JP5549555B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition suitably used for producing an electronic circuit board such as a printed wiring board or a flexible wiring board. More specifically, the present invention relates to a curable composition for ink jet that is suitable for a coverlay for protecting a metal wiring surface having a predetermined circuit pattern.

  For some time, when manufacturing electronic circuit boards such as printed wiring boards, flexible wiring boards, and semiconductor package boards, bismaleimide resin has been used as a protective film to protect conductive surfaces such as metal wiring that form a predetermined circuit pattern. I came.

  However, since these bismaleimide resins are hard and brittle, they have low adhesion to a flexible substrate and are not suitable for flexible substrate applications.

JP 2009-263624 A JP2009-161605 JP 2001-247640 A JP 09-3044 JP 03-70729 JP 03-70716 JP 63-48334

  It is providing the curable composition which can form the cured film which has favorable adhesiveness with respect to a polyimide film or a copper substrate, and is further excellent in a softness | flexibility under said condition.

The inventors of the present invention have a curable composition containing both the compound (A) represented by the formula (1) and the compound (B) represented by the formula (2), particularly for adhesion to a polyimide film or a copper substrate. The present inventors have found that a cured film having good properties and excellent flexibility can be formed, and the present invention has been completed based on this finding. The present invention includes the following items.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は互いに独立して炭素数１〜１００の有機基であり、式（２）中、Ｒ^４、Ｒ^６は互いに独立して水素又はメチルであり、Ｒ^５は炭素数１〜１００の有機基である。） [1] A curable composition containing the compound (A) represented by the formula (1) and the compound (B) represented by the formula (2).

(In the formula (1), R ¹ , R ² and R ³ are each independently an organic group having 1 to 100 carbon atoms. In the formula (2), R ⁴ and R ⁶ are each independently hydrogen or methyl. And R ⁵ is an organic group having 1 to 100 carbon atoms.)

（式（３）中、Ｒ^７は炭素数１〜１００の有機基である。） [2] The curable composition according to item [1], wherein R ¹ and R ^{3 in} formula (1) are each independently a structure represented by formula (3).

(In Formula (3), R ⁷ is an organic group having 1 to 100 carbon atoms.)

[3] The curable composition according to item [2], wherein R ^{7 in} formula (3) is at least one selected from the following formulas (R7-1) to (R7-7).

（式（４）中、Ｒ^８及びＲ^９は互いに独立して炭素数２〜１８のアルキレンであり、ｎは０〜２０の整数である。） [4] The curable composition according to any one of Items [1] to [3], wherein R ^{2 in} Formula (1) is a structure represented by Formula (4).

(In formula (4), R ⁸ and R ⁹ are each independently alkylene having 2 to 18 carbon atoms, and n is an integer of 0 to 20)

[5] The curable composition according to item [4], wherein R ⁸ and R ^{9 in} formula (4) are both ethylene, propylene or butylene, and n is an integer of 1 to 5.

（式中、ｎは１〜１０の整数である。） [6] The curable composition according to item [1], wherein the compound (A) represented by the formula (1) is at least one selected from the following formulas (a-1) to (a-12): object

(In the formula, n is an integer of 1 to 10.)

（式中、ｎは２〜５の整数である。） [7] The curable composition according to item [1], wherein the compound (A) represented by the formula (1) is at least one selected from the following formula (a-1) or (a-2): object

(In the formula, n is an integer of 2 to 5.)

（式中、ｎは２〜５の整数である。） [8] The curable composition according to item [1], wherein the compound (A) represented by the formula (1) is a compound of the following formula (a-1).

(In the formula, n is an integer of 2 to 5.)

（式（５）中、Ｒ^１０及びＲ^１１は互いに独立して、連続しない任意のメチレンが酸素で置き換えられてもよい炭素数１〜１８のアルキレン、芳香環を有する２価の基、又は置換基を有してよいシクロアルキレンであり、Ｘは下記式から選択される少なくとも１つである。）

[9] The curable composition according to items [1] to [8], wherein R ^{5 in} formula (2) is a structure represented by formula (5).

(In the formula (5), R ¹⁰ and R ¹¹ are independently of each other, an alkylene having 1 to 18 carbon atoms in which arbitrary methylene which is not continuous may be replaced with oxygen, a divalent group having an aromatic ring, or a substitution. A cycloalkylene which may have a group, and X is at least one selected from the following formula:

[10] The curable composition according to item [9], wherein R ¹⁰ and R ^{11 in} formula (5) are each independently a structure represented by the following formula.

[11] The curable composition according to any one of items [1] to [10], wherein R ⁴ and R ^{6 in} formula (2) are both methyl.

[12] The curable composition according to any one of Items [1] to [11], further comprising a thermosetting compound (C).

（式中、ｎは１〜５０の整数である） [13] The thermosetting compound (C) is N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and at least one compound selected from the group consisting of compounds represented by the following formulas (c-1) to (c-3) The curable composition according to Item [12].

(In the formula, n is an integer of 1 to 50)

[14] The curable composition according to any one of Items [1] to [13], further comprising a radical polymerizable compound (D) and a photopolymerization initiator (E).

[15] The curable composition according to any one of items [1] to [14], further comprising a flame retardant (F).

（式中、ｍは１又は２、ｎは１又は２であり、ｍ＋ｎは３である。） [16] The curable composition according to item [15], wherein the flame retardant (F) is a compound of the following formula (f-1):

(In the formula, m is 1 or 2, n is 1 or 2, and m + n is 3.)

[17] An electronic circuit board having a cured film formed on the substrate using the curable composition according to any one of items [1] to [16].

