 to 100 carbon atoms.]

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

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

[3] The process according to [1], wherein the diamine (a1) derived from a dimer acid is one or two or more diamines obtained by a reductive amination reaction of a dimer acid obtained from an unsaturated fatty acid and the unsaturated fatty acid is a crotonic acid, , Erucic acid (erucic acid), nerubic acid, linolic acid, phenolic acid, eleostearic acid, Mead acid, diacetic acid (diacetic acid), palmitoleic acid, oleic acid, elaidic acid, But are not limited to, homo-gamma-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentanenoic acid, osbond acid, The thermosetting ink composition according to the above [1] or [2], wherein the thermosetting ink composition is selected from cosapentaenoic acid, docosahexaenoic acid and nisic acid.

[4] The method according to any one of [1] to [4], wherein the diamine (a12) is at least one compound selected from the group consisting of 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, Phenyl ether, 3,3'-diaminodiphenylsulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, 3,3'-dimethyl-4,4'- M-phenylenediamine, m-phenylenediamine, m-phenylenediamine, m-phenylenediamine, m-phenylenediamine, m-phenylenediamine, Bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis (2-hydroxyethyl) Bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, 1,1-bis [4- Aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4- aminobenzyl) phenyl] methane, 2,5-bisaminomethylbicyclo [2.2.1] heptane, Bisaminomethylbicyclo [2.2.1] heptane, 9,9-bis (3-amyl (VIII), a compound represented by the following formula (XIII), and a compound represented by the following formula (i): < EMI ID = The thermosetting ink composition according to any one of the above [1] to [3], further comprising at least one selected from the group consisting of the thermosetting ink composition and the thermosetting ink composition.

[In the formula (VIII), A ⁴ represents a single bond, -O-, -COO-, -OCO-, -CO- , -CONH-, - (CH 2) p -, - (CH 2) p -O - or -O- (CH ₂ ) _p -, wherein 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; When the positional relationship between the two amino groups bonded to the benzene ring is para-position, R ¹⁰ may be alkyl of 1 to 30 carbon atoms, and when the positional relationship is meta-position, R ¹⁰ is alkyl of 1 to 30 carbon atoms Or at least one of -CH ₂ - in the alkyl may be substituted with at least one member selected from -CF ₂ -, -CHF-, -O-, -CH═CH- and -C≡C-, , At least one -CH ₃ of the alkyl may be substituted with at least one member selected from -CH ₂ F, -CHF ₂ and -CF ₃ , and the hydrogen bonded to the ring-forming carbon of the phenyl is -F, - _{CH 3, -OCH 3, -OCH 2} F, at least one may be substituted by member selected from -OCHF ₂ and -OCF _3.]

Wherein R ²⁸ and R ²⁹ are each independently alkyl having 1 to 3 carbon atoms or phenyl, and R ³⁰ is methylene, phenylene, or at least one hydrogen may be substituted with alkyl having 1 to 10 carbon atoms Each of x is independently an integer of 1 to 6, and y is an integer of 1 to 70. [

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

[5] The positive resist composition according to any one of [1] to [4], wherein the compound (a3) having two or more acid anhydride groups is at least one compound selected from the group consisting of pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, Phenone tetracarboxylic acid dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3' -Diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,3,4', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 4,4'-dihydroxyphenylsulfone bistrimellic acid dianhydride, Diphenyl ether tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, (3-methoxyphenyl) propane dianhydride, 3 ', 4,4'-diphenylmethane tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) Butane tetracarboxylic acid anhydride, methylcyclobutane tetracarboxylic acid anhydride Water, cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, ethanetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, 1,3-dihydro-1,3-dioxo- 5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] di-4,1-phenylene ester, 2,2- ) Propane dibenzoate-3,3 ', 4,4'-tetracarboxylic acid dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid oxy- Ester, p-phenylenebis (trimellitic acid monoester acid anhydride), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene- -Dicarboxylic acid anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, bicyclo [2,2,2] -2,3,5,6-tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3- 1,2-dicarboxylic acid anhydride, 4,4 '- [(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid dianhydride, ethylenediamine 4-acetic acid dianhydride, 3,4- , 2,3,4-tetrahydro-1-naphthalene succinic anhydride, and a compound represented by the following formula

To (4), wherein the thermosetting ink composition is at least one selected from the group consisting of the thermosetting ink composition and the thermosetting ink composition.

Wherein the terminal crosslinking agent represented by the formula (T1) is at least one selected from the group consisting of maleic anhydride, citraconic anhydride, allylnadic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4- The thermosetting resin composition according to any one of the above [1] to [5], which is at least one selected from phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic acid anhydride and 3- (triethoxysilyl) Ink composition.

Wherein the terminal crosslinking agent represented by the above formula (T2) is at least one selected from the group consisting of 4-ethynyl aniline, 3-ethynyl aniline, propargylamine, 3-aminobutyne, Aminole- styrene, 3-aminophenylacetylene, 4-aminophenylacetylene, 3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane. The thermosetting ink composition according to any one of the above [1] to [6], wherein the thermosetting ink composition is at least one selected from the group consisting of 3-aminopropyltrimethoxysilane.

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

[9] The process according to [1], wherein the solvent (B) is selected from the group consisting of ethyl acetate, ethanol, 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, di Ethylene 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, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetramethylene Cyclohexanone, 1,3-dioxolane, 1,4-dioxane, anisole, methyl benzoate, ethyl benzoate, 1-vinyl-2-methylpropionate Pyrrolidone, 2-pyrrolidone, 2-pyrrolidone, 2-pyrrolidone, Pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-epsilon-caprolactam, 1,3- Dimethyl-2-imidazolidinone, and? -Butyrolactone, wherein the thermosetting ink composition is at least one selected from the group consisting of dimethyl-2-imidazolidinone and? -Butyrolactone.

[10] The thermosetting ink composition according to the above [8] or [9], wherein the viscosity at 25 ° C and 20 rpm is 5 to 20 mPa · s.

[11] The thermosetting ink composition according to any one of [1] to [10], wherein the polyamic acid has a weight average molecular weight of 500 to 10,000 in terms of polystyrene measured by gel permeation chromatography.

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

[13] A method of applying an ink, comprising the step of coating a thermosetting ink composition according to any one of [1] to [12] by an inkjet coating method to form a coating film, and a step of curing the coating film.

[14] A process for producing a thermosetting ink composition, comprising the step of applying a thermosetting ink composition according to any one of [1] to [12] by an inkjet coating method to form a coating film, and a step of curing the coating film to form a polyimide film. A method for producing a polyimide film.

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

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

[17] An electronic device having the film substrate according to the above [16].

[Glossary]

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

The term " diamine derived from dimer acid " means a diamine having a structure formed by excluding two carboxy groups of dimer acid. Examples of diamines derived from dimeric acid include 2-carboxy groups (-COOH) of dimer acid, aminomethyl group (-CH ₂ -NH ₂ ) or amino group (-CH ₂ -NH ₂ ) -NH < ₂ >).

The term " residue of diamine derived from dimer acid " means a divalent group formed by excluding two amino groups in diamine (H ₂ NR ¹ -NH ₂ ) derived from dimeric acid, i.e., -R ₁ - Means a divalent group to be indicated.

The term "crosslinkable organic group" means an organic group having a crosslinking property, and examples thereof include a monovalent or divalent organic group having 2 to 100 carbon atoms and having a crosslinkable unsaturated bond, a divalent group represented by the following formula (α) An organic group, and a monovalent organic group represented by the following formula (?).

...식(α)

...식(β)

... (?)

... (β)

In the formulas (a) and (b), a plurality of R ^a are each independently hydrogen, alkyl of 1 to 20 carbon atoms, or alkoxy of 1 to 20 carbon atoms. At least one of the stages, ^a R is the alkoxy group. R ^b is a trivalent organic group having 1 to 20 carbon atoms (e.g., an aliphatic group, an aromatic group). R ^c is a divalent organic group having 1 to 20 carbon atoms (e.g., alkylene, arylene).

The term " 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 1 to 5, more preferably 1 to 3, and particularly preferably 1.

The "monovalent organic group having 2 to 100 carbon atoms having a crosslinkable unsaturated bond" includes, for example, alkenyl having 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 6) carbon atoms; Alkynyl having 2 to 20 (preferably 2 to 10, more preferably 2 to 6) carbon atoms; Alkyldienyl having 4 to 20 (preferably 4 to 10, more preferably 4 to 6) carbon atoms; Cycloalkenyl having 3 to 20 (preferably 4 to 10) carbon atoms; -OR, -SR, -SO ₂ R (wherein each formula, R is the alkenyl or the alkynyl); A group formed by substituting at least one hydrogen in aryl having 6 to 30 (preferably 6 to 20, more preferably 6 to 12) carbon atoms with said alkenyl or said alkynyl; -OAr, -SAr, -SO ₂ Ar (wherein each formula, Ar is at least one hydrogen of the aryl group having 6 to 30 carbon atoms, preferably 6 to 20, more preferably 6 to 12, wherein the alkenyl or alkynyl Is a group formed by substitution with a nitro group.

As the 'divalent organic group having 2 to 100 carbon atoms having a crosslinkable unsaturated bond', for example, alkenylene or alkynylene having 2 to 20 (preferably 2 to 10, more preferably 2 to 6) carbon atoms; Cycloalkenylene having 3 to 20 (preferably 4 to 10) carbon atoms; -OR-, -SR-, -SO ₂ R- (each formula, R is the alkenylene or alkynylene above); A group formed by substituting at least one hydrogen of arylene having 6 to 30 (preferably 6 to 20, and more preferably 6 to 12) carbon atoms with said alkenyl, said alkynyl, arylalkenyl, or arylalkynyl ; -OAr-, -SAr-, -SO ₂ Ar- (each formula, Ar is a group having 6 to 30 carbon atoms, preferably 6 to 20, more preferably at least 1 of the 6 to 12 arylene hydrogen, the Al Or a group formed by substituting said alkynyl with said alkynyl; A divalent group represented by the following formula can be mentioned.

