KR20100068208A - Ink for ink jetting - Google Patents

Abstract

PURPOSE: An ink for an ink jet printer is provided to obtain good stability at a room temperature when polyamide acid is contained in a concentration more than 25 weight% and to form a thick film(more than 1 micron) through one jetting. CONSTITUTION: An ink for an ink jet includes polyamide acid having a cross-linkable group on a molecular end and an average molecular weight of 500~7,500. The polyamide acid is obtained through a reaction of a compound having two or more acid anhydrides, diamine, a terminal cross-linking agent which is marked as a chemical formula 1, and a terminal cross-linking agent which is marked as a chemical formula 2. The chemical formula 2 is H2N-R^2.

Description

Inkjet Inks {INK FOR INK JETTING}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to inkjet inks, and includes, for example, a polyamic acid composition for forming an insulating layer film in the production of electronic components, a polyimide film formed using the composition, and a film substrate on which the polyimide film is formed. The present invention relates to an electronic component having a film substrate.

Since polyimide is excellent in heat resistance and electrical insulation, it is a material widely used in the field of electronic communication (for example, refer patent documents 1-3).

When polyimide is used as a desired pattern film, conventionally, a pattern was formed using etching or photosensitive polyimide, but a large amount of chemical liquids such as photoresist, developer, etching solution, and peeling solution are required, Therefore, the method of forming a desired pattern film by inkjet is examined recently.

Various inkjet inks have been proposed (for example, see Patent Documents 4 to 5), but in order to discharge and print them as inkjet inks, various parameters such as viscosity, surface tension, and boiling point of a solvent must be optimized. For example, in terms of viscosity, it is generally required to have a low viscosity of about 1 to 20 mPa · s. Particularly, in the case of piezoelectric inkjet printing, the discharge pressure of the piezoelectric element is small. This becomes impossible. The surface tension should be adjusted in the range of 20 to 70 mN / m, preferably in the range of 20 to 40 mN / m. If the surface tension is small, the ink bleeds immediately after exiting the nozzle of the print head so that good droplets do not form. On the contrary, if it is too large, it will become impossible to form a maleist and discharge will become impossible. Moreover, the boiling point of a solvent needs to enter 100-300 degreeC, Preferably it is 150-250 degreeC. If the boiling point is too low, the solvent in the ink in the nozzle portion of the print head will evaporate. For this reason, the viscosity of the ink may change and it may not be ejected, or the components of the ink may be solidified. Conversely, if the boiling point is too high, the drying after printing may be too slow and the print pattern may deteriorate.

Since polyamic acid is relatively high in polyimide inkjet ink, it is necessary to increase the proportion of the solvent to reduce the polyamic acid content in the ink in order to prepare an ink having an optimum viscosity as the ink jet ink. However, this causes a problem that the thickness of the film obtained by one inkjetting becomes thin.

For example, by controlling the weight average molecular weight of the polyamic acid to 10,000 to 50,000, it is proposed to lower the viscosity of the ink and increase the content of the polyamic acid (see Patent Document 6, for example). However, when the weight average molecular weight was less than 10,000, sufficient mechanical strength was not obtained, so that the polymer concentration was as small as 15 to 20% by weight. In addition, since the viscosity is also relatively high at 15 to 25 mPa · s, there is a problem that ink jet ejection defects are likely to occur.

In addition, a thermosetting resin composition for inkjet containing a thermal crosslinking agent and a polyimide or polybenzoxazole having a weight average molecular weight of 300 to 9,000 having a group capable of reacting with the thermal crosslinking agent has been proposed (for example, Patent Document 7 Reference). It relates to a composition containing a polyimide or polybenzoxazole having a group such as phenolic hydroxyl group, carboxyl, sulfonamide and the like which can react with the thermal crosslinking agent, the composition comprising an epoxy compound, a methrol compound, an alkoxymethol compound, a bismale Since thermal crosslinking agents, such as a mid | middle, a bisimide compound which have an unsaturated bond, and an acetylene compound, are essential, storage stability and the remaining uncondensed thing at the time of thermosetting are a problem.

In addition, various compositions for inkjets in which the weight average molecular weight of the polymer is controlled have been proposed, but the soluble polyimide or other polymers having a weight average molecular weight defined in a very wide range or having solubility problems (for example, See Patent Documents 8-12). However, no ink jet ink using polyamic acid having a weight average molecular weight of 10,000 or less has been proposed.

On the other hand, the oligomer of the polyamic acid or polyimide obtained by making tetracarboxylic dianhydride, diamine, and a terminal crosslinking agent react at the molecular terminal is proposed (for example, refer patent documents 13-15). However, these oligomers provide a prepreg that produces a polyimide resin having good heat resistance, and is used as a matrix resin of a fiber-reinforced composite material using glass fibers, aramid fibers, carbon fibers, alumina fibers, silicon carbide fibers, and the like as reinforcing materials. will be. Prepreg is generally used by impregnating reinforcing fibers in a solution of 20% by weight or more, and its design concept and usage are completely different from those for inkjet inks. Or the imide compound which has a thermosetting functional group at the terminal is disclosed (for example, refer patent document 16), but this also does not presuppose use as an inkjet ink, but the viscosity required as an inkjet ink No optimization of surface tension was considered.

The crosslinkable group containing polyimide precursor which has crosslinking property in 5 to 99 mol% of the repeating unit of a specific structure and a molecular terminal is proposed (for example, refer patent document 17). Then, it is disclosed that an unsaturated group such as a carbon-carbon double bond is used as the terminal crosslinking agent, and that the storage stability of the polyamic acid is improved by leaving an amino group at the terminal of the molecule.

However, the above technique relates to a polyimide-based heat-resistant adhesive, which is used as an inkjet ink because a high-viscosity polyimide precursor solution is applied onto a substrate by casting, casting, kneading extrusion, or the like, and then heated and used as an adhesive. Clearly out of the range of possible viscosities.

Condensed system polymers, such as a polyimide, can obtain a high molecular weight body by combining the mole number of 2 types of monomer components. The said technique synthesize | combines high molecular weight polyamic acid by adjusting M1: M2 = 1.00: 0.90-0.999 when the mole number of the diamine and tetracarboxylic dianhydride of a monomer component is M1 and M2, respectively. Inevitably, it is difficult to prepare a high concentration and low viscosity solution, which is optimal for inkjet applications.

Moreover, the inkjet ink composition which has a crystalline resin which has a reactive group at both ends as an essential component is proposed (for example, refer patent document 18). The above technique is to inhibit sagging and bleeding by introducing a reactive group at a terminal of a crystalline resin such as an aromatic polyester, an aliphatic polyamide, an aromatic polyamide, or a polyolefin, and is generally known as an amorphous resin. It differs from the technique which has a crosslinkable group at the molecular terminal of the polyimide resin which exists, and controls a weight average molecular weight.

In order to solve the said problem, the low viscosity, high density | concentration thermosetting inkjet ink which controlled the molecular weight by making molecular crosslinking group react at the terminal of polyamic acid is proposed (refer patent document 19, 20). However, only inkjet ink containing a polyamic acid having a silicon-containing functional group such as triethoxysilyl group as a molecular crosslinking group is disclosed, and there is no description of having an unsaturated hydrocarbon structure as a molecular crosslinking group.

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

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

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

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

[Patent Document 5] Publication No. 2006-131730

[Patent Document 6] Japanese Patent Application Laid-Open No. 2005-187596

[Patent Document 7] Publication No. 2007-314647

[Patent Document 8] Publication No. 2000-101206

[Patent Document 9] Japanese Patent Application Laid-Open No. 2000-101240

[Patent Document 10] Japanese Patent Laid-Open No. 2000-129181

[Patent Document 11] Japanese Patent Application Laid-Open No. 2007-297480

[Patent Document 12] Publication No. 2006-124650

[Patent Document 13] Japanese Patent Application Laid-Open No. 59-167569

[Patent Document 14] Publication No. 64-542029

[Patent Document 15] Japanese Patent Application Laid-Open No. 2004-331801

[Patent Document 16] Japanese Patent Application Laid-Open No. 62-29584

[Patent Document 17] Japanese Patent Laid-Open No. 2001-323065

[Patent Document 18] Japanese Patent Laid-Open No. 2005-206820

[Patent Document 19] Japanese Patent Laid-Open No. 2009-035700

[Patent Document 20] Japanese Patent Laid-Open No. 2009-035702

There is a need for an ink jet ink containing polyamide acid at a high concentration of 25% by weight or more, which has good storage stability at room temperature storage and is capable of forming a relatively thick film (1 µm or more) by one jetting.

The present inventors earnestly examined in order to solve the said subject. As a result, in the polyamic acid (A) of the following structure contained in a thermosetting composition, it discovered that the said subject can be solved by using the polyamic acid (A) of 500-7,500 for inkjet ink. The invention was completed.

This invention has the following structures.

[1] obtained by reacting a compound (a1) having at least two acid anhydride groups, a diamine (a2), and a terminal crosslinking agent (a3) represented by formula (1) or a terminal crosslinking agent (a4) represented by formula (2) The inkjet ink which has a polyamic acid (A) which has a crosslinkable group at the molecular terminal, and has a weight average molecular weight of 500-7,500.

(In formula, R <^1> and R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure independently.)

[2] Compound (a1) having two or more acid anhydride groups is pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzo Phenonetetracarboxylic acid dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic acid dianhydride, 2,2 ', 3 , 3'-diphenylsulfontetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride , 2,2 ', 3,3'-diphenylethertetracarboxylic acid dianhydride, 2,3,3', 4'-diphenylethertetracarboxylic acid dianhydride, 2,2- [bis (3,4- Dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotremellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1 , 2,4,5-cyclohexanetetracarboxylic acid dianhydride, ethane tetracarboxylic dianhydride, and Butanetetracarboxylic dianhydride, p-phenylenebis (trimeric acid monoester acid anhydride), 4,4 '-[(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid dianhydride, ethylenediamine 4 Acetic anhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, 3,3,4-dicarboxy-1,2,3,4-tetrahydronaphthalenesuccinic acid dianhydride, 1,3 -Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-5,5-[(1-methylethylidene) di-4,1-phenylene] ester, 1,3-dihydro- The inkjet ink of the above-mentioned [1], which is at least one selected from the group consisting of 1,3-dioxo-5-isobenzofurancarboxylic acid and p-phenylenebis (trimeric acid monoester acid anhydride).

[3] diamine (a2) is 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1, 1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-amino Benzyl) phenyl] methane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, 1,1 -Bis [[4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4 -Aminobenzyl) phenyl] methane, diethylene glycol bis (3-aminopropyl) ether, 1,2-bis (2 -Aminoethoxy) ethane, 1,4-butanediolbis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] ound CAN, 4,4'-bis (4-aminophenoxy) biphenyl, 1,6-bis (4-((4-aminophenyl) methyl) phenyl) hexane, 1,3-bis (3-aminopropyl) Tetramethyldisiloxane, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,4-bis (3-aminopropyl) piperazine, N, N'-bis (3- Aminopropyl) ethylenediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, neopentylglycolbis (4-aminophenyl) ether, formula (4)

(Wherein R ³ and R ⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁵ is phenylene which may be substituted with methylene or alkyl, two x are independently integers of 1 to 6, y is an integer of 1 to 70 and a plurality of R ³ and R ^{4 present} And R ⁵ may be the same as or different from each other) and the following formula (IX)

(Wherein A ³ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or-(CH ₂ ) _p- (p is an integer of 1 to 6), R is ⁶ is a group having a steroid skeleton or a group having at least one ring structure selected from the group consisting of a cyclohexane ring and a benzene ring, and when the positional relationship between two amino groups bonded to the benzene ring is para ⁶ may be a C 1 -C 30 alkyl, wherein the positional relationship between the meta-position when one of R ⁶ is from 1 to 10 alkyl, or _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2 , or - Or phenyl which may be substituted with OCF _{3. In} the alkyl having 1 to 30 carbon atoms and alkyl having 1 to 10 carbon atoms, -CH ₂ -is -CF _2- , -CHF-, -O-, or -CH =. CH- or -C≡C- may be substituted, and any -CH ₃ may be substituted with CH ₂ F, -CHF ₂ or -CF ₃ ). On [1] Ink for inkjet described.