According to the curable composition which concerns on the preferable aspect of this invention, the adhesiveness with respect to a polyimide film or a copper substrate is favorable, Furthermore, the curable composition which can form the cured film which is excellent in a softness | flexibility can be provided. .
Furthermore, by using the curable composition according to a preferred embodiment of the present invention as an ink-jet ink, the amount of capital investment can be reduced and material loss can be reduced.

1. Curable composition of this invention The curable composition of this invention contains the compound (A) represented by Formula (1), and the compound (B) represented by Formula (2) together. It is.
Moreover, the curable composition of this invention can also contain an epoxy resin (C), a radically polymerizable compound (D), a photoinitiator (E), a flame retardant (F), and also as needed. Surfactants, colorants, polymerization inhibitors or solvents.
The curable composition of the present invention may be colorless or colored.

（式中、ｎは１〜１０の整数である。）
特に、柔軟性と密着性のバランスから、下記式の化合物がより好ましい。

（式中、ｎは２〜５の整数である。）
さらに、硬化性組成物の他成分との相溶性が優れるため、下記式の化合物がより一層好ましい。

（式中、ｎは２〜５の整数である。）
なお、式（１）のＲ^２の好ましい構造は式（４）であり、より好ましい構造は式（４）（−（−Ｒ^８−Ｏ−）ｎ−Ｒ^９−）においてＲ^８及びＲ^９が同一構造をとる場合であるので、例えばＲ^８及びＲ^９が共にエチレンである場合には、−Ｒ^２−Ｏ−の構造を−（−ＣＨ_２ＣＨ_２−Ｏ−）ｎ−のように書くことがある。 1.1 Compound (A ) represented by Formula (1 )
The curable composition of this invention contains the compound (A) represented by Formula (1).
The compound (A) represented by the formula (1) in the present invention is a compound obtained by, for example, reacting an organic carboxylic acid compound, an acid chloride or an acid anhydride with a compound having both an amino group and a hydroxyl group. When the curable composition contains the compound (A), the cured film obtained from the present cured composition has high flexibility and high adhesion to the copper substrate.
In particular, it is preferable that R ¹ and R ³ have a carboxy structure because adhesion to a copper substrate is further increased. The compound (A) having carboxy can be obtained by reacting an acid anhydride with a compound having both an amino group and a hydroxyl group.
As the acid anhydride, succinic acid anhydride, maleic acid anhydride, citraconic acid anhydride, phthalic acid anhydride, cyclohexene dicarboxylic acid anhydride, and trimellitic acid anhydride are preferable. Among these, maleic anhydride is more preferable because the cured film obtained has high flexibility, and trimellitic anhydride is more adhesive to the copper substrate of the obtained cured film.
A compound having both an amino group and a hydroxyl group preferably has an alkylene chain or an alkylene glycol chain because the resulting cured film has high flexibility. As the alkylene glycol chain, an ethylene glycol chain, a propylene glycol chain, and a butylene glycol chain are preferable in terms of a balance between flexibility and adhesion.
Preferable examples of the compound (A) include the following structures.

(In the formula, n is an integer of 1 to 10.)
In particular, a compound of the following formula is more preferable from the balance of flexibility and adhesion.

(In the formula, n is an integer of 2 to 5.)
Furthermore, since the compatibility with the other component of a curable composition is excellent, the compound of a following formula is still more preferable.

(In the formula, n is an integer of 2 to 5.)
A preferable structure of the ^{R 2} of formula (1) is a formula (4), more preferable structure of the formula ^{(4) (- (- R} 8 -O-) n-R 9 -) in ^{R 8} and ^{R 9} For example, when R ⁸ and R ⁹ are both ethylene, the structure of —R ² —O— is represented as — (— CH ₂ CH ₂ —O—) n—. I have to write.

  The compound (A) represented by the formula (1) is preferably 10 to 70% by weight of the total amount of the curable composition excluding the solvent because the resulting cured film has high flexibility. More preferably, it is 15-60 weight% from the balance with adhesiveness, More preferably, it is 20-50 weight%.

（式（５）中、Ｒ^１０及びＲ^１１は互いに独立して、連続しない任意のメチレンが酸素で置き換えられてもよい炭素数１〜１８のアルキレン、芳香環を有する２価の基、又は置換基を有してよいシクロアルキレンであり、Ｘは下記式から選択される少なくとも１つである。）

Ｒ^１０及びＲ^１１は、互いに独立して、芳香環を有する炭素数６〜５０の２価の基であることが好ましく、さらに、Ｒ^１０及びＲ^１１が下記式で表される構造であると、得られる硬化膜の耐熱性が高いのでより好ましい。

また、式（２）においてＲ^４及びＲ^６がともにメチルであると、硬化性組成物の他成分との相溶性が優れるためより一層好ましい。 1.2 Compound (B) represented by Formula (2)
The curable composition of this invention contains the compound (B) represented by Formula (2).
The compound (B) represented by Formula (2) in this invention is a compound obtained by making a diamine and an acid anhydride react, for example. When the curable composition contains the compound (B), the cured film obtained from the cured composition has high adhesion to the polyimide film and high heat resistance. In particular, in the formula (2), it is preferable that R ⁵ has a structure represented by the formula (5) because the flexibility of the obtained cured film is increased.

(In the formula (5), R ¹⁰ and R ¹¹ are independently of each other, an alkylene having 1 to 18 carbon atoms in which arbitrary methylene which is not continuous may be replaced with oxygen, a divalent group having an aromatic ring, or a substitution. A cycloalkylene which may have a group, and X is at least one selected from the following formula:

R ¹⁰ and R ¹¹ are preferably each independently a bivalent group having 6 to 50 carbon atoms having an aromatic ring, and R ¹⁰ and R ¹¹ have a structure represented by the following formula: Since the resulting cured film has high heat resistance, it is more preferable.

