JP2014001321A - Photocurable inkjet ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ink for ink jet which can form a cured film which is balancedly excellent in fire retardancy, adhesion to a base material, and resistance in a saturation vapor pressure test.SOLUTION: A photocurable inkjet ink contains phosphorus-containing (meth)acrylate (A) represented by the following formula (1), and epoxy resin (B). In the formula (1), R, Rand Rare each independently a 1-20C alkylene, a, b and c are each independently an integer satisfying a+b+c≥1 in the range of 0-10, d, e and f are each independently an integer of 1-10, Ris a phosphorus-containing carbonyl group, Ris univalent organic group, and Ris hydrogen or 1-6C alkyl.

Description

  The present invention relates to a photocurable ink-jet ink suitably used for producing an electronic circuit board such as a printed wiring board for forming a display element such as a liquid crystal display element or an EL (electroluminescence) display element. More specifically, the present invention relates to an ink jet ink suitable for a coverlay film for protecting a metal wiring surface forming a predetermined circuit pattern, a solder resist, or the like.

  Conventionally, a photolithography method using a photoresist has been used for manufacturing electronic circuit boards such as (flexible) printed wiring boards and semiconductor package boards. In the method of manufacturing an electronic circuit board by this photolithography method, for example, in the case of a printed wiring board, a photoresist layer is formed on a copper foil of a copper-clad laminate, and the layer is exposed through a photomask or the like. The uncured portion is removed to form a resist pattern. Next, a portion of the copper foil not covered with the resist pattern is removed by etching, and then the resist pattern is removed to obtain a printed wiring board.

  However, the method for manufacturing a printed wiring board as described above requires a large amount of capital investment because it takes a long time and a lot of cost to manufacture a photomask. Further, since pattern exposure using a photomask is necessary, the process is complicated and the operation is complicated.

  In recent years, in order to solve these problems, a method has been developed in which a photosensitive material is directly applied onto a substrate using an inkjet method to form a pattern (for example, Japanese Patent Laid-Open No. 56-66089 (Patent Document). 1), Japanese Patent Application Laid-Open No. 62-181490 (Patent Document 2), Japanese Patent Application Laid-Open No. 6-237063 (Patent Document 3) and Japanese Patent Application Laid-Open No. 7-131135 (Patent Document 4). Since this method does not require pattern exposure, etching, and development, which have been necessary in the past, it is expected to have a small capital investment and a small material loss.

  Examples of the photosensitive material used in such an ink jet method include coverlay ink, solder resist ink, and the like, and generally adhesion to a substrate, resistance in a saturated vapor pressure test (hereinafter also referred to as “PCT”), and the like. Properties such as flame retardancy are required.

  So far, various compositions have been proposed as photosensitive materials having excellent flame retardancy (for example, Japanese Patent Application Laid-Open No. 2001-48956 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2001-312054 (Patent Document 6). JP, 2003-277470, A (patent document 7), JP, 2005-221722, A (patent document 8), JP, 2006-284911, A (patent document 9), JP, 2008-299293, patent (patent) Reference 10) and Japanese Patent No. 4776724 (Patent Document 11)).

  In addition, the applicant of the present application has proposed a photosensitive inkjet ink excellent in flame retardancy (see JP 2009-167376 A (Patent Document 12)).

JP 56-66089 A JP 62-181490 A JP-A-6-237063 JP 7-131135 A Japanese Patent Laid-Open No. 2001-48956 JP 2001-312054 A JP 2003-277470 A JP-A-2005-221722 JP 2006-284911 A JP 2008-299293 A Japanese Patent No. 4776724 JP 2009-167376 A

  Since the compositions described in Patent Documents 5 to 11 have high viscosity, they cannot be ejected by an ink jet apparatus.

  Even if the ink composition described in Patent Documents 5 to 11 is diluted with a common solvent or a monomer having a radical polymerizable double bond and has a viscosity that can be ejected by an ink jet apparatus, it is obtained from the ink. The adhesion of the cured film to the metal or resin, resistance to PCT and flame retardance were low.

  Moreover, the composition described in the Example of the said patent document 12 may not have sufficient adhesiveness to base materials, such as a metal and resin.

  The present invention has been made in view of such a situation, and an object of the present invention is to provide an inkjet ink capable of forming a cured film having excellent balance in flame retardancy, adhesion to a substrate, resistance in PCT, and the like. And

  The inventors of the present application can form a cured film in which an ink containing a phosphorus-containing (meth) acrylate having a specific structure and an epoxy resin is excellent in a good balance in flame retardancy, adhesion to a substrate, resistance in PCT, and the like. And the present invention was completed based on this finding.

  [1] A photocurable inkjet ink containing a phosphorus-containing (meth) acrylate (A) represented by the following formula (1) and an epoxy resin (B).

（式（１）中、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立に、炭素数１〜２０のアルキレンであり、ａ、ｂおよびｃはそれぞれ独立に、０〜１０の範囲でａ＋ｂ＋ｃ≧１を満たす整数であり、ｄ、ｅおよびｆはそれぞれ独立に、１〜１０の整数であり、Ｒ⁴は下記式（２）で表される基であり、Ｒ⁵は１価の有機基であり、Ｒ⁶は水素または炭素数１〜６のアルキルである。）

(In the formula (1), R ¹ , R ² and R ³ are each independently alkylene having 1 to 20 carbon atoms, and a, b and c are each independently a + b + c ≧ 1 in the range of 0 to 10). D, e and f are each independently an integer of 1 to 10, R ⁴ is a group represented by the following formula (2), R ⁵ is a monovalent organic group, R ⁶ is hydrogen or alkyl having 1 to 6 carbon atoms.)

（式（２）中、Ｒ⁷は、水素または炭素数１〜６のアルキルであり、Ｒ⁸およびＲ⁹はそれぞれ独立に、炭素数１〜２０の１価の有機基であり、Ｒ⁸およびＲ⁹は互いに結合して２価の環状基を形成してもよい。）

(In Formula (2), R ⁷ is hydrogen or alkyl having 1 to 6 carbon atoms, R ⁸ and R ⁹ are each independently a monovalent organic group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ may bond to each other to form a divalent cyclic group.)

[2] The photocurable inkjet ink according to [1], wherein R ⁴ in the formula (1) is a group represented by the following formula (3).

（式（３）中、Ｒ¹⁰は、水素または炭素数１〜６のアルキルである。）

(In the formula (3), R ¹⁰ is hydrogen or alkyl having 1 to 6 carbon atoms.)

[3] The photocurable inkjet according to [1] or [2], wherein R ⁵ in the formula (1) is a group represented by the formula (2) or a group represented by the following formula (4): ink.

（式（４）中、Ｒ⁶は水素または炭素数１〜６のアルキルである。）

(In the formula (4), R ⁶ is hydrogen or alkyl having 1 to 6 carbon atoms.)

  [4] In any one of [1] to [3], the epoxy resin (B) has a group represented by the following formula (B-1), formula (B-2), or formula (B-3). The photocurable inkjet ink as described.

