JP5435054B2 - Ink jet ink and cured film forming method obtained from the ink - Google Patents

Description

  The present invention relates to an inkjet ink, and specifically, the present invention relates to an inkjet ink used for manufacturing a liquid crystal display element, an EL display element, a printed wiring board, and the like. The present invention further relates to a method for producing an inkjet ink, an ink application method using the inkjet ink, a cured film obtained by the inkjet ink, a cured film forming method, and an electronic circuit board on which the cured film is formed.

Patterned cured films are used in many parts of liquid crystal display elements such as spacers, insulating films, and protective films, and many photocurable compositions have been proposed for this application ( For example, refer to JP 2004-287232 A (Patent Document 1). As a method for producing a patterned cured film using a photocurable composition, a photolithographic method in which ultraviolet rays are irradiated through a mask having a desired pattern and a portion not exposed to ultraviolet rays is removed by development. Is common.
However, this method requires a dedicated line equipped with an exposure machine, a developing machine, etc., and the capital investment is large.
Under these circumstances, an ink jet method having advantages such as a small capital investment amount, no use of a developer, and high use efficiency of materials has been proposed in recent years, and a composition used for this has also been proposed ( For example, refer to JP2003-302642A (Patent Document 2).
However, when patterning (drawing) with these compositions by the ink jet method, the droplets ejected from the ink jet head spread on the substrate after landing, and it is difficult to form a high-definition pattern by reducing the resolution. .

JP 2004-287232 A JP 2003-302642 A

  Under the above-described circumstances, for example, there is a demand for ink-jet ink in which droplets ejected from an ink-jet head are less spread after landing.

  The inventors of the present invention have disclosed an inkjet ink that can suppress the spread after landing by blending a polymer having a structural unit of the following formula (1) with a compound having a double bond and a photopolymerization initiator. And the present invention was completed based on this finding. The present invention includes the following ink jet ink, ink jet ink manufacturing method, ink application method using ink jet ink, cured film obtained by ink jet ink, cured film forming method, and cured film formed Provide electronic circuit boards and the like.

[1] The following formula (1)

(In the formula, R ¹ and R ² are each independently alkyl having 1 to 3 carbon atoms or phenyl.)
A photocurable inkjet ink comprising a polymer (A) having a structural unit represented by formula (B), a compound (B) having a double bond, and a photopolymerization initiator (C).
[2] The following formula (4)

(Wherein R ¹ and R ² are each independently alkyl or phenyl having 1 to ³ carbon atoms, and R ³ is an organic group in which arbitrary hydrogen having 1 to 20 carbon atoms may be substituted with fluorine. , R ⁴ is alkylene having 1 to 12 carbons or phenylene which may have a substituent, R ⁵ is hydrogen or alkyl having 1 to 5 carbons, n is an integer of 1 to 100, and m is (It is an integer of 1 to 5.)
A photocurable inkjet ink comprising a polymer (A) having a structural unit represented by formula (B), a compound (B) having a double bond, and a photopolymerization initiator (C).
[3] The polymer (A) is represented by the following formula (2)

(Wherein R ¹ and R ² are each independently alkyl or phenyl having 1 to ³ carbon atoms, and R ³ is an organic group in which arbitrary hydrogen having 1 to 20 carbon atoms may be substituted with fluorine. , R ⁴ is alkylene having 1 to 12 carbons or phenylene which may have a substituent, R ⁵ is hydrogen or alkyl having 1 to 5 carbons, n is an integer of 1 to 100, and m is (It is an integer of 1 to 5.)
The photocurable inkjet ink according to [1] or [2], which is a copolymer of a radical polymerizable monomer represented by the formula (1) and another radical polymerizable monomer.

[4] The other radical polymerizable monomer is one or more selected from the group consisting of a radical polymerizable monomer having a carboxyl, a radical polymerizable monomer having a thermally crosslinkable functional group, and an N-substituted maleimide. The jet ink for photocurable ink as described.
[5] The photocurable inkjet ink according to [4], wherein the thermally crosslinkable functional group is one or more selected from the group consisting of oxirane, oxetane, and hydroxy.

[6] The polymer (A) is at least the following formula (2)

(Wherein R ¹ and R ² are each independently alkyl or phenyl having 1 to ³ carbon atoms, and R ³ is an organic group in which arbitrary hydrogen having 1 to 20 carbon atoms may be substituted with fluorine. , R ⁴ is alkylene having 1 to 12 carbons or phenylene which may have a substituent, R ⁵ is hydrogen or alkyl having 1 to 5 carbons, n is an integer of 1 to 100, and m is (It is an integer of 1 to 5.)
[1] or [2], which is a copolymer obtained by polymerizing a mixture of monomers containing a radical polymerizable monomer represented by the formula: (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate. ] The photocurable inkjet ink as described in any one of the above.
[7] The following formula (5)
Wherein R ¹ and R ² are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁶ is each independently methylene, phenylene or alkyl-substituted phenylene, and m is independently (It is an integer from 1 to 6, and n is an integer from 1 to 100.)
A photocurable inkjet ink comprising a polymer (A) having a structural unit represented by formula (B), a compound (B) having a double bond, and a photopolymerization initiator (C).
[8] The polymer (A) is represented by the following formula (3):
Wherein R ¹ and R ² are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁶ is each independently methylene, phenylene or alkyl-substituted phenylene, and m is independently (It is an integer from 1 to 6, and n is an integer from 1 to 100.)
The photocurable ink-jet ink according to [1] or [7], which is a copolymer obtained by reacting a diamine represented by the above and a compound having an acid anhydride group.

