JP5282415B2 - Inkjet ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide inkjet ink containing a polyimide resin having a low coefficient of linear expansion and widely used, and imparting good printability, toughness and good workability. <P>SOLUTION: The inkjet ink contains at least one kind of alkenyl-substituted nadimides (A) represented by general formula (1). In the formula (1), l is 2-6; m is 0-4; l+m&le;6 is satisfied; R<SP>1</SP>and R<SP>2</SP>independently expresses any of H, 1-12C alkyl, 3-6C alkenyl; 5-8C cycloalkyl, 6-8C aryl or 7-8C benzyl; and n is an integer of 1-4. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an ink-jet ink containing a specific alkenyl-substituted nadiimide compound for forming an insulating film layer, for example, in the manufacture of electronic components, and further, a polyimide film formed using the ink-jet ink, and the polyimide film formed And an electronic component having the film substrate.

Polyimide is a material widely used in the field of electronic communication because of its excellent heat resistance and electrical insulation [see, for example, Patent Document 1, Patent Document 2, and Patent Document 3].
In the case of using polyimide as a desired pattern film, conventionally, it has been common to form a pattern using etching or photosensitive polyimide. However, in recent years, methods for forming a desired pattern film by inkjet have been studied. Yes.

  Various ink-jet inks have been proposed [see, for example, Patent Document 4 and Patent Document 5]. However, when a polyimide-based ink is prepared, since it is a relatively high polymer, it has an optimum viscosity as an ink-jet ink. In order to prepare the ink, it is necessary to increase the solvent ratio to reduce the content of polyamic acid or polyimide in the ink. As a result, there is a problem that the thickness of the film obtained by one ink jetting is reduced.

  Thermosetting polyimides such as maleimide type, acetylene type, nadic acid type, etc. are obtained by three-dimensional crosslinking of low molecular weight, low viscosity compounds having an unsaturated group at the terminal, so the viscosity is low even at relatively high concentrations. It is easier to process than the linear polyimide. Because it exhibits good heat resistance and less voids and cracks during curing, it has excellent properties as a matrix resin for molding materials and laminate materials, and a film that can be obtained by a single ink jetting is conventionally used. There is a merit that also becomes thicker.

A mono-alkenyl-substituted nadiimide compound in which only one alkenyl is substituted on the above-mentioned nadic acid type thermosetting polyimide is also a thermosetting compound that can be polymerized by heating to become a solid product (polyimide) having an imide bond. [See, for example, Patent Document 6, Patent Document 7, Patent Document 8, and Patent Document 9].
Monoalkenyl-substituted nadiimide compound is a material for forming thermosetting polyimide, and is a low molecular weight imide monomer having a bulky structure. Therefore, it is soluble in most organic solvents except aliphatic hydrocarbons, and in a solution state. Even when stored for a long period of time, it does not cause crystal precipitation or gelation and can be used stably. Although the detailed curing mechanism is unknown, heating causes the double-bonded Ene reaction or Diels-Alder reaction in the alkenyl and norbornene skeletons to form a three-dimensional crosslinked structure. In this way, it shows solubility in general-purpose solvents, and cured products have good heat resistance, mechanical properties, electrical properties, and chemical resistance, so resin modifiers, heat-resistant paints, various coating materials, heat resistance Development of applications for adhesives is under consideration.

However, the ink containing the monoalkenyl-substituted nadiimide compound is cured while being melted and fluidized during heating, and thus unevenness such as bleeding and bulge occurs, and the printability is not sufficient. In particular, when ink is applied and cured on a substrate such as a printed wiring board on which different substance surfaces appear alternately, a uniform film may not be formed.
Furthermore, the resin film formed by heat-curing monoalkenyl-substituted nadiimide is relatively fragile and may have a relatively high linear expansion coefficient, and therefore has limited applications.

  An alkenyl-substituted nadiimide compound (in this specification, in order to distinguish it from a monoalkenyl-substituted nadiimide compound, an alkenyl-substituted nadiimide compound is substituted with two or more alkenyls (one in the general formula (1) is 2 or more). ) Is a thermosetting polyimide forming material similar to the monoalkenyl-substituted nadiimide compound, and application development to resin modifiers and the like has been studied [for example, Patent Document 10, Patent Document 11, Patent Reference 12 and Patent Document 13]. However, in these documents, there is no description of using an alkenyl-substituted nadiimide compound in which alkenyl is increased in order to improve poor printability such as bleeding or bulge in resin pattern drawing using ink jet. Furthermore, there is no description that increasing the alkenyl makes the heat-cured resin film tough, improves operability, and has a low linear expansion coefficient and high versatility.

JP 2000-039714 A JP 2003-238683 A JP 2004-094118 A JP 2003-213165 A JP 2006-131730 A JP 59-080662 A JP-A-60-124619 JP-A-61-018761 Japanese Patent Laid-Open No. 05-301948 JP-A-2-256662 Japanese Patent Laid-Open No. 3-52954 JP 2003-509492 A JP-A-7-2756

  There is a need for a resin that can generate a polyimide film with good printability because the resin does not flow during thermosetting and there is no unevenness such as bleeding or bulging. Furthermore, regarding a resin film formed by heat curing, a tough, good workability, low linear expansion coefficient and highly versatile resin is required.

  In view of the above circumstances, the present inventors have found that at least one of the above problems can be solved by an inkjet ink containing an alkenyl-substituted nadiimide having a specific structure.

[1] One embodiment of the present invention is an inkjet ink containing at least one alkenyl-substituted nadiimide (A) represented by the following general formula (1).


(In Formula (1), l is 2-6, m is 0-4, 1 + m ≦ 6 is satisfied, R ¹ and R ² are each independently hydrogen, alkyl having 1 to 12 carbons, carbon Any one of alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 8 carbon atoms or benzyl having 7 to 8 carbon atoms, and n is an integer of 1 to 4;

When n = 1, R ³ is an organic group having 1 to 30 carbon atoms or a silicon compound represented by the following general formula (2).

In formula (2), R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, halogen or a monovalent organic group, which may be the same or different. Y is an organic group having 1 to 20 carbon atoms.

When n = 2, R ³ is an organic group having 1 to 140 carbon atoms or a group represented by the following general formula (3),

In formula (3), R ⁷ and R ⁸ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁹ is each independently methylene, phenylene or alkyl-substituted phenylene, and x is Each independently represents an integer of 1 to 6, and y is an integer of 1 to 70. Here, more preferable y is an integer of 1-15.

When n = 3, R ³ is a group represented by the following general formula (4) or (4 ′),


In the formula (4), R represents hydrogen, fluorine, chlorine, —OH, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₂ CF ₂ H, —OCF _2. CFHCF ₃ , or alkyl having 1 to 10 carbon atoms,
In formulas (4) and (4 ′), R ¹⁰ , R ¹¹ and R ¹² are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═. CH— may be replaced, and any hydrogen in the alkylene or a group in which methylene in alkylene is replaced with —CH═CH— may be replaced with fluorine.

When n = 4, R ³ is a group represented by the following general formula (5).

In formula (5), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═CH—. Any hydrogen in the alkylene or in the group in which methylene in the alkylene is replaced with —CH═CH— may be replaced with fluorine. )

[2] In a preferred embodiment of the present invention, R ¹ and R ² in the general formula (1) are each independently hydrogen, alkyl having 1 to 6 carbons or alkenyl having 3 to 6 carbons. The ink-jet ink according to [1].
[3] Another preferred embodiment of the present invention is the ink-jet ink according to the above [1] or [2], wherein m in the general formula (1) is 0 and R ¹ is hydrogen. .

[4] According to still another preferred embodiment of the present invention, n in the above general formula (1) is 2, and R ³ is alkylene having 2 to 20 carbon atoms. O— or —CH═CH— may be replaced, and any hydrogen in the alkylene or in which methylene in alkylene is replaced by —CH═CH— may be replaced by fluorine}, carbon number 5-8 cycloalkylene, arylene having 6 to 12 carbon _{^{atoms, - (R 50) a -C}} 6 H 4 -R 51 - ( wherein, a is an integer of 0 or ^{1, R 50} and ^{R 51} are each Independently a group having 1 to 4 carbon atoms), a group represented by —C ₆ H ₄ —TC ₆ H ₄ —, —C ₆ H ₄ —TC ₆ H ₄ —TC _6. H ₄ - or _{-C 6 H 4 -T'-C 6} H _{-T-C 6 H 4 -T'-} C 6 H 4 - { However, T is a single bond, an alkylene having 1 to 6 carbon _{atoms, -C (CH 3) 2 -} , - C (CF 3) 2 -, —CO—, —O—, —S— or —SO ₂ —, and T ′ is —CH ₂ — or —O—. }, A group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced by a hydroxyl group, a group represented by the following general formula (3), or a group represented by the following formula (6) The inkjet ink according to any one of [1] to [3], which is a group to be formed.

(In Formula (3), R ⁷ and R ⁸ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁹ is each independently methylene, phenylene or alkyl-substituted phenylene, x Are each independently an integer of 1 to 6, and y is an integer of 1 to 70.)

[5] Yet another preferred embodiment of the present invention is the above [1], wherein n in the general formula (1) is 2, and R ³ is a group represented by the following formula (9) or (10): It is an inkjet ink as described in any one of-[4].

[6] Yet another preferred embodiment of the present invention is the above [1] to [3], wherein n in the general formula (1) is 4, and R ³ is a group represented by the following formula (11). Any one of the ink-jet inks.

[7] Yet another preferred embodiment of the present invention is the ink-jet ink according to any one of [1] to [6], further including a polymer compound (B) having a weight average molecular weight of 10,000 or more. .
[8] Yet another preferred embodiment of the present invention is the ink-jet ink according to the above [7], wherein the polymer compound (B) is at least one of polyamic acid or polyimide.
[9] Yet another preferred embodiment of the present invention is the ink-jet ink according to any one of [1] to [8], further including a solvent (C).
[10] In another preferred embodiment of the present invention, the solvent (C) is selected from the group consisting of 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. At least one selected from the group consisting of acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, butyl cellosorb and γ-butyrolactone This is the inkjet ink according to the above [9].

[11] In another embodiment of the present invention, a coating film is formed by applying the inkjet ink described in any one of [1] to [10] above by an inkjet coating method, and the coating film is heat-treated. It is a polyimide film or a pattern-like polyimide film obtained.
[12] Still another embodiment of the present invention is a process for forming a coating film by applying the inkjet ink described in any of the above [1] to [10] by an inkjet coating method, and the coating film It is a polyimide film formation method including the process of heat-processing and forming a polyimide film.
[13] Yet another embodiment of the present invention is a film substrate in which a polyimide film is formed on a substrate by the polyimide film forming method described in [12] above.
[14] Yet another embodiment of the present invention is an electronic component having the film substrate described in [13] above.

  When the ink-jet ink according to the preferred embodiment of the present invention is used, since the crosslinking point is large and the molecular weight is large, the resin hardly flows during heating and curing, and unevenness such as bleeding and bulge is unlikely to occur. Therefore, printability is good and a uniform polyimide film can be formed. Since the formed film has many crosslinking points, the coefficient of linear expansion is low, and it is tough and has good workability. Moreover, the polyimide film formed from the ink-jet ink according to the preferred embodiment of the present invention has, for example, high heat resistance and electrical insulation, and improves the reliability and yield of electronic components.