  [5] The epoxy resin (B) is a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenyl aralkyl novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a trisphenol methane type epoxy resin, or a bisphenol S. Type epoxy resin, tetraphenylolethane type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, naphthalene skeleton type epoxy resin, and dicyclopentadiene skeleton type epoxy resin. [1] to [4] The photocurable inkjet ink according to any one of [4].

[6] The photocurable inkjet ink according to any one of [1] to [5], further including an epoxy resin curing agent (C).
[7] The photocurable inkjet ink according to any one of [1] to [6], further including a compound (D) having a radical polymerizable double bond other than the phosphorus-containing (meth) acrylate (A).
[8] The photocurable inkjet ink according to any one of [1] to [7], further including a photopolymerization initiator (E).

[9] A cured film formed from the photocurable inkjet ink according to any one of [1] to [8].
[10] An electronic circuit board comprising the cured film according to [9].
[11] An electronic component having the electronic circuit board according to [10].

  The photocurable ink-jet ink of the present invention can form a cured film that is excellent in ejection properties, has excellent balance in flame retardancy, adhesion to a substrate, and resistance in PCT.

1. Photocurable inkjet ink The photocurable inkjet ink of the present invention (hereinafter also referred to as “ink of the present invention”) includes a phosphorus-containing acrylate (A) and an epoxy resin (B) represented by the following formula (1). .
Such an ink of the present invention is excellent in ejection properties, and a cured film obtained from the ink is excellent in balance with respect to flame retardancy, adhesion to a substrate, resistance to PCT, and the like.

  The ink of the present invention is a compound having a radical polymerizable double bond other than the epoxy resin curing agent (C) and the phosphorus-containing (meth) acrylate (A) as long as it does not impair the effects of the present application, if necessary. (D), a photoinitiator (E), and other components may be included.

  In this specification, “(meth) acrylate” is used to indicate both or one of acrylate and methacrylate.

1-1. Phosphorus-containing (meth) acrylate (A)
The phosphorus-containing (meth) acrylate (A) (hereinafter also referred to as “compound (A)”) is a compound having a structure represented by the following formula (1).

（式（１）中、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立に、炭素数１〜２０のアルキレンであり、ａ、ｂおよびｃはそれぞれ独立に、０〜１０の範囲でａ＋ｂ＋ｃ≧１を満たす整数であり、ｄ、ｅおよびｆはそれぞれ独立に、１〜１０の整数であり、Ｒ⁴は下記式（２）で表される基であり、Ｒ⁵は１価の有機基であり、Ｒ⁶は水素または炭素数１〜６のアルキルである。）

(In the formula (1), R ¹ , R ² and R ³ are each independently alkylene having 1 to 20 carbon atoms, and a, b and c are each independently a + b + c ≧ 1 in the range of 0 to 10). D, e and f are each independently an integer of 1 to 10, R ⁴ is a group represented by the following formula (2), R ⁵ is a monovalent organic group, R ⁶ is hydrogen or alkyl having 1 to 6 carbon atoms.)

（式（２）中、Ｒ⁷は、水素または炭素数１〜６のアルキルであり、Ｒ⁸およびＲ⁹はそれぞれ独立に、炭素数１〜２０の１価の有機基であり、Ｒ⁸およびＲ⁹は互いに結合して２価の環状基を形成してもよい。）

(In Formula (2), R ⁷ is hydrogen or alkyl having 1 to 6 carbon atoms, R ⁸ and R ⁹ are each independently a monovalent organic group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ may bond to each other to form a divalent cyclic group.)

Examples of alkylene of R ^1, R ² and carbon atoms in R ³ 1 to 20, preferably an alkylene having 1 to 12 carbon atoms, more preferably an alkylene having 1 to 6 carbon atoms.
Examples of the alkylene having 1 to 20 carbon atoms include methylene, ethylene, propylene, trimethylene, isopropylidene, tetramethylene, pentamethylene, hexamethylene and heptamethylene. Among these, methylene, ethylene and trimethylene are preferable, More preferred is ethylene.

A, b and c are each preferably an integer such that a + b + c is 1 to 15, and more preferably an integer such that a + b + c is 1 to 6.
By using the compound (A) in which a + b + c in the formula (1) is in the above range, a cured film having excellent flame retardancy can be obtained even if the amount of the compound (A) added is small. Therefore, a cured film having excellent flame retardancy can be obtained, and an ink having excellent discharge properties can be obtained.

  The d, e and f are preferably each independently an integer of 2 to 10.

The alkyl having 1 to 6 carbon atoms in R ⁶ and R ^7, preferably an alkyl of 1 to 3 carbon atoms.
R ⁶ and R ⁷ are preferably hydrogen.

Examples of the organic group having 1 to 20 carbon atoms in R ⁸ and R ⁹ include a hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom.

  The hydrocarbon group having 1 to 20 carbon atoms is preferably a hydrocarbon group having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, chain hydrocarbon groups such as n-hexyl and n-heptyl; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl and cyclohexyl; aromatic hydrocarbon groups such as phenyl, biphenyl and naphthyl; .

  As a C1-C20 hydrocarbon group containing an oxygen atom, a C1-C12 hydrocarbon group is preferable, such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, phenoxy, propenyloxy, cyclohexyloxy and methoxymethyl A group having an ether bond; a group having a carbonyl group such as acetyl, propionyl, isopropionyl and benzoyl; a group having an ester group such as acetyloxy, propionyloxy, isopropionyloxy and benzoyloxy;

As R ⁸ and R ⁹ , at least one of them is preferably a C 1-20 hydrocarbon group containing an oxygen atom, and one of them is a C 1-20 hydrocarbon group containing an oxygen atom. More preferably, the other is a hydrocarbon group having 1 to 20 carbon atoms.
As a C1-C20 hydrocarbon group containing the said oxygen atom, a C1-C12 hydrocarbon group which has an ether bond is preferable.

Examples of the divalent cyclic group formed by combining R ⁸ and R ⁹ with each other include a divalent organic group having 2 to 40 carbon atoms, and a divalent hydrocarbon group having 2 to 24 carbon atoms. In addition, a C 2-24 divalent hydrocarbon group containing an oxygen atom is preferable.

R ⁴ is preferably a group represented by the following formula (3) because it has good flame retardancy and is a stable compound.

（式（３）中、Ｒ¹⁰は、水素または炭素数１〜６のアルキルであり、好ましくは水素または炭素数１〜３のアルキルであり、より好ましくは水素である。）

(In the formula (3), R ¹⁰ is hydrogen or alkyl having 1 to 6 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms, more preferably hydrogen.)

The monovalent organic group in R ⁵ in the formula (1) is not particularly limited, such as the groups exemplified as R ⁸ and R ⁹ can be mentioned.
R ⁵ in the formula (1) is preferably the same group as the R ⁴ or a group represented by the following formula (4). The group represented by the formula (2) or the following formula (4) The group represented by formula (3) is more preferred, and the group represented by the following formula (4) is more preferred.

（式（４）中、Ｒ⁶は前記式（１）中のＲ⁶と同義である。）

(In the formula (4), R ⁶ has the same meaning as R ⁶ in the formula (1).)