[4] terminal crosslinking agent (a3) is maleic anhydride, citraconic anhydride, itaconic anhydride, arylnadic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-ethynylphthalic anhydride, phenylethy The at least one selected from the group consisting of nilphthalic anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, exo-3, 6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, and aryl pumpkin acid anhydride The inkjet ink according to [1].

[5] The terminal crosslinking agent (a4) is 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutyne, 4-aminobutyne, 5-aminopentine, 4-aminopentine, arylamine, 7- The inkjet ink according to the above [1], which is at least one selected from the group consisting of aminopeptin, m-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 3-aminophenylacetylene and 4-aminophenylacetylene. .

[6] The inkjet ink according to any one of [1] to [5], further comprising a solvent (B).

[7] The solvent (B) is ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1 , 4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, di Ethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethyl Ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol mono Methyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1- Methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2 -Pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl 2-pyrrolidone, N, N-diethylacetami , N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone described in the above [6]. Inkjet Ink.

[8] The inkjet ink according to the above [6] or [7], wherein the solvent (B) does not contain 20% by weight or more of the amide solvent based on the total weight of the solvent.

[9] The inkjet ink according to the above [6] or [7], wherein the solvent (B) does not contain an amide solvent.

n1+0.5×n3 및 0.02

n1/n2

0.5의 관계가 되도록 반응시킴으로써 얻어지는, 분자 말단에 가교성 기를 갖는 폴리아미드산(A)을 포함하는 상기 [1]에 기재된 잉크젯용 잉크.[10] When the number of moles of the compound (a1) having two or more acid anhydride groups used in the reaction is n1, the number of moles of the diamine (a2) is n2 and the number of moles of the terminal crosslinking agent (a3) is n3, respectively. Molar number of n2

n1 + 0.5 × n3 and 0.02

n1 / n2

The inkjet ink as described in said [1] containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5.

n1-0.5×n4 및 0.2

n2/n1

0.5의 관계가 되도록 반응시킴으로써 얻어지는, 분자 말단에 가교성 기를 갖는 폴리아미드산(A)을 포함하는 상기 [1]에 기재된 잉크젯용 잉크.[11] When the number of moles of the compound (a1) having two or more acid anhydride groups used in the reaction is n1, the number of moles of the diamine (a2) is n2, and the number of moles of the terminal crosslinking agent (a4) is n4, Molar number n2

n1-0.5 × n4 and 0.2

n2 / n1

The inkjet ink as described in said [1] containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5.

[12] The inkjet ink according to any one of [1] to [11], wherein the weight average molecular weight of the polyamic acid (A) is 500 to 3,500.

[13] The inkjet ink according to [12], wherein the weight average molecular weight of the polyamic acid (A) is from 500 to 2,500.

[14] The inkjet ink according to any one of the above [1] to [13], which contains 25 to 60 parts by weight of a polyamic acid (A) with respect to 100 parts by weight of an inkjet ink.

[15] A process of forming a polyamic acid film by applying the ink jet ink according to any one of [1] to [14] by an inkjet coating method and heating the polyamic acid film to form a polyimide film. Obtained polyimide membrane or patterned polyimide membrane.

[16] A process of forming a polyamic acid film by applying the ink for inkjet ink according to any one of [1] to [14] by an inkjet coating method and drying the same, and heating the polyamic acid film to form a polyimide film. An ink coating method comprising a step.

[17] A polyimide film forming method, wherein a polyimide film is formed using the ink coating method described in [16] above.

[18] A film substrate on which a polyimide film is formed on a substrate by the method of forming a polyimide film according to [17].

[19] An electronic component having the film substrate according to the above [18].

[20] A polyamic acid having a crosslinkable group at a molecular terminal obtained by reacting a compound (a1) having at least two acid anhydride groups, a diamine (a2), and a terminal crosslinking agent (a3) represented by Formula (1) ( A thermosetting composition comprising A),

n1+0.5×n3 및 0.02

n1/n2

0.5의 관계가 되도록 반응시킴으로써 얻어지는, 분자 말단에 가교성 기를 갖는 폴리아미드산(A)을 포함하는 열경화성 조성물.When the mole number of the compound (a1) which has two or more acid anhydride groups used for reaction, n1, the mole number of diamine (a2) is n2, and the mole number of terminal crosslinking agent (a3) is n3, each mole Number n2

n1 + 0.5 × n3 and 0.02

n1 / n2

The thermosetting composition containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5.

(In formula, R <^1> is a C2-C100 organic group which has an unsaturated hydrocarbon structure.)

[21] A polyamic acid having a crosslinkable group at a molecular terminal, obtained by reacting a compound (a1) having at least two acid anhydride groups, a diamine (a2), and a terminal crosslinking agent (a4) represented by Formula (2) ( A thermosetting composition comprising A),

n1-0.5×n4 및 0.2

n2/n1

0.5의 관계가 되도록 반응시킴으로써 얻어지는, 분자 말단에 가교성 기를 갖는 폴리아미드산(A)을 포함하는 열경화성 조성물.When the mole number of the compound (a1) which has two or more acid anhydride groups used for reaction, n1, the mole number of diamine (a2) is n2, and the mole number of terminal crosslinking agent (a4) is n4, each mole number n2

n1-0.5 × n4 and 0.2

n2 / n1

The thermosetting composition containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5.

(In formula, R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure.)

Although "organic device" is not specifically limited in this specification, For example, a C1-C100 hydrocarbon group is mentioned.

Moreover, as a monovalent organic group, the C1-C20 alkoxy which may have a substituent specifically, the C6-C20 aryloxy which may have a substituent, the amino which may have a substituent, the silyl which may have a substituent, alkylthio which may have a substituent (of -SY ^1, formula, Y ¹ represents an alkyl of 2 to 20 carbon atoms which may have a substituent.), of arylthio (-SY ^2, expression which may have a substituent, Y ² represents an aryl having 6 to 18 carbon atoms which may have a substituent.), An alkylsulfonyl which may have a substituent (-SO ₂ Y ³ , wherein Y ³ represents alkyl having 2 to 20 carbon atoms which may have a substituent. And arylsulfonyl (-SO ₂ Y ^{4 in} which Y ⁴ represents an aryl having 6 to 18 carbon atoms which may have a substituent) may be mentioned.

In the present specification, a hydrocarbon having a "carbon 1-20 hydrocarbon group" may be saturated or unsaturated, or may be saturated or unsaturated. When a C1-C20 hydrocarbon is acyclic, it may be linear or branched. In the "hydrocarbon group having 1 to 20 carbon atoms", alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, alkyldienyl having 4 to 20 carbon atoms, aryl having 6 to 18 carbon atoms and carbon atoms 7-20 alkylaryl, C7-20 arylalkyl, C4-20 cycloalkyl, C4-20 cycloalkenyl, etc. are contained.

In this specification, it is preferable that "the C1-C20 alkyl" is C1-C10 alkyl, and it is more preferable that it is C2-C6 alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, the "alkenyl having 2 to 20 carbon atoms" is preferably alkenyl having 2 to 10 carbon atoms, and more preferably alkenyl having 2 to 6 carbon atoms. Examples of alkenyl include, but are not limited to, vinyl, aryl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylaryl, 2-butenyl and the like.

In this specification, it is preferable that "the alkynyl of C2-C20" is a C2-C10 alkynyl, and it is more preferable that it is a C2-C6 alkynyl. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, butynyl and the like.

In this specification, it is preferable that "the C4-C20 alkyldienyl" is a C4-C10 alkyldienyl, and it is more preferable that it is a C4-C6 alkyldienyl. Examples of alkyldienyl include, but are not limited to, 1,3-butadienyl and the like.

In this specification, it is preferable that "the C6-C18 aryl" is C6-C10 aryl. Examples of the aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenyl, anthryl, phenanthryl and the like.

In this specification, it is preferable that "the C7-C20 alkylaryl" is a C7-C12 alkylaryl. Examples of alkylaryls include, but are not limited to, o-tril, m-tril, p-tril, 2,3-xysilyl, 2,4-cycylyl, 2, 5-chisilyl, o-cumenyl, m- Cumenyl, p-cumenyl, mesityl and the like.

In this specification, it is preferable that "the C7-C20 arylalkyl" is C7-C12 arylalkyl. Examples of arylalkyl include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4- Phenyl butyl, 5-phenylpentyl, etc. are mentioned.

In this specification, it is preferable that "the C4-C20 cycloalkyl" is a C4-C10 cycloalkyl. Examples of cycloalkyl include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

In this specification, it is preferable that "cycloalkenyl having 4 to 20 carbon atoms" is cycloalkenyl having 4 to 10 carbon atoms. Examples of cycloalkenyl include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

In this specification, it is preferable that "alkoxy of C1-C20" is C1-C10 alkoxy, and it is more preferable that it is C2-C6 alkoxy. Examples of the alkoxy include, but are not limited to, ethoxy, propoxy, butoxy, pentyloxy and the like.

In this specification, it is preferable that "the C6-C20 aryloxy" is C6-C10 aryloxy. Examples of the aryloxy include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy and the like.

In the present specification, "alkylthio (-SY ¹ , in which Y ¹ represents alkyl having 2 to 20 carbon atoms which may have a substituent)" and "alkylsulfonyl (-SO ₂ Y ³ , wherein Y ³ Represents C1-C20 alkyl which may have a substituent. ", It is preferable that Y <^1> and Y <^3> are C2-C10 alkyl, and it is more preferable that it is C2-C6 alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, "arylthio (-SY ² , in which Y ² represents aryl having 6 to 18 carbon atoms which may have a substituent)" and "arylsulfonyl (-SO ₂ Y ⁴ , in which Y ⁴ Represents C6-C18 aryl which may have a substituent. "It is preferable that Y <^2> and Y <^4> are C6-C10 aryl. Examples of the aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenyl, anthryl, phenanthryl and the like.

"C1-C20 hydrocarbon group", "C1-C20 alkoxy", "C6-C20 aryloxy", "amino", "silyl", "alkylthio", "arylthio", "alkyl sulfonate" A substituent may be introduced in "fonyl" and "arylsulfonyl". As this substituent, ester, carboxyl, amide, alkyn, trimethylsilyl, amino, phosphonyl, thio, carbonyl, nitro, sulfo, imino, halogeno, alkoxy, etc. are mentioned, for example. In this case, one or more substituents may be introduced to the position which can be substituted, and the maximum number which can be substituted may be introduce | transduced, Preferably 1-4 may be introduce | transduced. When the number of substituents is two or more, each substituent may be the same May be different.

In the present specification, examples of the "amino which may have a substituent" include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

In the present specification, examples of the "silyl which may have a substituent" include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, Triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxysilyl and the like.

As mentioned above, although the specific example of monovalent organic group was mentioned, the specific example of a bivalent organic group in this specification can mention the group which increased the valence one by one in the monovalent organic group described in this specification. Similarly, in this specification, as a specific example of tetravalent organic group, the group which increased three valences again in the monovalent organic group described in this specification is mentioned.