Wherein R is a hydrogen atom or allyl, and A is a methylene or oxygen atom.

The expression " at least one " A " may be replaced by " B " in the description of each expression is such that the position of " A " Or more, it means that the positions can be selected without restriction.

For example, the expression " at least one " A " may be substituted by at least one kind selected from " B ", " C ", and " D " A " is replaced with " B ", " C ", and " D "Quot; is replaced with at least two of "

According to the present invention, it is possible to form a cured film which realizes low water absorption without impairing solvent solubility of the contained components in the ink, and also has excellent insulating properties (e.g. low dielectric constant), good adhesion to plated copper, A thermosetting ink composition capable of forming a cured film having good resistance to an aqueous solution and the like, and its use.

Therefore, the polyimide film formed from the thermosetting ink composition of the present invention is, for example, sufficiently low in water absorption, high in insulation, excellent in adhesion to a substrate, and excellent in drug resistance. Therefore, reliability and product yield of the electronic component can be improved by using the ink.

Hereinafter, the thermosetting ink composition of the present invention, the application method of the ink, the polyimide film and the production method thereof, the film substrate, and the electronic component 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 ".

1. Thermosetting ink composition

The thermosetting ink composition of the present invention contains a specific amide acid (A), and preferably further 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 Amidic acid (A)

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

Amide acid represented by the following formula (A1) (hereinafter also referred to as 'amide acid (A1)').

An amide acid represented by the following formula (A2) (hereinafter also referred to as an 'amide acid (A2)').

(A3) having at least two acid anhydride groups, a terminal cross-linking agent represented by the following formula (T1), at least one diamine (a2) represented by the following formula (Hereinafter also referred to as " polyamic acid (A3) ") having a crosslinkable organic group at the molecular end, obtained by reacting one or both terminal crosslinking agents of the terminal crosslinking agent represented by the formula

That is, in the present invention, the amide acid (A), which is a component contained in the thermosetting ink composition, is at least one selected from an amide acid (A1), an amide acid (A2) and a polyamide acid (A3).

In the formulas (A1) and (A2), R ¹ is a residue of a 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 following formula (T1).

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

The weight average molecular weight of the polyamic acid (A3) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 10,000. In order to further improve the solubility of the polyamic acid (A3) in the solvent (B) and lower the viscosity of the ink, the weight average molecular weight thereof is more preferably 500 to 9,000, and still more preferably 500 to 8,000. On the other hand, the amide acids (A1) and (A2) are of the monomer type, but in the present invention, the molecular weight is also defined as the weight average molecular weight in terms of polystyrene measured by the GPC method. The weight-average molecular weight of the amide acids (A1) and (A2) is preferably 500 to 10,000, more preferably 500 to 9,000, and still more preferably 500 to 8,000.

The (poly) amide acid having a weight average molecular weight lower than the lower limit value is chemically and mechanically stable in a step of forming a polyimide film by heat treatment without evaporation. (Poly) amide acid having a weight average molecular weight of not more than the upper limit value is superior in solubility to the solvent (B), and by using the polyamic acid, the (poly) amide acid has a high concentration of not less than 15% by weight, The ejection stability of the ink can be improved, and at the same time, the film thickness of the obtained coating film can be increased.

The weight average molecular weight of the amic acid (A) can be measured by gel permeation chromatography (GPC). Specifically, the obtained amidic acid (A) is diluted with N, N-dimethylformamide (DMF) so that the concentration of the amidic acid (A) is about 1% by weight to prepare a diluted solution. Two columns of GF-510HQ and GF-310HQ manufactured by SHOWA DENKO KK were connected in this order and the diluted solution was subjected to GPC method at a column temperature of 40 ° C and a flow rate of 0.5 ml / , And then converting it into polystyrene.

All three amides (A) have a diamine structure derived from a dimer acid. The amide acid (A) having the above structure contributes greatly to the improvement of the low water absorption of the obtained cured film, the resistance to chemicals (for example, an aqueous alkali solution) and the adhesion to a substrate (for example, plated copper). In addition, since the solubility in the solvent (B) is high, it is easy to prepare an ink for general use such as an ink jet.

Since all of the three amide acids (A) have a crosslinkable organic group at the molecular end, the crosslinking structure derived from the amide acid (A) is formed by heating the ink of the present invention. Therefore, in the present invention, a polyimide film having sufficient mechanical strength can be obtained from amide acid (A) having a small molecular weight of, for example, 500 to 10,000 in weight average molecular weight.

The content of the amide acid (A) is usually 15 to 60% by weight, preferably 15 to 55% by weight, more preferably 15 to 50% by weight in the thermosetting ink composition of the present invention. With this concentration range, when the ink of the present invention is used for an inkjet application, an appropriate viscosity is obtained for the inkjet, and the thickness of the film obtained by one ink jetting becomes most appropriate, thereby improving the accuracy of jetting.

In the present specification, diamines derived from dimer acid are also referred to as 'dimer acid diamine (a1)', diamines other than diamine derived from dimer acid are also referred to as 'other diamine (a2)', dimer acid diamine (a1) Diamine (a12) ", and the compound having two or more acid anhydride groups is also referred to as" acid anhydride (a3) ", and at least one diamine containing other diamine (a2) The terminal crosslinking agent is also referred to as 'terminal crosslinking agent (T1)', and the terminal crosslinking agent represented by formula (T2) is also referred to as 'terminal crosslinking agent (T2)'.

The diamine type diamine (a1), the other diamine (a2), the acid anhydride (a3), the terminal crosslinking agent (T1) and the terminal crosslinking agent (T2), which can be used for obtaining the amide acid (A), will be described below.

1.1.1 Dimeric diamine (a1)

The dimer acid diamine (a1) is obtained, for example, by a reductive amination reaction of a dimer acid. The reaction can be carried out by a known method (e.g., Japanese Patent Application Laid-Open No. 09-12712) such as a reduction method using ammonia and a catalyst.

The dimer acid is a dibasic acid obtained by bifunctionalization of an unsaturated fatty acid by an intermolecular polymerization or the like. But it usually contains monomeric acid, trimeric acid and the like in addition to dimeric acid. After the reaction, a double bond remains in the obtained molecule, but in the present invention, the dimer acid includes a double bond in the molecule which is reduced by hydrogenation to become a saturated dibasic acid.

The dimer acid is obtained, for example, by carrying out polymerization of an unsaturated fatty acid using a Lewis acid and a Bronsted acid as a catalyst. The dimer acid can be produced by a known method (e.g., Japanese Patent Application Laid-Open No. 09-12712).

Examples of the unsaturated fatty acid include unsaturated fatty acids such as crotonic acid, myristic oleic acid, palmitoleic acid, oleic acid, elaidic acid, benzoic acid, valoleic acid, eicosanic acid, erucic acid, nerubonic acid, linolic acid, Lauric acid, stearidic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosepentanoic acid, osbond acid, sardine acid, stearic acid, Tetracosapentaenoic acid, docosahexaenoic acid, and nisic acid. The number of carbon atoms of the unsaturated fatty acid is usually 4 to 24, preferably 14 to 20.

For example, in the case of producing a dimeric acid by using linolic acid, the resulting mixture generally contains a dimeric acid having 36 carbon atoms as a main component, but a monomeric acid having a carbon number of 18 and a trimer acid having a carbon number of 54 are also generally contained in a small amount as a subcomponent , And structures in which the origins of the raw materials are various colors.

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

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

Examples of commercial products of the dimeric diamine (a1) include Basamine 551 (trade name, product of Cognis Japan), and free amine 1074 (product name of Croda Japan KK) . The diaminic acid diamine (a1) also includes a compound formed by hydrogenating a diamine obtained by a reductive amination reaction of a dimeric acid. As a commercially available product thereof, for example, Vasamin 552 (trade name, Cognis Japan ) Products).

1.1.2 Other diamines (a2)

A detailed description of the other diamine (a2) will be given later. Compound examples ".

1.1.3 Acid anhydride (a3)

A detailed description of the acid anhydride (a3) will be given later, Compound examples ".

1.1.4 Terminal Crosslinking Agent (T1)

The terminal crosslinking agent (T1) is represented by the following 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 and having a crosslinkable unsaturated bond, Is a bivalent organic group.

As the terminal crosslinking agent (T1), for example,

Maleic anhydride, citraconic anhydride, itaconic anhydride, allylnadic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, Compounds having a crosslinkable unsaturated bond such as 2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, and allyl succinic anhydride;

(triethoxysilyl) phenylsuccinic anhydride, m- (triethoxysilyl) phenylsuccinic anhydride, m- (triethoxysilyl) phenylsuccinic anhydride, p- Compounds having a bivalent organic group represented by the formula (?) Such as phenylsuccinic anhydride, 3- (trimethoxysilyl) propyl succinic anhydride and 3- (triethoxysilyl) propyl succinic anhydride.

Among the terminal crosslinking agents (T1), 4-ethynylphthalic anhydride, 4-ethynylphthalic anhydride, 4-ethylhexylphthalic anhydride, 4-ethylhexylphthalic anhydride, Phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic acid anhydride and 3- (triethoxysilyl) propyl succinic anhydride are preferable.

The terminal crosslinking agent (T1) may be used alone or in admixture of two or more, but from the viewpoint of uniformly controlling the crosslinking density, it is preferable to use only one type.