  One embodiment of the present invention is an inkjet ink containing at least one alkenyl-substituted nadiimide (A) represented by the general formula (1). In a preferred embodiment of the present invention, the inkjet ink further comprises a polymer compound (B) and a solvent (C).

In the present invention, as described above, monoalkenyl-substituted nadiimide and alkenyl-substituted nadiimide are distinguished from each other. The monoalkenyl-substituted nadiimide refers to a compound having one alkenyl as a substituent, and the alkenyl-substituted nadiimide is a compound having 2 to 6 alkenyl as a substituent (wherein l in the general formula (1) is 2 to 6) ) And their mixtures.
The alkenyl-substituted nadiimide (A) used in the present invention is represented by the following general formula (1).

In formula (1), l is 2-6, m is 0-4, 1 + m ≦ 6 is satisfied, R ¹ and R ² are each independently hydrogen, alkyl having 1 to 12 carbons, carbon number 3-6 alkenyl, C5-C8 cycloalkyl, C6-C8 aryl, or C7-C8 benzyl, n is an integer of 1-4.
Examples of the alkyl having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1 -Methylpentyl, 3-ethylbutyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl 3,3-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-u And a group such as ndecyl and n-dodecyl. Among these, methyl, ethyl, propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-hexyl, n- Examples include groups such as dodecyl.
Examples of the alkenyl having 3 to 6 carbon atoms include groups such as 1-methylethenyl, propenyl, butyryl, pentenyl, hexenyl, etc. Among these, 1-methylethenyl, 1-methylpropenyl, 1-methylbutyryl, 1 Groups such as -methylpentenyl, 2-propenyl, 3-butyryl, 4-pentenyl, 5-hexenyl and the like.
Examples of the cycloalkyl having 5 to 8 carbon atoms include groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Among these, cyclopentyl, cyclohexyl, and cyclooctyl are preferable.
Examples of the aryl having 6 to 8 carbon atoms include groups such as phenyl, tolyl, xylyl, p-ethylphenyl, m-ethylphenyl, o-ethylphenyl, and among these, phenyl, tolyl, xylyl are preferable. Is mentioned.
Examples of benzyl having 7 to 8 carbon atoms include groups such as benzyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, and among these, benzyl is preferable.
The above substituent represented by R ¹ or R ² may be further substituted with another substituent.
Examples of such a substituent include a hydroxyl group and a group such as halogen such as fluorine and chlorine.

In the present invention, it is preferable that R ¹ and R ² in the general formula (1) each independently represent hydrogen, alkyl having 1 to 6 carbons, or alkenyl having 3 to 6 carbons.
In the present invention, m in the general formula (1) is 0, it is preferred that R ¹ is hydrogen.

  It is understood that the alkenyl substituted nadiimide (A) used in the present invention can exist as various geometric isomers. The present invention therefore relates to ink jet inks comprising both individual isomers and mixtures of such isomers.

1 Alkenyl-substituted nadiimide (A)
The alkenyl-substituted nadiimide (A) includes an alkenyl-substituted nadiimide compound in which n is 1 (A-1: hereinafter simply referred to as “alkenyl-substituted nadiimide”), an alkenyl-substituted nadiimide compound in which n is 2 (A- 2: hereinafter simply referred to as “bisalkenyl-substituted nadiimide”), alkenyl-substituted nadiimide compound in which n is 3 (A-3: hereinafter, sometimes simply referred to as “trisalkenyl-substituted nadiimide”), n is 4 is an alkenyl-substituted nadiimide compound (A-4: hereinafter, simply referred to as “tetrakisalkenyl-substituted nadiimide”).

1.1 Alkenyl-substituted nadiimide (A-1)
In the general formula (1), when n = 1, R ³ is hydrogen, a hydroxyl group, an organic group having 1 to 30 carbon atoms, or a silicon compound represented by the following general formula (2).
Examples of the organic group having 1 to 30 carbon atoms include methyl, 2-ethylhexyl, allyl, isopropenyl, cyclohexyl, phenyl, benzyl, 2-hydroxyethyl, 2,2-dimethyl-3-hydroxypropyl, 2, 3-hydroxypropyl, 3-hydroxy-1-propenyl, 4-hydroxy-cyclohexyl, 4-hydroxyphenyl, 3-hydroxyphenyl, p-hydroxybenzyl, 3-trimethoxysilylpropyl, 3-triethoxysilylpropyl, 3-methyldimethoxysilylpropyl, 3-methyldiethoxysilylpropyl, 4-trimethoxysilylbutyl, 4-triethoxysilylbutyl, 4-methyldimethoxysilylbutyl, 4-methyldiethoxysilylbutyl, p-trimethoxysilylphenyl , P-trietoki Silylphenyl, p-methyldimethoxysilylphenyl, p-methyldiethoxysilylphenyl, m-trimethoxysilylphenyl, m-triethoxysilylphenyl, m-methyldimethoxysilylphenyl, m-methyldiethoxysilylphenyl, allylphenyl, Diallylphenyl, triallylphenyl, benzenesulfonyloxy, 2-benzenesulfonyloxyethyl, methanesulfonyloxy, 2,2-dimethyl-3-methanesulfonyloxypropyl, 2- (2-p-toluenesulfonyloxyethoxy) ethyl, 4 -Groups such as methanesulfonyloxyphenyl and 2-methanesulfonyloxyethyl, among which, methyl, 2-ethylhexyl, allyl, isopropenyl, cyclohexyl, phenyl, Ziryl, 3-trimethoxysilylpropyl, 3-triethoxysilylpropyl, 3-methyldimethoxysilylpropyl, 3-methyldiethoxysilylpropyl, 4-trimethoxysilylbutyl, 4-triethoxysilylbutyl, p-trimethoxysilyl Phenyl, p-triethoxysilylphenyl, m-trimethoxysilylphenyl, m-triethoxysilylphenyl, allylphenyl, diallylphenyl, triallylphenyl, benzenesulfonyloxy, 2-benzenesulfonyloxyethyl, methanesulfonyloxy, 2, Examples include 2-dimethyl-3-methanesulfonyloxypropyl, 2- (2 ″ -p-toluenesulfonyloxyethoxy) ethyl, 4-methanesulfonyloxyphenyl, 2-methanesulfonyloxyethyl, and the like. .


In formula (2), R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, halogen or a monovalent organic group, which may be the same or different. Y is an organic group having 1 to 20 carbon atoms.
Examples of the monovalent organic group include alkoxy such as methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy, alkenoxy such as ethenoxy, propenoxy and butenoxy, alkyl such as acetoxy, methyl and ethyl, phenyl, naphthyl and tosyl and the like. A group such as aryl is exemplified, and among these, a group such as alkoxy such as methoxy, ethoxy and propoxy, alkyl such as methyl, and aryl such as phenyl is preferable.
Examples of the organic group having 1 to 20 carbon atoms include groups such as methylene, ethylene, propylene, phenylene, and benzylene. Among these, propylene and phenylene are preferable.

Examples of the synthesis method of the alkenyl-substituted nadiimide compound in which n is 1 used in the present invention include the following methods, but are not limited thereto. 1.0-3.0 mol of alkenyl-substituted nadic acid anhydride is mixed with 1.0 mol of monoamine in an aprotic polar solvent such as THF, ethyl acetate, etc., stirred and dried under reduced pressure to obtain amic acid. Thereafter, amic acid is heated or chemically dehydrated and closed in a solvent, purified by a silica gel column, and then confirmed to be the target imide compound by NMR, IR, and GPC. As another method, for example, the monoamine and maleic anhydride are mixed and stirred in an aprotic polar solvent such as THF or ethyl acetate, and dried under reduced pressure to obtain amic acid. Thereafter, 1.0-3.0 mol of alkenyl-substituted cyclopentadiene is mixed with 1.0 mol of monomaleimide obtained by heating or amidating the amide acid chemically in a solvent and purifying by a silica gel column. After that, the target imide compound is confirmed by NMR, IR, and GPC.
Examples of the alkenyl-substituted nadiimide compound in which n is 1 used in the present invention include the following.

Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-hydroxyethyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2,2-dimethyl-3-hydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2,3-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-hydroxy-cyclohexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {2- (2-hydroxyethoxy) ethyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- {2- (2-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {2- (2-hydroxyethoxy) ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {2- (2-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4- (4-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

N- (3-trimethoxysilylpropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-triethoxysilylpropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-methyldimethoxysilylpropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-methyldiethoxysilylpropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-trimethoxysilylbutyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-triethoxysilylbutyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-methyldimethoxysilylbutyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-methyldiethoxysilylbutyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-trimethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-triethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-methyldimethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-methyldiethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (m-trimethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (m-triethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (m-methyldimethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (m-methyldiethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

N- (benzenesulfonyloxy) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-benzenesulfonyloxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (methanesulfonyloxy) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2,2-dimethyl-3-methanesulfonyloxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2- (2′-p-toluenesulfonyloxyethoxy) ethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-methanesulfonyloxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-methanesulfonyloxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (benzenesulfonyloxy) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-benzenesulfonyloxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (methanesulfonyloxy) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2 ′, 2′dimethyl-3′-methanesulfonyloxypropyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2- (2 ″ -p-toluenesulfonyloxyethoxy) ethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-methanesulfonyloxyphenyl) -methallyl rubicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-methanesulfonyloxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (benzenesulfonyloxy) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-benzenesulfonyloxyethyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (methanesulfonyloxy) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2,2-dimethyl-3-methanesulfonyloxypropyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2- (2-p-toluenesulfonyloxyethoxy) ethyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-methanesulfonyloxyphenyl) -methallylmethyl rubicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-methanesulfonyloxyethyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

As said alkenyl substituted nadiimide (A-1), a preferable thing is
N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

Also,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

Also,
N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

N- (3-trimethoxysilylpropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3-triethoxysilylpropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-trimethoxysilylbutyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4-triethoxysilylbutyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-trimethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-triethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (m-trimethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (m-triethoxysilylphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

As the alkenyl-substituted nadiimide (A-1), more preferable is
N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

Also,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

N- (benzenesulfonyloxy) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-benzenesulfonyloxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (methanesulfonyloxy) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2,2-dimethyl-3-methanesulfonyloxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2 ′-(2-p-toluenesulfonyloxyethoxy) ethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4′-methanesulfonyloxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-methanesulfonyloxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and the like.

  These alkenyl-substituted nadiimides (A-1) may be used alone or as a mixture thereof.