In the formula (2), it is more preferable that R ⁴ and R ⁶ are both methyl because the compatibility with the other components of the curable composition is excellent.

  The compound (B) represented by the formula (2) is preferably 10 to 70% by weight of the total amount of the curable composition excluding the solvent, because the obtained cured film has high adhesion to the polyimide film. From the balance with flexibility and heat resistance, it is more preferably 15 to 60% by weight, still more preferably 20 to 50% by weight.

1.3 Thermosetting compound (C)
The curable composition of this invention may have a thermosetting compound (C).
In the present invention, the thermosetting compound (C) is not particularly limited as long as it is a compound having a functional group that can be thermally cured, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, and an epoxy curing agent. .
The thermosetting compound (C) is preferably 3 to 70% by weight of the total amount of the curable composition excluding the solvent because the resulting cured film has high chemical resistance. More preferably, it is 5 to 50 weight% from the balance with a softness | flexibility and heat resistance, More preferably, it is 10 to 40 weight%.

1.3.1 Epoxy resin Specific examples of the epoxy resin include, for example, phenol novolak type, cresol novolak type, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, bisphenol S type, tris Phenolmethane type, tetraphenolethane type, bixylenol type or biphenol type epoxy compound, alicyclic or heterocyclic epoxy compound, epoxy compound having dicyclopentadiene type or naphthalene type structure, etc. Preferable phenol novolak type, cresol novolak type, bisphenol A type, bisphenol F type epoxy compound, and more preferable among them are bisphenol A type and bisphenol F type epoxy compound because of excellent chemical resistance of the cured film. Yes.

As commercially available products of epoxy resins, jER828, 834, 1001, 1004 (trade name; Mitsubishi Chemical Corporation), Epicron 840, 850, 1050, 2055, (trade name; DIC Corporation), Epototo YD-011, YD-013, YD-127, YD-128 (trade name; Toto Kasei Co., Ltd.), D.E.R. 317, 331, 661, 664 (trade name; Dow Chemical Co., Ltd.), Araldite 6071, 6084, GY250, GY260 (trade name; Huntsman Japan Co., Ltd.), Sumie Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (Product name: Sumitomo Chemical Co., Ltd.), A.E.R. 330, 331, 661, 664 (Product name: Asahi Kasei Co., Ltd.), etc. 152, 154 (trade name; Mitsubishi Chemical Corporation), D.E.R. 431, 438 (trade name; Dow Chemical Co., Ltd.), Epicron N-730, N-770, N-865 (Trade name; DIC Corporation), Epototo YDCN-701, YDCN-704 (trade name; Toto Kasei Co., Ltd.), Araldite ECN1235, ECN1273, ECN1299 (trade name; Huntsman Japan Co., Ltd.), XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 (trade name; Nippon Kayaku Co., Ltd.), Sumie Epoxy ESCN-195X, ESCN-220 (trade name; Sumitomo Chemical ( Novolak epoxy compounds such as A.E.R.ECN-235 and ECN-299 (trade name; ADEKA); Cron 830 (trade name; DIC Corporation), JER807 (trade name; Mitsubishi Chemical Corporation), Epototo YDF-170 (trade name; Toto Kasei Co., Ltd.), YDF-175, YDF-2001, YDF-2004 Bisphenol F type epoxy compounds such as Araldite XPY306 (trade name; Huntsman Japan Co., Ltd.); Hydrogenation of Epototo ST-2004, ST-2007, ST-3000 (trade name; Toto Kasei Co., Ltd.) Bisphenol A type epoxy compound; alicyclic epoxy compound such as Celoxide 2021 (trade name; Daicel Chemical Industries, Ltd.), Araldite CY175, CY179 (trade name; Huntsman Japan Co., Ltd.); YL-933 (trade name) ; Mitsubishi Chemical Corporation), EPPN-501, EPPN-502 (trade names; Dow Chemical Corporation) )) And other trihydroxyphenylmethane type epoxy compounds; YL-6056, YX-4000, YL-6121 (trade name; Mitsubishi Chemical Corporation) and other bixylenol type or biphenol type epoxy compounds or mixtures thereof; EBPS- 200 (trade name; Nippon Kayaku Co., Ltd.), EPX-30 (trade name; ADEKA Corp.)), EXA-1514 (trade name; DIC Corp.), etc .; bisphenol S type epoxy compounds; JER157S (product) Name: Bisphenol A novolak type epoxy compound such as Mitsubishi Chemical Corporation; tetraphenylolethane such as YL-931 (trade name; Mitsubishi Chemical Corporation), Araldite 163 (trade name; Huntsman Japan Co., Ltd.) Type epoxy compound; Araldite PT810 (trade name; Huntsman Japan Ltd.), TEP Heterocyclic epoxy compounds such as C (trade name; Nissan Chemical Industries, Ltd.); Naphthalene-containing epoxy compounds such as HP-4032, EXA-4750, EXA-4700 (trade name; DIC Corporation); HP-7200 And epoxy compounds having a dicyclopentadiene skeleton, such as HP-7200H and HP-7200HH (trade name; DIC Corporation).
The epoxy compound used in the curable composition of the present invention may be a single compound or a mixture of two or more compounds.

  In addition to the aforementioned epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidyl) from the viewpoint of adhesion of the cured film to the substrate Glycidylamines such as (aminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane can be used.

1.3.2 Phenol resin As the phenol resin, a novolak resin obtained by a condensation reaction between an aromatic compound having a phenolic hydroxyl group and an aldehyde, a homopolymer of vinyl phenol (including a hydrogenated product), or vinyl phenol And a vinylphenol copolymer (including a hydrogenated product) of these and a compound copolymerizable therewith is preferably used.