The inkjet ink according to the preferred embodiment of the present invention has good storage stability, for example, at room temperature storage of the ink. Further, by using an ink jet ink containing a high concentration of polyamic acid of 25% by weight or more according to a preferred embodiment of the present invention, it is possible to form a polyimide film having a relatively thick film thickness (1 µm or more) by one jetting.

The polyamic acid of the present invention has a weight average molecular weight in the range of 900 to 7,500 and is capable of obtaining sufficient mechanical strength during film formation. Since the weight average molecular weight is small, both low viscosity suitable for inkjet printing and high concentration of 25% by weight or more can be achieved.

In addition, in the case of using the inkjet ink according to the preferred embodiment of the present invention for forming the patterned polyimide film, the material consumption is overwhelmingly small because only the necessary parts are printed by inkjet printing, and no photomask is required, so that a large quantity Production is possible and the number of processes required for manufacturing is small.

The polyimide film formed from the inkjet ink of the present invention has high heat resistance and electrical insulation, for example, and can improve the reliability and production yield of electronic components.

The present invention provides a thermosetting composition comprising the polyamic acid (A). Moreover, the inkjet ink containing polyamic acid (A) or the inkjet ink containing polyamic acid (A) and a solvent (B) is provided. Further, an ink coating method using these inks, a polyamide film forming method using a coating method, and the like are provided.

The ink used in the present invention may be either colored or colorless.

One. Polyamic acid (A)

The polyamic acid (A) contained in the inkjet ink of the present invention is a compound (a) having at least two acid anhydride groups, a diamine (a2), a terminal crosslinking agent (a3) represented by formula (1) or a formula ( It can obtain by making the terminal crosslinking agent (a4) shown by 2) react. In formula, R <^1> and R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure independently. This polyamic acid (A) has a crosslinkable group at a molecular terminal. The crosslinkable group in this invention means the functional group containing an unsaturated bond (for example, a double bond, a triple bond), for example.

n1+0.5×n3 및 0.02

n1/n2

0.5의 관계가 되도록 반응시킴으로써 본 발명에 이용되는 폴리아미드산(A)이 얻어진다.When the terminal crosslinking agent (a3) is used in the reaction, the number of moles of the compound (a1) having two or more acid anhydride groups is n1, the number of moles of the diamine (a2) is n2, and the number of moles of the terminal crosslinking agent (a3) is n3. When each mole is n2

n1 + 0.5 × n3 and 0.02

n1 / n2

By making it react so that it may become 0.5, the polyamic acid (A) used for this invention is obtained.

The weight average molecular weight of the polyamic acid (A) obtained by making the said number of moles of n1, n2, n3 become said relationship is 500-7,500, and can be used suitably for inkjet ink.

n1-0.5×n4 및 0.2

n2/n1

0.5의 관계가 되도록 반응시킴으로써 본 발명에 이용되는 폴리아미드산(A)이 얻어진다.In addition, when the terminal crosslinking agent (a4) is used in the reaction, the number of moles of the compound (a1) having two or more acid anhydride groups is n1, the number of moles of the diamine (a2) is n2 and the number of moles of the terminal crosslinking agent (a4). When n4 is used, each mole number is n2

n1-0.5 × n4 and 0.2

n2 / n1

By making it react so that it may become 0.5, the polyamic acid (A) used for this invention is obtained.

The weight average molecular weight of the polyamic acid (A) obtained by making the number-of-moles of n1, n2, n3 become said relationship is 500-7,500, and can be used suitably for inkjet ink.

The structural unit represented by Formula (3) is formed by reaction with the compound (a1) and diamine (a2) which have two or more acid anhydride groups. In this formula, R <^3> and R <^4> is a C2-C100 organic group each independently.

In addition, the molecular terminal group represented by following formula (5) is formed by reaction of terminal crosslinking agent (a4) and an acid anhydride group, and the molecule | numerator represented by following formula (6) by reaction of terminal crosslinking agent (a3) and an amino group Terminal groups are formed. Here, R <^1> and R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure independently.

The polyamic acid (A) contained in the inkjet ink of the present invention controls the weight average molecular weight to 500 to 7,500 by the molecular terminal groups represented by the formulas (5) and (6) acting as the end sealant of the polyamic acid. can do.

In addition, since the molecular terminal groups represented by the formulas (5) and (6) form a crosslinked structure by heating, when the weight average molecular weight is 500 to 7,500, a rigid membrane is obtained from the small polyamic acid (A).

Below, the compound (a1), diamine (a2), terminal crosslinking agent (a3), and terminal crosslinking agent (a4) which have two or more acid anhydride groups which can be used for obtaining a polyamic acid (A) are demonstrated.

1.1 Mountain anhydride  Compound having two or more ( a1 )

Specific examples of the compound (a1) having two or more acid anhydride groups used in the synthesis of the polyamic acid (A) in the present invention include radicals having anhydride groups such as styrene-maleic anhydride copolymer and methyl methacrylate-maleic anhydride copolymer. The copolymer of a polymerizable monomer and another radically polymerizable monomer, tetracarboxylic dianhydride, etc. are mentioned. As tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3'- benzophenone tetracarboxylic acid 2, for example Anhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic acid dianhydride, 2,2 ', 3,3'-di Phenylsulfontetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2 ' , 3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylethertetracarboxylic dianhydride, 2,3- [bis (3,4-dicarboxyphenyl)] Hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5 Cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride and Tetracarboxylic acid dianhydride, p-phenylenebis (trimeric acid monoester acid anhydride), 4,4 '-[(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid dianhydride, ethylenediamine tetraacetic acid Dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, 3,3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene succinic acid dianhydride, the following formula a1- Tetracarboxylic dianhydride, such as the compound shown by 1-a1-73, is mentioned.

Among the above specific examples of the compound having two or more acid anhydrides, in formula a1-1, a1-5, a1-6, a1-7, a1-8, a1-9, a1-14, a1-18, a1-20 The compound shown is preferable because it has high solubility in a solvent and can prepare a high concentration of ink. In addition, although high transparency is required depending on the use of the inkjet ink, in such a case, styrene-maleic anhydride copolymer, a1-6, a1-7, a1-8, a1-9, a1-14, a1-18 Particular preference is given to using compounds appearing in and the like.

In addition, only one type may be used for the compound which has the acid anhydride group described above, and may mix and use two or more types.

1.2 diamine ( a2 )

The diamine (a2) in which the synthesis of the polyamic acid (A) is used in the present invention is not particularly limited as long as it has two amino groups. For example, 3,3'-diaminodiphenylsulfone, 4,4 ' -Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminobenzyl) phenyl] methane, the following formula (II)-( The compound shown by (i) is mentioned.

In the formula (Ⅱ), A ¹ is - (Ch _{2) m} -, where m is an integer from 1-6.

In formulas (IV), (VI) and (iii), A ¹ is a single bond, -O-, -S-, -SS-, -SO _2- , CO-, -CONH-, -NHCO-,- C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -S- (CH ₂ ) _m -S-, M is an integer of 1-6 here.

In formulas (iii) and (iii), A ₂ is a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or C1-3 of an alkylene, hydrogen bonded to the cyclohexane ring or the benzene ring may be substituted with -F, -CH _3.

As diamine represented by Formula (II), the diamine represented by Formula (II-1)-(II-3) is mentioned, for example.

As diamine represented by Formula (III), the diamine represented by Formula (III-1) and (III-2) is mentioned, for example.

As diamine represented by Formula (IV), the diamine represented by Formula (IV-1) and (IV-3) is mentioned, for example.

As diamine represented by Formula (V), the diamine represented by Formula (V-1) (V-5)-is mentioned, for example.

As diamine represented by Formula (VI), the diamine represented by Formula (VI-1) (VI-30)-is mentioned, for example.

As diamine represented by a formula (i), the diamine represented by formula (VII-1)-(X-6) is mentioned, for example.

As diamine represented by a formula (i), the diamine represented by formula (VII-1)-(X-11) is mentioned, for example.

Among the specific examples of the diamine (a2) represented by formulas (II) to (iii), more preferably formulas (V-1) to (V-5), formulas (VI-1) to (VI-12) and formulas Diamines represented by (VI-26), formula (VI-27), formula (VII-1), formula (VII-2), formula (VII-6), and formula (VII-1) to (VII-5). These are mentioned, More preferably, the diamine represented by Formula (VI-1) (VI-12)-is mentioned.

Among them, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodi Phenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminobenzyl) phenyl] methane and the like It can be used preferably.

In this invention, the diamine represented by a formula can also be mentioned as diamine (a2) used for the synthesis | combination of a polyamic acid (A).

Equation (Ⅸ) of, A ³ is a single bond, -O-, -COO-, -OCO-, -CO- , -CONH- or - (CH _{2) p} -, where p is an integer from 1 to 6 .

R ⁶ in the formula (V) is a group having a steroid skeleton or a group having at least one ring structure selected from the group consisting of a cyclohexane ring and a benzene ring, and the positional relationship between two amino groups bonded to the benzene ring. the para wiil when R ⁶ is alkyl of 1 to 30 carbon atoms, or the position relationship when the meta or alkyl having a carbon number of _{1 ~ 10 -F, -CH 3,} -OCH 3, -OCH 2 F, -OCHF 2 , or - Or phenyl which may be substituted with OCF _{3. In} the alkyl having 1 to 30 carbon atoms and alkyl having 1 to 10 carbon atoms, -CH ₂ -is -CF _2- , -CHF-, -O-, or -CH =. CH- or -C≡C- may be substituted, and arbitrary -CH ₃ may be substituted with CH ₂ F, -CHF _2, or -CF ₃ .

In the formula (V), the two amino groups are bonded to the phenyl ring carbon, but preferably the binding positional relationship between the two amino groups is meta or para. Moreover, when two amino groups make the binding relationship of "R <^6> -A < ³ >> 1st-position respectively, it is preferable to couple to 3rd and 5th positions, or 2nd and 5th positions, respectively.

As diamine represented by a formula (i), the diamine represented by formula (VII-1)-(X-11) is mentioned, for example.

In formulas (VII-1), (VII-2), (VII-7) and (VII-8), R ¹⁸ is an organic group having 1 to 30 carbon atoms, but among them, alkyl having 3 to 12 carbon atoms or 3 to 3 carbon atoms. 12 alkoxy is preferable, and a C5-12 alkyl or a C5-12 alkoxy is more preferable. In addition, in said formula (VII-3)-(VII-6) and (VII-9)-(VII-11), R <^19> is a C1-C30 organic group, Among these, C1-C10 alkyl or Alkoxy having 1 to 10 carbon atoms is preferable, and alkyl having 3 to 10 carbon atoms or alkoxy having 3 to 10 carbon atoms is more preferable.

As diamine represented by a formula (i), the diamine represented by the following formula (VII-12)-(VII-17) is mentioned further, for example.

In formula (VII-12)-(VII-15), R <^20> is a C1-C30 organic group, C4-C16 alkyl is preferable, and C6-C16 alkyl is more preferable. In formula (VII-16) and formula (VII-17), R <^21> is a C1-C30 organic group, C6-C20 alkyl is preferable and C8-C20 alkyl is more preferable.

As diamine represented by a formula (i), the diamine represented by the following formula (VII-18)-(VII-38) is mentioned further, for example.

Formula (Ⅸ-18), (Ⅸ-19), (Ⅸ-22), (Ⅸ-24), (Ⅸ-25), (Ⅸ-28), (Ⅸ-30), (Ⅸ-31), ( In (VII-36) and (VII-37), R ²² is an organic group having 1 to 30 carbon atoms, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms is preferable, and alkyl having 3 to 12 carbon atoms or carbon atoms 3-12 alkoxy is more preferable. In addition, the formulas (VII-20), (VII-21), (VII-23), (VII-26), (VII-27), (VII-29), and (VII-32) to (VII-35) and in (ⅸ-38), R ²³ is hydrogen, -F, C 1 -C 12 alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF of 1 to 12 carbon atoms in the ₃ and 3 carbon atoms More preferable are alkyl of 12 or alkoxy having 3 to 12 carbon atoms. In said Formula (VII-33) and (VII-34), A <^9> is C1-C12 alkylene.