1.2 Bisalkenyl-substituted nadiimide (A-2)
In the general formula (1), when n = 2, R ³ is an organic group having 1 to 140 carbon atoms or a group represented by the following general formula (3).
Examples of the organic group having 1 to 140 carbon atoms include, for example, alkylene having 1 to 140 carbon atoms (arbitrary methylenes not adjacent to each other in alkylene may be replaced by —O— or —CH═CH—, Or any hydrogen in the group wherein methylene in alkylene is replaced with —CH═CH— may be replaced with fluorine, and replaced with —CO—, —O—, —S— or —SO ₂ —; May be a cycloalkylene having 1 to 140 carbon atoms, an arylene having 1 to 140 carbon atoms (hydrogen directly bonded to an aromatic ring of an aromatic hydrocarbon group may be replaced by a hydroxyl group or fluorine), and alkylenes thereof. Examples thereof include an organic group having 1 to 140 carbon atoms including a repeating structure of cycloalkylene and an arylene group. Among these, an aryl group having 1 to 20 carbon atoms is preferable. Xylene {any non-adjacent methylene in alkylene may be replaced with -O- or -CH = CH-, and any methylene in alkylene or in a group where methylene in alkylene is replaced with -CH = CH- May be replaced with fluorine}, a cycloalkylene having 3 to 8 carbon atoms, a hydrocarbon group containing a cycloalkylene having 4 to 12 carbon atoms, an arylene having 6 to 12 carbon atoms, — (R ⁵⁰ ) _a -C ₆ H ₄ -R ⁵¹ - (wherein, a is an integer of 0 or ^1, in each of ^{R 50} and ^{R 51} independently is an alkylene of 1 to 4 carbon atoms) groups represented by, -C _{6 H 4 -T-C 6 H 4} -, - C 6 H 4 -T-C 6 H 4 -T-C 6 H 4 - or _{-C 6 H 4 -T'-C 6} H 4 -T-C 6 _{H 4 -T'-C 6 H 4} - { However, T is a single If an alkylene having 1 to 6 carbon _{atoms, -C (CH 3) 2 -} , - C (CF 3) 2 -, - CO -, - O -, - S- or -SO ₂ - and is, T 'is —CH ₂ — or —O—. }, Or a group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced with a hydroxyl group.

In formula (3), R ⁷ and R ⁸ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁹ is each independently methylene, phenylene or alkyl-substituted phenylene, and x is Each independently represents an integer of 1 to 6, and y is an integer of 1 to 70. Here, more preferable y is an integer of 1-15.

In the present invention, preferably, R ³ in the general formula (1) is alkylene having 2 to 20 carbon atoms (any methylenes not adjacent to each other in alkylene are replaced by —O— or —CH═CH—). Or any hydrogen in the alkylene or a group in which methylene in the alkylene is replaced with —CH═CH— may be replaced with fluorine}, a cycloalkylene having 5 to 8 carbons, or 6 to 12 carbons _{^{arylene, - (R 50) a -C}} 6 H 4 -R 51 - ( wherein, a is an integer of 0 or ^1, in each of ^{R 50} and ^{R 51} independently is an alkylene of 1 to 4 carbon atoms) a group represented _{by, -C 6 H 4 -T-C} 6 H 4 -, - C 6 H 4 -T-C 6 H 4 -T-C 6 H 4 - or _-C 6 _H 4 -T'- _{C 6 H 4 -T-C 6} H 4 -T'-C H ₄ - {However, T is a single bond, an alkylene having 1 to 6 carbon _{atoms, -C (CH 3) 2 -} , - C (CF 3) 2 -, - CO -, - O -, - S- or - SO ₂ — and T ′ is —CH ₂ — or —O—. }, A group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced by a hydroxyl group, a group represented by the above general formula (3), or a group represented by the following formula (6) It is preferred that


In the present invention, it is also preferable that R ³ in the general formula (1) is a group represented by the following formula (9) or (10).

Further, in the present invention, R ³ in the general formula (1) may contain asymmetric alkylene or phenylene as described below.

Examples of the synthesis of the bisalkenyl-substituted nadiimide compound in which n is 2 used in the present invention include, but are not limited to, the following methods. An amide acid is obtained by mixing 2.0 to 4.0 moles of alkenyl-substituted nadic acid anhydride with 1.0 mole of diamine in an aprotic polar solvent such as THF, ethyl acetate and the like, stirring and drying under reduced pressure. Thereafter, amic acid is heated or chemically dehydrated and closed in a solvent, purified by a silica gel column, and then confirmed to be the target imide compound by NMR, IR, and GPC. As another method, for example, the diamine and maleic anhydride are mixed and stirred in an aprotic polar solvent such as THF or ethyl acetate, and dried under reduced pressure to obtain amic acid. Thereafter, the amide acid is mixed with 1.0 to 4.0 mol of alkenyl-substituted cyclopentadiene with 1.0 mol of bismaleimide obtained by heating or chemically dehydrating and cyclizing in a solvent, and purified by a silica gel column. Then, it is confirmed by NMR, IR and GPC that it is the target imide compound.
Specific examples of the bisalkenyl-substituted nadiimide compound in which n is 2 used in the present invention include the following.

N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
And oligomers thereof.

Also,
1,2-bis {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
1,2-bis {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
1,2-bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
Bis [2- {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
Bis [2- {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
1,4-bis {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,
1,4-bis {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,
And oligomers thereof.

Also,
N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
And oligomers thereof.

Also,
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
1,2-bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ethane,
1,2-bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ethane,
And oligomers thereof.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
And oligomers thereof.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
1,6-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -3-hydroxy-hexane,
1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -3,6-dihydroxy-dodecane,
1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane,
1,5-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane,
1,4-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-benzene,
And oligomers thereof.

Also,
1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene,
N, N′-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
And oligomers thereof.

Also,
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -2-hydroxy-phenoxy} phenyl] propane,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane,
Bis {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -4-hydroxy-phenyl} ether,
Bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone,
And oligomers thereof.

  Moreover, these bisalkenyl substituted nadiimides (A-2) may be used alone or as a mixture thereof.

As the bisalkenyl-substituted nadiimide (A-2), preferred is N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Also,
Bis [2- {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
Bis [2- {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
1,4-bis {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,
1,4-bis {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} butane.

Also,
N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
1,2-bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ethane,
1,2-bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ethanebis {4- (allylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane,
And bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
And bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone.

Also,
And bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone.

As the bisalkenyl-substituted nadiimide (A-2), more preferred are
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Also,
Bis [2- {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
Bis [2- {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
1,4-bis {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,
1,4-bis {3- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} butane.

Also,
N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Also,
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] hexafluoropropane,
1,2-bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ethane,
1,2-bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ethanebis {4- (allylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane,
And bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
And bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

1.3 Trisalkenyl-substituted nadiimide (A-3)
In the general formula (1), when n = 3, R ³ is a group represented by the following general formula (4) or (4 ′).


In the formula (4), R represents hydrogen, fluorine, chlorine, —OH, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₂ CF ₂ H, —OCF _2. CFHCF ₃ , or alkyl having 1 to 10 carbon atoms,
In formulas (4) and (4 ′), R ¹⁰ , R ¹¹ and R ¹² are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═. CH— may be replaced, and any hydrogen in the alkylene or a group in which methylene in alkylene is replaced with —CH═CH— may be replaced with fluorine.

  Examples of the synthesis of the trisalkenyl-substituted nadiimide compound in which n is 3 used in the present invention include, but are not limited to, the following methods. An amide acid is obtained by mixing 3.0 to 5.0 moles of alkenyl-substituted nadic acid anhydride with 1.0 mole of triamine in an aprotic polar solvent such as THF and ethyl acetate, stirring and drying under reduced pressure. Thereafter, amic acid is heated or chemically dehydrated and closed in a solvent, purified by a silica gel column, and then confirmed to be the target imide compound by NMR, IR, and GPC. As another method, for example, the above triamine and maleic anhydride are mixed and stirred in an aprotic polar solvent such as THF, ethyl acetate and the like, and dried under reduced pressure to obtain amic acid. Thereafter, the amide acid is heated or chemically dehydrated and ring-closed in a solvent, and the resulting trimaleimide (1.0 mol) is mixed with alkenyl-substituted cyclopentadiene (3.0 to 5.0 mol) and purified by a silica gel column. After that, the target imide compound is confirmed by NMR, IR, and GPC.

Specific examples of the trisalkenyl-substituted nadiimide compound in which n is 3 used in the present invention include tris {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) ethyl. } Amine,
Tris {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) butyl} amine,
Tris {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} hydroxymethane,
And tris {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

1.4 Tetrakisalkenyl-substituted nadiimide (A-4)
In the general formula (1), when n = 4, R ³ is a group represented by the following general formula (5).


In formula (5), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═CH—. Any hydrogen in the alkylene or in the group in which methylene in the alkylene is replaced with —CH═CH— may be replaced with fluorine.
In the present invention, R ³ in the general formula (1) is preferably a group represented by the following formula (11).

  Examples of the synthesis of a tetrakisalkenyl-substituted nadiimide compound in which n is 4 used in the present invention include, but are not limited to, the following methods. 4.0 mol of alkenyl-substituted nadic acid anhydride is mixed with 1.0 mol of tetraamine in an aprotic polar solvent such as THF, ethyl acetate, etc., stirred and dried under reduced pressure to obtain amic acid. Thereafter, amic acid is heated or chemically dehydrated and closed in a solvent, purified by a silica gel column, and then confirmed to be the target imide compound by NMR, IR, and GPC. As another method, for example, the above triamine and maleic anhydride are mixed and stirred in an aprotic polar solvent such as THF, ethyl acetate and the like, and dried under reduced pressure to obtain amic acid. Thereafter, 4.0-6.0 moles of alkenyl-substituted cyclopentadiene are mixed with 1.0 mole of tetramaleimide obtained by heating or chemically dehydrating and ring-closing the amic acid in a solvent, and purified by a silica gel column. After that, the target imide compound is confirmed by NMR, IR, and GPC.

  Specific examples of the tetrakisalkenyl-substituted nadiimide compound in which n is 4 used in the present invention include tetrakis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl. } Methane is mentioned.

  Since the preferred alkenyl-substituted nadiimide compound (A) of the present invention is a low molecular weight imide monomer having a bulky structure, it is soluble in most organic solvents, and even when stored in a solution state for a long period of time, crystals are precipitated. And can be used stably without gelation. Also, when heated, it does not flow and forms a highly printable three-dimensional cross-linked polyimide, and the cured polyimide has good flexibility, heat resistance, mechanical properties, electrical properties, chemical resistance Indicates.

2 Polymer compound (B)
The polymer compound (B) that can be further contained in the ink jet ink of the present invention includes polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, polypropylene, acrylic acid polymer, acrylate polymer, polyvinyl alcohol, poly Although it is high molecular compounds, such as oxyethylene, it is not limited to this. A polymer compound having a weight average molecular weight of 10,000 or more is preferable, and a polyimide polymer compound such as polyamic acid or soluble polyimide having a weight average molecular weight of 50,000 or more is more preferable. The polyamic acid or the imidized polymer thereof can be preferably mentioned, but is not limited thereto.
The polyamic acid can be obtained using at least the compound (b1) having two or more acid anhydride groups, the diamine (b2), and the monoamine (b3), but is limited to the polyamic acid obtained by the production method. Is not to be done.

  The compound (b1), diamine (b2), and monoamine (b3) having two or more acid anhydride groups that can be used to obtain a polyamic acid that is one of the preferred embodiments of the polymer compound (B) are shown below. ).