[9] The photocurable inkjet ink according to [8], wherein the compound having an acid anhydride group is tetracarboxylic dianhydride.
[10] The photocurable inkjet ink according to [8], wherein the compound having an acid anhydride group is a copolymer of a radical polymerizable monomer having an acid anhydride group and another radical polymerizable monomer.
[11] A compound having an acid anhydride group is a styrene-maleic anhydride copolymer, a methyl (meth) acrylate-maleic anhydride copolymer, a (meth) acrylic acid glycidyl-maleic anhydride copolymer, 2- [8] which is one or more selected from the group consisting of hydroxyethyl (meth) acrylate-maleic anhydride copolymer, styrene-itaconic anhydride copolymer and methyl (meth) acrylate-itaconic anhydride copolymer. The photocurable inkjet ink as described.

[12] The photocurable inkjet ink according to any one of [1] to [11], wherein the compound (B) having a double bond contains a (meth) acryloyl group.
[13] The photocurable inkjet ink according to [12], wherein the compound (B) having a double bond has one or more selected from the group consisting of oxirane, oxetane and hydroxy.
[14] Compound (B) having a double bond is glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate glycidyl ether, 1,4-cyclohexanedimethanol mono (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyl oxetane, 2-ethyl-2- (meth) acryloxymethyl oxetane, penta The photocurable inkjet ink according to [10], which is one or more selected from the group consisting of erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and isocyanuric acid ethylene oxide-modified di (meth) acrylate. .

[15] The photopolymerization initiator (C) is represented by the following formula (6)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently alkyl having 1 to 13 carbon atoms, X ¹ and X ² are each independently -O-, -O-O-, or- NH-)
A compound represented by the following formula (7):

(Wherein R ¹ , R ² and R ³ are each independently hydrogen or alkyl having 1 to 5 carbon atoms; R ⁴ is alkyl having 1 to 15 carbon atoms),
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- The photocurable inkjet ink according to any one of [1] to [14], which is one or more selected from the group consisting of 1.
[16] The photopolymerization initiator (C) is represented by the following formula (6):

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently alkyl having 1 to 13 carbon atoms, X ¹ and X ² are each independently -O-, -O-O-, or- NH-)
A compound represented by the following formula (7):

(Wherein R ¹ , R ² and R ³ are each independently hydrogen or alkyl having 1 to 5 carbon atoms; R ⁴ is alkyl having 1 to 15 carbon atoms),
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- The photocurable inkjet ink according to any one of [1] to [14], which contains 20 to 100% of one or more selected from the group consisting of 1 with respect to the total weight of the photopolymerization initiator (C). .

[17] 20 to 1,000 parts by weight of the compound (B) having a polymerizable double bond and 0.5 to 200 parts by weight of the photopolymerization initiator (C) with respect to 100 parts by weight of the polymer (A) The photocurable inkjet ink according to any one of [1] to [6].

[18] The following formula (2)

(In the formula, R ¹ and R ² are both methyl, R ³ is alkyl having 1 to 6 carbon atoms, R ⁴ is alkylene having 1 to 6 carbon atoms, and R ⁵ is hydrogen or 1 to carbon atoms. 3 is alkyl, m is an integer of 1 to 3, and n is an integer of 5 to 50)
A step of producing a polymer (A) by polymerizing a radical polymerizable monomer represented by: (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate;
To the polymer (A), glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether 1,4-cyclohexanedimethanol mono (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-ethyl-2- (meth) acryloxymethyloxetane, pentaerythritol tri (meth) acrylate, A compound (B) having one or more double bonds selected from the group consisting of dipentaerythritol penta (meth) acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate, and 2-methyl-1- [4- ( Methylthi ) Phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Step)
A method for producing a photocurable ink-jet ink comprising: [19] The following formula (3)
(Wherein R ¹ and R ² are both methyl, R ⁶ is alkylene having 1 to ⁶ carbon atoms, m is an integer of 1 to 3, and n is an integer of 10 to 20).
A diamine represented by: 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfone tetracarboxylic dianhydride, 2 , 3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, cyclobutanetetracarbo From the group consisting of acid dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride Reacting a selected compound having one or more acid anhydride groups to produce a polymer (A);
To the polymer (A), glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether 1,4-cyclohexanedimethanol mono (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-ethyl-2- (meth) acryloxymethyloxetane, pentaerythritol tri (meth) acrylate, A compound (B) having one or more double bonds selected from the group consisting of dipentaerythritol penta (meth) acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate, and 2-methyl-1- [4- ( Methylthi ) Phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Step)
For producing a photocurable inkjet ink comprising

[20] The ink-jet ink described in [1] to [17] or the ink-jet ink produced by the production method of [18] or [19] is applied by an ink-jet coating method and then dried and applied. An ink application method comprising a step of forming a film, and a step of irradiating the coating film with light to form a cured film.
[21] A cured film forming method for forming a cured film using the ink coating method according to [20].
[22] An electronic circuit board having a cured film formed on the substrate using the cured film forming method described in [21].
[23] An electronic component having the electronic circuit board according to [22].
[24] An electronic circuit board or display element having the cured film formed in [21].

  In addition, in this specification, in order to show both acrylic acid and methacrylic acid, it may describe as "(meth) acrylic acid".

The ink-jet ink according to a preferred embodiment of the present invention has little spread of the liquid after landing of droplets ejected from the ink-jet head, and high-definition patterning is possible. Moreover, the cured film obtained by the inkjet ink which concerns on the preferable aspect of this invention has high chemical resistance.
The display spacer obtained using the ink-jet ink according to the preferred embodiment of the present invention can be patterned with high definition, has high chemical resistance, and has fewer defects such as light leakage. High-definition liquid crystal panel can be manufactured with high yield.

1. Ink-jet ink of the present invention The ink-jet ink of the present invention comprises a polymer (A) having a structural unit represented by formula (1), a compound (B) having a double bond, and a photopolymerization initiator (C). It is a photocurable ink for inkjet.