Specific examples of the aromatic compound having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and m-butylphenol. P-butylphenol, o-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-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, or β-naphthol For example.
Similarly, examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

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

Specific examples of the phenol resin include Resitop PSM-6200 (trade name; Gunei Chemical Industry Co., Ltd.), Shonor BRG-555 (trade name; Showa Denko Co., Ltd.), Marcalinker MS-2P, Marcalinker CST70. Or Marcalinker PHM-C (trade name; Maruzen Petrochemical Co., Ltd.).
The phenol resin used in the curable composition of the present invention may be a single compound or a mixture of two or more compounds.

1.3.3 Melamine Resin Melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, but methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, Among them, etherified methylol melamine is preferable because of its good chemical resistance.

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

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

（式中、ｎは１〜５０の整数である） Most preferred as the thermosetting compound (C) is N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (1, from the viewpoint of adhesion of the cured film to the substrate. N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, and from the viewpoint of chemical resistance of the cured film, the following formula (c-1 ) To (c-3).

(In the formula, n is an integer of 1 to 50)

1.3.4 Epoxy Curing Agent When the curable composition of the present invention contains an epoxy resin, an epoxy curing agent may be further contained in order to further improve chemical resistance. As the epoxy curing agent, an acid anhydride curing agent, a polyamine curing agent, a catalytic curing agent, and the like are preferable.

  Specific examples of acid anhydride curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride , Trimellitic anhydride, or styrene-maleic anhydride copolymer.

Specific 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, or diaminodiphenylsulfone. Specific examples of the catalyst type curing agent include a tertiary amine compound or an imidazole compound.
The epoxy curing agent used in the photocurable inkjet ink composition may be a single compound or a mixture of two or more compounds.

1.4 Radical polymerizable compound (D)
The curable composition of the present invention may contain a radical polymerizable compound (D).
In the present invention, the radical polymerizable compound (D) is not particularly limited as long as it is a compound having at least one of (meth) acryloyl, allyl, and vinyl, and (meth) acryloyl from the viewpoint of photopolymerization. Particularly preferred are compounds having
The content of the radically polymerizable compound (D) is preferably 5 to 70% by weight of the total amount of the curable composition excluding the solvent because it can be adjusted to a viscosity suitable for the intended use, and the balance with other characteristics is preferable. In consideration, it is more preferably 7 to 65% by weight, and further preferably 10 to 60% by weight.

（式中、Ｒ^１、及びＲ^３はそれぞれ独立に炭素数が６〜１０のアルキレンであり、Ｒ²はヘキサメチレン、２，２，４−トリメチルヘキサメチレン、イソホロン、水添キシリレン、４，４−シクロヘキシルメタン、キシリレン、テトラメチルキシリレン、トルイレン、ジフェニルメタンであり、Ｒ^４、及びＲ^５はそれぞれ独立に水素又は炭素数が１〜６のアルキルであり、ｍ、及びｎはそれぞれ独立に１〜１０の整数である。） Specifically, isocyanuric acid ethylene oxide-modified di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate , Dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate , (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, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate , Phenyl (meth) acrylate, glycerol mono (meth) acrylate bisphenol F type ethylene oxide modified diacrylate, bisphenol A type ethylene oxide modified diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-cyclohexanedimethanol Acrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) ) Acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol Examples include hexa (meth) acrylate, ethylene oxide-modified tri (meth) acrylate phosphate, and urethane (meth) acrylate having the following structure.

(In the formula, R ¹ and R ³ are each independently alkylene having 6 to 10 carbon atoms, and R ² is hexamethylene, 2,2,4-trimethylhexamethylene, isophorone, hydrogenated xylylene, 4,4. -Cyclohexylmethane, xylylene, tetramethylxylylene, toluylene, diphenylmethane, R ⁴ and R ⁵ are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and m and n are each independently 1 to 1 (It is an integer of 10.)

  The compound having (meth) acryloyl may be a single compound or a mixture of two or more compounds.

1.5 Photopolymerization initiator (E)
The curable composition of the present invention may contain a photopolymerization initiator (E) in order to impart photocurability thereto. The photopolymerization initiator (E) is not particularly limited as long as it is a compound capable of generating radicals upon irradiation with ultraviolet rays or visible light, but is preferably an alkylphenone-based, acylphosphine oxide-based, titanocene-based photopolymerized compound, Of these, acylphosphine oxide photopolymerization initiators are particularly preferred from the viewpoint of photocurability.

  The content of the photopolymerization initiator is preferably 0.5 to 20% by weight of the total amount of the curable composition excluding the solvent because it becomes highly sensitive to the amount of light irradiation, and more preferably 1 to 15%. % By weight, more preferably 2 to 10% by weight.

Specific examples of the photopolymerization initiator (E) 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-benzi 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, 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-butylpe) Ruoxycarbonyl) 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-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-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'-bi (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-pyrrol-1-yl) -phenyl) titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide be able to.

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

1.6 Flame retardant (F)
The curable composition of the present invention may contain a flame retardant (F).
In the present invention, the flame retardant (F) is not particularly limited as long as it is a compound capable of imparting flame retardancy, but an organic phosphorus flame retardant is preferably used from the viewpoint of low toxicity, low pollution, and safety.

  The content of the flame retardant (F) is preferably 10 to 35% by weight of the total amount of the curable composition excluding the solvent, because it has a good balance with other properties and is excellent in flame retardancy, and more preferably 15 to 30% by weight, more preferably 20-25% by weight.

  Specific examples of the organic phosphorus flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphate. Phaphenanthrene-10 oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10 oxide and the like.