As diamine represented by a formula (i), the diamine represented by the following formula (VII-39)-(VII-48) is mentioned further, for example.

Among the diamines (a2) represented by the formula (VII), the diamines represented by the formulas (VII-1) to (VII-11) are preferable, and formulas (VII-2), (VII-4) and (VII-) 5) and the diamine represented by Formula (VII-6) are more preferable.

In this invention, the compound represented by following formula (i)-(v) is mentioned as the diamine (a2) used for the synthesis | combination of a polyamic acid (A).

Equation (ⅩⅠ) and (ⅩⅡ) of, R ¹⁰ is hydrogen or -CH _3, R ¹¹ are each independently hydrogen or an alkenyl group having 1 to 20 carbon atoms or alkyl having 2 to 20 carbon atoms al, A ⁶ represents a single independently A bond, -C (= 0)-or -CH _2- .

In formula ( ^XIII ), R <^13> and R <^14> is respectively independently hydrogen, C1-C20 alkyl, or phenyl.

In the formula (XI), one of the two "NH ₂ -Ph-A ⁶ -O-" (-Ph- represents phenylene) is bound to the third position of the steroid nucleus, the other is bound to the sixth position It is desirable to have. Moreover, it is preferable that two amino groups couple | bond with phenyl ring carbon, respectively, and couple | bond with the meta position or the para position with respect to the bonding position of A <^6> .

As diamine represented by Formula (XI), the diamine represented by Formula (XI-1)-(XI-4) can be mentioned, for example.

In formula (XIII), two "NH _2- (R ^14- ) Ph-A ⁶ -O-" (-Ph- represents phenylene) are each bound to a phenyl ring carbon, but preferably a steroid It is bonded to carbon of meta or para position with respect to the carbon which a nucleus bonds. In addition, although two amino groups couple | bond with the phenyl ring carbon, respectively, it is preferable to couple | bond with the meta position or para position with respect to A <^6> .

As a diamine represented by a formula (XIII), the diamine represented by formula (XIII-1) (XIII-8)-is mentioned, for example.

In the present invention, the diamine (a2) used in the synthesis of the polyamic acid (A) may further include compounds represented by formulas (XIII) and (XIV).

Equation (ⅩⅢ) of, R ¹⁵ is hydrogen or alkyl of 1 to 20 carbon atoms, and any -CH ₂ in the 2 to 20 carbon atoms in the alkyl - is -O-, -CH = CH- or -C≡C May be substituted with —A ⁷ is each 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 ring T is 1,4-phenylene or 1,4-cyclohexylene, h is 0 or 1.

In formula (XIV), R <^16> is C2-C30 alkyl, Among these, C6-C20 alkyl is preferable. R <^17> is hydrogen or C1-C30 alkyl, Among these, C1-C10 alkyl is preferable. A <^7> is respectively independently -O- or C1-C6 alkylene.

In said Formula (XIII), although two amino groups couple | bond with phenyl ring carbon, respectively, it is preferable to couple | bond with meta position or para with respect to A <^7> .

As a diamine represented by Formula (XIII), it is 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl]-, for example. 4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [[4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, formula ( And diamines represented by XIII-1) to XIII-9.

Among these, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, 1,1- Preferred are bis [4- (4-aminobenzyl) phenyl] cyclohexane and 1,1-bis [[4- (4-aminobenzyl) phenyl] 4-methylcyclohexane. In formulas (XIII-1) to (XIII-3), R ²⁴ is preferably hydrogen or alkyl having 1 to 20 carbon atoms, and in formulas (XIII-4) to (XIII-9), R is ²⁵ is preferably hydrogen or alkyl having 1 to 10 carbon atoms.

In said Formula (XIV), although two amino groups couple | bond with phenyl ring carbon, respectively, it is preferable to couple | bond with meta position or para position with respect to A <^7> .

As a diamine represented by a formula (XIV), the diamine represented by (XIV-1)-(XIV-3) is mentioned, for example.

In formula (XIV-1) to (XIV-3), R ²⁶ is alkyl having 2 to 30 carbon atoms, among these, alkyl having 6 to 20 carbon atoms is preferable, R ²⁷ is hydrogen or alkyl having 1 to 30 carbon atoms, Among these, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.

As mentioned above, although diamine (a2) used for the synthesis | combination of a polyamic acid (A) in this invention can use the diamine represented by Formula (I)-(XIV), for example, Diamines other than these diamines are used. Also available. For example, a naphthalene-based diamine having a naphthalene structure, a fluorene-based diamine having a fluorene structure, or a siloxane-based diamine having a siloxane bond can be used alone or in combination with other diamines.

Although siloxane diamine is not specifically limited, What is represented by following formula (4) can be used preferably in this invention.

In formula, R <^5> and R <^6> is independently C1-C3 alkyl or phenyl, R <^7> is independently methylene, phenylene, or phenylene which substituted at least 1 hydrogen by alkyl, x is independently 1- It is an integer of 6, y is an integer of 1-70.

Furthermore, in this invention, the diamine represented by following formula (11)-(18) is mentioned as a diamine (a2) used for the synthesis | combination of a polyamic acid (A). In formula, R <^30> and R <^31> is C3-C20 alkyl independently.

In addition, the diamine (a2) which can be used for synthesize | combining the polyamic acid (A) contained in the inkjet ink of this invention is not limited to the diamine of this specification, In addition to the range within which the objective of this invention is achieved, Various forms of diamines can be used.

In addition, only 1 type may be used for the diamine (a2) which can be used for synthesize | combining the polyamic acid (A) contained in the inkjet ink of this invention, and may mix and use 2 or more types. That is, as two or more types of combinations, the said diamine, the said diamine and other diamine, or diamines other than the said diamine can be used.

Moreover, although high transparency is required according to the use of inkjet ink, it is especially preferable to use 3,3'- diaminodiphenyl sulfone and the diamine which is an integer of y = 1-15 in Formula (4). .

1.3 terminal crosslinking agent ( a3 )

The terminal crosslinking agent (a3) which can be arbitrarily used for the synthesis of the polyamic acid (A) contained in the inkjet ink of the present invention is not particularly limited as long as it is represented by the following formula (1). In formula, R <^1> is a C2-C100 organic group which has an unsaturated hydrocarbon structure independently.

Specific examples of the terminal crosslinking agent (a3) include maleic anhydride, citraconic anhydride, itaconic anhydride, arylnadic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-ethynylphthalic anhydride, and 4-phenylene. A stynyl phthalic anhydride, cyclohexene- 1, 2- dicarboxylic acid dianhydride, exo-3, 6-epoxy- 1,2,3, 6- tetrahydro phthalic anhydride, an aryl zucchinic anhydride is mentioned. Among these, maleic anhydride, citraconic anhydride, and aryl nadic acid anhydride are preferable because of the excellent durability of the obtained film. Although only one type of these terminal crosslinking agents (a3) may be used, and two or more types may be mixed and used, it is preferable to use only one type from a viewpoint of controlling the crosslinking density uniformly.

1.4 Terminal crosslinking agent ( a4 )

The terminal crosslinking agent (a4) which can be arbitrarily used for the synthesis | combination of the polyamic acid (A) contained in the inkjet ink of this invention will not be specifically limited if it is represented by Formula (2). In formula, R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure independently.

Specific examples of the terminal crosslinking agent (a4) include 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutyne, 4-aminobutyne, 5-aminopentine, 4-aminopentine, arylamine, 7-amino Heptin, m-amino styrene, p-amino styrene, m-amino- (alpha)-methylstyrene, 3-aminophenyl acetylene, and 4-aminophenyl acetylene are mentioned. Among these, 4-ethynyl aniline, 3-ethynyl aniline, m-amino styrene, and p-amino styrene are preferable because of the excellent durability of the obtained film. Although only one type of these terminal crosslinking agents (a4) may be used and two or more types may be mixed and used, it is preferable to use only one type from a viewpoint of controlling the crosslinking density uniformly.

1.5 Polyamic acid (A)  Reaction Condition for Synthesis

The polyamic acid (A) can be synthesized by, for example, reacting a terminal crosslinking agent (a3) or a terminal crosslinking agent (a4), a compound (a1) having two or more acid anhydride groups, and a diamine (a2).

n1+0.5×n3 및 0.02

n1/n2

0.5의 관계가 되도록 반응시킴으로써 얻어진다.In the polyamic acid (A) of the present invention, the number of moles of the compound (a1) having two or more acid anhydride groups used in the reaction is n1, the number of moles of the diamine (a2) is n2 and the number of moles of the terminal crosslinking agent (a3). When n3 is used, the number of moles of each is n2

n1 + 0.5 × n3 and 0.02

n1 / n2

It is obtained by reacting so that it may become 0.5.

n1-0.5×n4 및 0.2

n2/n1

0.5의 관계가 되도록 반응시킴으로써 얻어진다.When the mole number of the compound (a1) having two or more acid anhydride groups used for the reaction is n1, the mole number of the diamine (a2) is n2 and the mole number of the terminal crosslinking agent (a4) is n4, n2

n1-0.5 × n4 and 0.2

n2 / n1

It is obtained by reacting so that it may become 0.5.

By satisfying the above relationship, it is possible to obtain a polyamic acid which has good storage stability at room temperature storage and can form a relatively thick film (1 µm or more) by one jetting.

1.1 reaction solvent

For example, a reaction used to synthesize a polyamic acid (A) by reacting a terminal crosslinking agent (a3) or a terminal crosslinking agent (a4) with a compound (a1) having two or more acid anhydride groups, and a diamine (a2). The solvent is not particularly limited as long as the polyamic acid (A) can be synthesized. As the reaction solvent, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol Monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether , Diethylene glycol diethyl ether, diethylene glycol hair Nomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether Propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), Triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl -2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N , N-diethylacetamine, N, N-dimethylpropionamide, N-methyl-ε-cap Lactam, 1,3-dimethyl-2-imidazole may be a lactone in Jolly dinon γ- and butynyl.

Among these, when propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methylethyl ether, diethylene glycol dimethyl ether and γ-butyrolactone are used, the ink with less damage to the inkjet head It is preferable because it can be.

Only one type of these reaction solvents may be used, or two or more types thereof may be mixed and used. In addition to the above reaction solvents, other solvents may be mixed and used.

When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the compound (a1), diamine (a2) having two or more acid anhydride groups, and the terminal crosslinking agent (a3) or the terminal crosslinking agent (a4), the reaction proceeds naturally. desirable. It is preferable to make reaction react at 0 degreeC-100 degreeC for 0.2 to 20 hours.

1.2 To the reaction system  Order of addition

In addition, the order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, a compound (a1) having two or more acid anhydride groups and a diamine (a2), a terminal crosslinking agent (a3) or a terminal crosslinking agent (a4) are simultaneously added to the reaction solvent, and a diamine (a2) and a terminal crosslinking agent (a3) A compound (a1) having two or more acid anhydride groups, a terminal crosslinking agent (a4) and a compound (a1) having two or more acid anhydride groups and a terminal crosslinking agent (a4) are dissolved in the reaction solvent after dissolving in a reaction solvent. After dissolving and further reacting the terminal crosslinking agent (a3) beforehand, diamine (a2) is added. Compound (a1) having two or more acid anhydride groups and diamine (a2) are reacted in advance to synthesize a copolymer. Any method, such as the method of adding a terminal crosslinking agent to a copolymer, can be used.