  In the inkjet ink of the present invention, 20 to 1,000 parts by weight of the compound (B) having a double bond and 0.5 to 200 parts of the photopolymerization initiator (C) with respect to 100 parts by weight of the polymer (A). It is preferable to contain by weight. In the inkjet ink of the present invention, the compound (B) having a double bond is 30 to 500 parts by weight and the photopolymerization initiator (C) is 1 to 100 parts by weight with respect to 100 parts by weight of the polymer (A). It is more preferable to contain.

  The ink-jet ink of the present invention includes, in addition to the polymer (A), the compound (B) having a double bond, and the photopolymerization initiator (C), a thermosetting compound, a solvent, and an additive that will be described later if desired. , Colorants and the like.

  The ink-jet ink of the present invention preferably has a viscosity at 25 ° C. of 2 to 500 mPa · s as measured with an E-type viscometer because the ink-jet ejection characteristics are improved. The inkjet discharge temperature is preferably 10 to 120 ° C., and the viscosity of the photocurable inkjet ink at the discharge temperature is preferably 2 to 30 mPa · s.

1.1 Polymer (A)
1.1.1 Constitution of polymer (A) The polymer (A) has a constitutional unit represented by the formula (1). R ¹ and R ^{2 in} formula (1) are each independently alkyl or phenyl having 1 to 3 carbon atoms, and among these, alkyl having 1 to 3 carbon atoms is preferable. Among these, it is preferable that both R ¹ and R ² are methyl.

It is preferable that a polymer (A) has a structural unit represented by Formula (4). In Formula (4), R ¹ and R ² are each independently alkyl or phenyl having 1 to ³ carbon atoms, and R ³ is an organic group in which arbitrary hydrogen having 1 to 20 carbon atoms may be substituted with fluorine. R ⁴ is alkylene having 1 to 12 carbons or phenylene which may have a substituent, and R ⁵ is hydrogen or alkyl having 1 to 5 carbons. Among these, it is preferable that both R ¹ and R ² are methyl. R ³ is preferably alkyl having 1 to 6 carbon atoms, and more preferably butyl. R ⁴ is preferably alkylene having 1 to 6 carbon atoms, and more preferably propylene. R ⁵ is preferably hydrogen or alkyl having 1 to 3 carbon atoms, and more preferably methyl. m is preferably an integer of 1 to 3, and more preferably 1. n is preferably from 5 to 50, and more preferably from 10 to 20.
Although the manufacturing method of the polymer (A) which has a structural unit represented by Formula (4) is not specifically limited, For example, as mentioned later, the radically polymerizable monomer represented by Formula (2) and other radical polymerization It synthesize | combines using the polymer (A) using a sex monomer.

Moreover, it is preferable that a polymer (A) has a structural unit represented by Formula (5). In formula (5), R ¹ and R ² are each independently alkyl or phenyl having 1 to 3 carbon atoms, and R ⁶ is each independently methylene, phenylene or alkyl-substituted phenylene. Among these, it is preferable that both R ¹ and R ² are methyl. R ⁶ is preferably alkylene having 1 to ⁶ carbon atoms, and more preferably propylene. m is preferably an integer of 1 to 3, and more preferably 1. n is preferably from 5 to 50, and more preferably from 10 to 20.
Although the manufacturing method of the polymer (A) which has a structural unit represented by Formula (5) is not specifically limited, For example, the compound which has a diamine and an acid anhydride group represented by Formula (3) as mentioned later Is made to react.

1.1.2 Production Method of Polymer (A) The production method of the polymer (A) is not particularly limited. For example, a radical polymerizable monomer represented by the formula (2) and another radical polymerizable monomer are used. It can be synthesized by copolymerizing and reacting a diamine represented by the formula (3) with a compound having an acid anhydride group.

(1) In the production formula (2) of the polymer (A) using the radical polymerizable monomer represented by the formula (2) and another radical polymerizable monomer , R ¹ and R ² are each independently carbon. R ³ is an alkyl or phenyl having 1 to ³ carbon atoms, R ³ is an organic group in which any hydrogen having 1 to 20 carbon atoms may be substituted with fluorine, and R ⁴ is an alkylene or substituent having 1 to 12 carbon atoms. R ⁵ is hydrogen or alkyl having 1 to 5 carbon atoms. Among these, it is preferable that both R ¹ and R ² are methyl. R ³ is preferably alkyl having 1 to 6 carbon atoms, and more preferably butyl. R ⁴ is preferably alkylene having 1 to 6 carbon atoms, and more preferably propylene. R ⁵ is preferably hydrogen or alkyl having 1 to 3 carbon atoms, and more preferably methyl. m is preferably an integer of 1 to 3, and more preferably 1. n is preferably an integer of 5 to 50, and more preferably an integer of 10 to 20. For example, in formula (2), R ¹ and R ² are both methyl, R ³ is butyl, R ⁴ is propyl, R ⁵ is methyl, m is 1, and n is 10 to 10 Examples of the radical polymerizable monomer that is 20 include “Silaplane FM-0711” (trade name) manufactured by Chisso Corporation.

Other radical polymerizable monomers copolymerized with the radical polymerizable monomer represented by the formula (2) include 3-methyl-3- (meth) acryloxymethyl oxetane and 3-ethyl-3- (meth) acryloxy. Methyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-methyl-2- (meth) acryloxymethyl oxetane, 2-ethyl-2 -(Meth) acryloxymethyl oxetane, 2-methyl-2- (meth) acryloxyethyl oxetane, 2-ethyl-2- (meth) acryloxyethyl oxetane, (meth) acrylic acid, maleic acid mono (2-methacrylic) Leuoxyethyl), mono (2-methacryloyloxyethyl) phthalate, cyclohexene-3,4-dicarbo Acid mono (2-methacryloyloxyethyl), crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid , Ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono (2-acryloyloxyethyl), styrene, methylstyrene, vinyltoluene, chloromethylstyrene, (meth) acrylamide, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, tricyclodecane dimethanol diacrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, methyl ( Meta) Acry , Cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) Acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, polystyrene macromonomer, polymethylmethacrylate macromonomer, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 1,4-cyclohexanedimethanol mono (Meth) acrylate, (meth) acrylate of caprolactone-modified tetrahydrofurfuryl alcohol, and the like can be mentioned. Two or more of these other radical polymerizable monomers can be used in combination.