2.1 Compound (b1) having two or more acid anhydride groups
Specific examples of the compound (b1) having two or more acid anhydride groups used in the present invention include an anhydride group such as a styrene-maleic anhydride copolymer and a methyl methacrylate-maleic anhydride copolymer. Examples include a copolymer of a radical polymerizable monomer and another radical polymerizable monomer, and a tetracarboxylic dianhydride represented by the following general formula (b1). In the general formula (b1), R ¹ is a tetravalent organic group. Examples of the tetracarboxylic dianhydride include 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, and 2,2 ′. , 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylethertetracarboxylic dianhydride 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), ethanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran- 3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohex Down-1,2-dicarboxylic acid anhydride include tetracarboxylic dianhydride such as compounds represented by the following formula B1-1～b1-73.

  Among the above specific examples of the compound having two or more acid anhydride groups, styrene-maleic anhydride copolymer, formula b1-1, b1-5, b1-6, b1-7, b1-8, b1-9 , B1-14, b1-18, and b1-20 are preferable because they have high solubility in a solvent and can prepare a high-concentration ink. Moreover, although high transparency is required depending on the use of the inkjet ink, in such a case, a styrene-maleic anhydride copolymer, b1-6, b1-7, b1-8, b1-9. , B1-14, b1-18 and the like are particularly preferable.

  In addition, the compounds having an acid anhydride group described above may be used singly or in combination of two or more.

2.2 Diamine (b2)
The diamine (b2) used in the present invention is not particularly limited as long as it has two amino groups, and examples thereof include compounds represented by the following general formulas (II) to (VIII).

[In the formula (II),
A ¹ is — (CH ₂ ) _m —, where m is an integer of 1 to 6,
In formulas (IV), (VI) and (VIII),
A ¹ is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C ( CF ₃ ) ₂ —, — (CH ₂ ) _m —, —O— (CH ₂ ) _m —O—, —S— (CH ₂ ) _m —S—, wherein m is an integer of 1 to 6. Yes,
A ² is a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 3 carbon atoms,
Hydrogen bonded to a cyclohexane ring or a benzene ring may be replaced with fluorine or —CH ₃ . ]

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

Examples of the diamine represented by the general formula (III) include diamines represented by the formulas (III-1) and (III-2).

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

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

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

Examples of the diamine represented by the general formula (VII) include diamines represented by the formulas (VII-1) to (VII-6).

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

  Among the specific examples of the diamine (b2) represented by the general formulas (II) to (VIII), more preferably, the formulas (V-1) to (V-5) and the formulas (VI-1) to (VI) -12), formula (VI-26), formula (VI-27), formula (VII-1), formula (VII-2), formula (VII-6), formula (VIII-1) to (VIII-5) Diamines represented by formula (V-6), formula (V-7), and diamines represented by formulas (VI-1) to (VI-12).

Examples of the diamine (b2) used in the present invention further include a diamine represented by the general formula (IX).

[In the formula (IX),
A ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _m — (wherein m is an integer of 1 to 6). ,
R ⁶ is a group having a steroid skeleton, a group represented by the following formula (X), or an alkyl group having 1 to 20 carbon atoms when the positional relationship between two amino groups bonded to the benzene ring is para. Or when the positional relationship is meta, it is alkyl having 1 to 10 carbons or phenyl,
In the alkyl, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, and —CH ₃ may be —CH _3. May be replaced by ₂ F, -CHF ₂ or -CF ₃ ,
The hydrogen bonded to the ring-forming carbon of the phenyl may be replaced with fluorine, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ or —OCF ₃ . ]

[In the formula (X),
A ⁴ and A ⁵ are each independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons;
R ⁷ and R ⁸ are each independently fluorine or —CH ₃ ;
Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl;
R ⁹ is hydrogen, fluorine, alkyl having 1 to 12 carbons, fluorine-substituted alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ . ,
a and b each independently represents an integer of 0 to 4;
c, d and e each independently represent an integer of 0 to 3, and when e is 2 or 3, the plurality of rings S may be the same group or different groups,
f and g each independently represent an integer of 0 to 2 and c + d + e ≧ 1. ]

In the general formula (IX), the two amino groups are bonded to the phenyl ring carbon. Preferably, the bonding position relationship between the two amino groups is preferably the meta position or the para position. Further, the two amino groups are preferably bonded to the 3rd and 5th positions or the 2nd and 5th positions, respectively, when the bonding position of “R ⁶ -A ³ —” is the 1st position.
Examples of the diamine represented by the general formula (IX) include diamines represented by the following formulas (IX-1) to (IX-11).

In the above formulas (IX-1), (IX-2), (IX-7) and (IX-8), R ¹⁸ is preferably alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons. More preferred is alkyl having 5 to 12 or alkoxy having 5 to 12 carbon atoms. In the above formulas (IX-3) to (IX-6) and (IX-9) to (IX-11), R ¹⁹ is preferably alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, More preferred is alkyl having 3 to 10 carbons or alkoxy having 3 to 10 carbons.

Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-12) to (IX-17).

In the above formulas (IX-12) to (IX-15), R ²⁰ is preferably alkyl having 4 to 16 carbons, and more preferably alkyl having 6 to 16 carbons. In the formula (IX-16) and the formula (IX-17), R ²¹ is preferably alkyl having 6 to 20 carbon atoms, more preferably alkyl having 8 to 20 carbon atoms.

  Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-18) to (IX-38).

The above formulas (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31), In (IX-36) and (IX-37), R ²² is preferably alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons is Further preferred. In addition, the above formulas (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX-35) ) And (IX-38), R ²³ is hydrogen, fluorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ ; More preferred is alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons. The equation (IX-33) in (IX-34), ^{A 9} is an alkylene having 1 to 12 carbon atoms.

Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-39) to (IX-48).

  Of the diamines (b2) represented by the general formula (IX), diamines represented by the formulas (IX-1) to (IX-11) are preferable, and the formulas (IX-2) and (IX-4) are preferred. More preferred are diamines represented by formula (IX-5) and formula (IX-6).

Examples of the diamine (b2) used in the present invention further include compounds represented by the following general formulas (XI) and (XII).

[In the formulas (XI) and (XII)
R ¹⁰ is —H or —CH ₃ , each R ¹¹ is independently hydrogen or alkyl or alkenyl having 1 to 20 carbon atoms;
Each A ⁶ is independently a single bond, —C (═O) — or —CH ₂ —;
In formula (XII),
R ¹³ and R ¹⁴ are each independently hydrogen, alkyl having 1 to 20 carbons, or phenyl. ]

In the general formula (XI), one of two “NH ₂ —Ph—A ⁶ —O—” (where —Ph— represents phenylene) is bonded to the 3-position of the steroid nucleus, and the other is 6 It is preferable that it is bonded to the position. The two amino groups are each bonded to the phenyl ring carbon, and preferably bonded to the meta position or the para position with respect to the bonding position of A ⁶ .
Examples of the diamine represented by the general formula (XI) include diamines represented by the formulas (XI-1) to (XI-4).

In the general formula (XII), two “NH ₂ — (R ¹⁴ —) Ph—A ⁶ —O—” (where —Ph— represents phenylene) are each bonded to a phenyl ring carbon. , Preferably bonded to carbon in the meta position or para position relative to the carbon to which the steroid nucleus is bonded. The two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to A ⁶ .
Examples of the diamine represented by the general formula (XII) include diamines represented by the formulas (XII-1) to (XII-8).

Examples of the diamine (b2) used in the present invention further include compounds represented by general formulas (XIII) and (XIV).

[In the formula (XIII),
R ¹⁵ is hydrogen or alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl having 2 to 20 carbon atoms is —O—, —CH═CH— or —C≡C—. May be replaced with
Each A ⁷ is independently —O— or alkylene having 1 to 6 carbons;
A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms,
Ring T is 1,4-phenylene or 1,4-cyclohexylene,
h is 0 or 1. ]

[In the formula (XIV),
R ¹⁶ is alkyl having 6 to 22 carbon atoms,
R ¹⁷ is hydrogen or alkyl having 1 to 22 carbons,
A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms. ]

In the general formula (XIII), the two amino groups are respectively bonded onto carbons of the benzene ring, it is preferably bonded in the meta or para to A ^7.
Examples of the diamine represented by the general formula (XIII) include diamines represented by the formulas (XIII-1) to (XIII-9).


In the above formulas (XIII-1) to (XIII-3), R ²⁴ is preferably hydrogen and alkyl having 1 to 20 carbons, and in (XIII-4) to (XIII-9), R ²⁵ is hydrogen and carbons More preferred are 1 to 10 alkyls.

In the general formula (XIV), the two amino groups are respectively bonded onto carbons of the benzene ring, it is preferably bonded in the meta or para position with respect to A ^7.
Examples of the diamine represented by the general formula (XIV) include diamines represented by (XIV-1) to (XIV-3).

In the formulas (XIV-1) to (XIV-3), R ²⁶ is an organic group having 2 to 30 carbon atoms, and among these, alkyl having 6 to 20 carbon atoms is preferable, and R ²⁷ is an alkyl group having 2 to 30 carbon atoms. Of these, hydrogen or alkyl having 1 to 10 carbon atoms is more preferable.

  As described above, for example, diamines represented by the general formulas (II) to (XIV) can be used as the diamine (b2) used in the present invention, but diamines other than these diamines can also be used. For example, a naphthalene diamine having a naphthalene structure, a fluorene diamine having a fluorene structure, a siloxane diamine having a siloxane bond, or the like can be used alone or mixed with another diamine.

The siloxane-based diamine is not particularly limited, but those represented by the following formula (12) can be preferably used in the present invention.


Wherein R ¹⁴ and R ¹⁵ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ¹⁶ is independently methylene, phenylene or alkyl-substituted phenylene, and x is independently 1 to 1 It is an integer of 6, and y is an integer of 1 to 70. Here, more preferable y is an integer of 1-15.

Furthermore, Preferably, the diamine represented by following formula (13)-(20) can be used as diamine (b2) used in this invention.

(In the formula, R ³⁰ and R ³¹ are each independently alkyl having 3 to 20 carbon atoms.)

In addition, the diamine (b2) that can be used in the present invention is not limited to the diamine described in the present specification, and various other forms of diamine may be used within the scope of achieving the object of the present invention. Can be used.
Moreover, the diamine (b2) which can be used by this invention can be used individually or in combination of 2 or more types. That is, as a combination of two or more kinds, the above diamines, the above diamine and other diamines, or diamines other than the above diamines can be used.

  Moreover, although high transparency is required depending on the use of the inkjet ink, in such a case, 3,3′-diaminodiphenylsulfone and y = 1 to 15 in the general formula (12) It is particularly preferable to use a diamine.

2.3 Monoamine (b3)
The monoamine (b3) used in the present invention is not particularly limited, but specific examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyl. Diethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyl Dimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, monoeta Ruamin, n- butylamine, aniline.
Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and p-aminophenyltrimethoxysilane are preferable, and 3-aminopropyltriethoxysilane is preferable from the viewpoint of excellent durability of the obtained film. Particularly preferred.
These monoamines can be used alone or in combination of two or more.