1.1.5 Terminal Crosslinking Agent (T2)

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

In the formula (T2), R ³ is a monovalent crosslinkable organic group having 2 to 100 carbon atoms, preferably a monovalent organic group having 2 to 100 carbon atoms and a crosslinkable unsaturated bond, Is a monovalent organic group.

As the terminal crosslinking agent (T2), for example,

4-aminobutyne, 5-aminopentyne, 4-aminopentyne, allylamine, 7-aminoheptyne, m-aminostyrene, a compound having a crosslinkable unsaturated bond such as p-aminostyrene, m-amino-a-methylstyrene, 3-aminophenylacetylene, and 4-aminophenylacetylene;

Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltri P-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenylmethyldiethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenylmethyldiethoxysilane, -Aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane, m-aminophenylmethyldiethoxysilane, and other compounds having a monovalent organic group represented by the formula (?).

Of the terminal crosslinking agent (T2), a compound having a crosslinkable unsaturated bond, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are preferable, and 4-ethynyl aniline, 3-ethynyl aniline, m-aminostyrene, p-aminostyrene, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are more preferable.

The terminal crosslinking agent (T2) may be used alone or in admixture of two or more, but from the viewpoint of uniformly controlling the crosslinking density, it is preferable to use only one type.

1.1.6 Synthesis conditions of amide acid (A)

Preferable synthesis conditions of the amide acid (A) will be described below.

≪ Synthesis of amide acids (A1) and (A2)

The amide acids (A1) and (A2) can be synthesized, for example, by reacting one or two amino groups of the dimeric diamine (a1) with the terminal crosslinking agent (T1).

≪ Synthesis of polyamic acid (A3) >

The polyamic acid (A3) can be obtained, for example, by reacting a diamine (a12) with an acid anhydride (a3) and then reacting the terminal amino group of the obtained reaction product with the terminal crosslinking agent (T1) and / Can be synthesized by reacting the terminal anhydride group of the terminal crosslinking agent (T2) with the terminal crosslinking agent (T2).

For example, the structural unit represented by the following formula (A3-1) is formed by the reaction of the diamine (a12) and the acid anhydride (a3), and the terminal crosslinking agent (T1) A molecular end group represented by the formula (T1 ') is formed, and a molecular end group represented by the following formula (T2') is formed by the reaction of the terminal cross-linker (T2) and the acid anhydride group. The polyamic acid (A3) has at least one of the above-mentioned molecular end groups.

...식(A3-1)

... (A3-1)

In the formula (A3-1), X is an organic group having 2 to 100 carbon atoms, specifically, a residue of an acid anhydride (a3), Y is a residue of a diamine (a12) (-R < ¹ > -) of the dimeric diamine (a1).

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

The molecular end groups represented by at least one kind selected from the formulas (T1 ') and (T2') serve as terminal endblocks of the polyamic acid, so that the terminal crosslinking agent (T1) and the terminal crosslinking agent By appropriately adjusting the amount of the at least one terminal cross-linking agent, the weight average molecular weight of the polyamic acid (A3) can be controlled to 500 to 10,000.

The number of moles of the diamine (a12) is n2, the number of moles of the acid anhydride (a3) is n3, and the number of moles of the terminal cross-linking agent (a3) T1) is n4, the reaction molar ratio is adjusted such that the respective molar numbers become the relationships of (1) 0.1 · n1 / n2 · 1.0 and (2) 0.5 · (n3 + 0.5 × n4) /n2.13 It is preferable to adjust it.

The number of moles of the diamine (a12) is n2, the number of moles of the acid anhydride (a3) is n3, and the amount of the terminal cross-linking agent (a3) (1 ') 0.1 · n1 / n2 · 1.0 and (2') 0.3 · n3 / (n2 + 0.5 × n5) · 1.3 when the number of moles of the compound (T2) It is preferable to adjust the molar ratio.

By using the polyamic acid (A3) prepared so as to satisfy the formula (1) or (1 '), a polyimide film excellent in heat resistance, adhesion, low dielectric constant and low absorptivity can be obtained . When the ratio is 0.5 or more in the formula (2) or the ratio is 0.3 or more in the formula (2 '), the alkali resistance and the plating adhesion of the obtained polyimide film are improved. When the ratio is 1.3 or less in the formulas (2) and (2 '), the solubility of the resulting polyamic acid (A3) in the solvent is improved.

By using the polyamic acid (A3) prepared so as to satisfy both of the formulas (1) and (2) (or the formulas (1 ') and (2')) It is possible to form a balanced polyimide film having excellent water absorption, good adhesion to plated copper, and good resistance to an aqueous alkali solution.

<Reaction solvent>

Examples of the reaction solvent that can be used in the synthesis of the amide acid (A) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol 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, ethylene glycol monomethyl ether acetate, ethylene 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, di 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 Propylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2 2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, (Trade name) manufactured by Idemitsu Kosan Co., Ltd., N- Methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone.

Among the reaction solvents, at least one selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether and? -Butyrolactone is dissolved in a reaction solvent It is preferable to use ink having little damage to the ink jet head.

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

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

&Lt; Addition sequence 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 in which one or both of the terminal cross-linking agent of the diamine (a12), the acid anhydride (a3), the terminal crosslinking agent (T1) and the terminal crosslinking agent (T2) A method in which a diamine (a12) and an acid anhydride (a3) are reacted in advance to synthesize a polymer and then a terminal cross-linking agent (T1) and a terminal cross-linking agent (T2) A method in which the diamine (a12) and the terminal crosslinking agent (T1) are dissolved in a reaction solvent, and then the acid anhydride (a3) and, if necessary, the terminal crosslinking agent (T2) are added; A method in which the diamine (a12) and the terminal crosslinking agent (T2) are dissolved in a reaction solvent, and then the acid anhydride (a3) and, if necessary, the terminal crosslinking agent (T1) are added; The acid anhydride (a3) and the terminal crosslinking agent (T2) are dissolved in a reaction solvent, and then the diamine (a12) and, if necessary, the terminal crosslinking agent (T1) are added.

1.2 Solvent (B)

The thermosetting ink composition of the present invention can be obtained, for example, by dissolving an amide 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 amide acid (A). Further, even if the solvent does not dissolve the amide acid (A) alone, it can be used as the solvent (B) by mixing with another solvent.

Examples of the solvent (B) include ethers such as ethyl acetate, ethanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl 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, di Ethylene glycol monoethyl Diethylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, 1,3-dioxolane, 1,4-dioxane, anisole, methyl benzoate, ethyl benzoate, 1- (3-methoxyethyl) propanoate, Ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylpropionamide, ethylamide (manufactured by Idemitsu Kosan Co., Ltd.) (Trade name), N-methyl-epsilon -caprolactam, 1,3-dimethyl-2-imidazolidinone, have.

Among the solvent (B), for example, in view of improving the durability of the ink-jet head, the ink composition of the present invention contains ethyl lactate, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, It is preferable that at least one selected from glycol methyl ethyl ether, propylene glycol monomethyl ether acetat, methyl 3-methoxypropionate and? -Butyrolactone is contained as the solvent (B).

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

Examples of the amide solvent include 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1- 2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-epsilon-caprolactam and 1,3-dimethyl-2-imidazolidinone, which are products of Umasan (Idemitsu Kosan Co., Ltd.).

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

It is preferable that the solvent (B) can be used in an amount such that the solid content concentration in the ink of the present invention is usually 15 to 80% by weight, particularly 20 to 80% by weight. In the present invention, the solid concentration refers to the total concentration of all components other than the solvent (B). When the content of the solvent (B) is not less than the above lower limit value, the viscosity of the ink is not excessively increased and the jetting property is improved. If the content of the solvent (B) is not more than the upper limit, the polyimide film that can be formed by one-time jetting does not become excessively blurred. As described above, the ink of the present invention can be suitably used for ink jet applications.

1.3 Additives

The thermosetting ink composition of the present invention may contain an additive depending on the intended characteristics. 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 adjusting agent, an antirust agent, an antiseptic agent, a fungicide, an antioxidant, 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, a compound having at least one oxirane ring or oxetane ring is referred to as an epoxy resin. In the present invention, as the epoxy resin, a compound having two or more oxirane rings can be preferably employed.

The concentration of the epoxy resin in the ink of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight. With this concentration range, the coating film formed of the ink of the present invention has good heat resistance, chemical resistance, and flatness.

As the epoxy resin, for example, a copolymer of 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, a monomer having an oxirane ring and other monomers .

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

(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (Meth) acrylates such as hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) .

Specific examples of preferred polymers of monomers having an oxirane ring and monomers having an oxirane ring and other monomers include polyglycidyl methacrylate, copolymers of methyl methacrylate and glycidyl methacrylate , Copolymers of benzyl methacrylate and glycidyl methacrylate, copolymers of n-butyl methacrylate and glycidyl methacrylate, copolymers of 2-hydroxyethyl methacrylate and glycidyl methacrylate , Copolymers of (3-ethyl-3-oxetanyl) methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate. When the ink of the present invention contains these epoxy resins, it is preferable because the heat resistance of the coating film formed with the ink becomes good.

Specific examples of the epoxy resin include epoxy resins 807, 815, 825, 827, 828, 190 P, 191 P, 1004, 1256 (Manufactured by Mitsubishi Chemical Corporation), and these epoxy resins were previously marketed by Japan Epoxy Resin Co., Ltd. as Epikoto (trade name)), trade name "Coraldehyde CY177", trade name "Coraldehyde CY184 (Manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), Trade name &quot; TECHNOA VG3101L &quot; (trade name, product of BASF), &quot; Ceroxides 2021P &quot;, &quot; Mitsui Chemicals, Inc.), N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, and N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane. Among them, the trade name of "CER184", "SERLOCIDE 2021P", "TECHMORE VG3101L" and "EPRIPHERIC RESIN 828" are preferred because the flatness of the obtained polyimide film is particularly good.