When the other radical polymerizable monomer is one or more selected from the group consisting of a radical polymerizable monomer having a carboxyl group, a radical polymerizable monomer having a thermally crosslinkable functional group, and an N-substituted maleimide, the inkjet of the present invention The spread after landing of the ink for use is preferably reduced.
In addition, when both (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate are used as the other radical polymerizable monomer, the spread after landing of the ink-jet ink of the present invention is further reduced. .

  The method for copolymerizing the radical polymerizable monomer represented by the formula (2) with other radical polymerizable monomers is not particularly limited, but radical polymerization in a solution using a solvent is preferable. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are generated from the polymerization initiator used in the polymerization, but is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 3 to 24 hours.

  The solvent used for the above polymerization reaction is preferably a solvent that dissolves the radical polymerizable monomer represented by the formula (2), other radical polymerizable monomers, and a copolymer to be formed. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxypropionate, N, N-dimethylformamide, acetic acid and the like may be mentioned, but a mixture thereof may also be used.

As a polymerization initiator used when synthesizing a copolymer of a radical polymerizable monomer having the structure of the formula (2) and another radical polymerizable monomer, a compound that generates a radical by heat, azobisisobutyronitrile, etc. Azo initiators, peroxide initiators such as benzoyl peroxide, and the like can be used.
In order to adjust the molecular weight of the copolymer, an appropriate amount of a chain transfer agent such as thioglycolic acid may be added.

  The polymer (A) which is a copolymer of the radical polymerizable monomer represented by the formula (2) and another radical polymerizable monomer has a weight average molecular weight of 1,500 determined by GPC analysis using polystyrene as a standard. A range of ˜100,000 is preferable because the ejection characteristics of the ink jet ink are improved. The weight average molecular weight of the copolymer is more preferably in the range of 2,000 to 20,000.

  When the polymer (A) is synthesized using the radical polymerizable monomer represented by the formula (2) and a copolymer of another radical polymerizable monomer, the radical polymerizable monomer and the other radical polymerizable monomer Is preferably in the range of 5:95 to 80:20 because the ink-jet ink of the present invention has a small spread after landing or good adhesion to the substrate. Among the above ranges, the weight ratio is more preferably in the range of 10:90 to 50:50.

(2) In production formula (3) of the polymer (A) using the diamine represented by formula (3) and the compound having an acid anhydride group , R ¹ and R ² each independently represent 1 carbon atom. ~ 3 alkyl or phenyl, each R ⁶ is independently methylene, phenylene or alkyl-substituted phenylene. Among these, it is preferable that both R ¹ and R ² are methyl. R ⁶ is preferably alkylene having 1 to ⁶ carbon atoms, and more preferably propylene. m is preferably an integer of 1 to 3, and more preferably 1. n is preferably an integer of 5 to 50, and more preferably an integer of 10 to 20. In formula (3), R ¹ and R ² are both methyl, R ⁶ is propylene, m is 1, and n is an integer of 10 to 20, for example, manufactured by Chisso Corporation “Silaplane FM-3311” (trade name).

The compound having an acid anhydride group that reacts with the diamine having the structure of the formula (3) is not particularly limited. However, use of tetracarboxylic dianhydride is preferable because the ejection characteristics of the inkjet ink are good. Specific examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydrides such as compounds represented by the following formulas a1-1 to a1-73.

  Among the specific examples of the tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2 , 3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic Acid dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexaph Oropropane dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, butanetetracarboxylic It is more preferable to use an acid dianhydride or the like.

When a copolymer of a radical polymerizable monomer having an acid anhydride group and another radical polymerizable monomer is used as a compound having an acid anhydride group that reacts with a diamine having the structure of formula (3), The ink jet ink of the present invention is preferable because the spread after landing is small. Specific examples of the copolymer include styrene-maleic anhydride copolymer, methyl (meth) acrylate-maleic anhydride copolymer, (meth) acrylic acid glycidyl-maleic anhydride copolymer, 2-hydroxyethyl. (Meth) acrylate-maleic anhydride copolymer, styrene-itaconic anhydride copolymer, methyl (meth) acrylate-itaconic anhydride copolymer, and the like. Among these, a styrene-maleic anhydride copolymer is preferable.
The compound having an acid anhydride may be a single compound or a mixture of two or more different compounds.

The method for synthesizing the compound synthesized by reacting the diamine represented by formula (3) with a compound having an acid anhydride group is not particularly limited, but it is preferable to react in a solution using a solvent. Although reaction temperature is not specifically limited, Usually, it is the range of 10 to 120 degreeC. Although reaction time is not specifically limited, Usually, it is the range of 3 to 24 hours.

The solvent used for the polymerization reaction is preferably a solvent that dissolves the diamine represented by the formula (3), the compound having an acid anhydride group, and the polymer (A) to be produced. Specific examples of the solvent include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and the like. May be.

Further, when the molecular weight of the polymer (A) obtained by reacting the diamine represented by the formula (3) with the compound having an acid anhydride group is within a predetermined range, the inkjet ink of the present invention. This is preferable because the inkjet discharge characteristics can be made appropriate. Therefore, in order to control the molecular weight of the polymer (A), a compound having one acid anhydride group, a monoamine, or the like may be further added.
Specific examples of the compound having one acid anhydride include maleic anhydride, phthalic anhydride, trimellitic anhydride and the like. Specific examples of monoamines include aniline, butylamine, benzylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-amino. Butyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Examples include methyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane.
In general, either a compound having one acid anhydride or a monoamine is used.