  The phosphorus-containing (meth) acrylate (A) used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

When the compound (A) is a mixture and includes a compound in which R ⁵ is the same group as R ⁴ or a compound represented by the formula (4), the total amount of the mixture is 100% by weight, The content ratio of the compound in which R ⁵ is the same group as R ⁴ is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, and R ⁵ is a group represented by the formula (4). The content ratio of the compound is preferably 10 to 70% by weight, more preferably 20 to 60% by weight.
Such a compound (A) (mixture) can be obtained by appropriately adjusting the type and amount of the raw material compound used when the compound (A) is synthesized.
Such a mixture is preferable because it can be easily synthesized.

The compound (A) (mixture of the compound (A)) is synthesized, for example, by reacting the compound (i) represented by the following formula (i) with a phosphine oxide compound (ii) having a P—H bond. can do.
In this case, the amount of compound (ii) to be used is preferably 0.1 to 0.7 equivalent, more preferably 0.3 to 0.6 equivalent, relative to 1 equivalent of acryloyl group of compound (i). .
It is preferable for the amount of compound (ii) used to be in the above-mentioned range since an ink having excellent flame retardancy, moderate viscosity and excellent dischargeability tends to be obtained.

（式（ｉ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁶、ａ、ｂ、ｃ、ｄ、ｅおよびｆは前記式（１）中のＲ¹、Ｒ²、Ｒ³、Ｒ⁶、ａ、ｂ、ｃ、ｄ、ｅおよびｆと同義であり、Ｒ¹¹は１価の有機基である。）

(In the formula (i), R ¹ , R ² , R ³ , R ⁶ , a, b, c, d, e and f are R ¹ , R ² , R ³ , R ⁶ , (It is synonymous with a, b, c, d, e and f, and R ¹¹ is a monovalent organic group.)

The monovalent organic group for R ^11, is not particularly limited, such as groups exemplified as R ⁸ and R ⁹ can be mentioned. R ¹¹ is preferably a group represented by the formula (4).

  Examples of the compound (i) include caprolactone-modified tris (acryloxyethyl) isocyanurate (trade name: Aronix M-327, manufactured by Toagosei Co., Ltd.) and the like, and a representative compound of the phosphine oxide compound (ii). 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: SANKO-HCA, manufactured by Sanko Co., Ltd.) and the like.

The content of the compound (A) in the ink of the present invention is preferably 5 to 40% by weight and more preferably 5 to 30% by weight with respect to 100% by weight of the total ink of the present invention.
When the compound (A) is a reaction product obtained by reacting the acrylate (i) and the phosphine oxide compound (ii), the total amount of the reaction product obtained is 5% by weight or more of the total amount of the ink. In view of obtaining an ink having excellent flame retardancy, it is more preferably 10% by weight or more of the total amount of the ink.

1-2. Epoxy resin (B)
The ink of the present invention contains an epoxy resin (B) (hereinafter also referred to as “compound (B)”).
When the ink of the present invention contains the epoxy resin (B), it is possible to obtain a cured film having excellent adhesion to a base material such as metal or resin and resistance to PCT.

  Although it does not restrict | limit especially as said epoxy resin (B), From the point that the cured film excellent in adhesiveness with a base material is obtained, following formula (B-1), Formula (B-2) or Formula (B) A resin having a group represented by -3) is preferable, and an epoxy resin having an aromatic ring is more preferable from the viewpoint that a cured film having excellent adhesion with a base material is obtained.

As such an epoxy resin (B), specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl aralkyl novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type At least one selected from the group consisting of epoxy resins, bisphenol S type epoxy resins, tetraphenylolethane type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, naphthalene skeleton type epoxy resins, and dicyclopentadiene skeleton type epoxy resins More preferably, it is a seed resin.
In addition, as the epoxy resin (B), phenol novolac type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, and dicyclopentadiene skeleton type epoxy resin are adhesive to substrates such as metals and resins. Is particularly preferable from the viewpoint of good.

As representative examples of such epoxy resins, jER152, 154 (trade name: manufactured by Mitsubishi Chemical Corporation), Epicron N-730A, N-770, N-865 (trade name: manufactured by DIC Corporation) , D.E.N.431, 438 (trade name: manufactured by Dow Chemical Japan), EPPN-201, RE-306 (trade name: manufactured by Nippon Kayaku Co., Ltd.), etc. resin;
Epototo YDCN-701, YDCN-704 (trade name: manufactured by Nippon Steel Chemical Co., Ltd.), Araldite ECN1235, ECN1273, ECN1299 (trade name: manufactured by Huntsman Japan Co., Ltd.), EOCN-1020, EOCN- 102S, EOCN-102S-65, EOCN-104S (trade name: manufactured by Nippon Kayaku Co., Ltd.), Sumi-Epoxy ESCN-195X, ESCN-220 (trade name: manufactured by Sumitomo Chemical Co., Ltd.), A. Cresol novolac type epoxy resins such as ER ECN-299 (trade name: manufactured by Asahi Kasei E-Materials Co., Ltd.);
NC-3000 (trade name: manufactured by Nippon Kayaku Co., Ltd.) and other biphenyl aralkyl novolac type epoxy resins;
jER828, 834, 1001, 1004 (trade name: manufactured by Mitsubishi Chemical Corporation), Epicron 840, 850, 1050, 1050, 2055 (trade name: manufactured by DIC Corporation), Epototo YD-011, YD-013, YD-127, YD-128 (trade name: manufactured by Nippon Steel Chemical Co., Ltd.), D.E.R.317, 331, 661, 664 (trade name: Dow Chemical Japan Co., Ltd.), Araldite 6071, 6084, GY250, GY260 (trade name: Huntsman Japan Co., Ltd.), Sumi-Epoxy ESA-011, ESA-014, ELA-115, Bisphenol A such as ELA-128 (trade name: manufactured by Sumitomo Chemical Co., Ltd.), A.E.R. 330, 331, 661, 664 (trade name: manufactured by Asahi Kasei E-Materials Co., Ltd.) Epoxy resins;
Epicron 830 (trade name: manufactured by DIC Corporation), jER807 (trade name: manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170 (trade name: manufactured by Nippon Steel Chemical Co., Ltd.), YDF-175, YDF- Bisphenol F type epoxy resins such as 2001, YDF-2004, Araldite XPY306 (trade name: manufactured by Huntsman Japan Co., Ltd.);
Techmore VG3101L (trade name: manufactured by Mitsui Chemicals Co., Ltd.), YL-933, jER1032H60 (trade name: manufactured by Mitsubishi Chemical Corporation), EPPN-501, EPPN-502 (trade names: manufactured by Dow Chemical Japan Co., Ltd.) ) Trisphenol methane type epoxy resin;
Bisphenol S type epoxy resins such as EBPS-200 (trade name: manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (trade name: manufactured by ADEKA Corp.), EXA-1514 (trade name: manufactured by DIC Corp.) ;
Tetraphenylolethane type epoxy resins such as YL-931 (trade name: manufactured by Mitsubishi Chemical Corporation), Araldite 163 (trade name: manufactured by Huntsman Japan Co., Ltd.);
Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 (trade name: manufactured by Mitsubishi Chemical Corporation) or mixtures thereof;
Naphthalene skeleton type epoxy resins such as HP-4032, EXA-4750, EXA-4700 (trade name: manufactured by DIC Corporation);
And dicyclopentadiene skeleton type epoxy resins such as HP-7200, HP-7200H, and HP-7200HH (trade name: manufactured by DIC Corporation).