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

1.3.2 Polyimide resin

The polyimide resin is not particularly limited as long as it has an imide group. The polyimide resin may also include a structure derived from a dimer acid.

The concentration of the polyimide resin in the ink of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight. With this concentration range, the coating film formed with the ink of the present invention has good heat resistance, chemical resistance, and endurance.

The polyimide resin is obtained, for example, by imidizing an amide acid obtained by reacting an acid anhydride with a diamine. As the acid anhydride, for example, there can be mentioned a compound having two acid anhydride groups among the acid anhydrides (a3) usable for the synthesis of the amide acid (A). Examples of the diamine include dimer acid diamine (a1) and other diamine (a2) which can be used for the synthesis of amide acid (A).

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

1.3.3 Polymerizable Monomers

Examples of the polymerizable monomer include monofunctional polymerizable monomers having hydroxyl, monofunctional polymerizable monomers having no hydroxyl, bifunctional (meth) acrylates, and polyfunctional (meth) acrylates having three or more functionalities. .

The concentration of the polymerizable monomer in the ink of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight. With this concentration range, the coating film formed of the ink of the present invention has good heat resistance, chemical resistance, and flatness.

Examples of the monofunctional monomer having hydroxyl include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) And 4-cyclohexanedimethanol mono (meth) acrylate. Of these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferable in that the film to be formed can be made flexible.

Examples of monofunctional polymerizable monomers having no hydroxyl include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, isobonyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, t- butyl (meth) acrylate, cyclohexyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, glycerol mono (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (Meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) (Meth) acryloxymethyloxetane, 3-ethyl-3- (Meth) acryloxyethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (Meth) acryloyloxymethyloxetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (Meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide, N-phenylmaleimide, (3-ethyl-3-oxetanyl) (Meth) acrylic acid,? -Chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, (Meth) acrylate, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl] There may be mentioned the product [2- (meth) acryloyl oxyethyl], [2-oxyethyl (meth) acrylate] cyclohexene-3,4-dicarboxylic acid mono.

Examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric 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 and dipentaerythritol diacrylate .

Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri Acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, pentaerythritol tetra Alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (Meth) acrylate, dipentaerythritol hexa (metha) acrylate, caprolactone modified dipentaerythritol hexa (metha) acrylate, ethylene oxide modified phosphoric acid penta (meth) Isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.

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

1.3.4 Surfactants

The surfactant can be used to improve the wettability, leveling property, or coatability of the ink of the present invention to the base substrate, and it is preferable that the surfactant can be used in an amount of 0.01 to 1% by weight of the ink of the present invention.

Byk-300, Byk-306, Byk-335, Byk-310, and Byk can be used as the surfactant in order to improve the applicability of the ink of the present invention. Silicone surfactants such as "-341", "Byk-344" and "Byk-370" (manufactured by BYK Japan KK); Acrylic surfactants such as BYK-354, BYK-358 and BYK-361 (manufactured by VICK Chemie Japan); And fluorine surfactants such as DFX-18, Futagent 250 and Futazent 251 (manufactured by NEOS COMPANY Ltd.).

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

1.3.5 Antistatic agent

The antistatic agent can be used for preventing the charging of the ink of the present invention, and is preferably usable in an amount of 0.01 to 1% by weight in the ink of the present invention.

As the antistatic agent, a known antistatic agent can be used. Specifically, metal oxides such as tin oxide, tin oxide-antimony oxide complex oxide, and tin oxide-indium oxide composite oxide; Quaternary ammonium salts.

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 silane coupling agent can be used. The coupling agent is preferably used in the ink of the present invention in an amount of 0.01 to 3% by weight.

Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Preferable examples include gamma -vinylpropyltrimethoxysilane, gamma -vinylpropyltriethoxysilane, gamma -acryloylpropylmethyldimethoxysilane, gamma -acryloylpropyltrimethoxysilane, gamma -propyltrimethoxysilane, gamma- Acryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloyl Methyldiethoxysilane,? -Methacryloylpropyltriethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane ,? -glycidoxypropyltriethoxysilane,? -aminopropylmethyldimethoxysilane,? -aminopropyltrimethoxysilane,? -aminopropylmethyldimethoxysilane,? -aminopropyltriethoxysilane, N- Aminoethyl-gamma-iminopropylmethyldimethoxysilane, N- Aminoethyl-gamma -aminopropyldiethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltriethoxysilane , N-phenyl- gamma -aminopropylmethyldimethoxysilane, N-phenyl- gamma -aminopropylmethyldiethoxysilane, gamma -mercaptopropylmethyldimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma-mercapto Propyl methyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane.

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

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. The epoxy curing agent is preferably used in an amount of 0.2 to 5% by weight of the ink of the present invention.

Examples of the epoxy curing agent include organic acid dihydrazide compounds, imidazoles and derivatives thereof, dicyandiamides, aromatic amines, polyvalent carboxylic acids and polyvalent carboxylic acid anhydrides. Specific examples include organic acid dihydrazide compounds such as adipic acid dihydrazide and 1,3-bis (hydrazinocarbonyl) -5-isopropylhydantoin; Phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, 2-phenylimidazole, Imidazole derivatives such as 4-methyl-5-hydroxymethylimidazole; Dicyandiamides such as dicyandiamide; Polyvalent carboxylic acids such as trimellitic acid; There may be mentioned polyvalent carboxylic anhydrides such as phthalic anhydride, trimellitic acid anhydride, and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride. Of these, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferable.

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

1.3.8 Pigments or dyes

Examples of the pigment include at least one selected from the group consisting of boron nitride, aluminum nitride, silicon carbide, alumina, magnesia, silica, rutile type titanium oxide, zinc oxide, low valence titanium oxide and graphite. . Rutile type titanium oxide refers to white titanium oxide represented by TiO ₂ . The lower titanium oxide refers to black titanium oxide such as Ti ₃ O ₅ , Ti ₂ O ₃ , and TiO ₂ . For example, titanium dioxide (black), which is known as titanium black, is commercially available as Tiac D (trade name) available from Ako Kasei Co., Ltd. Examples of the dyes include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes.

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 at room temperature storage. In addition, by using the ink, it is possible to form a balanced polyimide film having low water absorption, good insulating property, chemical resistance and substrate adhesion.

In particular, in the present invention, it is possible to achieve both a high concentration of 15% by weight or more of the solid content concentration and a low viscosity suitable for inkjet printing, thereby improving the ejection stability of the ink and increasing the film thickness of the resulting coating film. The ink of the present invention having such characteristics can be suitably used particularly as an inkjet ink.

1.4.1 Viscosity

When the thermosetting ink composition of the present invention is used for an inkjet application, the viscosity of the ink composition at 25 ° C and 20 rpm is usually 1 to 50 mPa · s, preferably 5 to 30 mPa · s, more preferably 5 to 30 mPa · s, 20 mPa 占 퐏, and further preferably 8 to 20 mPa 占 퐏. When the viscosity at 25 占 폚 is in the above range, the jetting accuracy by the ink jet application method is improved. If the viscosity at 25 占 폚 is lower than the upper limit, ink-jet ejection failure is difficult to occur.

When the inkjet head is jetted by heating, the viscosity at 20 rpm while heating the ink composition (discharge temperature (preferably 30 to 120 ° C)) is usually 1 to 50 mPa · s, preferably 5 to 30 mPa · s s, more preferably from 8 to 20 mPa · s, further preferably from 5 to 15 mPa · s. When the viscosity is within the above range, the jetting accuracy by the ink-jet application method is improved. If the viscosity is lower than the upper limit, ink-jet discharge failure is difficult to occur.

On the other hand, the viscosity is 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 캜 is usually 20 to 70 mN / m, preferably 20 to 40 mN / m. When the surface tension is within the above range, good droplets can be formed by jetting, and a meniscus can be formed.

2. Ink application method and polyimide film production method

The method of applying the ink of the present invention comprises the steps of (1) coating the ink of the present invention on a substrate by an ink-jet coating method to form a coating film (coating film formation step), and (2) Curing treatment step). The method for producing a polyimide film of the present invention is a method for forming a polyimide film using the above-mentioned coating method.

When an ink for an ink jet printer is printed in a pattern shape (e.g., a line shape or a square shape), a polyimide film of a pattern shape is formed. In the present specification, unless otherwise stated, the polyimide film is assumed to include a patterned polyimide film.

2.1 Coating process

As the ink jet application method, various types are available depending on the ink ejection method. Examples of the discharging method include a piezoelectric element type, a bubble jet (registered trademark) type, a continuous jet type, and an electrostatic induction type.

A preferable discharging method when applying by using the ink of the present invention is a piezoelectric element type. The head of the piezoelectric element type comprises a nozzle formation substrate having a plurality of nozzles, a pressure generating element formed of a piezoelectric material and a conductive material arranged to face the nozzle, and an ink filling the periphery of the pressure generating element, An on-demand ink jet application head which displaces a pressure generating element by an applied voltage and discharges a small droplet of ink from a nozzle.

The ink-jet applying device is not limited to the configuration in which the application head and the ink containing portion are separately provided, and a configuration in which they are separated from each other may be adopted. In addition, the ink accommodating portion is mounted on the carriage in such a manner that the ink accommodating portion is detachably or non-removably integrated with the applying head. In addition, the ink accommodating portion is provided at a fixing portion of the apparatus, and ink is supplied to the applying head through the ink supplying member, Or may be in the form of supplying.