2.4 Reaction Conditions of Polyamic Acid The polyamic acid that can be used in the present invention is such that the compound (b1) having two or more acid anhydride groups is 1 mol, and the diamine (b2) is 0.05 to 0.00. It is preferable that 8 mol and monoamine (b3) are obtained by reacting 0.4 to 1.9 mol. Moreover, 0.1 to 0.6 mol of diamine (b2) and 0.8 to 1.8 mol of diamine (b3) are reacted per 1 mol of the compound (b1) having two or more acid anhydride groups. More preferably, it is obtained.

2.4.1 Reaction solvent The solvent used to obtain the polyamic acid using at least the compound (b1) having two or more acid anhydride groups, the diamine (b2), and the monoamine (b3), Although it is not particularly limited as long as it can be synthesized, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. Kill.
Among these, it is preferable to use propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, or diethylene glycol dimethyl ether because an ink with less damage to the ink jet head can be obtained.
These reaction solvents can be used alone or as a mixed solvent of two or more. In addition to the reaction solvent, other solvents can 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 in total of the compound (b1) having two or more acid anhydride groups, the diamine (b2), and the monoamine (b3), the reaction proceeds smoothly. . The reaction is preferably performed at 0 to 100 ° C. for 0.2 to 20 hours.

2.4.2 Order of addition to reaction system The order of addition of reaction raw materials to the reaction system is not particularly limited. That is, the compound (b1) having two or more acid anhydride groups, the diamine (b2), and the monoamine (b3) are simultaneously added to the reaction solvent, and the diamine (b2) and the monoamine (b3) are dissolved in the reaction solvent. The compound (b1) having two or more acid anhydride groups is added later, the compound (b1) having two or more acid anhydride groups and the monoamine (b3) are reacted in advance, and then the diamine (b2) is added. In any method, a compound (b1) having two or more acid anhydride groups is reacted in advance with a diamine (b2) to synthesize a copolymer, and then a monoamine (b3) is added to the copolymer. Can be used.

2.5 Weight average molecular weight of polymer compound (B) The polymer compound (B) used in the present invention preferably has a weight average molecular weight of 10,000 or more. In particular, when a polyamic acid having a weight average molecular weight of 65,000 to 500,000 is used, a polyimide film having a uniform film thickness can be obtained, and the characteristics of the resulting polyimide film, such as mechanical strength and flexibility, are good, so that the inkjet ink As preferred. When a polyamic acid having a weight average molecular weight of 65,000 or more is used, the resulting polyimide film has strong mechanical strength, good flexibility without cracking, and a polyimide film having a uniform thickness can be obtained. Therefore, it can be preferably used as an inkjet ink. On the other hand, when a polyamic acid having a weight average molecular weight of 500,000 or less is used, stable ink jet printing is possible. In order to further improve the inkjet printability of the inkjet ink and the mechanical strength of the resulting polyimide film, the weight average molecular weight of the polyamic acid is more preferably 70,000 to 210,000, and particularly preferably 80,000 to 180,000. .

  The weight average molecular weight of the polymer compound (B) can be measured by a gel permeation chromatography (GPC) method. Specifically, the obtained polymer compound (B) was diluted with tetrahydrofuran (THF) or the like so as to have a concentration of about 1% by weight, and columns G4000HXL, G3000HXL, G2500HXL and G2000HXL manufactured by Tosoh Corporation were used. It can be determined by measuring by gel permeation chromatography (GPC) using THF as a developing agent and converting to polystyrene.

3 Solvent (C)
The inkjet ink of the present invention can be obtained, for example, by dissolving the alkenyl-substituted nadiimide compound (A) and, if necessary, the polymer compound (B) in the solvent (C). Therefore, the solvent contained in the inkjet ink of the present invention is not particularly limited as long as it is a solvent that can dissolve the alkenyl-substituted nadiimide compound (A) and, if necessary, the polymer compound (B). Further, even if the solvent alone does not dissolve the alkenyl-substituted nadiimide compound (A) and, if necessary, the polymer compound (B), it is used as a solvent (C) contained in the ink-jet ink by mixing with another solvent. It is possible.

  Specific examples of the solvent (C) contained in the inkjet ink include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, ethyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl Ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, propylene glycol mono Examples include tilether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethanol, 2-propanol, dioxane, ethylene glycol, and butyl celsorb. .

As described above, there is no particular limitation on the solvent contained in the ink jet ink of the present invention, but depending on the specifications of the ink head of the ink jet printer, corrosion or swelling may occur depending on the type of solvent used by the joining member or the filter material that is present. There is a case. Alternatively, the selection of the solvent (C) is very important since the ink head is clogged with a solvent having a high drying speed.
As a result of intensive studies by the present inventors, in terms of improving the durability of the ink-jet head, clogging the head, and ejecting ink, ethyl lactate, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene It has been found that glycol monomethyl ether acetate, methyl 3-methoxypropionate, γ-butyrolactone, butyl celsolob and the like are particularly preferable as the solvent (C).
Furthermore, since the surface tension of the ink greatly affects the applicability of the inkjet ink, the surface tension of the ink is adjusted to 20 to 45 mN / m, preferably 30 to 40 mN / m.
If the surface tension is greater than 45 mN / m, the ink meniscus at the ink ejection port may become unstable and ink cannot be ejected. If the surface tension is less than 20 mN / m, the applied droplets will spread and the shape of the coating pattern will be large. Getting worse.
In order to adjust the surface tension to a range of 20 to 45 mN / m, selection of a solvent is important. A kind of solvent having a surface tension in the range of 20 to 45 mN / m may be used, but a solvent having a large surface tension (for example, γ-butyrolactone: 43 mN / m) and a solvent having a small surface tension (for example, diethylene glycol methylethyl) A mixture of ether: 24 mN / m or ethylene glycol monobutyl ether: 32 mN / m is preferred because the surface tension can be finely adjusted by the solvent composition.

Further, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, diethylacetamide, N-methylpropionamide, N, N, N ′ Amide solvents such as alkenyl-substituted nadiimide compound (A) and polymer Since it is a good solvent for the compound (B), it can be preferably used, but on the other hand, the durability of the ink jet head is difficult and attention is required.
Therefore, in the solvent (C) contained in the inkjet ink of the present invention, the above-mentioned particularly preferable solvent is preferably contained in an amount of 80% by weight or more, more preferably 90% by weight or more of the solvent (C).

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

4. Concentrations of alkenyl-substituted nadiimide compound (A), polymer compound (B) and solvent (C) in inkjet ink of the present invention The concentration of the alkenyl-substituted nadiimide compound (A) in the inkjet ink is not particularly limited in the present invention. Is preferably 1 to 99% by weight, more preferably 10 to 80% by weight, and particularly preferably 22 to 70% by weight. These concentration ranges are preferable because jetting accuracy is high.
In the present invention, the concentration of the polymer compound (B) in the inkjet ink is not particularly limited, but is preferably 0 to 50% by weight, more preferably 0 to 25% by weight, and further preferably 0 to 12.5% in order to keep the viscosity low. Weight percent is particularly preferred.
In the present invention, the concentration of the solvent (C) in the inkjet ink is not particularly limited, but is preferably 1 to 99% by weight, more preferably 20 to 90% by weight, and particularly preferably 30 to 78% by weight. These concentration ranges are preferable because jetting accuracy is high.
When used as an inkjet ink, the higher the concentration of the alkenyl-substituted nadiimide compound (A) and the polymer compound (B), the greater the thickness of the resulting polyimide film, which is preferable, but on the other hand, the viscosity tends to increase. Therefore, in some cases, there arises a problem that the ink cannot be ejected by the ink jet printer. As a result of intensive studies by the present inventors, it has been found that it can be preferably used as an inkjet ink capable of forming a polyimide film having a large film thickness, particularly within the above-mentioned concentration range.

5 Additives added to the ink jet ink of the present invention The ink jet ink of the present invention is obtained by mixing an alkenyl-substituted nadiimide compound (A), a polymer compound (B) if necessary, and a solvent (C) if necessary. It is done.
Furthermore, depending on the intended properties, the ink jet ink of the present invention may be an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, an epoxy curing agent such as trimellitic acid, an aminosilicon compound, a solvent, Select and add additives such as pH adjusters, rust inhibitors, antiseptics, antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, water-soluble polymers, etc. It can be obtained by mixing and dissolving.

(1) Epoxy resin The inkjet ink of the present invention may further contain an epoxy resin. The epoxy resin contained in the inkjet ink of the present invention is not particularly limited as long as it has oxirane, but a compound having two or more oxiranes is preferable.

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

  Examples of the epoxy resin include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having an oxirane, and a copolymer of a monomer having an oxirane and another monomer. It is done.

Specific examples of the monomer having oxirane include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.
Specific examples of the monomer having an oxirane and other monomers copolymerized include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (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 oxirane and the copolymer of the monomer having oxirane and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, Examples include n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer. be able to. It is preferable that the ink-jet ink of the present invention contains these epoxy resins because the heat resistance of the coating film formed from the ink-jet ink is improved.

Specific examples of the epoxy resin that can be included in the inkjet ink of the present invention include trade names “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 190P”, "Epicoat 191P" (manufactured by Yuka Shell Epoxy Co., Ltd.), trade name "Epicoat 1004", "Epicoat 1256" (above, Japan Epoxy Resin Co., Ltd.), trade name "Araldite CY177", trade name " Araldite CY184 (manufactured by Ciba-Geigy Japan), trade names “Celoxide 2021P”, “Celoxide 3000”, “EHPE-3150” (Daicel Chemical Industries), trade name “Techmore VG3101L” (Mitsui Chemicals, Inc.) )), N, N, N ′, N′-tetraglycidyl-m-ki Diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', mention may be made of N'- tetraglycidyl-4,4'-diaminodiphenylmethane.
Among these, the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “Techmore VG3101L”, and the trade name “Epicoat 828” are preferable because the resulting polyimide film has particularly good flatness.

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

(2) The acrylic resin inkjet ink may further contain an acrylic resin. The acrylic resin contained in the inkjet ink is not particularly limited as long as it has an acrylic group or a methacrylic group.

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

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

  Specific examples of the monofunctional polymerizable monomer having hydroxyl include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or 1,4-cyclohexanedimethanol mono Mention may be made of (meth) acrylates. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are particularly preferable because the formed film is flexible.

Specific examples of the monofunctional polymerizable monomer having no hydroxyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3-methyl-3- (meth) acryloxy. Methyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl- 3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) ) Acryloxymethyl oxetane, (meth) acrylic acid, Chill (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, methylstyrene, chloromethylstyrene, (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 , Polystyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloylmorpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl] , Mono [2- (meth) acryloyloxyethyl maleate], or mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate.

  Specific examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol. Diacrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol diacrylate, trimethylolpropane diacrylate, or dipentaerythritol diacrylate Acrylate can be mentioned.

Specific examples of trifunctional or higher polyfunctional (meth) acrylates are trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Mention may be made of ethylene oxide-modified phosphoric acid tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, or urethane (meth) acrylate.
These acrylic resins may be used alone or in combination of two or more.