1. 6 Of polyamic acid (A)  Configuration

The polyamic acid (A) contained in the inkjet ink of the present invention has a structural unit represented by formula (3), for example, and is selected from the group of molecular terminal groups represented by formulas (5) and (6). It has one or more molecular terminal groups.

This polyamic acid (A) can be synthesized by, for example, reacting the terminal crosslinking agent (a3) or the terminal crosslinking agent (a4) described above, a compound (a1) having two or more acid anhydride groups, and a diamine (a2). have. That is, Formula (3), which is a structural unit of the polyamic acid (A), is used for the reaction between a compound (a1) having two or more acid anhydride groups having two or more polymerization groups and a diamine (a2) having two polymerization groups. Can be obtained by On the other hand, since the terminal crosslinking agent (a3) and the terminal crosslinking agent (a4) have only one polymerization group, these compounds constitute a molecular terminal group in the polyamic acid (A). That is, R <^2> of Formula (5) is a residue of a terminal crosslinking agent (a4), and R <^1> of Formula (6) is a residue of a terminal crosslinking agent (a3). In addition, the relationship between the structure of the said polyamic acid (A), and a monomer is only an example. Moreover, the manufacturing method of polyamic acid (A) is not limited to the said method, either.

 1.7 Of polyamic acid (A)  Weight average molecular weight

In the present invention, a polyamic acid (A) having a weight average molecular weight of 500 to 7,500 can be used as the inkjet ink. The polyamic acid (A) having a weight average molecular weight of 500 or more is chemically and mechanically stable without evaporation in the step of forming a polyimide film by heat treatment, and the polyamic acid (A) having a weight average molecular weight of 7,500 or less is a solvent. Since the solubility to and low viscosity can be improved, the film thickness of the coating film obtained can be enlarged. In addition, in this invention, in order to further improve "solubility" with respect to the solvent of polyamic acid (A), and to make it low viscosity, it is preferable that the weight average molecular weight is 500-3,500, and it is more preferable that it is 500-2,500.

The weight average molecular weight of the polyamide membrane (A) can be measured by gel permeation chromatography (GPC). Specifically, the obtained polyamic acid (A) is diluted with tetrahydrofuran (THF) so that the concentration of the polyamic acid is 1% by weight, and the columns G4000HXL, G3000HXL, G2500HXL and G2000HXL manufactured by Tosoh Corp. are used. THF can be determined by gel permeation chromatography (GPC) using polyvinyl chloride (GPC) as a developing agent.

2 solvents (B)

The inkjet ink of the present invention can be obtained by dissolving polyamic acid (A) in a solvent (B), for example. Therefore, the solvent contained in the inkjet ink of the present invention is not particularly limited as long as the solvent can dissolve the polyamic acid (A). Moreover, even if it is a solvent which does not melt | dissolve polyamide acid (A) alone, it can use as a solvent (B) contained in inkjet ink by mixing with another solvent.

Specific examples of the solvent (B) contained in the inkjet ink include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxypropionate methyl, 3-ethoxypropionate ethyl, cyclohexanone, 1,3-dioxolane, Ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, di Propylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, Dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol Monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), Propylene glycol monomethyl ether (1-methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pi Rollidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2 -Pyrrolidone, 1 -Acetyl-2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ- Butyrolactone is mentioned.

Among these solvents, for example, ethyl lactate, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol monomethyl ether acetate in terms of durability of the inkjet head. , Methyl 3-methoxypropionate and γ-butyrolactone are preferably included as the solvent (B).

However, among these solvents, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) in terms of durability of the inkjet head 2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, Amide solvents such as N-methyl-ε-caprolactam and 1,3-dimethyl-2-imidazolidinone are preferably not included at least 80% by weight relative to the total weight of the solvent (B), and are preferably at least 60% by weight. It is more preferable not to contain it, It is still more preferable not to contain 40 weight% or more, It is still more preferable not to contain 20 weight% or more, It is especially preferable not to contain all.

Only one type of these solvents may be used, or two or more types thereof may be mixed and used. Moreover, it is preferable to add and use a solvent so that solid content concentration in an inkjet ink may be 25 to 80 weight%.

3 of the present invention For inkjet  In ink Of polyamic acid (A)  density

Although the density | concentration of the polyamic acid (A) in an inkjet ink in this invention is not specifically limited, It is preferable to contain 25-60 weight part of polyamic acid (A) with respect to 100 weight part of inkjet ink, and it is 25-55 It is more preferable to contain a weight part, and it is especially preferable to contain 30-50 weight part. If it is these concentration ranges, the thickness of the film | membrane obtained by one inkjetting becomes optimal, and since jetting precision is high, it is preferable.

4 For inkjet  Additives added to the ink

Depending on the desired properties, the ink for ink jet is an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, an epoxy hardener, a pH adjuster, a rust preventive agent, a preservative, an antiseptic agent, an antioxidant, a reducing agent, an evaporation accelerator, a chelating agent. And additives such as water-soluble polymers, pigments, and dyes can be selected and added as necessary, followed by uniformly mixing and dissolving them.

4. 1 epoxy resin

The epoxy resin which may be added to the inkjet ink is not particularly limited as long as it has oxirane or oxetane, but a compound having two or more oxiranes is preferable.

Although the density | concentration of the epoxy resin in an inkjet ink is not specifically limited, 0.1-20 weight% is preferable and 1-10 weight% is more preferable. If it is this concentration range, the heat resistance, chemical-resistance, and flatness of the coating film formed from the inkjet ink will be favorable.

Examples of the epoxy resins include bisphenol A epoxy resins, glycidyl ester epoxy resins, alicyclic epoxy resins, polymers of monomers having oxiranes and copolymers of monomers having oxiranes and other monomers. .

Specific examples of the monomer having an oxirane include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.

Moreover, as a specific example of another monomer copolymerizing with the monomer which has an oxirane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acryl Late, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide. .

Preferred examples of the polymer of the monomer having an oxirane and the copolymer of the monomer having an oxirane and other monomers include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer and benzyl methacrylate-. Glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3- Oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, or a styrene-glycidyl methacrylate copolymer. When inkjet ink contains these epoxy resins, since the heat resistance of the coating film formed from the inkjet ink becomes favorable, it is preferable.

As a specific example of an epoxy resin, brand name "Epicoat 807", "Epicoat 815", "Epicoat 825", "Epicoat 827", "Epicoat 828", "Epicoat 190P", "Epicoat 191P" (or more) , Emulsified shell epoxy company), brand name "Epicoat 1004", "Epicoat 1256" (above, Japan epoxy resin Co., Ltd. product), brand name "Araldite CY177", brand name "Araldite CY184" ( Nippon Chiba Co., Ltd.), brand names "Celoxide 2021P", "Celoxide 3000", "EHPE-3150" (made by Daicel Chemical Industries, Ltd.), brand name "Techmore VG3101L" (Mitsui Chemical Co., Ltd.) )), N, N, N ', N'- tetraglycidyl-m-xylenediamine, 1, 3-bis (N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminediphenylmethane is mentioned. Among these, brand names "Araldite CY184", brand names "Celoxide 2021P", brand names "Techmore VG3101L", and brand names "Epicoat 828" are preferable because the flatness of the resulting polyimide film is particularly good.

Only one type of epoxy resin may be used, or two or more types may be mixed and used.

4. 2 acrylic resin

The acrylic resin which may be added to the inkjet ink is not particularly limited as long as it has an acrylic group or a methacryl group.

Although the density | concentration of the acrylic resin in an inkjet ink is not specifically limited, 0.1-20 weight% is preferable and 1-10 weight% is more preferable. If it is this concentration range, the heat resistance, chemical-resistance, and flatness of the coating film formed from the inkjet ink will be favorable.

As the acrylic resin, for example, a homopolymer of a polyfunctional polymerizable monomer having a hydroxyl, a monofunctional polymerizable monomer not having a hydroxyl, a bifunctional (meth) acrylate, or a trifunctional or higher polyfunctional (meth) acrylate Or copolymers of these monomers.

As a specific example of the monofunctional polymerizable monomer which has the said hydroxyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or 1, 4-cyclohexane dimethanol mono (meth) acrylate is mentioned. Especially, 4-hydroxybutyl acrylate and 1, 4- cyclohexane dimethanol monoacrylate are preferable at the point which can make the film | membrane formed soft.

As a specific example of the monofunctional polymerizable monomer which does not have a hydroxyl, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, methylglycidyl (meth) acrylate, 3-methyl- 3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (meth) Acryloxyethyl oxetane, p-vinylphenyl-3-ethyl oxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) Acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate , Butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, styrene, meth Styrene, chloromethyl styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, (meth) acrylamide, tricyclo [5 . 2. 1. 0 ^2.6 ] Decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate , (Meth) acrylate of polystyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloyl morpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, ethylene oxide adduct of lauryl alcohol , (Meth) acrylic acid, crotonic acid, α croacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, monosuccinate [2- (meth) Acryloyloxyethyl], mono maleic acid [2- (meth) acryloyloxyethyl], or cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl]. .

As a specific example of bifunctional (meth) acrylate, bisphenol Fethylene oxide modified diacrylate, bisphenol Aethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, polyethyleneglycol diacrylate, polypropylene Glycol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1 And 4-cyclohexane dimethanol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, trimetholpropane diacrylate, or dipentaerythritol diacrylate. .

As a specific example of trifunctional or more than trifunctional polyfunctional (meth) acrylate, a trimethol propane tri (meth) acrylate, ethylene oxide modified trimethol propane tri (meth) acrylate, and a propylene oxide modified trimethol propane tree ( Meta) acrylate, epichlorohydrin modified trimetholpropane tri (meth) acrylate, ditrimetholpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tree (meth) ) Acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) Acrylate, alkyl modified pentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tree (meth Ta) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, tris [(meth) acryloxyethyl] iso Cyanurate, caprolactone modified tris [(meth) acryloxyethyl] isocyanurate, or urethane (meth) acrylate is mentioned. One type of these acrylic resins may be used, or may mix and use two or more types.

4. 3 surfactant

As surfactant which may be added to inkjet ink, since applicability | paintability can be improved, brand name "Byk-300", "Byk-306", "Byk-335", "Byk-310", " Silicone-based surfactants such as Byk-341 '', "Byk-344", and "Byk-370" (manufactured by Big Chemi Co., Ltd.); Acrylic surfactant, such as a brand name "Byk-354", "Byk-358", "Byk-361" (made by BIC Chemi Co., Ltd.), brand name "DFX-18", "putagent 250", "putagent 251" And fluorine-based surfactants such as NEOS Corporation. One type of these surfactant may be used, or may mix and use two or more types.

Surfactant is used in order to improve the wettability, leveling property, or applicability | paintability to a base substrate, It is preferable to add 0.01-1 weight part with respect to 100 weight part of inkjet ink.

4. 4 Antistatic Agent

It does not specifically limit as antistatic agent which may be added to inkjet ink, A well-known antistatic agent can be used. Specific examples thereof include metal oxides and quaternary ammonium salts such as tin oxide, tin oxide and antimony oxide composite oxide, tin oxide and indium oxide composite oxide. These antistatic agents may use only one type, or may mix and use two or more types.

An antistatic agent is used in order to prevent an electric charge, and it is preferable to add 0.01-1 weight part with respect to 100 weight part of inkjet ink.