In the case of providing the ink tank with a structure for applying a preferable negative pressure to the application head, the ink tank may be provided with an absorber disposed on the ink containing portion of the ink tank, And a spring having a spring portion for exerting an urging force in the direction of expansion. The application device may take the form of a line printer which is formed by aligning the application device over a range corresponding to the full width of the application medium, other than employing the serial application method.

When the viscosity of the ink of the present invention is high, it is preferable to heat the inkjet head to 30 to 80 캜, and then apply the ink after lowering the viscosity of the ink.

A coating film can be formed by applying the ink of the present invention onto a substrate by an ink jet coating method and then drying (removing the solvent) in a hot plate or an oven. By the above drying, a coating film is formed on the substrate to such an extent that the shape can be maintained.

Drying conditions vary depending on the kind and blending ratio of the contained components of the ink, but are usually from 70 to 120 캜, from 5 to 15 minutes when using an oven, and from 1 to 15 minutes when using a hot plate.

2.2 Curing process

The curing treatment is carried out in, for example, a hot plate or an oven in order to obtain heat resistance, chemical resistance, flatness, and sufficient mechanical strength of the coating film, whereby the entire surface or a predetermined pattern shape (e.g., ) Polyimide film is formed.

The curing treatment is usually carried out at 180 to 350 占 폚, preferably 200 to 300 占 폚. The curing treatment time (heating time) is, for example, 30 to 90 minutes when using an oven and 5 to 30 minutes when using a hot plate. The curing treatment is not limited to the heat treatment, and may be UV treatment, irradiation with an ion beam, electron beam, gamma ray, or the like. In this manner, a polyimide film is formed.

In the case of producing a patterned polyimide film, in the present invention, since ink is ejected (conversely) only to a necessary portion by inkjet printing, it is possible to form a polyimide film by using other methods such as etching in photolithography The amount of material used is overwhelmingly small, and there is no need to use a photomask. Therefore, in the present invention, it is possible to mass-produce various kinds of polyimide films, and the number of steps required for manufacturing can be reduced.

3. Polyimide film

The polyimide film of the present invention is obtained in the above-described thermosetting ink composition. For example, the thermosetting ink composition of the present invention is applied onto a substrate by an ink-jet coating method to form a coating film, and then the coating film is cured.

In the ink of the present invention, the solid content concentration can be set high as described above. For this reason, in the present invention, a polyimide film having a thickness of usually 2 μm or more, preferably 2 to 10 μm can be obtained by one-time ink jetting, and the film thickness is larger than the film thickness of the polyimide film obtained in the conventional ink. For example, when a thick insulating film having a thickness of about 10 mu m is formed, the number of times of overcoating can be reduced and the manufacturing process of the insulating film can be shortened by using the ink of the present invention.

The insulating film formed of the polyimide film of the present invention has a low water absorbability and exhibits good adhesion with the substrate in the use of a printed wiring board (in particular, a flexible wiring board), exhibits good resistance to chemicals, Has a high mechanical strength and can improve the reliability and product yield of electronic parts.

4. Film substrate

The film substrate of the present invention has a film and the above-described polyimide film formed on the film. The film substrate can be produced, for example, by forming a polyimide film on a film on which wirings are formed (for example, a polyimide film) according to the above-described 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 limited thereto, and can be formed on a known substrate.

Examples of the substrate applicable to the present invention include a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, a paper substrate, and the like, which are suitable for various standards such as FR-1, FR-3, FR-4, CEM- Epoxy substrate, green epoxy substrate, and BT resin substrate.

Examples of other substrates applicable to the present invention include a substrate made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, Or may be a substrate having on it a); (Zirconium), zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate, lead titanate (PT), lead zirconate titanate (PZT) (PLZT) zirconium titanate zirconate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide, beryllium oxide, silicon oxide, silicon carbide, silicon nitride ), A substrate formed of ceramics such as boron nitride (boron nitride), zinc oxide, water light, ferrite, stearate, forsterite, spinel and spodumene (which may be a substrate having these ceramics on its surface); (Polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polyethylene cyclohexylene dimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, Polyimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer, liquid crystal polymer, polyimide resin, polyamide resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyetherimide resin, (Which may be a substrate having these resins on its surface); Semiconductor substrates such as silicon, germanium, and gallium arsenide; A glass substrate; A substrate on which an electrode material such as tin oxide, zinc oxide, indium tin oxide (ITO), and antioxidant tin oxide (ATO) is formed on the surface; gel sheets such as? GEL (alpha gel),? GEL (beta gel),? GEL (theta gel) and? GEL (gamma gel) (registered trademark of Taica Corporation).

5. Electronic parts

The electronic component of the present invention is an electronic component having the above-mentioned film substrate. As described above, a flexible electronic component can be obtained by using the film substrate of the present invention. As an application method of the present invention, for example, an insulating film for a flexible wiring and an electronic part using the insulating film can be mentioned.

6. Examples of compounds

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

6.1 Other diamines (a2)

The other diamine (a2) is not particularly limited as long as it contains two amino groups and excludes diamines derived from dimeric acid. Examples thereof include m-xylylenediamine, p-xylylenediamine, 2.2.1] heptane, compounds represented by the following formulas (I) to (VII), and compounds represented by the following formulas (i) ) To (iii).

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

In the formulas (III), (V) and (VII), A ² represents 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 -, wherein n is an integer from 1 to 6.

In the formulas (VI) and (VII), two A ^{3 s} present are each independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) ₂ -, -C ₃ ) _2- or an alkylene of 1 to 3 carbon atoms.

Among the above-mentioned formula (I) to formula (VII), a cyclohexane ring or a benzene ring having at least one hydrogen is, or may be substituted with at least one member selected from -F, and -CH _3.

In the above formula (i), n is an integer of 1 to 50. Examples of commercially available products of the compound represented by the above formula (i) include Jefamine D-230 (trade name, manufactured by Huntsman) and Jefamin D-400 (trade name, manufactured by Huntsman).

In the formula (ii), Y is an integer of 1 to 40, and X + Z is an integer of 1 to 6. Examples of commercial products of the compound represented by the formula (ii) include Jeffamine HK-511 (trade name, product of Huntsman), Jeffamine ED-600 (product name, (Trade name, manufactured by Huntsman), and Zephamine ED-2003 (trade name, manufactured by Huntsman).

In the formula (iii), n is an integer of 1 to 10, and X is an integer of 1 to 10. Examples of commercial products of the compound represented by the formula (iii) include Zephamine EDR-148 (trade name, manufactured by Huntsman), Zephamine EDR-176 (trade name, manufactured by Huntsman) And diethylene glycol bis (3-aminopropyl) ether (available from Aldrich).

Examples of the compound represented by the formula (I) include compounds represented by the following formulas (I-1) to (I-3). Examples of the compound represented by the formula (II) include compounds represented by the following formulas (II-1) to (II-2). Examples of the compound represented by the formula (III) include compounds represented by the following formulas (III-1) to (III-3). Examples of the compound represented by the formula (IV) include compounds represented by the following formulas (IV-1) to (IV-5). Examples of the compound represented by the formula (V) include compounds represented by the following formulas (V-1) to (V-30). Examples of the compound represented by the formula (VI) include compounds represented by the following formulas (VI-1) to (VI-6). Examples of the compound represented by the formula (VII) include compounds represented by the following formulas (VII-1) to (VII-12).

Among other diamines (a2), 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone , Bis [3- (4-aminophenoxy) phenyl] sulfone, 3,3'-dimethyl-4,4'- diaminodiphenylmethane, 2,2- ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m- Bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [ Bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1, 2.2.1] heptane, and 2,6-bisaminomethylbicyclo [2.2.1] heptane are preferable as the starting material Do.

Other diamines (a2) include compounds represented by the following formula (VIII).

Among the above-mentioned formula (VIII), A ⁴ represents a single bond, -O-, -COO-, -OCO-, -CO- , -CONH-, - (CH 2) p -, - (CH 2) p -O- Or -O- (CH ₂ ) _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; When the positional relationship between the two amino groups bonded to the benzene ring is para-position, R ¹⁰ may be alkyl of 1 to 30 carbon atoms, and when the positional relationship is meta-position, R ¹⁰ is alkyl of 1 to 30 carbon atoms Or phenyl.

The alkyl of 1 to 30 carbon atoms in R ¹⁰ may be either linear or branched. At least one -CH ₂ - of the alkyl may be substituted with at least one member selected from -CF ₂ -, -CHF-, -O-, -CH = CH- and -C≡C-, and at least One -CH ₃ may be substituted with at least one member selected from -CH ₂ F, -CHF _2, and -CF ₃ .

Hydrogen which is bonded to a ring carbon in the form of phenyl in R ¹⁰ is _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2 , and at least one may be substituted by member selected from -OCF ₃ .

In the formula (VIII), although two amino groups are bonded to the phenyl ring carbon, the bond positional relationship of the two amino groups is preferably a meta-position or a para-position. Furthermore, it is preferable that the two amino groups are respectively bonded to the 3 rd and 5 th positions, or to the 2 nd and 5 th positions when the bonding position of 'R ¹⁰ -A ⁴ -' to the benzene ring is set to 1, respectively.

Examples of the compound represented by the formula (VIII) include compounds represented by the following formulas (VIII-1) to (VIII-11).

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

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

Examples of the compound represented by the formula (VIII) include compounds represented by the following formulas (VIII-12) to (VIII-17).

Among the above-mentioned formula (VIII-12) to formula (VIII-15), R ¹³ is an alkyl group containing 1 to 30 carbon atoms, 4 carbon atoms preferably from a to 16 alkyl, more preferably a C 6 -C 16 alkyl.