（式中、ｍは０〜２の整数であり、ｎは１〜３の整数であり、ｍ＋ｎは３である。） Among these flame retardants, in particular, HFA-3003 having a condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide structure, which is a compound represented by the following formula (trade name; Showa Polymer) (Co., Ltd.) is preferable because there is no bleed out of the flame retardant even when the cured film obtained from the curable composition is exposed to a high temperature state.

(In the formula, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 3.)

  The flame retardant (F) may be one kind of compound selected from the above-described compounds or the like, or may be a mixture of two or more kinds thereof.

  The flame retardant (F) described above can be produced by a known method, and is also commercially available, such as HFA-3003 made by Showa Polymer Co., Ltd.

1.7 Other components The curable composition of the present invention may contain a colorant, a solvent, a surfactant, a polymerization inhibitor and the like in order to further improve various properties.

1.7.1 Colorant The curable composition of the present invention may contain a colorant , for example, to facilitate discrimination from the substrate when examining the state of the cured film. As the colorant, dyes and pigments are preferable. The colorant used may be a single compound or a mixture of two or more compounds.
When the content of the colorant is 0.01 to 10% by weight of the total amount of the curable composition, it is preferable because the inspection of the cured film is easy, and when considering the balance with other characteristics, more preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight.

1.7.2 Solvent The curable composition of the present invention may contain a solvent in order to improve the film surface uniformity of the obtained cured film. In addition, when the curable composition of the present invention is used as an inkjet ink, if the ink contains a low boiling point solvent, the solvent volatilizes and the viscosity of the ink increases and the nozzle head of the inkjet head is clogged. Sometimes. Therefore, a solvent having a boiling point of 100 to 300 ° C. is particularly preferable.

Specific examples of the solvent having a boiling point of 100 to 300 ° C. include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, and butyl methoxyacetate. , Methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl toxipropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, 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, tri Propylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monome Ether ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl 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, acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tolu Ene, xylene, anisole, γ-butyrolactone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, or dimethylimidazolidinone.
These solvents may be a single compound or a mixture of two or more different compounds.

  When the content of the solvent is 0 to 75% by weight of the total amount of the curable composition, the ink jet ink has a good balance between the ejection property and other characteristics, more preferably 0 to 70% by weight, and still more preferably. Is 0 to 65% by weight.

1.7.3 Surfactant The curable composition of the present invention may contain a surfactant in order to improve wettability to a base substrate and film surface uniformity of the obtained cured film, for example. As the surfactant, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used.
Specific examples of the surfactant include silicon surfactants such as Byk-300, 306, 335, 310, 341, 344, and 370 (trade name: Big Chemie Japan Co., Ltd.), Acrylic surfactants such as Byk-354, 358, and 361 (trade name; Big Chemie Japan Co., Ltd.), DFX-18, Footage 250, or 251 (trade name; Neos Co., Ltd.), Fluorosurfactants such as Megafac F-479 (trade name; DIC Corporation) can be used.

  The surfactant used in the curable composition of the present invention may be a single compound or a mixture of two or more compounds.

  When the content of the surfactant is 0.001 to 1% by weight of the total amount of the curable composition, the film surface uniformity of the cured film is preferably improved, and more preferably 0 in view of the balance with other characteristics. 0.005 to 0.1% by weight, more preferably 0.01 to 0.05% by weight.

1.7.4 Polymerization inhibitor The curable composition of the present invention may contain, for example, a polymerization inhibitor in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, or phenothiazine. Among these, phenothiazine is preferable because the change in viscosity is small even during long-term storage.
The polymerization inhibitor used in the curable composition of the present invention may be a single compound or a mixture of two or more compounds.

  The content of the polymerization inhibitor is preferably 0.01 to 1% by weight of the total amount of the curable composition because the change in viscosity is small even during long-term storage, and more preferably in consideration of the balance with other properties. 0.05 to 0.5% by weight.

2. Preparation method of curable composition The curable composition of this invention can be prepared by mixing each component used as a raw material by a well-known method. In particular, the ink of the present invention is prepared by mixing the components (A) to (B) and, if necessary, the components (C) to (E) and other components, and filtering the resulting solution. It is preferred that For the filtration, for example, a fluororesin membrane filter is used.

3. Viscosity of curable composition The curable composition of the present invention is preferably adjusted to a viscosity range suitable for a desired coating method. The viscosity can be adjusted by optimizing the amount of solvent or (meth) acrylic monomer. When the curable composition of the present invention is used as an inkjet ink, the viscosity measured with an E-type viscometer at a discharge temperature (preferably 10 to 120 ° C.) is preferably 1 to 30 mPa · s, and 2 to 25 mPa · s. It is more preferable if it is 3 to 20 mPa · s.
When a curable composition having a viscosity at 25 ° C. of 30 mPa · s or more is used as an inkjet ink, more stable ejection can be achieved by heating the inkjet head to lower the viscosity during ejection.
When the inkjet head is heated, it is preferable to use an ink that does not contain a solvent, because the viscosity of the ink may increase due to volatilization of the solvent. In that case, the viscosity of the ink is preferably adjusted by appropriately selecting the type and content of the (meth) acrylic monomer.

4). Storage of curable composition When the curable composition of the present invention is stored at -20 to 20 ° C, the viscosity change during storage is small and the storage stability is good.

5). Application of curable composition by inkjet method The curable composition of the present invention can be applied using a known inkjet application method. As an inkjet coating method, for example, a method in which mechanical energy is applied to ink to eject (apply) the ink from an inkjet head (so-called piezo method), and a coating method in which thermal energy is applied to the ink to apply ink (application method) So-called bubble jet (registered trademark) system.
By using the inkjet coating method, the curable composition can be applied in a predetermined pattern. As a result, ink can be applied only to necessary portions, and the cost can be reduced as compared with the photolithography method.