4. 5 Coupling agent

-비닐프로필트리메톡시실란,

-비닐프로필트리에톡시실란,

-아크릴로일프로필메틸메톡시실란,

-아크릴로일프로필트리메톡시실란,

-아크릴로일프로필메틸에톡시실란,

-아크릴로일프로필트리에톡시실란,

-메타크릴로일프로필메틸디메톡시실란,

-메타크릴로일프로필트리메톡시실란,

-메타크릴로일프로필메틸디에톡시실란,

-메타크릴로일프로필트리에톡시 실란,

-글리시독시프로필메틸디메톡시실란,

-글리시독시프로필트리메톡시실란,

-글리시독시프로필메틸디에톡시실란,

-글리시독시프로필트리에톡시실란,

-아미노프로필메틸디메톡시실란,

-아미노프로필트리메톡시실란,

-아미노프로필메틸디메톡시실란,

-아미노프로필트리에톡시실란, N-아미노에틸-

-이미노프로필메틸디메톡시실란, N-아미노에틸-

-아미노프로필트리메톡시실란, N-아미노에틸-

-아미노프로필트리에톡시실란, N-페닐-

-아미노프로필트리메톡시실란, N-페닐-

-아미노프로필트리에톡시실란, N-페닐-

-아미노프로필메틸디메톡시실란, N-페닐-

-아미노프로필메틸디에톡시실란,

-메르캅토프로필메틸디메톡시실란,

-아미노프로필트리메톡시실란,

-메르캅토프로필메틸디에톡시실란,

-메르캅토프로필트리에톡시실란,

-이소시아네이트프로필메틸디에톡시실란,

-이소시아네이트프로필트리에톡시실란이다. 이들 중에서도

-비닐프로필트리디메톡시실란,

-아크릴로일프로필트리메톡시실란,

-메타크릴로일프로필트리메톡시실란,

-이소시아네이트프로필트리에톡시실란이 특히 바람직하다.As a coupling agent which may be added to the ink for an inkjet, it does not specifically limit but a well-known coupling agent can be used. The coupling agent to be added is preferably a silane coupling agent, and examples thereof include a trialkoxysilane compound or a dialkoxysilane compound. Preferably, for example

Vinylpropyltrimethoxysilane,

Vinylpropyltriethoxysilane,

Acryloylpropylmethylmethoxysilane,

Acryloylpropyltrimethoxysilane,

-Acryloylpropylmethylethoxysilane,

-Acryloylpropyltriethoxysilane,

Methacryloylpropylmethyldimethoxysilane,

Methacryloylpropyltrimethoxysilane,

Methacryloylpropylmethyldiethoxysilane,

Methacryloylpropyltriethoxy silane,

Glycidoxypropylmethyldimethoxysilane,

Glycidoxy propyltrimethoxysilane,

Glycidoxypropylmethyldiethoxysilane,

Glycidoxypropyltriethoxysilane,

Aminopropylmethyldimethoxysilane,

Aminopropyltrimethoxysilane,

Aminopropylmethyldimethoxysilane,

-Aminopropyltriethoxysilane, N-aminoethyl-

-Iminopropylmethyldimethoxysilane, N-aminoethyl-

-Aminopropyltrimethoxysilane, N-aminoethyl-

-Aminopropyltriethoxysilane, N-phenyl-

-Aminopropyltrimethoxysilane, N-phenyl-

-Aminopropyltriethoxysilane, N-phenyl-

-Aminopropylmethyldimethoxysilane, N-phenyl-

Aminopropylmethyldiethoxysilane,

Mercaptopropylmethyldimethoxysilane,

Aminopropyltrimethoxysilane,

Mercaptopropylmethyldiethoxysilane,

Mercaptopropyltriethoxysilane,

Isocyanatepropylmethyldiethoxysilane,

Isocyanatepropyltriethoxysilane. Among these

Vinylpropyltridimethoxysilane,

Acryloylpropyltrimethoxysilane,

Methacryloylpropyltrimethoxysilane,

Isocyanatepropyltriethoxysilane is particularly preferred.

Only one type of these coupling agents may be used, or two or more types may be mixed and used. It is preferable that a coupling agent adds 0.01-3 weight part with respect to 100 weight part of inkjet ink, and is used.

4. 6 epoxy curing agent

The epoxy curing agent that may be added to the inkjet ink is not particularly limited, and a known epoxy curing agent can be used. Specific examples include organic acid dihydrazide compounds, imidazoles and derivatives thereof, dicyandiamide, aromatic amines, polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and the like. More specifically, organic acids dihydrazide, such as dicyandiamide, such as dicyandiamide, adipic acid dihydrazide, 1, 3-bis (hydrazinocarbonethyl) -5-isopropyl hydantoin, 2,4- Diamino-6- [2'-ethylimidazoline- (1 ')]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl- Acid anhydrides such as imidazole derivatives such as 5-hydroxymethylimidazole, phthalic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, or trimellitic acid Can be mentioned.

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

Only one type of these epoxy curing agents may be used, or two or more types thereof may be mixed and used. It is preferable that an epoxy hardening | curing agent adds 0.2-5 weight part with respect to 100 weight part of inkjet ink, and is used.

5 For inkjet  ink

5. 1 For inkjet  Viscosity of ink

In the present invention, the viscosity of the inkjet ink is not particularly limited, but when jetting at normal temperature (25 ° C), the jetting accuracy by the inkjet coating method is improved if the viscosity is 1 to 50 mPa · s. Preferred at Moreover, the viscosity of the inkjet ink at 25 degreeC becomes like this. More preferably, it is 5-30 mPa * s, More preferably, it is 8-15 mPa * s (25 degreeC). If the viscosity is smaller than 15 mPa · s (25 ° C.), inkjet ejection failure does not occur.

When jetting by heating the ink head, the viscosity of the inkjet ink at a heating temperature (preferably 40 to 120 ° C) is preferably 1 to 50 mPa · s, more preferably 5 to 30 mPa · s, more preferably 8 to 8 15 mPa · s is particularly preferred. If the viscosity at the heating temperature is less than 15 mPa · s, no inkjet discharge defect occurs.

5. 2 For inkjet  Surface tension of ink

The surface tension of the inkjet ink of the present invention is usually 20 to 70 mN / m, preferably 20 to 40 mN / m.

If the surface tension is in this range, good droplets can be formed by jetting, and a meniscus can be formed.

6 Polyimide film

The inkjet ink of the present invention is applied onto the surface of a substrate by inkjet, and heat-treated with a hot plate or an oven to form a polyimide film having a predetermined pattern shape (for example, a line shape) which is turned on the entire surface. In addition, formation of the polyimide membrane of this invention is not limited to heat processing, The process of UV processing, an ion beam, an electron beam, or a gamma ray may be sufficient.

6. 1 Inkjet  By coating method For inkjet  Application of ink

As the inkjet coating method, there are various types depending on the method of discharging ink. As the discharge method, for example, a piezoelectric element type, bubble jet (registered trademark) type, continuous injection type, or electrostatic induction type may be mentioned. The ink according to the present invention can be ejected by various methods by appropriately selecting each component contained in the ink, and the inkjet ink can be applied in a predetermined pattern shape.

A preferable discharge method for applying the ink using the ink according to the present invention is a piezoelectric element type. This piezoelectric element type head has an on demand ink jet comprising a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite the nozzle, and an ink filling the periphery of the pressure generating element. It is a coating head, the pressure generating element is displaced by an applied voltage, and a small droplet of ink is discharged from the nozzle.

The inkjet coating apparatus is not limited to a structure in which the application head and the ink containing portion are separate, but may be used as a structure in which they are not separated. In addition, the ink receiving portion is integrally detachably attached to the application head and detachably mounted on the carriage, and is installed on a fixed portion of the apparatus to supply ink to the application head through an ink supply member, for example, a tube. It may be.

In the case where the ink tank is provided with a structure for exerting a desired negative pressure on the application head, an absorbent body is disposed in the ink containing portion of the ink tank, or the flexible ink containing portion and the direction in which the contents thereof are expanded. The form provided with the spring part which acts the elastic support force of the etc. can be employ | adopted. In addition to adopting the serial coating method as described above, the coating apparatus may take the form of a line printer formed by aligning the coating elements over a range corresponding to the entire width of the coating medium.

6. 2 Of polyamic acid  Film formation

After the inkjet ink of the present invention is applied onto a substrate by an inkjet coating method, it is dried (removed solvent) by heating with a hot plate or an oven to form a film of polyamic acid.

The heating conditions vary depending on the type and the blending ratio of each component, but the film of polyamic acid is usually formed at 70 to 120 ° C. for 5 to 15 minutes using an oven and 1 to 5 minutes using a hot plate.

6. Formation of a Film of 3 Polyimide

After forming a film of polyamic acid, heat treatment is performed at 180 to 350 ° C, preferably 200 to 300 ° C, in order to imidize the polyamic acid. At this time, a polyimide membrane can be obtained by heat-processing for 30 to 90 minutes in the case of using an oven, and 5 to 30 minutes in the case of using a hot plate. When the film of polyamic acid is formed in pattern shape, a patterned polyimide film is formed. In this specification, unless otherwise indicated, a polyimide membrane contains a patterned polyimide membrane.

The polyimide film obtained in this way is an insulating film excellent in heat resistance and electrical insulation.

7 Film substrate

In the film substrate of the present invention, the inkjet ink of the present invention is formed on the entire surface or in a predetermined pattern shape (line shape, etc.) by, for example, an inkjet coating method on a substrate such as a polyimide film having wiring formed by an inkjet method or the like. After coating, the substrate is dried and further heated to obtain a polyimide film.

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

Examples of the substrate applicable to the present invention include glass epoxy substrates, glass composite substrates, paper phenolic substrates, and paper epoxy substrates suitable for various standards such as FR-1, FR-3, FR-4, CEM-3, or E668. And green epoxy substrates or BT resin substrates.

Moreover, as another board | substrate applicable to this invention, the board | substrate which consists of metals, such as copper, brass, phosphor bronze, helium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless, for example, has a surface of those metals May be a substrate); Aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicate (zircon) of zirconium, magnesium oxide (magnesia), aluminum titanate, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), zirconate titanate Lead lead (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (berria), silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (boron nitride) Boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel, or a substrate made of ceramics such as sporjumen (the substrate having the surface of these ceramics); PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylenedimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenyl Leneether resins, polyamide resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyetherimide resins, polyamideimide resins, epoxy resins, acrylic resins, Teflon®, thermoplastic elastomers, or A substrate (which may be a substrate having a surface of those resins) made of a resin such as a liquid crystal polymer; Semiconductor substrates such as silicon, germanium, or gallium arsenide; Glass substrates; Or a substrate having electrode materials such as tin oxide, zinc oxide, ITO, or ATO formed on the surface thereof; Gel sheets, such as (alpha) GEL (alpha gel), (beta) GEL (beta gel), (theta) GEL (sitter gel), or (gamma) GEL (gamma gel) (above, the registered trademark of Taika, Inc.), are mentioned.

8 Electronic Components

For example, the inkjet ink of this invention is apply | coated by the inkjet coating method on film substrates, such as a polyimide film in which wiring was previously formed, and then, the said film substrate is dried and heated again to a polyimide film which has insulation. A coated flexible electronic component can be obtained.

(Example)

Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.

The name of the compound (a1), diamine (a2), terminal crosslinking agent (a3), terminal crosslinking agent (a4), and solvent (B) which have two or more acid anhydride groups used by an Example and a comparative example is shown by abbreviation. This symbol is used in the following description.