  The epoxy resin (B) used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  The content of the epoxy resin (B) is preferably 0.5 to 30% by weight with respect to 100% by weight of the total amount of the ink of the present invention, because adhesion to metals and resins is improved, and is balanced with other materials. When considering the above, it is particularly preferably 0.5 to 20% by weight of the total amount of ink.

1-3. Epoxy resin curing agent (C)
The ink of the present invention preferably contains an epoxy curing agent (C) (hereinafter also referred to as “compound (C)”) from the viewpoint of further improving the chemical resistance of the resulting cured film.
As the epoxy curing agent (C), an acid anhydride curing agent, a polyamine curing agent, a catalyst curing agent and the like are preferable.

  Examples of the acid anhydride-based curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, Examples include merit acid anhydride and styrene-maleic anhydride copolymer.

  Examples of the polyamine curing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3-bis ( Aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and diaminodiphenylsulfone.

  Examples of the catalyst curing agent include tertiary amine compounds and imidazole compounds. Specific examples thereof include 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium. Examples include trimellitate, 2-phenylimidazoline, 1-cyanoethyl-2-ethyl-4-methylimidazole, and the like.

  Particularly preferred as the epoxy resin curing agent is a catalyst-based curing agent, among which 1-cyanoethyl-2-ethyl-4-methylimidazole and 1-cyanoethyl-2-undecylimidazolium trimellitate are desirable.

  The epoxy resin curing agent (C) used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  It is preferable that the addition amount of an epoxy resin hardening | curing agent (C) is 1-50 weight part with respect to 100 weight part of epoxy resins (B), Most preferably, it is 5-30 weight part.

1-4. Compound (D) having radically polymerizable double bond other than compound (A)
The ink of the present invention is a compound (D) having a radical polymerizable double bond other than the compound (A) (hereinafter referred to as “compound (D)”) from the viewpoint of adjusting the viscosity within a range not impairing the properties of the ink. It is also preferable to include. The compound (D) is preferable to the organic solvent because it is cured after light exposure.

Although it does not restrict | limit especially as said compound (D), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 4- cyclohexane dimethanol mono (meta) ) Acrylate, N-hydroxyethyl (meth) acrylamide, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) ) Acryloxymethyl Oxe , 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) acryloxymethyloxetane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, ω-carboxypolycaprolactone mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl succinate ], Mono [2- (meth) acryloyloxyethyl maleate], cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl], (meth) acrylamide, N, N-dimethyl (meta ) Acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, thioglycidyl (meth) acrylate, phenylthio Til (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, dicyclopentanyl (meth) acrylate, γ-butyrolactone (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) ) Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis [2- (meth) acryloyloxyethyl] hydroxyethyl isocyanurate, styrene, methylstyrene, chloromethylstyrene, N-cyclohexylmaleimide, N -Phenylmaleimide, vinyltoluene, polystyrene macromonomer, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, pentaerythritol di (me ) Acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (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 tri (meth) acrylate, Chlorhydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified triphosphate (Meth) acrylate, tris [2- (meth) acryloyloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, urethane (meth) acrylate, acid-modified epoxy (meth) acrylate, acid-modified ( (Meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate Such fine bisphenol S ethylene oxide modified di (meth) acrylate.

  Among these, the most suitable compound (D) for reducing the viscosity of the ink within a range not impairing the properties of the ink of the present invention is 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl. (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and isobornyl (meth) acrylate.

  The compound (D) used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  When the ink of the present invention contains the compound (D), the compounding amount of the compound (D) is preferably 10 to 70% by weight with respect to 100% by weight of the total amount of the ink of the present invention. Considering the balance with other materials used in the ink, it is particularly preferably 20 to 60% by weight of the total amount of ink.

1-5. Photopolymerization initiator (E)
The ink of the present invention preferably contains a photopolymerization initiator (E) (hereinafter also referred to as “compound (E)”).
The photopolymerization initiator (E) is more preferably a compound capable of generating radicals upon irradiation with ultraviolet rays or visible rays.

Specific examples of the photopolymerization initiator (E) capable of generating radicals upon irradiation with ultraviolet rays or visible light include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2 , 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -1,2-diphenylethane-1-one, camphorquinone, benzanthrone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycal Nyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 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′-di (t-butylperoxycarbonyl) benzophenone, 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, 2- (4′-methoxystyryl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, 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-mercaptobenzo Azole, 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-ethoxycarbonylphenyl) -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, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-) Yl) -phenyl) titanium, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2 Benzyl-1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, oxy-phenyl-acetic acid 2- [ 2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoylformate, bis (2,4,6-trimethylbenzoyl) phenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine ester, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2-methylbenzo) Le) -9H- carbazol-3-yl] - ethanone-1-(O-acetyl oxime) may be mentioned.

  Among these, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -Propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholino-1-propanone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone is preferred.

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

  The content of the photopolymerization initiator (E) is preferably 0.5 to 20% by weight based on 100% by weight of the total amount of the ink of the present invention. Is 1 to 20% by weight, more preferably 2 to 20% by weight.

1-6. Other components The ink of the present invention is an organic solvent, a polymerization inhibitor, a thermosetting compound other than an epoxy resin, a thermal polymerization initiator, an antioxidant, a colorant, etc., as necessary without departing from the scope of the present invention. Other components may be included.

1-6-1. Organic Solvent The ink of the present invention may contain an organic solvent for the purpose of adjusting ejection properties. By including a solvent, the viscosity and surface tension of the ink can be finely adjusted, and the discharge properties can be adjusted.
Although it does not restrict | limit especially as said organic solvent, It is preferable that it is an organic solvent whose boiling point is 100 to 300 degreeC.

  Specific examples of the organic solvent having a boiling point of 100 to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropion. Acid methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, dioxane, 3-methoxybutanol 3-methoxybutyl acetate, methyl 2-hydroxyisobutyrate, i-propyl 2-hydroxyisobutyrate, i-butyl 2-hydroxyisobutyrate, n-butyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , Diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol Diethylene glycol, propylene glycol, dipropylene glycol, benzyl alcohol, cyclohexanol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tripropylene glycol methyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate Tate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone , N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.

  The organic solvent that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  The content of the organic solvent is preferably 0.1 to 20% by weight with respect to 100% by weight of the total amount of the ink of the present invention, because an ink having a good balance between ejection properties and other characteristics can be obtained, more preferably 0. .2 to 10% by weight, more preferably 0.5 to 8% by weight, and particularly preferably 1 to 5% by weight.

1-6-2. Polymerization inhibitor The ink of the present invention may contain a polymerization inhibitor in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, dibutylhydroxytoluene and phenothiazine. Among these, phenothiazine is preferable because an ink with a small increase in viscosity can be obtained even in long-term storage.