  The polymer (A) obtained by reacting the diamine represented by the formula (3) with a compound having an acid anhydride group has a weight average molecular weight of 1,500 determined by GPC analysis using polystyrene as a standard. A range of ˜100,000 is preferable because the ejection characteristics of the inkjet ink are good. In particular, the weight average molecular weight is more preferably in the range of 2,000 to 20,000.

  When synthesizing the polymer (A) obtained by reacting the diamine represented by the formula (3) with a compound having an acid anhydride group, the weight of the diamine and the compound having an acid anhydride group When the ratio is reacted in the range of 5:95 to 80:20, it is preferable because the ink-jet ink of the present invention has a small spread after landing or good adhesion to the substrate. Among the above ranges, the weight ratio is more preferably in the range of 10:90 to 50:50.

1.2 Compound (B) having a double bond
The compound (B) having a double bond contained in the inkjet ink of the present invention is not particularly limited as long as it is a compound having a double bond, but when a compound having a (meth) acryloyl group is used, the inkjet of the present invention is used. This is preferable because the chemical resistance of the cured film of the ink for use is increased.
Specific examples of the compound having a (meth) acryloyl group include a compound represented by the above formula (2), 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxy. Methyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-methyl-2- (meth) acryloxymethyl oxetane, 2-ethyl-2 -(Meth) acryloxymethyl oxetane, 2-methyl-2- (meth) acryloxyethyl oxetane, 2-ethyl-2- (meth) acryloxyethyl oxetane, (meth) acrylic acid, maleic acid mono (2-methacrylic) Leuoxyethyl), mono (2-methacryloyloxyethyl) phthalate, cyclohexene-3,4-dicarboxylic acid (2-methacryloyloxyethyl), α-chloroacrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono (2-acryloyloxyethyl), (meth) acrylamide, tricyclo [5.2. 1.0 ^2,6 ] decanyl (meth) acrylate, tricyclodecane dimethanol diacrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate , Methyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenyl ( Acrylate), glycerol mono (meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 1,4-cyclohexanedimethanol mono ( (Meth) acrylate, caprolactone-modified tetrahydrofurfuryl alcohol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, epichlorohydride Modified diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) acrylate, epichlorohydrin modified dipropylene glycol di (Meth) acrylate, epichlorohydrin modified tripropylene glycol Di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, 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 acrylate methacrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol Tri (meth) acrylate, 1,6-hex Diol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, Caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, di Pentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol 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, allylated cyclohexyl di (meth) acrylate, bis [(Meth) acryloxyneopentyl glycol] adipate, 2,2-bis [4-((meth) acryloxy) phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane 2,2-bis [4-((meth) acryloxy) phenyl] methane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] methane, 2,2-bis [4-(( (Meth) acryloxy) phenyl] sulfone, 2,2-bis [4- ((Meth) acryloxypolyethoxy) phenyl] sulfone, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol (meth) acrylate, dicyclopentanyl di (meth) acrylate, ethylene oxide modified phosphoric acid Di (meth) acrylate, ethylene oxide-modified phosphoric acid tri (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, ethylene oxide-modified phosphoric acid tri (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate, tetrabromobisphenol A Di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, potassium Rorakuton modified tris [(meth) acryloxyethyl] isocyanurate, and (meth) acrylated isocyanurate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, urethane (meth) acrylate.
There are many commercially available urethane (meth) acrylates, for example, “NK Oligo UA-W2A”, “NK Oligo U-2PPA”, “NK Oligo U-4HA”, “NK Oligo” manufactured by Shin-Nakamura Chemical Co., Ltd. U-6HA "," NK Oligo U-6LPA "," NK Oligo U-15HA "," NK Oligo UA-32P "," NK Oligo 324A "(trade name) and the like.

  Among these specific examples, compounds having a thermally crosslinkable functional group such as oxirane, oxetane, and hydroxy are preferable. Specifically, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 1 , 4-cyclohexanedimethanol mono (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-ethyl-2- (meth) acryloxymethyloxetane, pentaerythritol tri (meth) acrylate, dipenta Erythritol penta (meth) acrylate and isocyanuric acid ethylene oxide modified di (meth) acrylate are particularly preferred.

  The compound (B) having a double bond may be a single compound or a mixture of two or more different compounds.

  The compound (B) having a double bond is preferably used in an amount of 20 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, based on 100 parts by weight of the polymer (A). Since the chemical resistance of a cured film becomes high, it is much more preferable.

1.3 Photopolymerization initiator (C)
The photopolymerization initiator (C) contained in the inkjet ink of the present invention is not particularly limited as long as it has the property of generating radicals upon irradiation with ultraviolet rays or visible light.

Specific examples of the photopolymerization initiator (C) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2 -Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 Dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 , 4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-penthi Ruoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- ( p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxy) Carbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 '-Bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) ) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-) Yl) -phenyl) titanium, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, a compound represented by the above formula (6) And compounds represented by the above formula (7).

  Here, as specific examples of the compound represented by the above formula (6), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra ( t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′- Examples include di (t-butylperoxycarbonyl) benzophenone, 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, and the like. Specific examples of the compound represented by the above formula (7) include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime) and the like.

  The photopolymerization initiator (C) may be a single compound or a mixture of two or more different compounds.

  Among these, the photopolymerization initiator (C) is a compound represented by the formula (6), a compound represented by the formula (7), 2-methyl-1- [4- (methylthio) phenyl] -2- It is preferably at least one selected from the group consisting of morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

  When the photopolymerization initiator (C) is contained in an amount of 20% by weight or more based on the weight of the ink-jet ink of the present invention, the resulting ink is preferable because of high sensitivity.

1.4 Additive The ink-jet ink of the present invention may further contain additives such as a heat-crosslinkable compound and a solvent.

1.4.1 Thermally crosslinkable compound Examples of the thermally crosslinkable compound that may be contained in the ink jet ink of the present invention include an epoxy resin, a melamine compound, a bisazide compound, and a radically polymerizable monomer having a thermally crosslinkable functional group. And a copolymer of a radically polymerizable monomer having a thermally crosslinkable functional group and another radically polymerizable monomer. Among these, it is preferable to use an epoxy resin.