(3) Surfactant When it is desired to improve the applicability of the inkjet ink, a surfactant that meets this purpose can be added. Specific examples of the surfactant added to the ink-jet ink of the present invention include trade names “Byk-300”, “Byk-306”, “Byk-335”, “Byk-310”, “Byk-341”. , “Byk-344”, “Byk-370” (manufactured by BYK-Chemie), etc .; trade names “Byk-354”, “ByK-358”, “Byk-361” (BIC・ Acrylic surfactants such as Chemie Co., Ltd., and fluorine surfactants such as trade names “DFX-18”, “Factent 250”, and “Factent 251” (manufactured by Neos) be able to.
These surfactants may be used alone or in combination of two or more.
The surfactant is used to improve the wettability, leveling property, or coating property to the base substrate, and is used by adding 0.01 to 1 part by weight to 100 parts by weight of the ink jet ink. Is preferred.

(4) Antistatic agent The antistatic agent added to the inkjet ink of the present invention is not particularly limited, and a known antistatic agent can be used. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, and tin oxide / indium oxide composite oxide, and quaternary ammonium salts.
These antistatic agents may be used alone or in admixture of two or more.
The antistatic agent is used to prevent electrification, and is preferably used by adding 0.01 to 1 part by weight to 100 parts by weight of the ink jet ink.

(5) Coupling agent The coupling agent added to the inkjet ink of the present invention is not particularly limited, and a known coupling agent can be used. The coupling agent to be added is preferably a silane coupling agent, and specific examples thereof include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyl Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyl Trimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyl Dimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopro Le triethoxysilane, .gamma. isocyanate propyl methyl diethoxy silane, .gamma. isocyanate propyl triethoxysilane and the like. Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane and the like are preferable.

These coupling agents may be used alone or in combination of two or more.
The coupling agent is preferably used by adding 0.01 to 3 parts by weight to 100 parts by weight of the ink jet ink.

(6) Epoxy curing agent The epoxy curing agent added to the inkjet ink of the present invention is not particularly limited, and a known epoxy curing agent can be used. Specific examples include organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, polyvalent carboxylic acids, and polyvalent carboxylic acid anhydrides. More specifically, dicyandiamides such as dicyandiamide, adipic acid dihydrazide, organic acid dihydrazides such as 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 2,4-diamino-6- [2′- Ethylimidazolyl- (1 ′)]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, imidazole derivatives such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, Examples include merit acid and acid anhydrides such as 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride.
Of these, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferable.

These epoxy curing agents may be used alone or in combination of two or more.
The epoxy curing agent is preferably used by adding 0.2 to 5 parts by weight to 100 parts by weight of the inkjet ink.

(7) Aminosilicon compound An aminosilicon compound can be added to the ink-jet ink of the present invention. Examples of the aminosilicon compound include paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and the like.
These aminosilicon compounds may be used alone or in combination of two or more.
The aminosilicon compound is used for improving adhesion to the substrate, and is preferably used by adding 0.05 to 2 parts by weight to 100 parts by weight of the ink jet ink.

6 Viscosity of Inkjet Ink In the present invention, the viscosity of the inkjet ink is not particularly limited, but when jetting is performed at room temperature, it is preferably 1 to 50 mPa · s (25 in terms of improving jetting accuracy by the inkjet coating method. ° C), more preferably 5 to 30 mPa · s (25 ° C), and still more preferably 8 to 20 mPa · s (25 ° C).
When jetting by heating the ink head, 1-50 mPa · s, preferably 5-30 mPa · s, more preferably at the heating temperature (temperature at which the alkenyl-substituted nadiimide compound does not cure, preferably 40-120 ° C.). May be 8 to 20 mPa · s.

7 Polyimide film The inkjet ink of the present invention can be applied to the substrate surface by inkjet and heat-treated with a hot plate or oven to form a polyimide film having a whole surface or a predetermined pattern (line shape, etc.). .
Conventionally, when a patterned polyimide film is formed, a photolithography technique is used, but a large amount of chemicals such as a photoresist, a developing solution, an etching solution, and a stripping solution are required, and more complicated processes are required. Met. In contrast, the patterned polyimide film formed using the ink-jet ink of the present invention draws on only the necessary portions by ink-jet printing, so the amount of material used is overwhelmingly small and a photomask is not used. It is characterized by being capable of mass production of varieties and requiring a small number of processes for manufacturing.

7.1 Application of Inkjet Ink by Inkjet Method There are various types of inkjet application methods depending on the ink ejection method. Examples include a piezoelectric element type, a bubble jet (registered trademark) type, a continuous jet type, and an electrostatic induction type. The ink according to the present invention can be jetted by various ejection methods by appropriately selecting each component contained in the ink, and ink jet ink can be applied in a predetermined pattern.

  A more preferable ejection method for applying the ink using the ink according to the present invention is a piezoelectric element type. The piezoelectric element-type head includes a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite to the nozzles, and ink filling the periphery of the pressure generating element. An on-demand ink jet coating head displaces a pressure generating element by an applied voltage and ejects a small droplet of ink from a nozzle.

The ink jet coating apparatus is not limited to the one in which the coating head and the ink container are separated, and may be one in which they are integrated so as not to be separated. The ink container is integrated with the application head so as to be separable or non-separable and mounted on the carriage, and is provided at a fixed portion of the apparatus so that the ink is supplied to the application head via an ink supply member, for example, a tube. It may be in the form of supplying.
In addition, when the ink tank is provided with a structure for applying a preferable negative pressure to the coating head, a configuration in which an absorber is disposed in the ink storage portion of the ink tank, or a flexible ink storage bag and the same A form having a spring portion that applies a biasing force in the direction of expanding the internal volume can be employed. The coating apparatus may take the form of a line printer in which coating elements are aligned over a range corresponding to the entire width of the coating medium, in addition to the serial coating method as described above.

7.2 After applying the ink-jet ink of the present invention on a substrate by ink-jet using a solvent-dry ink-jet coating method, the solvent (C) is removed by vaporization or the like by heating in a hot plate or oven. That is, a film of the alkenyl-substituted nadiimide compound (A) can be formed by drying. When the inkjet ink further contains the polymer compound (B), a composite film of the alkenyl-substituted nadiimide compound (A) and the polymer compound (B) can be formed.
Although the heating conditions vary depending on the type and blending ratio of each component, a temperature at which the alkenyl-substituted nadiimide compound (A) does not cure is preferable, usually 70 to 180 ° C, more preferably 80 to 120 ° C, and 5 to 5 when an oven is used. When a hot plate is used for 15 minutes, a film is formed in 1 to 5 minutes.

7.3 Formation of polyimide film In order to cure an alkenyl-substituted nadiimide compound after forming a film of alkenyl-substituted nadiimide compound (A) or a composite film of alkenyl-substituted nadiimide compound (A) and polymer compound (B) The polyimide film can be obtained by heat treatment, preferably at 150 to 350 ° C., more preferably at 200 to 300 ° C. (when using an oven, when using a hot plate for 30 to 90 minutes, 5-30 minutes). In addition, when the high molecular compound (B) is a polyamic acid, a polyamic acid ester, or the like, an imidization reaction by heat treatment also proceeds simultaneously.
When the film is formed in a pattern, a patterned polyimide film is formed. In this specification, unless otherwise specified, the polyimide film includes a patterned polyimide film.

  The polyimide film which is a preferable embodiment of the present invention thus obtained is an insulating film excellent in printability, workability, heat resistance, electrical insulation and dimensional stability. In addition, it is preferable that the ink-jet ink as a raw material contains an epoxy resin, because it is an insulating film that is relatively tough and excellent in chemical resistance, flatness, adhesion, and sputtering resistance.

8 Film Substrate The film substrate of the present invention is formed on the entire surface or a predetermined pattern (line shape) of the inkjet ink of the present invention on the substrate such as a polyimide film on which wiring is formed by a method such as inkjet. Etc.), and then the substrate is dried and further heated to form a polyimide film.

9 Electronic components For example, the ink-jet ink of the present invention is applied to a film substrate such as a polyimide film on which wiring is formed in advance by an ink-jet coating method, and then the film substrate is dried and further heated to be insulated. A flexible electronic component coated with a polyimide film having properties can be obtained.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.
The bisalkenyl-substituted nadiimide (a1) and tetrakisalkenyl-substituted nadiimide (a2) used in the following examples have two or more alkenyl groups substituted as represented by the following structural formula (in the general formula (1) On the other hand, bismonoalkenyl-substituted nadiimide (a3) and tetrakismonoalkenyl-substituted nadiimide (a4) used in the following comparative examples are compounds in which only one alkenyl group is substituted (general formula (1) 1 corresponds to 1). In addition, the number of alkenyl groups described in the following structural formula describes the average value (measured value) of the mixture as described later.

Bisalkenyl-substituted nadiimide (a1)
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane (hereinafter abbreviated as “BPANI-M”)

N, N′-dodecane-bis- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) (hereinafter abbreviated as “BPANI-12DA”)

Tetrakis alkenyl substituted nadiimide (a2)
Tetrakis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane (hereinafter abbreviated as “TPANI-TAM”)

Bismonoalkenyl-substituted nadiimide (a3)
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane (hereinafter abbreviated as “BANI-M”)
N, N′-dodecane-bis- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) (hereinafter abbreviated as “BANI-12DA”)

Tetrakis monoalkenyl substituted nadiimide (a4)
Tetrakis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane (hereinafter abbreviated as “TANI-TAM”)

[Synthesis Example 1] Synthesis of alkenyl-substituted cyclopentadiene Sodium hydride (49.2 g, 1.23 mol) and 18-crown ether (0.0428 g, 0.162 mol) were dissolved in tetrahydrofuran (120 mL). To this solution was added allyl chloride (110 g, 1.458 mol) at 0 ° C. Subsequently, cyclopentadiene (10 g, 162 mmol) was added at 0 ° C. After stirring at 0 ° C. for 2 hours, the mixture was stirred at room temperature for 48 hours, and further stirred at 50 ° C. for 4 hours. The reaction solution was added to water, extracted with toluene, and concentrated under reduced pressure to obtain alkenyl-substituted cyclopentadiene.

[Synthesis Example 2] Synthesis of alkenyl-substituted nadic acid anhydride Without purifying the obtained alkenyl-substituted cyclopentadiene, toluene (50 mL) and maleic anhydride (12.218 g, 124.6 mmol) were added to the solution. And stirred at 80 ° C. for 2 hours. Furthermore, after stirring at room temperature overnight, concentration under reduced pressure was performed to obtain a yellow solution. Since the solution was allowed to stand, it was separated into two layers, so that the lower layer was separated to obtain 43 g of a target crude alkenyl-substituted nadic acid anhydride in a yield of 97%. The obtained crude alkenyl-substituted nadic acid anhydride was confirmed by FT-IR, GPC, and H ¹ NMR.

  When the term overnight is used, it refers to a time of about 12-18 hours, and when “room temperature” is used, it refers to a temperature of about 20-25 ° C.