  The polymerization inhibitor that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  When the content of the polymerization inhibitor is 0.01 to 1% by weight with respect to 100% by weight of the total amount of the ink of the present invention, an ink having a small change in viscosity can be obtained even during long-term storage. In view of the balance, it is more preferably 0.01 to 0.5% by weight, still more preferably 0.01 to 0.1% by weight.

1-6-3. Thermosetting compound other than epoxy resin The ink of the present invention may contain a thermosetting compound other than an epoxy resin. The thermosetting compound is not particularly limited as long as it is a compound having a functional group that can be thermally cured, and examples thereof include bismaleimide, a phenol resin, a resin containing a phenolic hydroxyl group, and a melamine resin.

  The thermosetting compound other than the epoxy resin that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  When the content of the thermosetting compound other than the epoxy resin is 0.01 to 10% by weight with respect to 100% by weight of the total ink of the present invention, the heat resistance of the resulting cured film is preferably improved, and more preferably. Is 0.1 to 8% by weight, more preferably 0.5 to 5% by weight.

1-6-3-1. Bismaleimide Examples of the bismaleimide include a compound represented by the following formula (5).

In the formula (5), R ¹² and R ¹⁴ are each independently hydrogen or methyl, and R ¹³ is a divalent group represented by the following formula (6).

In the formula (6), R ¹⁵ and R ¹⁶ may each independently have an alkylene or substituent having 1 to 18 carbon atoms in which any methylene that is not continuous (not adjacent) may be replaced by oxygen. It is a divalent group having a good aromatic ring, or an optionally substituted cycloalkylene. Examples of the substituent include carboxyl, hydroxy, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. In view of obtaining a cured film having high heat resistance, R ¹⁵ and R ¹⁶ are preferably each independently one kind of divalent group selected from the following group (b).

  In said formula (6), X is 1 type of bivalent group chosen from the following group (c).

  The bismaleimide that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

1-6-3-2. As a phenol resin or a resin containing a phenolic hydroxyl group, a novolac resin obtained by a condensation reaction between an aromatic compound having a phenolic hydroxyl group and an aldehyde is preferably used. As a resin containing a phenolic hydroxyl group, A vinylphenol homopolymer (including a hydrogenated product) and a vinylphenol copolymer (including a hydrogenated product) of vinylphenol and a compound copolymerizable therewith are preferably used.

  Examples of aromatic compounds having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenol A, bisphenol F, terpene skeleton-containing diphenol, gallic acid, gallic acid ester, α-naphthol, and β-naphtho And the like.

  Specific examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde.

  Examples of the compound copolymerizable with vinylphenol include (meth) acrylic acid or a derivative thereof, styrene or a derivative thereof, maleic anhydride, vinyl acetate, and acrylonitrile.

  Specific examples of phenolic resins include Resitop PSM-6200 (trade name: manufactured by Gunei Chemical Industry Co., Ltd.), Shonor BRG-555 (trade name: manufactured by Showa Denko Co., Ltd.), and resins containing phenolic hydroxyl groups. Specific examples of these include Marcalinker MS-2G, Marcalinker CST70, and Marcalinker PHM-C (all trade names: manufactured by Maruzen Petrochemical Co., Ltd.).

  The phenol resin or resin containing a phenolic hydroxyl group used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

1-6-3-3. Melamine resin The melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde. It is done. Among these, a condensate of etherified methylol melamine is preferable in that the resulting cured film has good chemical resistance.

  Specific examples of the melamine resin include Nicalac MW-30, MW-30HM, MW-390, MW-100LM, MX-750LM (trade names: manufactured by Sanwa Chemical Co., Ltd.).

  The melamine resin that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

1-6-4. Thermal polymerization initiator The ink of the present invention may contain a thermal polymerization initiator in order to improve the curability of the ink by the heating step. Specific examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, di-t-butyl peroxide, Name Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-180 (trade name: Sanshin Chemical Industry Co., Ltd.) Can do. Among these, 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) are preferable.

  The thermal polymerization initiator that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  The content of the thermal polymerization initiator is preferably 10% by weight or less with respect to 100% by weight of the total amount of the ink of the present invention, and more preferably 0.005 to 10% by weight from the viewpoint of the addition effect and ejection stability. is there.

1-6-5. Antioxidant The ink of the present invention may contain an antioxidant in order to prevent oxidation of the resulting cured film or the like.

  Antioxidants include triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzyl Examples include hindered phenol compounds such as phosphonate diethyl ester, and amine compounds such as n-butylamine, triethylamine, and diethylaminomethyl methacrylate.

  The antioxidant that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  The content of the antioxidant is preferably 3% by weight or less with respect to 100% by weight of the total amount of the ink of the present invention, and more preferably 0.005 to 2% by weight from the viewpoint of the effect of addition and ejection stability. .

1-6-6. Colorant The ink of the present invention may be colored or colorless, but when inspecting the state of the cured film obtained by applying the ink to a substrate and curing it, In order to facilitate identification from the substrate, a colorant may be included. As the colorant, dyes and pigments are preferable.

  The colorant used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

  The content of the colorant is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the solid content in the ink of the present invention, because it is easy to inspect a cured film obtained from the ink. In view of the balance, it is more preferably 0.1 to 1 part by weight, still more preferably 0.1 to 0.5 part by weight.

1-7. Ink Storage When the ink of the present invention is stored at 5 to 25 ° C., the viscosity change during storage is small and the storage stability is good.

1-8. Viscosity of Ink The viscosity of the ink of the present invention at 25 ° C. measured with an E-type rotational viscometer is preferably 2 to 200 mPa · s. When the viscosity is in this range, the dischargeability by the ink jet device is good. The viscosity of the ink of the present invention at 25 ° C. is preferably 2 to 100 mPa · s.

1-9. Ink Preparation Method The ink of the present invention can be prepared by mixing each component as a raw material by a known method.
In particular, the ink of the present invention comprises the compound (A) and the compound (B) and, if necessary, the compound (C) to the compound (E) and other components mixed, and the resulting solution is made of, for example, a fluororesin. It is preferable to prepare by filtering using a membrane filter and degassing. The ink prepared in this way is excellent in dischargeability.

1-10. Application of Ink by Inkjet Method The ink of the present invention can be applied using a known inkjet method. Examples of the ink jet method include a piezo method in which mechanical energy is applied to the ink and ejected from the ink jet head, and a coating method (so-called thermal method) in which the thermal energy is applied to the ink and ink is ejected.

  By using the inkjet method, the ink of the present invention can be easily applied in a predetermined pattern, and a uniform pattern can be formed on a large substrate.

  As an inkjet head, what has the heat-emitting part which consists of a metal and / or a metal oxide is mentioned, for example. 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 device used when coating using the ink of the present invention, for example, energy corresponding to a coating signal is given to ink in an ink jet head having an ink storage portion in which ink is stored, and An apparatus that performs application (drawing) corresponding to the application signal while generating ink droplets can be used.