  As a preferable coating apparatus for performing coating using the curable composition of the present invention, for example, energy corresponding to a coating signal is given to ink in an ink jet head chamber having an ink storage section in which ink is stored, An apparatus that performs application (drawing) corresponding to the application signal while generating ink droplets by the energy is mentioned. Examples of the inkjet head include those having a heat generating part liquid contact surface containing a metal and / or a 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. 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 integrated so as not to be separated. The ink container is integrated with the ink jet head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the apparatus so that the ink is supplied to the ink jet head through an ink supply member, for example, a tube. It may be in the form of supplying.

6). Formation of Cured Film The cured film of the present invention is formed by applying the curable composition of the present invention to the substrate surface by a known method such as an ink jet method, and then irradiating the ink with light such as ultraviolet light or visible light. Obtained by heating to cure the coating.

In the case of irradiating with ultraviolet rays, visible rays, etc., the exposure dose is 10 to 10,000 mJ / cm ^{2 as} measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC. The degree is preferable, about 20 to 5,000 mJ / cm ² is more preferable, and about 40 to 1,000 mJ / cm ² is more preferable. Moreover, 250-500 nm is preferable and, as for wavelengths, such as an ultraviolet-ray and visible light to irradiate, 300-450 nm is more preferable.
The exposure machine is not particularly limited as long as it is an apparatus that radiates ultraviolet light, visible light, or the like in the range of 250 to 500 nm, such as a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, or a halogen lamp.

In the case of curing by heating, the heating device may be any of a hot plate, oven, far-infrared oven, etc., and the heating temperature and time are preferably 100 to 350 ° C. for 10 minutes to 6 hours, and 150 to 300 ° C. for 30 minutes to 2 hours is more preferable.
The cured film cured by light irradiation may be further heated, in which case it is preferably heated at 100 to 250 ° C. for 10 minutes to 3 hours, and heated at 150 to 230 ° C. for 30 minutes to 2 hours. It is more preferable. By heating after irradiation with ultraviolet rays, the cured film can be cured more firmly.

7). The “substrate” to which the curable composition of the present invention is applied is not particularly limited as long as it can be applied to the curable composition of the present invention. It may be a shape.

  The material of the substrate 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, fluorine resin, acrylic resin, polyamide , Plastic film such as polycarbonate and polyimide, cellophane, acetate, metal foil, laminated film of polyimide and metal foil, glassine paper, parchment paper, and polyethylene, clay binder, polyvinyl alcohol, starch or carboxymethylcellulose Examples thereof include paper and glass treated with (CMC) and the like.

  The substances constituting these substrates may be further added to pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents and / or electromagnetic waves, as long as the effects of the present invention are not adversely affected. You may contain additives, such as an inhibitor. Further, a part of the surface of the substrate may be formed with a material different from that of the substrate (coverlay or solder resist film).

  Although the thickness of a board | substrate is not specifically limited, Usually, it is about 10 micrometers-2 mm, and is suitably adjusted with the objective to use.

  If necessary, the surface on which the cured film of the substrate is formed may be subjected to easy adhesion treatment such as water repellent treatment, corona treatment, plasma treatment, or blast treatment, or an easy adhesion layer or color filter protective film may be provided on the surface. May be.

The use of the substrate is not particularly limited, but the cured film obtained from the curable composition of the present invention is excellent in chemical resistance and heat resistance, and therefore, manufacture of an electronic circuit substrate or the like having a metal circuit on the substrate surface. It is preferable to be used for.
The metal forming the electronic circuit is not particularly limited, but gold, silver, copper, aluminum, or ITO is preferable. A cured film obtained by applying the curable composition of the present invention to a substrate on which wirings made of these metals are formed in a predetermined pattern with an inkjet apparatus and curing the substrate functions as a coverlay film for the wirings. .

The thickness of the cured film of the present invention that functions as such a coverlay film is not particularly limited, but is usually 5 to 50 μm.
By mounting an IC chip, a capacitor, a resistor, a fuse or the like on the electronic circuit board manufactured using the cured film of the present invention as described above, for example, an electronic component for a liquid crystal display element can be manufactured. it can.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these. In addition, the symbol used in an Example is represented below.
NMP: N-methyl-2-pyrrolidone EDM: diethylene glycol methyl ethyl ether AEE: 2- (2-aminoethoxy) ethanol TMA: trimellitic anhydride MAA: maleic anhydride BM1: bis- (3-ethyl-5 Methyl-4-maleimidophenyl) methane BM2: 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane VGL: TECHMORE VG3101L (epoxy resin manufactured by Mitsui Chemicals, Inc.)
ARM: Aronix M-327 (acrylic monomer manufactured by Toa Gosei Co., Ltd.)
TPO: DAROCUR (trade name) TPO which is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (a photopolymerization initiator manufactured by BASF Japan Ltd.)
<Synthesis Example of Compound (A) Represented by Formula (1)>

[Synthesis Example 1]
In a 200 ml four-necked flask, 59.3 g of NMP, 10.5 g of AEE, and 9.8 g of MAA were added and stirred at 30 ° C. for 1 hour. Thereafter, 19.2 g of TMA was added, and the mixture was stirred at 110 ° C. for 2 hours and then cooled, and the compound of formula (1) (R ¹ was the formula (3), R ⁷ was the formula (R7-2), R ³ In Formula (3), R ⁷ is Formula (R7-7), R ² is Formula (4), R ⁸ is — (CH ₂ CH ₂ ) —, n = 1, and R ⁹ is — _(CH 2 _CH 2) -) is (A1) to obtain a 40 wt% NMP solution.