Mountain anhydride  Compound having two or more ( a1 )

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

BPDA: 3,3'-4,4'-diphenyltetracarboxylic acid dianhydride

TDA: 3,3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene pumpkin acid dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

TMHQ: p-phenylenebis (trimeric acid monoester acid anhydride)

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

BPDA-H: 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride

Diamine ( a2 )

DDS: 3,3'-diaminodiphenylsulfone

DDE: 4,4'-diaminodiphenyl ether

DDM: 4,4'-diaminodiphenylmethane

mDDM: 3,4'-diaminodiphenylmethane

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

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

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

ATU: 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane

Terminal crosslinking agent ( a3 )

MA: Maleic Anhydride

CA: Citraconic Anhydride

ANA: arylnadic acid anhydride

Terminal crosslinking agent ( a4 )

3-EA: 3-ethynylaniline

4-EA: 4-ethynylaniline

Solvent (B)

EDM: diethylene glycol methyl ethyl ether

GBL: γ butyrolactone

NMP: N-methyl-2-pyrrolidone

Synthesis Example 1 Synthesis of Polyamic Acid (1)

As shown in Table 1, a raw material was added to a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, and stirred for 5 hours at 40 ° C. under a dry nitrogen stream. A 25 wt% solution was obtained. The viscosity of this solution was 18.6 mPa * s (25 degreeC), and the weight average group molecular weight was 1550.

The viscosity of the solution was measured with an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI).

The weight average molecular weight of the polyamic acid is diluted with tetrahydrofuran (THF) so that the polyamic acid concentration is about 1% by weight, and the GPC apparatus: manufactured by Nippon Bunko Chemical Co., Ltd., JASCO GULLIVER 1500 ( The dilution liquid was used as a developing agent using the intelligent differential refractometer RI-1530), and it measured by GPC method and calculated | required by polystyrene conversion. The column was connected and used in this order by four of the column G4000HXL, G3000HXL, G2500HXL, and G2000HXL by the Tosoh Corporation, and measured on the conditions of the column temperature of 40 degreeC, and the flow rate of 1.0 ml / min.

Synthesis Example 2-15

Synthesis of Polyamic Acid (2) to (25)

A polyamic acid solution was prepared under the same conditions as in Synthesis Example 1 except that raw materials were added as shown in the fabric 1, and each was used as the polyamic acid (2) to (25).

The weight average molecular weight of the obtained polyamic acid (2)-(25) and the viscosity in 25 degreeC were measured on the conditions similar to the synthesis example 1. These measurement results were as showing in Table 1.

Synthetic example Polyamic acid Raw material Viscosity
(mPas)
Weight average molecular weight
(a1) (a2)
(a3) (a4) Solvent (B) Synthesis Example 1 (One) ODPA
3.31 g BAPP
17.51 - MA
4.18 - GBL
37.5 g EDM
37.5 g 18.6 1,550 Synthesis Example 2 (2) ODPA
5.19 g DDM
13.26 g - MA
6.56 g - NMP
37.5 g EDM
37.5 g 18.0 1,050 Synthesis Example 3 (3) BSAA
5.09 g BAPP
16.07 g MA
3.84 g NMP
37.5 g EDM
37.5 g 17.5 1,850 Synthesis Example 4 (4) TMHQ
6.56 g DDM
12.34 g - MA
6.10 g - NMP
37.5 g EDM
37.5 g 26.0 1,450 Synthesis Example 5 (5) ODPA
4.57g DDS
14.64 g - MA
5.78 g - GBL
52.5 g EDM
22.5 g 14.7 1,000 Synthesis Example 6 (6) ODPA
3.19 g BAPS-M
17.78 g - MA
4.03 g - GBL
52.5 g EDM
22.5 g 15.4 1,360 Synthesis Example 7 (7) ODPA
5.00 g DDM
12.78 g - CA
7.22 g - NMP
52.5 g EDM
22.5 g 20.0 1,040 Synthesis Example 8 (8) TDA
4.87 g DDM
12.86 g - CA
7.27 g - NMP
52.5 g EDM
22.5 g 19.0 930 Synthesis Example 9 (9) ODPA
2.80 g BAPP
14.82 g - ANA
7.37 g - NMP
37.5 g EDM
37.5 g 14.8 1,670 Synthesis Example 10 10 ODPA
5.19 g mDDM
13.26 g - MA
6.56 g - NMP
37.5 g EDM
37.5 g 14.1 960 Synthesis Example 11 (11) ODPA
5.16 g DDE
13.32 g - MA
6.52 g - NMP
37.5 g EDM
37.5 g 20.0 1,240 Synthesis Example 12 (12) BPDA
5.16 g mDDM
13.32 g - MA
6.52 g - NMP
52.5 g EDM
22.5 g 14.9 1,130 Synthesis Example 13 (13) CBDA
3.55 g DDM
14.35 g - MA
7.10 g - NMP
37.5 g EDM
37.5 g 16.3 990 Synthesis Example 14 (14) ODPA
3.41 g ATU
6.05 g BAPP
9.05 g MA
6.48g - NMP
37.5 g EDM
37.5 g 14.7 1,730 Synthesis Example 15 (15) ODPA
4.19 g ATU
7.42 g DDE
5.42 g MA
7.96 g - NMP
37.5 g EDM
37.5 g 15.6 1,700 Synthesis Example 16 (16) ODPA
2.38 g BAPP
18.87 g - MA
3.76 g - GBL
37.5 g EDM
37.5 g 13.4 1,290 Synthesis Example 17 (17) ODPA
2.81g BAPP
18.62 g - MA
3.56 g - GBL
37.5 g EDM
37.5 g 15.7 1,350 Synthesis Example 18 (18) ODPA
0.94 g BAPP
19.9 g - MA
4.16 g - GBL
60.0 g EDM
15.0 g 11.4 940 Synthesis Example 19 (19) BPDA-H
3.27 g BAPP
17.54 g - MA
4.19 g - NMP
52.5 g EDM
22.5 g 16.1 1,220 Synthesis Example 20 (20) BPDA-H
3.65 g DDE
14.33 g - MA
7.02 g - NMP
37.5 g EDM
37.5 g 13.2 640 Synthesis Example 21 (21) ODPA
4.45 g DDE
5.75 g 3o2o2o3DA
6.33 g MA
8.46 g - NMP
37.5 g EDM
37.5 g 13.6 1,760 Synthesis Example 22 (22) BPDA-H
4.41 g DDE
5.76 g 3o2o2o3DA
6.35 g MA
8.47 g - NMP
37.5 g EDM
37.5 g 12.3 1,460 Synthesis Example 23 (23) CBDA
2.65 g BAPP
11.09 g 3o2o2o3DA
5.95 g MA
5.30g - NMP
37.5 g EDM
37.5 g 11.7 1,760 Synthesis Example 24 (24) TMHQ
15.63 g DDM
3.38 g - - 4-EA
5.99g NMP
52.5 g EDM
22.5 g 20.3 2,410 Synthesis Example 25 (25) BSAA
14.44 g BAPP
5.69 g - - 3-EA
4.87 g NMP
52.5 g EDM
22.5 g 28.9 2,130

n1+0.5×n3 및 0.02

n1/n2

0.5가 되는 관계식의 결과를 표 2에 나타낸다.Further, when the mole number of the compound (a1) having two or more acid anhydride groups used in the reaction is n1, the mole number of the diamine (a2) is n2, and the mole number of the terminal crosslinking agent (a3) is n3, each mole is Number n2

n1 + 0.5 × n3 and 0.02

n1 / n2

The result of the relation which turns into 0.5 is shown in Table 2.

Synthesis Example
The relationship of moles (n2) n1 + 0.5 × n3 n1 / n2 Synthesis Example 1 0.043 0.032 0.25 Synthesis Example 2 0.067 0.050 0.25 Synthesis Example 3 0.039 0.029 0.25 Synthesis Example 4 0.062 0.047 0.25 Synthesis Example 5 0.059 0.044 0.25 Synthesis Example 6 0.041 0.031 0.25 Synthesis Example 7 0.064 0.048 0.25 Synthesis Example 8 0.065 0.049 0.25 Synthesis Example 9 0.036 0.027 0.25 Synthesis Example 10 0.067 0.050 0.25 Synthesis Example 11 0.067 0.050 0.25 Synthesis Example 12 0.067 0.051 0.26 Synthesis Example 13 0.072 0.054 0.25 Synthesis Example 14 0.044 0.044 0.25 Synthesis Example 15 0.054 0.054 0.25 Synthesis Example 16 0.046 0.027 0.17 Synthesis Example 17 0.045 0.027 0.20 Synthesis Example 18 0.048 0.024 0.06 Synthesis Example 19 0.043 0.032 0.25 Synthesis Example 20 0.072 0.048 0.17 Synthesis Example 21 0.057 0.057 0.25 Synthesis Example 22 0.058 0.058 0.25 Synthesis Example 23 0.054 0.041 0.25

n1-0.5×n4 및 0.2

n2/n1

0.5가 되는 관계식의 결과를 표 3에 나타낸다.When the terminal crosslinking agent (a4) is used, the number of moles of the compound (a1) having two or more acid anhydride groups is n1, the number of moles of the diamine (a2) is n2, and the number of moles of the terminal crosslinking agent (a4) is n4. When each mole is n2

n1-0.5 × n4 and 0.2

n2 / n1

Table 3 shows the result of the relation that becomes 0.5.

Synthesis Example The relationship of moles (n2) n1-0.5 × n4 n2 / n1 Synthesis Example 24 0.017 0.012 0.46 Synthesis Example 25 0.014 0.007 0.50

Example 1 Formation of Polyimide Film 1

The polyamic acid (1) synthesized in Synthesis Example 1 was used as an ink jet ink (1) as it is.

The inkjet coating apparatus DMP-2831 made by FUJIFILM Dimatix Co., Ltd. was set on a 1.5 mm thick glass epoxy resin double-sided copper coated plate at a dot pitch of 40 microns at a dot width of 5 cm in length, and a line coating of 5 cm in length was carried out at warm (40 ° C.). . The piezo voltage was 16 V and the driving frequency was 5 kHz. After drying a board | substrate for 5 minutes on the 80 degreeC hotplate, it heated for 30 minutes in 230 degreeC oven, and obtained the insulating polyimide film 1 formed in line shape.

The linearity of the line width and edge of the obtained polyimide membrane were observed with the optical microscope, and the film thickness was measured. The film thickness was made into the average value of the measured value of three places using the stylus type film thickness gauge ((alpha) step 200, the KLA-Tencor Japan make). The results are shown in Table 4. The line width maintained the width | variety when it apply | coated substantially, the linearity of the edge of a line was also favorable, and the line has sufficient thickness.

(Examples 2 to 25) Formation of Polyimide Films (2) to (25)

Inkjet ink was prepared on the same conditions as Example 1, and each was set as inkjet ink (2)-(25).

Only the head heating temperature was changed using the inkjet inks (2) to (25), and the other conditions were obtained under the same conditions as in Example 1 to obtain polyimide films (2) to (25).

The obtained polyimide membrane was evaluated on the conditions similar to Example 1. The results are shown in Table 4. In all the inkjet inks, the line width was maintained almost at the time of application, the linearity of the edge of the line was also good, and the line had a sufficient thickness.

Comparative Example 1 Polyamic Acid (C1)

The raw material was injected into the 300 ml four-necked flask used by the synthesis example 1, and it stirred for 5 hours at 40 degreeC under dry nitrogen stream, and obtained the 25 weight% solution of the pale yellow transparent polyamic acid (C1). The viscosity of this solution was 9.6 mPa * s (25 degreeC), and the weight average molecular weight was 3,400.

ODPA 11.4 g

DDS 2.1g

S330 11.5g

EDM 75.0 g

Comparative Example 2 Polyamic Acid (C2)

The raw material was injected into the 300 ml four-necked flask used by the synthesis example 1, and it stirred for 5 hours at 40 degreeC under dry nitrogen stream, and obtained the 25 weight% solution of the pale yellow transparent polyamic acid (C2). The viscosity of this solution was 10.2 mPa * s (25 degreeC), and the weight average molecular weight was 3,900.