  The ink jet coating apparatus is not limited to one in which the ink jet head and the ink container are separated, and may be one in which they are inseparably integrated. Further, the ink storage unit may be integrated with the ink jet head so as to be separable or non-separable and mounted on the carriage, or may be provided at a fixed portion of the apparatus. In the latter case, ink may be supplied to the ink jet head via an ink supply member, for example, a tube.

2. Cured film The cured film of the present invention is formed from the above-described ink of the present invention. Specifically, after the ink of the present invention is applied to the surface of a substrate by an ink jet method, light such as ultraviolet rays or visible light is applied to the ink. A film obtained by irradiating and curing the coating film is preferred.

  The use of the cured film of the present invention is not particularly limited, but the cured film obtained from the ink of the present invention is excellent in adhesion to a substrate such as metal or resin, resistance in PCT and flame retardancy, and in particular, a predetermined circuit. It is preferably used as a cover lay film for protecting the metal wiring surface forming the pattern, a solder resist, or the like.

Case of irradiation with ultraviolet light or visible light, exposure to radiation may be appropriately selected depending on the composition of the ink, but preferably about 100~5,000mJ / cm ^2, about 150~2000mJ / cm ² is More preferably, about 180 to 1000 mJ / cm ² is more preferable. Moreover, 200-500 nm is preferable and, as for wavelengths, such as an ultraviolet-ray and visible light to irradiate, 250-450 nm is more preferable.
In the present invention, the exposure amount is a value measured with an integrating light meter UIT-201 (trade name) equipped with a photoreceiver UVD-365PD (trade name) manufactured by USHIO INC.

  In addition, as an exposure machine, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a halogen lamp, an electrodeless lamp, etc. are mounted, and an apparatus that irradiates ultraviolet rays, visible rays, etc. in the range of 200 to 500 nm It is preferable that

  If necessary, the cured film cured by irradiation with light may be further heated and baked, and the cured film is cured more firmly by heating and baking at 80 to 250 ° C. for 10 to 60 minutes. be able to.

  In the present specification, the “base material” is not particularly limited as long as it can be an object to which the ink of the present invention is applied, and the shape is not limited to a flat plate shape, and may be a curved surface shape.

  Although it does not specifically limit as a base material which can be used for this invention, For example, the polyester resin base material which consists of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc .; The polyolefin resin base material which consists of polyethylene, a polypropylene, etc .; Organic polymer film made of vinyl, fluororesin, acrylic resin, styrene resin, polyamide, polycarbonate and polyimide; substrate made of cellophane; metal foil; laminated film of polyimide and metal foil; glass epoxy resin and metal foil Glossin paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol, starch, or carboxymethylcellulose (CMC), etc. that have a sealing effect; and glass base And the like.

In addition, these base materials are further added within the range that does not adversely affect the effects of the present invention, and further, pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents, and / or electromagnetic wave inhibitors. Etc. may also be included.
In addition, a part of the surface of the substrate may be subjected to surface treatment such as water repellent treatment, corona treatment, plasma treatment, or blast treatment if necessary, or the surface may be easily adhered layer, color filter protective film, hard coat film. May be provided.

  The thickness of the cured film of the present invention may be appropriately selected according to the desired application, but is preferably 1 μm to 50 μm, more preferably 5 μm to 20 μm.

3. Electronic Circuit Board The electronic circuit board of the present invention has the cured film. Examples of the electronic circuit board of the present invention include a rigid board, a flexible board, and a rigid flexible board.
As the flexible substrate, for example, the ink of the present invention is formed on the entire surface or a predetermined pattern (line shape or the like) by an ink jet method on a film-like base material such as a polyimide film in which wiring is formed in advance by the ink jet method or the like. The board | substrate obtained by apply | coating and forming a coating film and hardening the said coating film after that is mentioned.

  Although the metal which forms the said wiring (circuit) is not specifically limited, Gold, silver, copper, aluminum, or indium tin oxide (ITO) is preferable. A cured film obtained by applying the ink of the present invention to a substrate on which these wirings are formed in a predetermined pattern with an ink jet device and curing the substrate functions as a coverlay film, a solder resist, or the like that protects the wirings. To do.

  The use of the electronic circuit board of the present invention is not particularly limited, but the electronic circuit board manufactured using the cured film of the present invention that is excellent in heat resistance, adhesion to a base material and flame retardancy, an IC chip, By mounting a capacitor, a resistor, a fuse, or the like, for example, an electronic component for a liquid crystal display element can be created.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these. In the following, the photocurable inkjet ink obtained in the examples or comparative examples may be simply referred to as ink.
Table 1 below shows the usage amount (weight (g)) and evaluation results of the ink raw materials obtained in the examples and comparative examples.

[Production Example 1] <Production example of phosphorus-containing (meth) acrylate (A)>
A 100 mL three-necked flask is equipped with a thermometer and an air bubbling device, and caprolactone-modified tris (acryloxyethyl) isocyanurate (trade name: Aronix M-327, [in the above formula (1), R ^{1 to} R ³ is ethylene, R ⁴ and R ⁵ are acryloyl, R ⁶ is hydrogen, a + b + c≈3, d = e = f = 5.], Manufactured by Toagosei Co., Ltd.) 45.95 g And 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: SANKO-HCA, manufactured by Sanko Co., Ltd.), 12.97 g, and stirred at 110 ° C. for 6 hours. A composition containing phosphorus-containing (meth) acrylate represented by (1) (hereinafter abbreviated as “PA-1”) was obtained.
^{By 1} H-NMR, in the obtained PA-1, the CC double bond of the acryloyl group of caprolactone-modified tris (acryloxyethyl) isocyanurate was subjected to 9,10-dihydro-9-oxa-10-phosphine. It was confirmed that there was a compound having a structure in which a phosphorus atom of phenanthrene-10-oxide was added.

[Production Example 2] <Production Example of Phosphorus-Containing (Meth) acrylate>
A 50 mL three-necked flask was equipped with a thermometer and an air bubbling device. Tris- (2-acryloxyethyl) isocyanurate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.) 6.80 g and 3.48 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: SANKO-HCA, manufactured by Sanko Co., Ltd.) was added and stirred at 110 ° C. for 5 hours to contain phosphorus ( A composition containing meth) acrylate (hereinafter abbreviated as “PA-2”) was obtained.
^{By 1} H-NMR, in the obtained PA-2, 9,10-dihydro-9-oxa-10-phosphine was added to the C—C double bond of the acryloyl group of tris- (2-acryloxyethyl) isocyanurate. It was confirmed that a compound having a structure in which a phosphorus atom of faphenanthrene-10-oxide was added was present.

[Example 1]
PA-1 containing compound (A) synthesized in Production Example 1, EPPN-201 (trade name: manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin (B), 1-cyanoethyl- as epoxy resin curing agent (C) 2-ethyl-4-methylimidazole (trade name: 2E4MZ-CN, manufactured by Shikoku Kasei Co., Ltd.), tetrahydrofurfuryl acrylate (THFA) as compound (D), 2- (dimethylamino) as photopolymerization initiator (E) ) -2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG (hereinafter also referred to as “Irg379”)), BASF Japan Ltd. ), And phenothiazine (PT) as a photopolymerization inhibitor in the amounts shown in Table 1 and dissolved, and filtered through a 0.2 μm membrane filter. It is, filtrate (ink 1) was prepared.