[Synthesis Example 2]
In a 200 ml four-necked flask, 59.3 g of NMP, 10.5 g of AEE, and 19.2 g of TMA were added and stirred at 30 ° C. for 1 hour. Thereafter, 9.8 g of MAA was added, and the mixture was stirred at 110 ° C. for 2 hours and then cooled. The compound of the formula (1) (R ¹ was the formula (3), R ⁷ was the formula (R7-7), R ³ is the formula (3), R ⁷ is the formula (R7-2), R ² is the formula (4), R ⁸ is — (CH ₂ CH ₂ ) —, n = 1, and R ⁹ is _{- (CH 2 CH 2) -} ) is (A2) was obtained in 40 wt% NMP solution.

<Synthesis Example of Compound (B) Represented by Formula (2)>
A 100 ml four-necked flask was charged with 22.4 g of citraconic anhydride and 41.05 g of diamine BAPP (trade name; Wakayama Seika Kogyo Co., Ltd.), dissolved at 140 ° C., and further generated at 160 ° C. for 2 hours. The reaction is conducted while removing water vapor, and the compound of formula (2) (R ⁴ and R ⁶ are both methyl, R ⁵ is the formula (5), R ¹⁰ is the formula (R10-6), and X is the formula ( 59.9 g of (B1) which is X-2) and R ¹¹ is the formula (R10-6)).

[Example 1]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 1.
(A) 2.5000 g of a 40 wt% NMP solution of (A1)
(B) BM2 1.0000g
Solvent EDM 1.5000g
Other phenothiazine 0.0020g
It was 13.2 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (Toki Sangyo Co., Ltd. TV-22, and the same below).

  The curable composition 1 is injected into an ink jet cartridge, and this is mounted on an ink jet apparatus (DMP-2811 manufactured by FUJIFILM Dimatix), using a head for 10 pl, discharge voltage (piezo voltage) 16 V, head temperature 30 ° C. Width on the copper surface of Viroflex (trade name; Toyobo Co., Ltd.), which is a 35-μm thick copper-clad laminate obtained by laminating a copper foil on polyimide under the discharge conditions of a drive frequency of 5 kHz and a coating frequency of once. A line of 1 mm × 100 mm in length, each having a space between the lines of 1 mm, and a line & space pattern in which 10 lines were drawn was formed. Then, it dried for 10 minutes on an 80 degreeC hotplate, and also baked for 30 minutes in 250 degreeC oven, and obtained the cured film of the line pattern.

[Example 2]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 2.
(A) 40 wt% NMP solution of (A2) 2.5000 g
(B) BM2 1.0000g
Solvent EDM 1.5000g
Other phenothiazine 0.0020g
It was 15.1 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (Toki Sangyo Co., Ltd. TV-22, and the same below).

  The curable composition 2 was poured into an ink jet cartridge, and a cured film having a line pattern was obtained in the same manner as in Example 1.

[Example 3]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 3.
(A) 2.5000 g of a 40 wt% NMP solution of (A1)
(B) (B1) 1.0000 g
Solvent EDM 1.5000g
Other phenothiazine 0.0020g
It was 12.8 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (Toki Sangyo Co., Ltd. TV-22, and the same below).

  The curable composition 3 was injected into an ink jet cartridge, and a cured film having a line pattern was obtained in the same manner as in Example 1.

[Comparative Example 1]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 4.
(B) (B1) 1.0000 g
Solvent EDM 1.5000g
Other phenothiazine 0.0010g
It was 8.8 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (Toki Sangyo Co., Ltd. TV-22, and the same below).

  The curable composition 4 was injected into an ink jet cartridge, and a cured film having a line pattern was obtained in the same manner as in Example 1.

[Comparative Example 2]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 5.
(B) (B1) 1.0000 g
(C) Ethylene glycol diglycidyl ether 1.000 g
Solvent NMP 1.5000g
Solvent EDM 1.5000g
Other phenothiazine 0.0020g
It was 4.3 mPa · s (25 ° C.) when the viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd., TV-22, hereinafter the same).

  The curable composition 5 was poured into an ink jet cartridge, and a cured film having a line pattern was obtained in the same manner as in Example 1.

The copper-clad laminates formed with the cured films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were folded with the copper surface inside, and the bottom area was 4 cm ² and the weight was 500 g on the crease. A weight was placed for 10 seconds. After repeating this 10 times, the fold portion was observed with a 50 × optical microscope.
Next, Sumitomo 3M tape “56 Tape” (adhesion strength 5.5 N / 10 mm) was applied to the surface on which the cured film was formed, and the tape was peeled off after rubbing 10 times using an eraser. . The case where the cured film remained was marked with ◯, and the case where the cured film was peeled was marked with x.
The evaluation results are shown in Table 1.

実施例１〜３は、比較例に較べて柔軟性、密着性に優れている。 Table 1

Examples 1-3 are excellent in a softness | flexibility and adhesiveness compared with a comparative example.

[Example 4]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 6.
(A) 40% NMP solution of (A1) 2.5000 g
(B) BM2 0.5000g
(C) VGL 0.5000g
Solvent EDM 1.5000g
Other phenothiazine 0.0020g
It was 16.3 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (Toki Sangyo Co., Ltd. TV-22, and the same below).

  The curable composition 6 was injected into an ink jet cartridge, and a cured film having a line pattern was obtained in the same manner as in Example 1.