[Synthesis Example 3] Synthesis of alkenyl-substituted nadiimide (BPANI-M) (Synthesis of Example Compound)
Put a stir bar and prepare a 200 ml eggplant-shaped flask with a glass stopper on a stirrer, charge the raw materials as shown below, and stir at room temperature overnight, then under reduced pressure at room temperature (vacuum gauge pressure 0.1 Pa), The solvent was evaporated to obtain an amic acid. 49912 g of this amic acid was reprecipitated with n-hexane to obtain 3.0734 g of amic acid powder. This amic acid was transferred to a petri dish, placed in an oven heated to 180 ° C. for 30 minutes, and dehydrated and cyclized to obtain 2.8655 g of BPANI-M as a solid imidized product. Identification of the imidized product was performed using FT-IR, GPC, and H ¹ NMR. Infrared absorption spectrum by FT-IR is stretching vibration ^{1710 cm} -1 of the imide ring group, it was 1776 cm ^-1. The number average molecular weight Mn measured by GPC is 748, and a peak attributed to BANI-M (a compound of l = 1 in the above formula (1): number average molecular weight Mn = 479) which is a monoalkenyl-substituted nadiimide described later is observed. As a result, it was confirmed that the compound of l = 1 in the formula (1) was not contained. When H ¹ NMR (chemical shift is shown in FIG. 1) was measured, an average of 4.4 alkenyl substituents were contained in one molecule.
Alkenyl substituted nadic acid anhydride 7.8663 g
4,4-diaminodiphenylmethane 2.1365 g
Tetrahydrofuran 10.0g

[Synthesis Example 4] Synthesis of alkenyl-substituted nadiimide (BPANI-12DA) (Synthesis of Example Compound)
Put a stir bar and prepare a 200 ml eggplant-shaped flask with a glass stopper on a stirrer, charge the raw materials as shown below, and stir at room temperature overnight, then under reduced pressure at room temperature (vacuum gauge pressure 0.1 Pa), The solvent was evaporated to obtain an amic acid. This amic acid was transferred to a petri dish, placed in an oven heated to 180 ° C. for 30 minutes, and dehydrated and cyclized to obtain 8.3863 g of BPANI-12DA, an imidized product of a brown liquid. This imide compound was subjected to column purification with a developing solvent in a volume ratio of ethyl acetate: hexane = 3: 1 to obtain 6.3821 g of purified imidized product. The imide compound was identified using FT-IR, GPC, and H ¹ NMR. Infrared absorption spectrum by FT-IR is stretching vibration ^{1696 cm} -1 of the imide ring group, it was 1766cm ^-1. The number average molecular weight Mn measured by GPC is 854, and a peak attributed to BANI-12DA (a compound of l = 1 in the formula (1): number average molecular weight Mn = 585), which is a monoalkenyl-substituted nadiimide described later, is observed. As a result, it was confirmed that the compound of l = 1 in the formula (1) was not contained. When H ¹ NMR (chemical shift is shown in FIG. 2) was measured, an average of 5.4 alkenyl substituents were contained in one molecule.
Alkenyl substituted nadic acid anhydride 7.8507 g
1,12-dodecanediamine 2.1552 g
Tetrahydrofuran 10.0g

[Synthesis Example 5] Synthesis of alkenyl-substituted nadiimide (TPANI-TAM) (Synthesis of Example Compound)
Put a stir bar and prepare a 200 ml eggplant-shaped flask with a glass stopper on a stirrer, charge the raw materials as shown below, and stir at room temperature overnight, then under reduced pressure at room temperature (vacuum gauge pressure 0.1 Pa), The solvent was evaporated to obtain an amic acid. A Dean-Stark tube and a condenser are attached to the eggplant flask containing the amic acid, put into 40 g of toluene, refluxed at 116 ° C. for 3 hours, dehydrated and closed, and 11.648 g of TPANI-TAM which is a crude imidized brown solid. Obtained. This imide compound was subjected to column purification with a developing solvent having a volume ratio of chloroform: methanol = 1: 1 to obtain 3.8737 g of a purified imidized product. The imide compound was identified using FT-IR, GPC, and H ¹ NMR. Infrared absorption spectrum by FT-IR is stretching vibration ^{1712 cm} -1 of the imide ring group, it was 1776 cm ^-1. The number average molecular weight Mn by GPC is 1517, and a peak attributed to TANI-TAM (a compound of l = 1 in the formula (1): number average molecular weight Mn = 885) which is a monoalkenyl-substituted nadiimide described later is not observed. From the above, it was confirmed that the compound of l = 1 in the formula (1) was not contained. When H ¹ NMR (chemical shift is shown in FIG. 3) was measured, an average of 12.5 alkenyl substituents were contained in one molecule.
Alkenyl substituted nadic acid anhydride 9.5402 g
Tetrakisaminophenylmethane 2.4878 g
Tetrahydrofuran 10.0g

[Synthesis Example 6] As the monoalkenyl-substituted nadiimide (BANI-M), a commercially available product (manufactured by Maruzen Petrochemical Co., Ltd.) was used.

[Synthesis Example 7] Synthesis of monoalkenyl-substituted nadiimide (BANI-12DA) (synthesis of comparative compound)
Prepare a 300 ml eggplant-shaped flask with a stir bar on a stirrer, charge the raw materials as shown below, and go through the same procedure as in Synthesis Example 4 except that the oven heating temperature is 160 ° C. 5.93 g of BANI-12DA which is a liquid imidized product was obtained. The identity of the imidized product was confirmed by infrared absorption spectrum (stretching vibration of imide ring carbonyl group 1692 cm ⁻¹ , 1766 cm ⁻¹ ) using FT-IR. The number average molecular weight Mn was 585.
Monoalkenyl substituted nadic acid anhydride 4.03 g
1,12-dodecanediamine 1.97 g
Tetrahydrofuran 200.0ml

Synthesis Example 8 Synthesis of Monoalkenyl-Substituted Nadiimide (TANI-TAM) (Synthesis of Comparative Compound)
A 100 ml eggplant-shaped flask containing a stirrer was prepared on a stirrer, charged with raw materials as shown below, and subjected to the same method as in Synthesis Example 5 except that the heating temperature of the oven was 160 ° C. 2.97 g of TANI-TAM which is an imidized product was obtained. Identification of the imidized product was confirmed by infrared absorption spectrum (stretching vibration of imide ring carbonyl group 1706 cm ⁻¹ , 1776 cm ⁻¹ ) using FT-IR. The number average molecular weight Mn was 885.
Monoalkenyl substituted nadic acid anhydride 2.04 g
Tetrakisaminophenylmethane 0.96g
Tetrahydrofuran 7.0g

[Synthesis Example 9] Synthesis of polyamic acid solution Raw materials were charged as shown below into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, and the temperature was 25 ° C under a dry nitrogen stream Was stirred for 5 hours to obtain a 12% weight solution of a pale yellow transparent polyamic acid. The viscosity of this solution was 5100 mPa · s (25 ° C.). The weight average molecular weight measured by GPC was 117,000. This solution was used as a polyamic acid (POLY-1) solution.
3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 1.03 g
1,37 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane
γ-butyrolactone 17.60 g

[Example 1] Inkjet ink (1)
Prepare 6cc of a screw tube bottle (Azwan Laboran Pack) containing a stir bar on a stirrer and charge the raw materials as shown below. The solid content of BPANI-M obtained in Synthesis Example 3 is completely Stir until dissolved to obtain a 30 wt% solution of yellow transparent BPANI-M. The viscosity of this solution was 19 mPa · s (25 ° C.).
BPANI-M (Example compound) 0.60 g
Diethylene glycol methyl ethyl ether 0.70g
γ-butyrolactone 0.70g

[Example 2] Inkjet ink (2)
The bottles used in Example 1 were charged with the raw materials as shown below and stirred until the solid content was completely dissolved to obtain a 50 wt% solution of BPANI-12DA obtained in Synthesis Example 4. The viscosity of this solution was 20 mP · s (25 ° C.).
BPANI-12DA (Example compound) 0.60 g
γ-butyrolactone 0.70g
Diethylene glycol methyl ethyl ether 0.70g

[Example 3] Inkjet ink (3)
The bottles used in Example 1 were charged with raw materials as shown below, stirred until the solid content of TPANI-TAM obtained in Synthesis Example 5 was completely dissolved, and 30% by weight of yellow transparent TPANI-TAM A solution was obtained. The viscosity of this solution was 14 mPa · s (25 ° C.).
TPANI-TAM (Example compound) 0.60 g
Diethylene glycol methyl ethyl ether 0.70g
γ-butyrolactone 0.70g

Example 4 Inkjet ink (4)
The bottles used in Example 1 were charged with raw materials other than POLY-1 obtained in Synthesis Example 9 as shown below, and stirred until the solid content of BPANI-M obtained in Synthesis Example 3 was completely dissolved. Further, the amic acid solution POLY-1 was mixed to obtain a brown transparent inkjet ink. The viscosity of this solution was 32 mPa · s (25 ° C.).
BPANI-M (Example compound) 0.33 g
POLY-1 (Amic acid solution) 0.36 g
Diethylene glycol methyl ethyl ether 0.38g
γ-butyrolactone 0.67 g

[Comparative Example 1] Inkjet ink (5)
The bottles used in Example 1 were charged with raw materials as shown below and stirred until the solid content of BANI-M obtained in Synthesis Example 6 was completely dissolved, and 40% by weight of yellow transparent BANI-M A solution was obtained. The viscosity of this solution was 15.2 mPa · s (25 ° C.).
BANI-M (product of Maruzen Petrochemical Co., Ltd.) (Comparative compound) 4.00 g
Diethylene glycol methyl ethyl ether 3.00 g
γ-butyrolactone 3.00 g

Comparative Example 2 Inkjet ink (6)
A bottle was prepared in the same manner as in Example 1 except that 20 cc of the screw tube bottle was used. The raw materials were charged as shown below, and stirred until the solid content of BANI-12DA obtained in Synthesis Example 7 was completely mixed to obtain a brown transparent BANI-12DA 50 wt% solution. The viscosity of this solution was 15.8 mPa · s (25 ° C.).
BANI-12DA (Comparative compound) 6.00 g
Diethylene glycol methyl ethyl ether 3.00 g
γ-butyrolactone 3.00 g

[Comparative Example 3] Inkjet ink (7)
A bottle was prepared in the same manner as in Example 1 except that 20 cc of the screw tube bottle was used. The raw materials were charged as shown below, and stirred until the solid content of TANI-TAM obtained in Synthesis Example 8 was completely dissolved to obtain a 30 wt% solution of brown transparent TANI-TAM. The viscosity of this solution was 13.8 mPa · s (25 ° C.).
TANI-TAM (Comparative compound) 3.60 g
Diethylene glycol methyl ethyl ether 4.20g
γ-butyrolactone 4.20 g

[Example 5] Inkjet coating (1)
The inkjet ink (1) prepared in Example 1 was used as an inkjet ink, and was set to a dot pitch of 20 microns with a dot width of 0.75 mm on a glass substrate having a thickness of 0.75 mm using an inkjet coating apparatus DMP-2831 manufactured by FUJIFILM Dimatix. Then, a 2 cm long line was applied. The setting of the heater of the inkjet head was 40 ° C., the piezoelectric voltage was 21 V, and the driving frequency was 5 kHz. The substrate was dried on an 80 ° C. hot plate for 5 minutes and then heated in an oven at 230 ° C. for 30 minutes to obtain a polyimide insulating film formed in a line shape.
The resulting polyimide film was observed for line width and line width uniformity with an optical microscope, and the film thickness was measured. For the film thickness, a stylus type film thickness meter α step 200 manufactured by KLA-Tencor Japan Co., Ltd. was used, and the average value of three measured values was defined as the film thickness. The results are shown in Table 1. The line had a sufficient thickness.