  As a result of measuring the viscosity of ink 1 at 25 ° C. using an E-type rotational viscometer (trade name: TV-22, manufactured by Toki Sangyo Co., Ltd., the same shall apply hereinafter), it was 99 mPa · s.

  Ink 1 is injected into an ink jet cartridge, which is mounted on an ink jet apparatus (trade name: DMP-2831, manufactured by FUJIFILM Dimatics), using a 10 pl head, discharge voltage (piezo voltage) 21 V, head temperature 70 ° C. On the copper surface of Viroflex (trade name: manufactured by Toyobo Co., Ltd.), which is a 35 μm thick copper clad laminate in which copper foil is laminated on polyimide under discharge conditions of a drive frequency of 5 kHz and a coating frequency of once. A square pattern coating film having a size of 3 cm was drawn at the center.

Using a UV irradiation device (trade name: J-CURE 1500, manufactured by JATEC Corporation, the same shall apply hereinafter), the substrate on which the pattern coating film of ink 1 was formed was irradiated with ultraviolet rays at 1000 mJ / cm ² and further at 180 ° C. The coating was cured by heating in an oven for 30 minutes. A substrate 1 on which a cured film pattern having a thickness of 11 μm was formed was obtained.

[Example 2]
As epoxy resin (B), instead of EPPN-201, jER1032H60 (trade name: manufactured by Mitsubishi Chemical Corporation) was used, and the amount was changed as shown in Table 1, and the same procedure as in Example 1 was performed. Ink 2 having the composition shown in Table 1 below was prepared.

  As a result of measuring the viscosity of the ink 2 at 25 ° C. using an E-type rotational viscometer, it was 87 mPa · s.

  A substrate 2 on which a cured film pattern having a thickness of 8 μm was formed in the same manner as in Example 1 except that the ink 2 was used and the ejection voltage (piezo voltage) was changed to 20 V.

[Example 3]
As epoxy resin (B), instead of EPPN-201, jER807 (trade name: manufactured by Mitsubishi Chemical Corporation) was used, and the amount was changed as shown in Table 1, and the same procedure as in Example 1 was performed. Ink 3 having the composition shown in Table 1 below was prepared.

  As a result of measuring the viscosity of the ink 3 at 25 ° C. using an E-type rotational viscometer, it was 40 mPa · s.

  A substrate 3 on which a cured film pattern having a thickness of 8 μm was formed was obtained in the same manner as in Example 1 except that the ink 3 was used and the ejection voltage (piezo voltage) was changed to 22 V and the head temperature was 50 ° C.

[Example 4]
Except for using HP-7200 (trade name: manufactured by DIC Corporation) instead of EPPN-201 as the epoxy resin (B), the composition as shown in Table 1 below is the same as in Example 1. Ink 4 was prepared.

  As a result of measuring the viscosity of the ink 4 at 25 ° C. using an E-type rotational viscometer, it was 94 mPa · s.

  A substrate 4 on which a cured film pattern having a thickness of 12 μm was formed was obtained in the same manner as in Example 2 using ink 4.

[Example 5]
Example 1 except that NC-3000 (trade name: manufactured by Nippon Kayaku Co., Ltd.) was used instead of EPPN-201 as the epoxy resin (B), and the blending amount was changed as shown in Table 1. In the same manner, an ink 5 having the composition shown in Table 1 below was prepared.

  As a result of measuring the viscosity of the ink 5 at 25 ° C. using an E-type rotational viscometer, it was 91 mPa · s.

  A substrate 5 on which a 9 μm thick cured film pattern was formed was obtained in the same manner as in Example 1 except that the ink 5 was used and the ejection voltage (piezo voltage) was changed to 20V.

[Example 6]
As epoxy resin (B), instead of EPPN-201, EOCN-102S-65 (trade name: manufactured by Nippon Kayaku Co., Ltd.) was used, except that the amount was changed as shown in Table 1. In the same manner as in Example 1, ink 6 having the composition shown in Table 1 below was prepared.

  As a result of measuring the viscosity of the ink 6 at 25 ° C. using an E-type rotational viscometer, it was 96 mPa · s.

  A substrate 6 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 using ink 6.

[Comparative Example 1]
Ink 7 was prepared in the same manner as in Example 1 except that the epoxy resin (B) was not used and the blending amount was changed as shown in Table 1.

  As a result of measuring the viscosity of the ink 7 at 25 ° C. using an E-type rotational viscometer, it was 72 mPa · s.

  A substrate 7 on which a cured film pattern having a thickness of 10 μm was formed was obtained in the same manner as in Example 1 except that the ink 7 was used and the ejection voltage (piezo voltage) was changed to 20 V and the head temperature was 60 ° C.

[Comparative Example 2]
Ink 8 was prepared in the same manner as in Example 1 except that PA-2 synthesized in Production Example 2 was used instead of PA-1.

  As a result of measuring the viscosity of the ink 8 at 25 ° C. using an E-type rotational viscometer, it was 97 mPa · s.

  A substrate 8 on which a cured film pattern having a thickness of 10 μm was formed by using the ink 8 in the same manner as in Example 1 was obtained.

[Comparative Example 3]
Instead of PA-1, HFA-3003 (trade name: manufactured by Showa Denko KK, condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide) was used, and the blending amounts were shown in Table 1. Ink 9 was prepared in the same manner as in Example 1, except that the changes were made as shown in FIG.

  As a result of measuring the viscosity of the ink 9 at 25 ° C. using an E-type rotational viscometer, it was 95 mPa · s.

  A substrate 9 on which a 11 μm thick cured film pattern was formed was obtained in the same manner as in Example 1 except that the ink 9 was used and the head temperature was changed to 60 ° C.

[Comparative Example 4]
Instead of PA-1, HFA-6127 (trade name: manufactured by Showa Denko KK, caprolactone-modified dipentaerythritol hexaacrylate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Ink 10 was prepared in the same manner as in Example 1, except that the addition amount was changed as shown in Table 1.

  As a result of measuring the viscosity of the ink 10 at 25 ° C. using an E-type rotational viscometer, it was 90 mPa · s.

  A substrate 10 on which a 9 μm-thick cured film pattern was formed was obtained using the ink 10 in the same manner as in Example 2.

[Comparative Example 5]
Instead of PA-1, HFA-6127 (trade name: manufactured by Showa Denko KK, caprolactone-modified dipentaerythritol hexaacrylate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Ink 11 was prepared in the same manner as in Example 1, except that the addition reaction product was used, the epoxy resin (B) was not used, and the blending amount was changed as shown in Table 1.

  As a result of measuring the viscosity of the ink 11 at 25 ° C. using an E-type rotational viscometer, it was 97 mPa · s.

  A substrate 11 on which a cured film pattern having a thickness of 11 μm was formed using the ink 11 was obtained in the same manner as in Example 1.