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

Examples of the compound represented by the above formula (VIII) include compounds represented by the following formulas (VIII-18) to (VIII-38).

(VIII-18), (VIII-19), (VIII-22), (VIII-24), (VIII-25), (VIII- In the formulas (VIII-31), (VIII-36) and (VIII-37), R ¹⁵ is an organic group having 1 to 30 carbon atoms and is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms More preferably an alkyl having 3 to 12 carbon atoms or an alkoxy having 3 to 12 carbon atoms.

(VIII-20), (VIII-21), VIII-23, VIII-26, VIII-27, VIII- expression from the (VIII-35) and formula (VIII-38), R ¹⁶ is hydrogen, -F, alkoxy having 1 to 12 carbon atoms alkyl, having from 1 to _{12, -CN, -OCH 2 F, -OCHF} 2 , or - OCF ₃ , and is preferably an alkyl having 3 to 12 carbon atoms or an alkoxy having 3 to 12 carbon atoms.

Among the above-mentioned formula (VIII-33) and formula (VIII-34), A ⁵ is an alkylene of 1 to 12 carbon atoms.

Examples of the compound represented by the above formula (VIII) include compounds represented by the above formulas (VIII-39) to (VIII-48).

(VIII-2), (VIII-4), (VIII-2), (VIII-3) 5) and (VIII-6) are more preferable.

Other diamines (a2) include compounds represented by the following formulas (IX) to (X).

In the formulas (IX) and (X), R ¹⁷ is hydrogen or -CH ₃ , and the two R ^{18 s} present are each independently hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, The two A ⁶ present are each independently a single bond, -C (= O) - or -CH ₂ -. In formula (X), R ¹⁹ and R ²⁰ are each independently hydrogen, alkyl of 1 to 20 carbon atoms or phenyl.

In the above formula (IX), two 'NH ₂ -Ph-A ⁶ -O-' (-Phe- represents phenylene) bonded to the B ring of the steroid nucleus is bonded to the steroid nucleus at the third And the other is connected to the sixth position. The two amino groups are each bonded to a phenyl ring carbon, but it is preferable that the two amino groups are bonded to a meta-position or a para-position with respect to the bonding position of A ^{6 to} the phenyl ring.

In the formula (X), two 'NH ₂ - (R ²⁰ -) Ph-A ⁶ -O-' (--Phe- indicates phenylene) are each bonded to a phenyl ring carbon, If you think is the ^{'Ph-a 6 -O- - -} (R 20) NH 2' a bond, the steroid nucleus, and the ring of the steroid nucleus ^{_{'NH 2 - Ph-a 6}} -O- - (R 20)' The positional relationship is preferably a meta-position or a para-position. The two amino groups are each bonded to a phenyl ring carbon, but it is preferable that the two amino groups are bonded to a meta or para position with respect to A &lt; ^{6 &} gt ;.

Examples of the compound represented by the formula (IX) include compounds represented by the following formulas (IX-1) to (IX-4).

Examples of the compound represented by the formula (X) include compounds represented by the following formulas (X-1) to (X-8).

Other diamines (a2) include compounds represented by the following formula (XI) and compounds represented by the following formula (XII).

In the formula (XI), R ²¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ - in the alkyl is -O-, -CH = CH- or -C≡C- And each of A 2 to A ⁷ is independently -O- or alkylene having 1 to 6 carbon atoms, A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms, and the ring T is 1,4-phenylene Or 1,4-cyclohexylene, and h is 0 or 1.

In the formula (XII), R ²² is alkyl having 2 to 30 carbon atoms, and among them, alkyl having 6 to 20 carbon atoms is preferable. R ²³ is hydrogen or alkyl having 1 to 30 carbon atoms, and among these, alkyl having 1 to 10 carbon atoms is preferable. The two A ⁹ present are each independently -O- or alkylene having 1 to 6 carbon atoms.

In the formula (XI), each of the two amino groups is bonded to the phenyl ring carbon, but it is preferable that the two amino groups are bonded to the meta or para position with respect to A &lt; ^{7 &} gt ;. In the formula (XII), the two amino groups are bonded to the phenyl ring carbon, respectively, but it is preferable that the two amino groups are bonded to the meta or para position with respect to A &lt; ^{9 &} gt ;.

Examples of the compound represented by the above formula (XI) include 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1- Phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, , And compounds represented by the following formulas (XI-1) to (XI-9).

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

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

Examples of the compound represented by the formula (XII) include compounds represented by the following formulas (XII-1) to (XII-3).

In the formulas (XII-1) to (XII-3), R ²⁶ is alkyl having 2 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and R ²⁷ is hydrogen or alkyl having 1 to 30 carbon atoms Among them, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.

Examples of the other diamines (a2) include m-xylylenediamine, p-xylylenediamine, 2,5-bisaminomethylbicyclo [2.2.1] heptane, 2,6-bis Aminomethylbicyclo [2.2.1] heptane, the compounds represented by the above formulas (I) to (XII), and the compounds represented by the above formulas (i) to (iii) However, diamines other than these compounds may also be used. For example, naphthalene diamine having a naphthalene structure, fluorene diamine having a fluorene structure, and siloxane diamine having a siloxane bond can be used alone or in combination with a compound represented by the above formula (I) to (XII) Can be used in admixture with the diamines of the above-mentioned examples.

As the siloxane diamine, for example, there can be mentioned a compound represented by the following formula (XIII).

In the above formula (XIII), R ²⁸ and R ²⁹ are each independently alkyl having 1 to 3 carbon atoms or phenyl, R ³⁰ is methylene, phenylene, or phenylene having at least one hydrogen substituted with alkyl having 1 to 10 carbon atoms Each of x is 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 such a case, y is particularly preferably an integer of 1 to 15. R ²⁸ , R ²⁹ and R ³⁰ , which are present in plural numbers, may be mutually the same or different.

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

Other diamines (a2) include compounds represented by the following formulas (11) to (18).

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

Other diamines (a2) that can be used for synthesizing the amide acid (A) are not limited to diamines exemplified above, but various other types of diamines can be used within the scope of attaining the object of the present invention.

The other diamines (a2) which can be used for synthesizing the amide acid (A) may be used alone or in a mixture of two or more. In other words, as a combination of two or more kinds, diamines other than the above-exemplified diamines and diamines other than the above-exemplified diamines may be mentioned. Particularly, it is preferable to use at least one compound selected from the group consisting of m-xylylenediamine, p-xylylenediamine, 2,5-bisaminomethylbicyclo [2.2.1] heptane, 2,6-bisaminomethylbicyclo [2.2.1] heptane, At least one member selected from a compound represented by the formula (I) to (VII), a compound represented by the formula (VIII), a compound represented by the formula (i), a siloxane-based diamine and a fluorene-

6.2 Acid anhydride (a3)

As the acid anhydride (a3), for example, tetracarboxylic acid anhydride; Copolymers of maleic anhydride and styrene, copolymers of maleic anhydride and methyl methacrylate, and radical polymerizable monomers having acid anhydride groups and other radical polymerizable monomers.

Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), 2,2 ', 3,3'-diphenyl Sulfonic tetracarboxylic acid dianhydride (BPS-TME), 3,3 ', 4'-diphenylsulfonetetracarboxylic acid dianhydride, 4,4'-dihydroxyphenylsulfone bistrimelic acid dianhydride (BPS- , 4,4'-diphenyl ether tetracarboxylic acid dianhydride (ODPA), 2,2 ', 3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid Dianhydride, 3,3 ', 4,4'-diphenylmethane tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride (6FDA), ethylene glycol bis Anhydrotrimellitate), cyclobutane tetracarboxylic acid anhydride, methylcyclobutane Cyclohexanetetracarboxylic acid dianhydride, ethanetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, 1,3-dihydro-1,3-dioxolan- (2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] di-4,1-phenylene ester, 2,2-bis Hydroxyphenyl) propane dibenzoate-3,3 ', 4,4'-tetracarboxylic acid dianhydride (TMBPA), 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid oxydi- (Trimellitic acid monoester acid anhydride) (TMHQ), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride (BPDA -H), bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic acid dianhydride, 5- (2,5- (BSAA), 4,4'- [(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid anhydride, Ethylenediamine tetraacetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, and the compounds represented by the following formulas 1-1 to 1-57 .

Among the specific examples of the tetracarboxylic acid dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride , 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic acid dianhydride, 2,2- [bis (3,4- Phenyl)] hexafluoropropane dianhydride, cyclobutane tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, p-phenylene bis (trimellitic acid monoester acid anhydride ), 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, 4,4 '- [(isopropylidene) bis (A) having high solubility in the solvent (B) can be obtained by using an anhydride such as p-phenyleneoxy)] diphthalic acid dianhydride, BPS-TME, TMBPA and OPPBP- It is preferable to be so.

In addition, high transparency is required depending on the use of the ink for ink jet. In this case, a copolymer of maleic anhydride and styrene, 3,3 ', 4,4'-benzophenone tetracarboxylic acid anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexa Butane tetracarboxylic acid dianhydride, p-phenylene bis (trimellitic acid monoester acid anhydride), 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, 4,4' - [(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid dianhydride, BPS-TME, TMBPA, OPPBP -TME is particularly preferred.

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

<Examples>

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited to these examples. The names of the diamine type diamine (a1), the other diamine (a2), the acid anhydride (a3), the terminal crosslinking agent (T1), the terminal crosslinking agent (T2) and the solvent (B) used in Examples and Comparative Examples are abbreviated All. These abbreviations are used in the following descriptions.