[Example 6] Inkjet coating (2)
The ink-jet ink (2) prepared in Example 2 was used as an ink-jet ink, the line was applied and baked under the same conditions as in Example 5 except that the head heater was 30 ° C. and the piezoelectric voltage was 19 V. The obtained polyimide insulating film was evaluated. The results are shown in Table 1. The line had a sufficient thickness.

[Example 7] Inkjet coating (3)
Using the ink-jet ink (3) prepared in Example 3 as the ink-jet ink, except that the head heater is 30 ° C. and the piezo voltage is 19 V, line coating and baking are performed under the same conditions as in Example 5, The obtained polyimide insulating film was evaluated. The results are shown in Table 1. The line had a sufficient thickness.

[Example 8] Inkjet coating (4)
Using the inkjet ink (4) prepared in Example 4 as an inkjet ink, except that the head heater is 60 ° C. and the piezoelectric voltage is 20 V, line coating and baking are performed under the same conditions as in Example 5, The obtained polyimide insulating film was evaluated. The results are shown in Table 1. The line had a sufficient thickness.

[Comparative Example 4] Inkjet coating (5)
Using the ink-jet ink (5) prepared in Comparative Example 1 as an ink-jet ink, except that the head heater is 30 ° C. and the piezo voltage is 23 V, line coating and baking are performed under the same conditions as in Example 5, The obtained polyimide insulating film was evaluated. The results are shown in Table 1. The line had a sufficient thickness, but a bulge was formed in the resin film, and printing unevenness was observed.

From this result, it was found that the ink according to the present invention can be ejected by ink jetting and no bulge or the like occurs, so that there is no printing unevenness and the printing property is good.

[Example 9] Flow test and heat resistance test of film The heat resistance test of the inkjet inks of Example 1 and Comparative Example 1 was performed. 1 ml of inkjet ink was dropped onto a glass substrate and spin coating was performed. After the substrate was dried for 5 minutes on an 80 ° C. hot plate, the resin surface was partly shaved with a knife, heated in an oven at 230 ° C. for 30 minutes, and further heated in an oven heated to 250 ° C. for 30 minutes. After drying at 80 ° C., after heating at 230 ° C., and after heating at 250 ° C., the shape of the shaved film was observed to examine the presence or absence of film flow (reflow) during heating. At the same time, the thickness of the polyimide insulating film obtained was measured, and the reduction rate was calculated. This reduction rate was regarded as heat resistance. The results are shown in Table 2.

From the results in Table 2, it can be seen that the ink-jet ink obtained in Example 1 is excellent in heat resistance. In addition to the results shown in Table 1, it can be seen that there is no flow (reflow) of the film, and printability such as bleeding and bulge is good. From these results, it was found that increasing the alkenyl group of the alkenyl-substituted nadic acid anhydride can improve the heat resistance and printability such as bleeding and bulge.

[Example 10] Measurement of linear expansion coefficient and brittleness of resin film Linear expansion of imide compounds obtained from Synthesis Examples 4 and 7 and polyimide films obtained from Examples 1, 3, 4 and Comparative Examples 1 and 3 Coefficient measurements were made. A liquid imidized product and ink were applied onto an aluminum foil and heated in an oven at 230 ° C. for 30 minutes to obtain a polyimide film. However, only Example 8 was baked at 300 ° C. for 30 minutes. This film was peeled from the aluminum foil, and the linear expansion coefficient from 100 ° C. to 200 ° C. was measured using TMA100 (manufactured by SEIKO I & E). The results are shown in Table 3.
In addition, the brittleness was evaluated as “◯” if it was possible to measure without being broken even when it was bent, and “x” if it was impossible to measure because the film was brittle and fractured before measurement.

From the results in Table 3, the polyimide film obtained from the ink of the present invention (Examples 1 and 3) is more fragile than the polyimide film obtained from the comparative ink (Comparative Examples 1 and 3) using the same diamine. It can be seen that there is an improvement. In addition, it can be seen that the polyimide film obtained from the example compound of Synthesis Example 4 has a linear expansion coefficient about half that of the polyimide film obtained from the comparative compound of Synthesis Example 7 using the same diamine. From these results, it was found that increasing the alkenyl group of the alkenyl-substituted nadic acid anhydride can improve the mechanical strength of the film and reduce the linear expansion coefficient.
From the above, it was found that the compound of the present invention is excellent in mechanical properties.
Furthermore, the polyimide film obtained from the ink of Example 4 to which the amic acid solution (POLY-1) was added was replaced with the polyimide film obtained from the ink of Example 1 to which the amic acid solution (POLY-1) was not added. In comparison, it can be seen that the linear expansion coefficient is increased. This indicates that the mechanical properties of the film can be changed by mixing a polymer compound.

[Example 11] Electrical characteristics of polyimide film The electrical characteristics of the polyimide films obtained from Examples 1 to 3 and Comparative Examples 1 to 3 were measured. 1 mL of ink was applied on a chromium substrate, a thin film was formed by spin coating, dried on a hot plate at 80 ° C. for 5 minutes, and cured in an oven at 230 ° C. for 30 minutes. Then, aluminum was vapor-deposited on the polyimide resin film shape, and the electrode was created. The dielectric constant and dielectric loss tangent were measured using LCR METER (manufactured by HEWLETT PACKERD), and volume resistivity, withstand voltage, and dielectric strength were measured using ULTRAHIGH RESISTANCE METER 4263B (manufactured by ADVANTEST). Table 4 shows the obtained results.

As is clear from Table 4, it was found that the polyimide insulating films obtained from Examples 1 and 2 were excellent in withstand voltage. The polyimide insulating films obtained from Example 1, Example 2 and Example 3 were able to lower the dielectric constant compared to the polyimide films obtained from Comparative Example 1, Comparative Example 2 and Comparative Example 3. .
From the above, it was found that the compound of the present invention is also excellent in terms of electrical characteristics.

  Examples of the utilization method of the present invention include an insulating film for a flexible wiring board and an electronic component using the same.

FIG. 1 is the H ¹ NMR of bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane prepared in Synthesis Example 3. FIG. 2 is an H ¹ NMR of N, N′-dodecane-bis- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) prepared in Synthesis Example 4. FIG. 3 is an H ¹ NMR spectrum of tetrakis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane prepared in Synthesis Example 5.

Claims (14)

An inkjet ink containing at least one alkenyl-substituted nadiimide (A) represented by the following general formula (1).
(In Formula (1), l is 2-6, m is 0-4, 1 + m ≦ 6 is satisfied, R ¹ and R ² are each independently hydrogen, alkyl having 1 to 12 carbons, carbon Any one of alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 8 carbon atoms or benzyl having 7 to 8 carbon atoms, and n is an integer of 2 to 4 ;
When n = 2, R ³ is an organic group having 1 to 140 carbon atoms or a group represented by the following general formula (3),
In formula (3), R ⁷ and R ⁸ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁹ is each independently methylene, phenylene or alkyl-substituted phenylene, and x is Each independently represents an integer of 1 to 6, and y is an integer of 1 to 70.
When n = 3, R ³ is a group represented by the following general formula (4) or (4 ′),
In the formula (4), R represents hydrogen, fluorine, chlorine, —OH, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₂ CF ₂ H, —OCF _2. CFHCF ₃ , or alkyl having 1 to 10 carbon atoms,
In formulas (4) and (4 ′), R ¹⁰ , R ¹¹ and R ¹² are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═. CH— may be replaced, and any hydrogen in the alkylene or a group in which methylene in alkylene is replaced with —CH═CH— may be replaced with fluorine.
When n = 4, R ³ is a group represented by the following general formula (5).
In formula (5), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═CH—. Any hydrogen in the alkylene or in the group in which methylene in the alkylene is replaced with —CH═CH— may be replaced with fluorine. ) The inkjet ink according to claim 1, wherein R ¹ and R ² in the general formula (1) are each independently hydrogen, alkyl having 1 to 6 carbons, or alkenyl having 3 to 6 carbons. The inkjet ink according to claim 1, wherein m in the general formula (1) is 0, and R ¹ is hydrogen. In the general formula (1), n is 2, and R ³ is an alkylene having 2 to 20 carbon atoms {any methylene in alkylene not adjacent to each other may be replaced by —O— or —CH═CH—. Well, any hydrogen in the alkylene or a group in which methylene in the alkylene is replaced with —CH═CH— may be replaced with fluorine}, a cycloalkylene having 5 to 8 carbon atoms, a 6 to 12 carbon atoms Arylene, — (R ⁵⁰ ) _a —C ₆ H ₄ —R ⁵¹ — (wherein a is an integer of 0 or 1, and R ⁵⁰ and R ⁵¹ are each independently alkylene having 1 to 4 carbon atoms). a group represented _{by, -C 6 H 4 -T-C} 6 H 4 -, - C 6 H 4 -T-C 6 H 4 -T-C 6 H 4 - or _-C 6 _H 4 -T'-C _{6 H 4 -T-C 6 H} 4 -T'-C 6 H 4 - { However, T is a single bond, an alkylene having 1 to 6 carbon _{atoms, -C (CH 3) 2 -} , - C (CF 3) 2 -, - CO -, - O -, - S- or -SO ₂ - in Yes, T ′ is —CH ₂ — or —O—. }, A group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced by a hydroxyl group, a group represented by the following general formula (3), or a group represented by the following formula (6) The inkjet ink according to any one of claims 1 to 3, which is a group to be formed.
(In Formula (3), R ⁷ and R ⁸ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁹ is each independently methylene, phenylene or alkyl-substituted phenylene, x Are each independently an integer of 1 to 6, and y is an integer of 1 to 70.)
The inkjet ink according to claim 1, wherein n in the general formula (1) is 2, and R ³ is a group represented by the following formula (9) or (10).
The inkjet ink according to claim 1, wherein n in the general formula (1) is 4, and R ³ is a group represented by the following formula (11).
  The inkjet ink according to any one of claims 1 to 6, further comprising a polymer compound (B) having a weight average molecular weight of 10,000 or more.   The inkjet ink according to claim 7, wherein the polymer compound (B) is at least one of polyamic acid or polyimide.   The inkjet ink according to claim 1, further comprising a solvent (C).   The solvent (C) 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, The inkjet ink according to claim 9, wherein the inkjet ink is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, butyl cellosolve and γ-butyrolactone.   A polyimide film or a patterned polyimide film obtained by applying the inkjet ink according to claim 1 by an inkjet coating method to form a coating film, and subjecting the coating film to a heat treatment.   A polyimide film comprising a step of applying the ink jet ink according to claim 1 by an ink jet coating method to form a coating film, and a step of heat-treating the coating film to form a polyimide film. Forming method.   A film substrate in which a polyimide film is formed on a substrate by the method for forming a polyimide film according to claim 12.   An electronic component having the film substrate according to claim 13.