[Comparative Example 6]
Instead of PA-1, caprolactone-modified tris (acryloxyethyl) isocyanurate (trade name: Aronix M-327, manufactured by Toagosei Co., Ltd.), which is a polyfunctional acrylate, is used without using the epoxy resin (B). Ink 12 was prepared in the same manner as in Example 1 except that the blending amount was changed as shown in Table 1.

  The viscosity of the ink 12 measured at 25 ° C. using an E-type rotational viscometer was 35 mPa · s.

  A substrate 12 on which a 9 μm thick cured film pattern was formed was obtained in the same manner as in Example 1 except that the ink 12 was used and the head temperature was changed to 50 ° C.

[Comparative Example 7]
Table 1 shows the blending amounts using caprolactone-modified tris (acryloxyethyl) isocyanurate (trade name: Aronix M-327, manufactured by Toagosei Co., Ltd.), which is a polyfunctional acrylate, instead of PA-1. Ink 13 was prepared in the same manner as in Example 1 except that the above was changed.

  As a result of measuring the viscosity of the ink 13 at 25 ° C. using an E-type rotational viscometer, it was 57 mPa · s.

  A substrate 13 on which a cured film pattern having a thickness of 10 μm was formed by using the ink 13 in the same manner as in Comparative Example 1 was obtained.

(Ink ejection test)
Disturbance of a 3 cm square pattern on the substrates (1 to 13) obtained in each Example and Comparative Example and blurring of printing were observed to evaluate ink ejection properties. The evaluation criteria are as follows.
◎: No pattern disturbance or printing blurring ○: Pattern distortion or printing blurring hardly △: Pattern disturbance or printing blurring much ×: Ink cannot be ejected (that is, pattern cannot be formed)

(Normal adhesion evaluation method)
Double-sided copper-clad laminate (trade name: MCL-E-679FG, [a structure in which copper foil (1), glass epoxy resin layer and copper foil (2) are laminated in this order], manufactured by Hitachi Chemical Co., Ltd.) Apply chemical polishing treatment, and apply the ink obtained in the example or comparative example on one side of the substrate (on the copper foil (1)) by the inkjet method under the same conditions as those for preparing the substrates 1 to 13. After the coating film was formed by UV irradiation, the coating film was cured by irradiating with ultraviolet rays at 1000 mJ / cm ² using a UV irradiation apparatus and further heating in an oven at 180 ° C. for 30 minutes. Thereafter, the obtained cured film surface and a glass epoxy sheet (trade name: SHG-1A, manufactured by McEight Co., Ltd.) were attached with an adhesive and dried. The copper foil (copper foil (2)) and the glass epoxy resin layer on the side where the ink of the double-sided copper-clad laminated substrate was not applied is scraped off from the obtained laminate, and the copper laminated on the glass epoxy sheet via an adhesive Only the laminate of the foil (1) and the cured film was left. Cut only the copper foil (1) into a strip with a width of about 5 mm, and pull the copper foil in a direction of 180 ° with respect to the cured film surface using a tensile tester (trade name: EZ Graph, manufactured by Shimadzu Corporation). It peeled off and the adhesive strength was measured.
Those having an adhesion strength of 0.8 [kN / m] or more were judged to have sufficient adhesion to the copper substrate.

(Tolerance evaluation method in saturated vapor pressure test (PCT))
In the same manner as described above, after the ink was applied, the coating film was cured and stored in a test furnace at 120 ° C. and 98% RH for 15 hours. Thereafter, the adhesion strength was measured by the same method as the evaluation method for adhesion in a normal state.
Those having an adhesion strength of 0.8 [kN / m] or more even after being stored in a test furnace for 15 hours were judged to be resistant to PCT.

(Flame retardancy evaluation method)
About flame retardance, it judged based on UL94 specification. Specifically, the inks obtained in the examples and comparative examples were respectively placed on the substrate 1 so that the thickness was 20 to 30 μm on a polyimide film (Kapton (registered trademark) 100H; manufactured by Toray DuPont Co., Ltd.) substrate. The film was coated by the ink jet method under the same conditions as those for preparing No. 13 and the coating film was irradiated with ultraviolet rays at 1000 mJ / cm ² using a UV irradiation apparatus, and then heat cured at 190 ° C. for 30 minutes. About the obtained cured film, the thin material perpendicular | vertical combustion test based on UL94 specification was done, and it evaluated based on UL94 specification. As a result, when the evaluation was VTM-0, the cured film was judged to have flame retardancy.

  It turns out that the ink of Examples 1-6 can form the cured film which is excellent in the flame retardance, the adhesiveness with a base material, the tolerance in PCT, etc. compared with the ink of Comparative Examples 1-7.

  As described above, the cured film obtained from the ink of the present invention is excellent in properties such as flame retardancy, adhesion to a base material, and resistance to PCT, and thus is used favorably as a material for an electronic circuit board. be able to.

Claims (11)

The photocurable inkjet ink containing phosphorus containing (meth) acrylate (A) represented by following formula (1), and an epoxy resin (B).

(In the formula (1), R ¹ , R ² and R ³ are each independently alkylene having 1 to 20 carbon atoms, and a, b and c are each independently a + b + c ≧ 1 in the range of 0 to 10). D, e and f are each independently an integer of 1 to 10, R ⁴ is a group represented by the following formula (2), R ⁵ is a monovalent organic group, R ⁶ is hydrogen or alkyl having 1 to 6 carbon atoms.)

(In Formula (2), R ⁷ is hydrogen or alkyl having 1 to 6 carbon atoms, R ⁸ and R ⁹ are each independently a monovalent organic group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ may bond to each other to form a divalent cyclic group.) The photocurable inkjet ink according to claim 1, wherein R ⁴ in the formula (1) is a group represented by the following formula (3).

(In the formula (3), R ¹⁰ is hydrogen or alkyl having 1 to 6 carbon atoms.) The photocurable inkjet ink according to claim 1 or 2, wherein R ⁵ in the formula (1) is a group represented by the formula (2) or a group represented by the following formula (4).

(In the formula (4), R ⁶ is hydrogen or alkyl having 1 to 6 carbon atoms.) The light according to any one of claims 1 to 3, wherein the epoxy resin (B) has a group represented by the following formula (B-1), formula (B-2), or formula (B-3). Curable inkjet ink.

  Epoxy resin (B) is phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl aralkyl novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, bisphenol S type epoxy resin , At least one resin selected from the group consisting of a tetraphenylolethane type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a naphthalene skeleton type epoxy resin, and a dicyclopentadiene skeleton type epoxy resin. The photocurable inkjet ink of any one of 1-4.   Furthermore, the photocurable inkjet ink of any one of Claims 1-5 containing an epoxy resin hardening | curing agent (C).   Furthermore, the photocurable inkjet ink of any one of Claims 1-6 containing the compound (D) which has radically polymerizable double bonds other than phosphorus containing (meth) acrylate (A).   Furthermore, the photocurable inkjet ink of any one of Claims 1-7 containing a photoinitiator (E).   The cured film formed from the photocurable inkjet ink of any one of Claims 1-8.   An electronic circuit board comprising the cured film according to claim 9.   An electronic component comprising the electronic circuit board according to claim 10.