  The epoxy resin is not particularly limited as long as it has oxirane, but a compound having two or more oxiranes is preferable.

Specific examples of the epoxy resin include a polymer of a monomer having an oxirane, and a copolymer of a monomer having an oxirane and another monomer.
Specific examples of the monomer having oxirane include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate.
Specific examples of other monomers copolymerized with the monomer having oxirane include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene , Chloromethylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and the like.

  Polymers of monomers having oxirane, and copolymers of monomers having oxirane and other monomers include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate- Use of a glycidyl methacrylate copolymer, a 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer and a styrene-glycidyl methacrylate copolymer is preferred because the chemical resistance of the coating film after the ink is cured is increased.

In addition to the above specific examples, the epoxy resin that can be included in the inkjet ink of the present invention is, for example, “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827” manufactured by Yuka Shell Epoxy Co., Ltd. ”,“ Epicoat 828 ”,“ Epicoat 190P ”,“ Epicoat 191P ”(trade name),
"Epicoat 1004", "Epicoat 1256" (trade name) manufactured by Japan Epoxy Resin Co., Ltd., "Araldite CY177", "Araldite CY184" (trade name) manufactured by Ciba-Geigy Japan, "Celoxide" manufactured by Daicel Chemical Industries, Ltd. 2021P "," Celoxide 3000 "," EHPE-3150 "(trade name)," Techmore VG3101L "(trade name) manufactured by Mitsui Chemicals, Inc., N, N, N ', N',-tetraglycidyl-m-xylene Diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like can be used. Among these epoxy resins, “Epicoat 828”, “Techmore VG3101”, “Celoxide 2021P”, and “Araldite CY184” are preferable because the chemical resistance of the coating film after the ink is cured becomes high.

  In the ink-jet ink of the present invention, when the heat-crosslinkable resin is contained in an amount of 5 to 500 parts by weight with respect to 100 parts by weight of the polymer (A), the chemical resistance of the cured film of the resulting ink is increased. Preferably, the amount is 10 to 300 parts by weight.

1.4.2 Solvent Examples of the solvent that may be contained in the inkjet ink of the present invention include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, and methoxyacetic acid. Methyl, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Acid methyl, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene Glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate , Ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, die Glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, .gamma.-butyrolactone, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, dimethyl imidazolidinone.

  Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate Diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate, butyl acetate γ-butyrolactone and dimethylimidazolidinone are preferably used.

  The ink-jet ink of the present invention preferably contains a solvent so that the components other than the solvent are 30% or more of the whole, since the spread after landing of the obtained ink becomes small, and preferably contains 50% or more. More preferably.

1.4.3 Other Additives The ink-jet ink of the present invention can contain additives other than the above-described additives in order to improve resolution, coating uniformity, and adhesiveness. Such additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, coating improvers such as silicone resins, silane Examples thereof include adhesion improvers such as coupling agents, ultraviolet absorbers such as alkoxybenzophenones, anti-aggregation agents such as sodium polyacrylate, and alkali solubility promoters such as organic carboxylic acids.

Specific examples of additives that may be contained in the inkjet ink of the present invention include “EFKA-745”, “EFKA-46”, “EFKA-47”, “EFKA-47EA” manufactured by Morishita Sangyo Co., Ltd. “EFKA Polymer 100”, “EFKA Polymer 400”, “EFKA Polymer 401”, “EFKA Polymer 450” (trade name), “Solspurs 3000”, “Sols Birds 5000”, “Sols Birds 9000”, “Sols Birds” manufactured by Lubrizol Corporation. “12000”, “Sols Birds 13240”, “Sols Birds 13940”, “Sols Birds 17000”, “Sols Birds 20000”, “Sols Birds 24000”, “Sols Birds 24000 GR”, “Sols Birds 26000”, “Sols Birds 28000”, “Sols Birds” 2000 ”(trade name),“ Disperse Aid 6 ”,“ Disperse Aid 8 ”,“ Disperse Aid 15 ”,“ Disperse Aid 9100 ”(trade name) manufactured by San Nopco, manufactured by Kyoeisha Chemical Industries, Ltd. “Polyflow No. 75”, “Polyflow No. 90”, “Polyflow No. 95 (trade name),“ Disperbeek 161 ”,“ Disperbeek 162 ”,“ Disperbake ”manufactured by Big Chemie Japan (Disperbyk) 163 "," Disperbyk 164 "," Disperbyk 166 "," Disperbyk 170 "," Disperbyk 180 "," Disperbake " (Disperbyk) 181 "," Disperbyk 182 "(trade name), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoro Alkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, Polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl Ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, Sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, alkyl diphenyl ether disulfone Acid salt, BYK300, "BYK310", "B K320 "," BYK330 "," BYK346 "(trade name), manufactured by Kyoeisha Chemical Industrial Co., Ltd. of" Polyflow No. 45 "," Polyflow KL-245 ", etc. are mentioned.
These additives can be used alone or in admixture of two or more.

  Among these additives, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxy) It is preferable to use a compound selected from ethylene ether), fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates as an additive because the resulting ink jet ink has good ejection characteristics.

1.4.4 Colorant The photocurable ink-jet ink of the present invention may further contain a colorant. For example, a pigment such as copper phthalocyanine is preferably used as the colorant.

2 Application of Inkjet Ink by Inkjet Method The inkjet ink according to the present invention can be used in an inkjet coating method having a step of coating by a known inkjet method. Examples of the inkjet coating method include a method of applying ink by applying mechanical energy to the ink, and a coating method of applying ink by applying thermal energy to the ink.
By using the ink jet coating method, the ink can be applied in a predetermined pattern. As a result, ink can be applied only to the necessary portions, thereby reducing costs.