ODPA 10.8g

BAPP 3.4g

S330 10.9g

EDM 75.0 g

Comparative Example 3 Formation of Polyimide Film (C1)

The solution of polyamic acid (C1) was used as the inkjet ink (C1) as it is.

An insulating film C1 of polyimide was obtained under the same conditions as in Example 1 except that the inkjet ink C1 was used as the inkjet ink.

The obtained polyimide film (C1) was evaluated on the conditions similar to Example 1. As a result, the line width of the polyimide film (C1) was 60 micrometers. In addition, the film thickness of the line of the polyimide film (C1) was 1.20 micrometers.

Comparative Example 4 Formation of Polyimide Film (C2)

The solution of polyamic acid (C2) was used as the inkjet ink (C2) as it is.

The insulating film C2 of polyimide was obtained on the same conditions as Example 1 except having used inkjet ink (C2) as inkjet ink.

The obtained polyimide membrane (C2) was evaluated under the same conditions as in Example 1. As a result, the line width of the polyimide film (C2) became 70 micrometers. In addition, the film thickness of the line of the polyimide film (C2) was 1.10 micrometers.

In Table 4, the result of Examples 1-25 and Comparative Examples 3 and 4 is put together.

Inkjet ink Head heating temperature Line width (㎛) Film thickness (㎛) Example 1 (One) 40 65 1.25 Example 2 (2) 40 75 1.30 Example 3 (3) 40 70 1.15 Example 4 (4) 50 100 1.25 Example 5 (5) 30 75 1.10 Example 6 (6) 30 65 1.00 Example 7 (7) 45 60 1.15 Example 8 (8) 45 55 1.15 Example 9 (9) 30 85 1.20 Example 10 10 30 80 1.15 Example 11 (11) 45 120 1.35 Example 12 (12) 35 140 1.25 Example 13 (13) 35 70 1.32 Example 14 (14) 35 75 1.30 Example 15 (15) 35 70 1.40 Example 16 (16) 35 75 1.35 Example 17 (17) 35 75 1.35 Example 18 (18) 30 80 1.20 Example 19 (19) 35 75 1.35 Example 20 (20) 30 85 1.25 Example 21 (21) 30 90 1.20 Example 22 (22) 30 90 1.25 Example 23 (23) 30 100 1.22 Example 24 (24) 55 55 1.21 Example 25 (25) 65 70 1.10 Comparative Example 3 (C1) 30 60 1.20 Comparative Example 4 (C2) 30 70 1.10

Example 26 Constant Temperature Stability of Polyimide Inks

The storage stability at normal temperature of the inkjet ink 1 obtained in Example 1 was evaluated. The viscosity of the solution was measured with an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI). The viscosity was measured over time at 1 day, 3 days, 1 week, 2 weeks, 30 days, 60 days, 90 days and 120 days at room temperature storage. As shown in FIG. 1, there was no large viscosity change.

(Example 27)

The viscosity change was measured over time under the same conditions as in Example 16 except that the ink jet ink 2 was used. As shown in FIG. 2, there was no big viscosity change.

(Comparative Example 5)

The viscosity change was measured over time under the same conditions as in Example 15 except that the ink jet ink (C1) was used as the ink jet ink.

As shown in FIG. 3, thickening occurred after two weeks of room temperature storage, the viscosity rapidly increased on the 30th day, and the ink solidified after two months.

(Comparative Example 6)

The viscosity change was measured over time under the same conditions as in Example 16 except that the ink jet ink (C2) was used.

As shown in FIG. 4, the viscosity rose rapidly on the 14th day, and the ink solidified on the 30th day.

As an application method of this invention, the insulating film for flexible wiring boards, and the electronic component using the same are mentioned, for example.

1 is a graph showing the storage stability of the inkjet ink 1.

Fig. 2 is a graph showing the storage stability of the ink jet ink 2;

3 is a graph showing the storage stability of the ink jet ink C1.

4 is a graph showing the storage stability of the inkjet ink C2.

Claims (21)

To a molecular terminal obtained by reacting a compound (a1) having at least two acid anhydride groups, a diamine (a2), and a terminal crosslinking agent (a3) represented by formula (1) or a terminal crosslinking agent (a4) represented by formula (2) An inkjet ink comprising a polyamic acid (A) having a crosslinkable group and having a weight average molecular weight of 500 to 7,500.

(In formula, R <^1> and R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure independently.) The method of claim 1, Compound (a1) having two or more acid anhydride groups is pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarb Main dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2 ', 3,3' -Diphenylsulfontetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2, 2 ', 3,3'-diphenylethertetracarboxylic acid dianhydride, 2,3,3', 4'-diphenylethertetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl Hexafluoropropane 2 anhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride and Tetracarboxylic acid dianhydride, p-phenylenebis (trimeric acid monoester acid anhydride), 4,4 '-[(isopropylidene) bis (p-phenyleneoxy)] diphthalic acid dianhydride, ethylenediamine tetraacetic acid Dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, 3,3,4-dicarboxy-1,2,3,4-tetrahydronaphthalenesuccinic acid dianhydride, 1,3- Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-5, 5-[(1-methylethylidene) di-4, 1-phenylene] ester, 1,3-dihydro-1 Ink jet ink of at least one selected from the group consisting of, 3-dioxo-5-isobenzofurancarboxylic acid and p-phenylenebis (trimeric acid monoester acid anhydride). The method of claim 1, Diamine (a2) is 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3 , 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-aminobenzyl) phenyl ] Methane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl ) Phenyl] methane, diethylene glycol bis (3-aminopropyl) ether, 1,2-bis (2-a Minoethoxy) ethane, 1,4-butanediolbis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane , 4,4'-bis (4-aminophenoxy) biphenyl, 1,6-bis (4-((4-aminophenyl) methyl) phenyl) hexane, 1,3-bis (3-aminopropyl) tetra Methyldisiloxane, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,4-bis (3-aminopropyl) piperazine, N, N'-bis (3-amino Propyl) ethylenediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, neopentylglycol bis (4-aminophenyl) ether, formula (4)

(In formula, R <^3> and R <^4> is independently C1-C3 alkyl or phenyl, R <^5> is phenylene which may be substituted by methylene or alkyl, Two x is an integer of 1-6 independently, y is an integer of 1 to 70 and a plurality of R ³ and R ^{4 present} And R ⁵ may be the same as or different from each other) And the following formula (IX)

(Wherein A ³ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or-(CH ₂ ) _p- (p is an integer of 1 to 6), R is ⁶ is a group having a steroid skeleton or a group having at least one ring structure selected from the group consisting of a cyclohexane ring and a benzene ring, and R ⁶ when the positional relationship between the two amino groups bonded to the benzene ring is para is may be a C 1 -C 30 alkyl, wherein the positional relationship between meta wiil when R ⁶ is alkyl, or _{-F, -CH 3, -OCH 3,} -OCH having a carbon number of 1 ~ 10 ₂ F, -OCHF ₂ or -OCF ₃ is the contribution phenyl optionally substituted with, in the 1 to 30 carbon atoms and alkyl of 1 to 10 carbon atoms in the alkyl arbitrary -CH ₂ - is _{-CF 2 -, -CHF-, -O-,} -CH = CH -Or -C≡C- may be substituted, and arbitrary -CH ₃ may be substituted with CH ₂ F, -CHF _2, or -CF _3. ) ; Inkjet ink of at least one selected from the group consisting of compounds represented by. The method of claim 1, Terminal crosslinking agent (a3) is maleic anhydride, citraconic anhydride, itaconic anhydride, arylnadic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-ethynylphthalic anhydride, 4-phenylethynyl fu One or more inkjet inks selected from the group consisting of deoxidized anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, and aryl pumpkin anhydride . The method of claim 1, Terminal crosslinker (a4) is 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutin, 4-aminobutin, 5-aminopentin, 4-aminopentin, arylamine, 7-aminopentin, Inkjet ink of at least one selected from the group consisting of m-amino styrene, p-amino styrene, m-amino-α-methyl styrene, 3-aminophenylacetylene and 4-aminophenylacetylene. 6. The method according to any one of claims 1 to 5, An ink jet ink further comprising a solvent (B). The method of claim 6, The solvent (B) is ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl Ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4 Dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol Isopropylmethyl ether, dipropylene glycol monomethyl ether, die Tylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol mono Methyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1- Methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2 -Pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl 2-pyrrolidone, N, N-diethylacetami At least one inkjet ink selected from the group consisting of N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone. The method of claim 6, An inkjet ink, wherein the solvent (B) does not contain 20% by weight or more of the amide solvent based on the total weight of the solvent. The method of claim 6, Inkjet ink in which the solvent (B) does not contain an amide solvent. The method of claim 1, When the mole number of the compound (a1) which has two or more acid anhydride groups used for reaction, n1, the mole number of diamine (a2) is n2, and the mole number of terminal crosslinking agent (a3) is n3, each mole number is n2

n1 + 0.5 × n3 and 0.02

n1 / n2

The inkjet ink containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5. The method of claim 1, When the mole number of the compound (a1) which has two or more acid anhydride groups used for reaction, n1, the mole number of diamine (a2) is n2, and the mole number of terminal crosslinking agent (a4) is n4, each mole number n2

n1-0.5 × n4 and 0.2

n2 / n1

The inkjet ink containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5. The method according to any one of claims 1 to 5 and 7 to 11, An ink jet ink, wherein the weight average molecular weight of the polyamic acid (A) is 500 to 3,500. 13. The method of claim 12, An inkjet ink, wherein the weight average molecular weight of the polyamic acid (A) is 500 to 2,500. The method according to any one of claims 1 to 5 and 7 to 13, The inkjet ink containing 25-60 weight part of polyamic acid (A) with respect to 100 weight part of inkjet inks. A polyimide film or a patterned polyimide film obtained by applying the inkjet ink according to claim 1 to form a polyamic acid film by applying an inkjet coating method and heat treating the polyamic acid film to form a polyimide film. An ink coating method comprising the step of applying the inkjet ink according to claim 1 by an inkjet coating method, followed by drying to form a polyamic acid film, and heating the polyamic acid film to form a polyimide film. The polyimide film formation method of forming a polyimide film using the ink coating method of Claim 16. A film substrate on which a polyimide film is formed on a substrate by the polyimide film forming method according to claim 17. An electronic component having the film substrate according to claim 18. A polyamic acid (A) having a crosslinkable group at a molecular terminal obtained by reacting a compound (a1) having at least two acid anhydride groups, a diamine (a2), and a terminal crosslinking agent (a3) represented by formula (1) It is a thermosetting composition containing, When the mole number of the compound (a1) which has two or more acid anhydride groups used for reaction, n1, the mole number of diamine (a2) is n2, and the mole number of terminal crosslinking agent (a3) is n3, each mole number n2

n1 + 0.5 × n3 and 0.02

n1 / n2

The thermosetting composition containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5.

(In formula, R <^1> is a C2-C100 organic group which has an unsaturated hydrocarbon structure.) A polyamic acid (A) having a crosslinkable group at a molecular terminus, obtained by reacting a compound (a1) having at least two acid anhydride groups, a diamine (a2), and a terminal crosslinking agent (a4) represented by Formula (2) It is a thermosetting composition containing, When the number of moles of the compound (a1) having two or more acid anhydride groups used for the reaction is n1, the number of moles of the diamine (a2) is n2, and the number of moles of the terminal crosslinking agent (a4) is n4, the number of moles of each is n2.

n1-0.5 × n4 and 0.2

n2 / n1

The thermosetting composition containing the polyamic acid (A) which has a crosslinkable group in a molecule terminal obtained by making it react so that it may become 0.5.

(In formula, R <^2> is a C2-C100 organic group which has an unsaturated hydrocarbon structure.)

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