The dimer acid diamine (a1)

P-1074; PURIAMIN 1074 (trade name, manufactured by Croda Japan Co., Ltd.)

Other diamines (a2)

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

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

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

...화합물 1

... compound 1

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

...화합물 2

... compound 2

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

...화합물 3

... compound 3

In this equation, n is a mixture of 6.1

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

...화합물 4

... compound 4

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

DDE: 4,4'-diaminodiphenyl ether

DA8: 1,8-diaminooctane

DA12: 1,12-diaminododecane

The acid anhydride (a3)

BSAA: 4,4 '- [(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid anhydride

BPS-TME: 4,4'-dihydroxyphenylsulfone bistrimelic acid dianhydride (Compound 5 below)

...화합물 5

... compound 5

TMHQ: p-phenylenebis (trimellitic acid monoester acid anhydride) (Compound 6 below)

...화합물 6

... Compound 6

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

...화합물 7

... Compound 7

DSDA: 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride

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

OPPBP-TME: The following compound 8

...화합물 8

... Compound 8

ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid is anhydride

BPDA-H: 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid is anhydride

The terminal crosslinking agent (T1)

MA: maleic anhydride

TESA: 3- (triethoxysilyl) propyl succinic anhydride

ANA: Allylnadic anhydride

4-EPA: 4-phenylethynylphthalic anhydride

The terminal crosslinking agent (T2)

APSE: 3-aminopropyltriethoxysilane

Solvent (B) (reaction solvent)

EDM: diethylene glycol methyl ethyl ether

NMP: N-methyl-2-pyrrolidone

GBL:? -Butyrolactone

[Measurement of physical properties]

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

The weight average molecular weight of the amic acid (A) is obtained by diluting the obtained amide acid (A) with N, N-dimethylformamide (DMF) so that the concentration of the amide acid (A) is about 1% by weight, : Using the JASCO GULLIVER 1500 (Intelligent Differential Refractometer RI-1530) manufactured by JASCO Co., Ltd., the diluted solution was measured by the GPC method as a developing agent, Column GF-510HQ and GF-310HQ, which are products of SHOWA DENKO KK, were connected in this order, and the column temperature was 40 ° C , And a flow rate of 0.5 ml / min.

[Example 1]

31.50 g of EDM, 31.50 g of NMP, and 27.12 g of P-1074 as dimer acid diamine (a1) were added to a 300 ml four-necked flask equipped with a thermometer, a stirrer, g, and 9.88 g of MA was added as a terminal cross-linking agent (T1) while stirring in a dry nitrogen stream, followed by stirring at 40 캜 for 5 hours. As a result, a 37 wt% solution (ink) of light yellow transparent amidic acid (A) was obtained. The viscosity of this ink was 14.8 mPa 占 퐏 (25 占 폚), and the amide acid (A) had a weight average molecular weight of 800.

[Example 2]

39.50 g of EDM as the solvent (B), 39.50 g of NMP and 12.50 g of P-1074 as the dimer acid diamine (a1) were placed in a 300 ml four-necked flask equipped with a thermometer, a stirrer, g, and 2.30 g of MA was added as a terminal crosslinking agent (T1) while stirring in a dry nitrogen stream, followed by stirring at 40 占 폚 for 1 hour. Then, 6.10 g of BSAA was added as the acid anhydride (a3), and the mixture was stirred at 40 DEG C for 5 hours. As a result, a 21 wt% solution (ink) of a yellow transparent amidic acid (A) was obtained. The viscosity of the ink was 16.1 mPa 占 퐏 (25 占 폚), and the amide acid (A) had a weight average molecular weight of 6,000.

[Examples 3 to 5, Examples 7 to 10]

A solution (ink) of amidic acid (A) was prepared in the same manner as in Example 2 except that the raw materials were added as shown in Table 1 in Example 2, and the weight of the obtained amidic acid (A) The average molecular weight and the viscosity of the ink at 25 캜 were measured.

[Example 6]

41.50 g of EDM, 41.50 g of NMP, and P-1074 as dimer acid diamine (a1) were added to a 300 ml four-necked flask equipped with a thermometer, a stirrer, a feedstock feed auxiliary and a nitrogen gas inlet, g, and 1.66 g of MA was added thereto as a terminal cross-linking agent (T1) while stirring in a dry nitrogen stream, and the mixture was stirred at 40 占 폚 for 1 hour. Then, 3.03 g of BPS-TME and 2.32 g of TMHQ as an acid anhydride (a3) were added thereto at the same time, followed by stirring at 40 DEG C for 5 hours. As a result, a 17 wt% solution (ink) of yellow transparent amidic acid (A) was obtained. The viscosity of the ink was 14.0 mPa 占 퐏 (25 占 폚), and the weight average molecular weight of the amide acid (A) was 7,500.

 [Example 11]

39.00 g of EDM as a solvent (B), 39.00 g of NMP and P-1074 as a dimer acid diamine (a1) in a 300 ml four-necked flask equipped with a thermometer, a stirrer, and 3.71 g of BAPP as the other diamine (a2), 2.21 g of MA as a terminal crosslinking agent (T1) was added thereto while stirring in a dry nitrogen stream, and the mixture was stirred at 40 ° C for 1 hour. Then, 8.80 g of BSAA was added as the acid anhydride (a3), and the mixture was stirred at 40 DEG C for 5 hours. As a result, a 22 wt% solution (ink) of a yellow transparent amidic acid (A) was obtained. The viscosity of this ink was 14.5 mPa 占 퐏 (25 占 폚), and the amide acid (A) had a weight average molecular weight of 5,000.

[Examples 12 to 17, Examples 21 to 23]

A solution (ink) of amidic acid (A) was prepared in the same manner as in Example 11, except that the raw materials were added as shown in Table 2 in Example 11, and the weight of the obtained amidic acid (A) The average molecular weight and the viscosity of the ink at 25 캜 were measured.

[Example 18]

39.00 g of EDM, 39.00 g of NMP, and 11.61 g of P-1074 as dimer acid diamine (a1) were added to a 300 ml four-necked flask equipped with a thermometer, a stirrer, and 4.78 g of APSE as a terminal crosslinking agent (T2), 5.61 g of BSAA was added as an acid anhydride (a3) while stirring in a dry nitrogen stream, and the mixture was stirred at 40 ° C for 5 hours. As a result, a 22 wt% solution (ink) of a yellow transparent amidic acid (A) was obtained. The viscosity of this ink was 14.1 mPa 占 퐏 (25 占 폚), and the amide acid (A) had a weight average molecular weight of 1,800.

[Examples 19 to 20]

A solution (ink) of amidic acid (A) was prepared in the same manner as in Example 18, except that the raw materials were added as shown in Table 2 in Example 18, and the weight of the obtained amidic acid (A) The average molecular weight and the viscosity of the ink at 25 캜 were measured.

[Comparative Examples 1 to 11]

An amide acid solution (ink) was prepared in the same manner as in Example 11 except that the charging was carried out in the same manner as in Example 11 except that the weight average molecular weight of the obtained amide acid and the weight average molecular weight Was measured. However, in Comparative Examples 8 to 11, there was a precipitate, and a uniform ink which was solubilized could not be prepared.

Details of the respective conditions and physical properties of the examples and comparative examples are shown in Tables 1 to 4.

The evaluation methods of the inks obtained in Examples and Comparative Examples are described below.

[Ink characteristics]

(i) Evaluation of stable discharge time

The ink obtained in Examples and Comparative Examples was poured into an ink jet cartridge and mounted on an ink jet apparatus (DMP-2800 manufactured by FUJIFILM Dimatix). The ink was discharged at a discharging voltage (piezo voltage) of 16 V, , And the ejection shape was observed under the condition of a driving frequency of 5 kHz. During jetting, ink is ejected in the vertical direction, and ink droplets that contribute to the original image recording when the ink is dripped from the nozzles are ejected in the form of satellites (i.e., : Small droplet) was not caused to occur as a normal ejection, and the time during which ejection was normally continued from the start of jetting was observed. The observation was carried out for 20 minutes from the start of jetting, and the maximum value of the stable discharge time was 20 minutes.

[Formation of cured film]

The ink obtained in Examples and Comparative Examples was poured into an ink jet cartridge and mounted on an inkjet apparatus (DMP-2811, manufactured by FUJIFILM Dimatix). Using a head of 10 pL, a discharge voltage (piezo voltage) , The driving frequency is 5 kHz, the number of application times is 4 times for the ink having an amidic acid concentration of less than 20% by weight, 3 times for the ink of 20 to 25% by weight and less than 25% A square pattern of 40 mm x 40 mm was formed on a copper foil surface of a substrate (Neoplex NEX-13FE (trade name)) (manufactured by Mitsui Chemicals, Inc.) (thickness: 12.5 m) laminated on polyimide . Thereafter, the film was dried on a hot plate at 80 DEG C for 10 minutes, and further baked at each of the temperature conditions shown in Table 5 using an oven to obtain cured films each having a thickness of 8 to 11 mu m.

(ii) Resistance to aqueous alkaline solutions

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

AA: No coloring occurs at the interface between the cured film and the copper foil, and no abnormalities such as peeling are seen.

· CC: Coloration occurs at the interface between the cured film and the copper foil, and some problems such as peeling are seen.

(iii) plating test

 Electroless copper plating was performed on the cured film obtained above using an electroless copper plating solution PEA (product of UUEMURA & CO., LTD.) (Manufactured by Uemura & Co., Ltd.) , And the adhesion of the plated copper was observed.

AA: Plated copper was attached on the cured film.

CC: The cured film was dissolved, and the plated copper was not adhered.