A preferable coating unit for performing coating using the ink according to the present invention includes, for example, a coating unit including an ink storage unit that stores these inks and a coating head. Examples of the coating unit include a coating unit that causes thermal energy corresponding to a coating signal to act on ink and generates ink droplets by the energy.
The coating head has, for example, a heating part wetted surface containing metal and / or metal oxide. Specific examples of the metal and / or metal oxide include metals such as Ta, Zr, Ti, Ni, and Al, and oxides of these metals.

  As a preferable coating apparatus for performing coating using the ink according to the present invention, for example, energy corresponding to a coating signal is given to the ink in the chamber of the coating head having an ink storage section in which the ink is stored, and the energy A device for generating ink droplets by means of the above.

  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.

3. Formation of Cured Film The cured film of the present invention irradiates the ink with light such as ultraviolet rays and visible rays after the ink-jet ink of the present invention is ejected onto the surface of a substrate such as a substrate using a known inkjet coating method. Is obtained. The portion of the ink irradiated with light is cured as a three-dimensional cross-linked body by polymerization of the acrylic monomer, and the spread of the ink can be effectively suppressed. Therefore, when the ink-jet ink of the present invention is used, a high-definition pattern can be drawn.
When ultraviolet rays are used as the irradiation light, the amount of the irradiation ultraviolet rays is preferably about 10 to 500 mJ / cm ^{2 in} i-line.
If necessary, the ink drawn on the surface of the substrate may be further heated, and it is particularly preferable to heat at 150 to 220 ° C. for 10 to 100 minutes.

The substrate used in the present invention is not particularly limited. For example, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, fluororesin, and acrylic resins. Sealed with plastic film such as resin, polyamide, polycarbonate, polyimide, cellophane, acetate, metal foil, glassine paper, parchment paper, or polyethylene, clay binder, polyvinyl alcohol, starch, carboxymethylcellulose (CMC) Examples include treated paper. In addition, the substances constituting these base materials may further include pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents, and the like, as long as the effects of the present invention are not adversely affected. An additive such as an electromagnetic wave inhibitor may be included.
The thickness of the substrate is not particularly limited, but is usually about 10 μm to 2 mm, and is appropriately adjusted depending on the purpose of use, but is preferably 15 to 500 μm, and more preferably 20 to 200 μm.

  If necessary, the surface for forming a cured film of the base material may be subjected to an easy adhesion treatment such as a corona treatment, a plasma treatment or a blast treatment, or an easy adhesion layer may be provided on the surface.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Synthesis Example 1] Synthesis of Polymer (A-1) The following compound was charged into a four-necked flask equipped with a stirrer and heated at reflux temperature for 6 hours.
2-butanone 150.0g
Benzyl methacrylate 30.0g
Chisso Corporation Silaplane FM-0711 10.0g
2-hydroxyethyl methacrylate 5.0 g
Methacrylic acid 5.0 g
Dimethyl 2,2'-azobis (2-methylpropionate) 2.0g

The reaction solution was cooled to room temperature and poured into a large amount of hexane. The produced soot-like precipitate was vacuum-dried at 100 Pa and 40 ° C. for 20 hours, and the resulting mass was pulverized and again vacuum-dried under the same conditions to obtain a polymer (A-) that is the polymer (A) of the present invention. 42.1 g of the powder of 1) was obtained. The weight average molecular weight calculated | required by GPC analysis of the obtained polymer (A-1) was 14,000.
The weight average molecular weight is obtained by diluting the obtained polymer powder with tetrahydrofuran so that the polymer concentration is about 1% by weight. GPC apparatus: JASCO GOLDIVER 1500 (intelligent differential refractometer RI-1530 ) Was measured by GPC method using tetrahydrofuran as a developing agent, and calculated by polystyrene conversion. Four columns, Tosoh Corporation columns G4000HXL, G3000HXL, G2500HXL and G2000HXL, were connected in this order and measured under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min.

[Synthesis Example 2] Synthesis of Polymer (A-2) The following compound was charged into a four-necked flask equipped with a stirrer and heated at 40 ° C for 10 hours.
3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 15.5 g
Styrene / maleic anhydride copolymer (molar ratio 1: 1, molecular weight 1,500) 7.1 g
Chisso Corporation Silaplane FM-311 15.0g
1,2 g of 3,3′-diaminodiphenylsulfone
116.7 g of N-methyl-2-pyrrolidone

  The reaction solution was cooled to room temperature to obtain a 30 wt% N-methyl-2-pyrrolidone solution of the polymer (A-2) which is the polymer (A) of the present invention. The weight average molecular weight calculated | required by GPC analysis of the obtained polymer (A-2) was 9,000.

[Synthesis Example 3] Comparative Synthesis Example The following compound was charged into a four-necked flask equipped with a stirrer and heated at reflux temperature for 6 hours.
2-butanone 150.0g
Benzyl methacrylate 40.0g
2-hydroxyethyl methacrylate 5.0 g
Methacrylic acid 5.0 g
Dimethyl 2,2'-azobis (2-methylpropionate) 2.0g

  The reaction solution was cooled to room temperature and poured into a large amount of hexane. The soot-like precipitate produced was vacuum-dried at 100 Pa and 40 ° C. for 20 hours, and the resulting mass was pulverized and vacuum-dried again under the same conditions to obtain 44.3 g of polymer powder. The weight average molecular weight calculated | required by GPC analysis of the obtained polymer was 15,000.

[ Reference Example 1]
The following compositions were mixed and dissolved, and filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.5 μm to prepare a photocurable inkjet ink as follows. The polymer (A-1) of Synthesis Example 1 as the polymer (A), and bisphenol A ethylene oxide-modified diacrylate (Aronix (trade name) M210, manufactured by Toagosei Co., Ltd.) as the compound (B) having a double bond. As the photopolymerization initiator (C), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE (trade name) 369 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used.
3.0 g of polymer (A-1) of synthesis example 1
4-hydroxybutyl acrylate 10.0 g
Aronix M210 3.0g
IRGACURE 369 1.0g

  The viscosity of the obtained photocurable inkjet ink at 25 ° C. was 155 mPa · s. The viscosity was measured with an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI).