Using the cured films of Example 1 and Example 4, a plating resistance test was performed. The copper-clad laminate on which the cured film was formed was immersed in a 30 ° C. palladium aqueous solution (trade name: KAT-450, Pd concentration: 12 mg / L, Uemura Kogyo Co., Ltd.) for 1 minute and washed with water. After being immersed in an electrolytic nickel plating solution (trade name: Nimden NPR-4, Ni concentration 4.5 g / L, Uemura Kogyo Co., Ltd.) for 30 minutes and washed with water, the surface state of the cured film was observed with a microscope. Subsequently, after immersing in an electroless gold plating solution (trade name: Goblite TAM-55, Au concentration 1 g / L, Uemura Kogyo Co., Ltd.) at 80 ° C. for 10 minutes, the same observation was performed. . The evaluation criteria are as follows.
A: The cured film does not blister or peel off, and no discoloration is observed.
○: Although a slight discoloration is observed in the cured film, there is no blistering or peeling.
(Triangle | delta): Many blisters, peeling, and discoloration are seen by a cured film.
X: The cured film was completely peeled off.
The evaluation results are shown in Table 2.

熱硬化性化合物（Ｃ）の添加により、耐めっき性が向上した。 Table 2

The addition of the thermosetting compound (C) improved the plating resistance.

[Example 5]
The following were mixed and dissolved, and then filtered through a PTFE membrane filter (1 μm) to prepare a curable composition 7.
(A) 2.5000 g of a 40 wt% NMP solution of (A1)
(B) BM2 0.5000g
(D) ARM 0.5000g
(E) TPO 0.2000g
Solvent EDM 1.2000g
Other phenothiazine 0.0020g
It was 19.6 mPa * s (25 degreeC) when the viscosity was measured using the E-type viscosity meter (Toki Sangyo Co., Ltd. TV-22, and the same below).

The curable composition 7 is injected into an ink jet cartridge, and this is mounted on an ink jet apparatus (DMP-2811 of FUJIFILM Dimatix Co., Ltd.), and a 10 pl head is used, and a discharge voltage (piezo voltage) 16 V, a head temperature 35 Ten line patterns having a width of 1 mm and a length of 100 mm were formed at intervals of 1 mm on a Kapton film substrate having a thickness of 100 μm under the discharge conditions of 1 ° C., a driving frequency of 5 kHz, and the number of coating times. The substrate was irradiated with ultraviolet light having a wavelength of 365 nm at a UV exposure amount of 2000 mJ / cm ² and then baked in an oven at 250 ° C. for 30 minutes to obtain a cured film having a line pattern.
Further, the curable composition 1 of Example 1 was injected into an ink jet cartridge, and this was mounted on an ink jet apparatus (DMP-2811 from FUJIFILM Dimatix Co., Ltd.), and a discharge voltage (piezo voltage) was used using a head for 10 pl. 10 line patterns having a width of 1 mm and a length of 100 mm were formed at intervals of 1 mm on a Kapton film substrate having a thickness of 100 μm under discharge conditions of 16 V, a head temperature of 35 ° C., a driving frequency of 5 kHz, and the number of coatings of 1 time. The substrate was dried on an 80 ° C. hot plate for 10 minutes and further baked in an oven at 250 ° C. for 30 minutes to obtain a cured film having a line pattern.
The width of the line pattern was measured using a 50 × optical microscope. The evaluation results are shown in Table 3.

ラジカル重合性化合物（Ｄ）および光重合開始剤（Ｅ）を添加し、紫外線を照射した場合は、描画した時と同じパターンサイズの硬化膜を得ることができた。 Table 3

When the radical polymerizable compound (D) and the photopolymerization initiator (E) were added and irradiated with ultraviolet rays, a cured film having the same pattern size as when drawn could be obtained.

Claims (11)

A curable composition comprising a compound (A) that is at least one selected from the following formulas (a-1) to (a-12) and a compound (B) represented by formula (2): The compound (A) is 10 to 70% by weight of the total amount of the curable composition excluding the solvent, and the compound (B) is 10 to 70% by weight of the total amount of the curable composition excluding the solvent. .

(In the formula, n is an integer of 1 to 10.)

(In formula (2), R ⁴ and R ⁶ are each independently hydrogen or methyl, R ⁵ is a structure represented by formula (5),

In the formula (5), R ¹⁰ and R ¹¹ are independently of each other, an alkylene having 1 to 18 carbon atoms in which arbitrary methylene which is not continuous may be replaced with oxygen, a divalent group having an aromatic ring, or a substituent. And X is at least one selected from the following formulae. )

The curable composition according to claim 1, wherein the compound (A) is at least one selected from the following formula (a-1) or (a-2).

(In the formula, n is an integer of 2 to 5.) The curable composition of Claim 1 whose compound (A) is a compound of a following formula (a-1).

(In the formula, n is an integer of 2 to 5.) The curable composition according to any one of claims 1 to 3, wherein R ¹⁰ and R ¹¹ in the formula (5) are structures independently represented by the following formula.

Equation (2) The curable composition according to any one of claims 1 to 4 R ⁴ and R ⁶ are both methyl in. Furthermore, the curable composition as described in any one of Claims 1-5 containing a thermosetting compound (C). The thermosetting compound (C) is N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and at least one compound selected from the group consisting of compounds represented by the following formulas (c-1) to (c-3), Item 7. The curable composition according to item 6.

(In the formula, n is an integer of 1 to 50) Furthermore, the curable composition as described in any one of Claims 1-7 containing a radically polymerizable compound (D) and a photoinitiator (E).   Furthermore, the curable composition as described in any one of Claims 1-8 containing a flame retardant (F). The curable composition of Claim 9 whose flame retardant (F) is a compound of a following formula (f-1).

(In the formula, m is 1 or 2, n is 1 or 2, and m + n is 3.)   The electronic circuit board by which the cured film was formed on the board | substrate using the curable composition as described in any one of Claims 1-10.