Next, a copper plating layer having a thickness of 20 탆 was formed on the cured film after electroless copper plating, using an electrolytic copper plating solution EPL manufactured by Uemura Kogyo Co., Ltd. A nick of 2 mm x 30 mm was put into the copper plating layer with a cutter to peel off the interface between the copper plating layer and the cured film at the edge of the sliver edge to obtain a peel test sample. This sample was set in a tensile tester EZGraph manufactured by Shimadzu Corporation and the peel strength was measured.

(iv) Absorption rate measurement

A cured film was prepared in the same manner as in [Formation of a cured film] except that the substrate to be formed was changed to an aluminum foil, and the aluminum foil was peeled off to obtain a single film. This was immersed in ultrapure water at room temperature for 24 hours, and water droplets adhered to the surface of the membrane were wiped off with a nonwoven fabric, and the change in weight of the membrane was observed with a balance. Absorption rate (%) = (change in weight of membrane before and after absorption × 100) / (weight of membrane before absorption).

(V) Measurement of dielectric constant

The ink obtained in Examples and Comparative Examples was poured into an ink jet cartridge and mounted on an inkjet apparatus (DMP-2811 manufactured by FUJIFILM Dimatix), and a discharge voltage (piezo voltage) of 16 V and a head temperature of 30 DEG C , A drive frequency of 5 kHz, and a coating pattern of 70 mm x 50 mm on the chromium substrate in two times for the ink having an amide acid concentration of 25% by weight or less and one time for the ink having a concentration higher than 25% by weight. Thereafter, the film was dried on a hot plate at 80 DEG C for 10 minutes, and further baked in an oven under the respective temperature conditions shown in Table 5 to obtain cured films each having a thickness of 2 to 4 mu m. Thereafter, aluminum was vapor-deposited on the cured film to form an electrode. The dielectric constant was measured using a PASSIJON LCR meter E4980A (Agilent Technologies, Inc.).

The results of the above evaluation are shown in Table 5 for Examples and Comparative Examples.

When the thermosetting ink composition of the present invention is used as an inkjet ink, the ink is excellent in discharge stability from the inkjet head. Further, the cured film obtained from the ink exhibits resistance to alkali aqueous solution and adhesion to the copper plating layer Excellent in dielectric constant and absorptivity, and good as an insulating film.

Claims (17)

An amide acid represented by the following formula (A1);
An amide acid represented by the following formula (A2); And
(A3) having at least two acid anhydride groups, a terminal crosslinking agent represented by the following formula (T1), a compound represented by the following formula (T2), a diamine compound (a3) At least one amide acid (A) selected from a polyamic acid having a crosslinkable organic group at the molecular end, obtained by reacting one or both terminal crosslinking agents of the terminal crosslinking agent represented by the general formula (1).

[In the formulas (A1) and (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 2 to 100 carbon atoms.]

In the formula (T1), R ² is a divalent crosslinkable organic group having 2 to 100 carbon atoms. In formula (T2), R ³ is a monovalent crosslinkable organic group having 2 to 100 carbon atoms. The thermosetting ink composition according to claim 1, which is an inkjet ink. 3. The method according to claim 1 or 2,
The diamine (a1) derived from a dimer acid is one or more diamines obtained by a reductive amination reaction of a dimer acid obtained from an unsaturated fatty acid,
Wherein the unsaturated fatty acid is at least one selected from the group consisting of crotonic acid, myristic oleic acid, palmitoleic acid, oleic acid, elaidic acid, benzoic acid, valoleic acid, eicosanic acid, erucic acid, nerubic acid, linolic acid, phenolic acid, eleostearic acid, But are not limited to, Mead acid, dihomo-gamma-linolenic acid, eicosatrienoic acid, stearidic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentanenoic acid, , Tetracosapentaenoic acid, docosahexaenoic acid, and nisic acid. 3. The method according to claim 1 or 2,
In addition to the diamine (a1) derived from a dimer acid, the diamine (a12) may be a 3,3'-diaminodiphenylmethane, a 4,4'-diaminodiphenylmethane, a 4,4'- Diaminodiphenylsulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, 3,3'-dimethyl-4,4'- diaminodiphenylmethane, 2,2- (4-aminophenoxy) phenyl] propane, m-phenylenediamine, p-phenylenediamine, m-xylylene, Bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4 (4-aminophenoxy) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4- aminobenzyl) phenyl] cyclohexane, 1,1- Phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] methane, 2,5-bisaminomethylbicyclo [2.2.1] heptane, 2,6- Bicyclo [2.2.1] heptane, 9,9-bis (3-aminov (VIII), a compound represented by the following formula (XIII), and a compound represented by the following formula (i): wherein R 1 and R 2 each independently represent a hydrogen atom, Wherein the thermosetting ink composition further comprises at least one selected.

[In the formula (VIII), A ⁴ represents a single bond, -O-, -COO-, -OCO-, -CO- , -CONH-, - (CH 2) p -, - (CH 2) p -O - or -O- (CH ₂ ) _p , wherein 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; When the positional relationship between the two amino groups bonded to the benzene ring is para-position, R ¹⁰ may be alkyl of 1 to 30 carbon atoms, and when the positional relationship is meta-position, R ¹⁰ is alkyl of 1 to 30 carbon atoms Or at least one of -CH ₂ - in the alkyl may be substituted with at least one member selected from -CF ₂ -, -CHF-, -O-, -CH═CH- and -C≡C-, , At least one -CH ₃ of the alkyl may be substituted with at least one member selected from -CH ₂ F, -CHF ₂ and -CF ₃ , and the hydrogen bonded to the ring-forming carbon of the phenyl is -F, - _{CH 3, -OCH 3, -OCH 2} F, at least one may be substituted by member selected from -OCHF ₂ and -OCF _3.]

Wherein R ²⁸ and R ²⁹ are each independently alkyl having 1 to 3 carbon atoms or phenyl, and R ³⁰ is methylene, phenylene, or phenyl substituted with at least one hydrogen of alkyl having 1 to 10 carbon atoms Each of x is independently an integer of 1 to 6, and y is an integer of 1 to 70.]

... (i)
[In the above formula (i), n is an integer of 1 to 50.] 3. The method according to claim 1 or 2,
The compound (a3) having two or more acid anhydride groups is preferably selected from pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl Sulfone tetracarboxylic acid dianhydride, 2,3,4 ', 4'-diphenylsulfonetetracarboxylic acid dianhydride, 4,4'-dihydroxyphenylsulfone bistrimellic acid dianhydride, 3,3', 4,4 ' - diphenyl ether tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3 '(4,4'-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutane tetracarboxylic acid Dianhydride, methylcyclobutane tetracarboxylic acid is anhydrous , Cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, ethanetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, 1,3-dihydro-1,3-dioxo-5 (2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] di-4,1-phenylene ester, 2,2-bis (4-hydroxyphenyl) Propane dibenzoate-3,3 ', 4,4'-tetracarboxylic acid dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid oxy-4,1-phenylene ester , p-phenylenebis (trimellitic acid monoester acid anhydride), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene- Dicarboxylic acid anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, bicyclo [2,2,2] 2,3,5,6-tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3- 1, 2-dicarboxylic acid anhydride, 4,4 '- [(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, 2,3,4-tetrahydro-1-naphthalene succinic anhydride, a compound represented by the following formula

Wherein the thermosetting ink composition is a thermosetting ink composition. 3. The method according to claim 1 or 2,
Wherein the terminal crosslinking agent represented by the formula (T1) is at least one selected from the group consisting of maleic anhydride, citraconic anhydride, allylnadic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-ethynylphthalic anhydride, Wherein the thermosetting ink composition is at least one selected from anhydrides, cyclohexene-1,2-dicarboxylic acid anhydrides and 3- (triethoxysilyl) propyl succinic anhydrides. 3. The method according to claim 1 or 2,
Wherein the terminal crosslinking agent represented by the formula (T2) is at least one selected from the group consisting of 4-ethynyl aniline, 3-ethynyl aniline, propargylamine, 3-aminobutyne, 4-aminobutyne, Aminostyrene, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane. And trimethoxysilane. The thermosetting ink composition according to claim 1, wherein the thermosetting ink composition is a thermosetting ink composition. The thermosetting ink composition according to claim 1 or 2, further comprising a solvent (B). The process according to claim 8, wherein the solvent (B) is at least one selected from the group consisting of ethyl acetate, ethanol, ethylene glycol, propylene glycol, glycerin, 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 diethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol mono 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, tetra 1,3-dioxolane, 1,4-dioxane, anisole, methyl benzoate, ethyl benzoate, 1- (3-methoxyethyl) propanoate, Ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, Methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N- -Dimethyl-2-imidazolidinone, and? -Butyrolactone. 9. The method of claim 8,
And a viscosity at 25 占 폚 and 20 rpm of 5 to 20 mPa 占 퐏. 3. The method according to claim 1 or 2,
Wherein the weight average molecular weight of the polyamic acid in terms of polystyrene measured by gel permeation chromatography is 500 to 10,000. 3. The method according to claim 1 or 2,
Wherein the content of the amide acid (A) in the thermosetting ink composition is 15 to 60% by weight. A method for applying an ink, comprising the step of applying a thermosetting ink composition according to any one of claims 1 to 3 by an inkjet coating method to form a coating film, and a step of curing the coating film. A process for producing a polyimide film, which comprises a step of applying a thermosetting ink composition according to claim 1 or 2 by an inkjet coating method to form a coating film, and a step of curing the coating film to form a polyimide film. A polyimide film obtained by using the method for producing a polyimide film according to claim 14. A film substrate having a film and a polyimide film formed on the film by using the method for manufacturing a polyimide film according to claim 14. An electronic part having the film substrate according to claim 16.