Using this photo-curable ink-jet ink, a 5 cm straight line was drawn on a polyimide substrate using a Dimatix ink-jet coating apparatus DMP-2800. At this time, the drawing conditions were set so that the line width and the width between the lines were the same. In this specification, such drawing is referred to as “line and space application”. The number of coatings was 1, the line width was 500 μm, the jetting speed from the nozzle was 10 times / s, and the jetting temperature was 80 ° C. The substrate after jetting was irradiated with 40 mJ / cm ² of i-line using an ultra-high pressure mercury lamp, and then heated in an oven at 160 ° C. for 30 minutes to obtain a cured film formed in a line shape.

  The line width and edge linearity of the obtained cured film were observed with an optical microscope. The results are shown in Table 1. The line width was almost the same as that applied, and the linearity of the edge of the line was good.

[Example 2]
The following compositions were mixed and dissolved, and filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.5 μm to prepare a photocurable inkjet ink as follows.
The polymer (A-2) of Synthesis Example 2 is used as the polymer (A), and the bisphenol A ethylene oxide-modified diacrylate (Aronix (trade name) M210 manufactured by Toagosei Co., Ltd.) is used as the compound (B) having a double bond. As the photopolymerization initiator (C), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE (trade name) 369 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used.
10.0 g of a 30 wt% solution of the polymer (A-2) of Synthesis Example 2
4-hydroxybutyl acrylate 10.0 g
Aronix M210 5. 0g
IRGACURE 369 1.5g

  The viscosity of the obtained photocurable ink-jet ink at 25 ° C. was 74 mPa · s.

Using this photo-curable inkjet ink, line and space coating was performed in the same manner as in Reference Example 1. However, the jetting temperature was 65 ° C. The substrate after jetting was irradiated with 40 mJ / cm ² of i-line using an ultra-high pressure mercury lamp, and then heated in an oven at 160 ° C. for 30 minutes to obtain a cured film formed in a line shape.

  The line width and edge linearity of the obtained cured film were observed with an optical microscope. The results are shown in Table 1. The line width was almost the same as that applied, and the linearity of the edge of the line was good.

[Comparative Example 1]
The following composition was mixed and dissolved, and filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.5 μm to prepare a photocurable ink jet ink.
3.0 g of the polymer of Synthesis Example 3
4-hydroxybutyl acrylate 10.0 g
Aronix M210 3. 0g
IRGACURE 369 1.0g

  The viscosity of the obtained photocurable inkjet ink at 25 ° C. was 69 mPa · s.

Using this photo-curable inkjet ink, line and space coating was performed in the same manner as in Reference Example 1. However, the jetting temperature was 65 ° C. The substrate after jetting was irradiated with 40 mJ / cm ² of i-line using an ultra-high pressure mercury lamp, and then heated in an oven at 160 ° C. for 30 minutes to obtain a cured film formed in a line shape.

  The line width and edge linearity of the obtained cured film were observed with an optical microscope. The results are shown in Table 1. The line width was wider than the applied width, and the edge of the line was also jagged.

  The inkjet ink of the present invention is used, for example, in etching resists and protective films used for electronic circuit boards, spacers and protective films for liquid crystal displays, insulating films for flexible wiring boards, and electronic components using these. Can do.

Claims (3)

Following formula (1)

(In the formula, R ¹ and R ² are each independently alkyl having 1 to 3 carbon atoms or phenyl.)
A photocurable inkjet ink comprising a polymer (A) having a structural unit represented by formula (B), a compound having a double bond (B), and a photopolymerization initiator (C),
The polymer (A) is represented by the following formula (3)
Wherein R ¹ and R ² are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁶ is each independently methylene, phenylene or alkyl-substituted phenylene, and m is independently (It is an integer from 1 to 6, and n is an integer from 1 to 100.)
A diamine represented in a copolymer obtained by reacting a compound having an acid anhydride group,
The compound (B) having a double bond includes glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate glycidyl ether, 1,4-cyclohexanedimethanol mono (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-ethyl-2- (meth) acryloxymethyloxetane, pentaerythritol tri Including one or more selected from the group consisting of (meth) acrylate, dipentaerythritol penta (meth) acrylate and isocyanuric acid ethylene oxide modified di (meth) acrylate,
20 to 1,000 parts by weight of the compound (B) having a double bond and 0.5 to 200 parts by weight of the photopolymerization initiator (C) with respect to 100 parts by weight of the polymer (A),
The photocurable inkjet ink, wherein the compound having an acid anhydride group is tetracarboxylic dianhydride . The photopolymerization initiator (C) is represented by the following formula (6)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently alkyl having 1 to 13 carbon atoms, X ¹ and X ² are each independently -O-, -O-O-, or- NH-)
A compound represented by the following formula (7):
(Wherein R ¹ , R ² and R ³ are each independently hydrogen or alkyl having 1 to 5 carbon atoms; R ⁴ is alkyl having 1 to 15 carbon atoms),
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- The photocurable inkjet ink according to claim 1, which is at least one selected from the group consisting of 1 . The photopolymerization initiator (C) is represented by the following formula (6)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently alkyl having 1 to 13 carbon atoms, X ¹ and X ² are each independently -O-, -O-O-, or- NH-)
A compound represented by the following formula (7):
(Wherein R ¹ , R ² and R ³ are each independently hydrogen or alkyl having 1 to 5 carbon atoms; R ⁴ is alkyl having 1 to 15 carbon atoms),
2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- one or more selected from the group consisting of 1, containing 20-100% of the total weight of the photopolymerization initiator (C), light-curable inkjet ink according to claim 1.