TWI643887B - Resistive ink and cured product thereof, protective film for line and manufacturing method thereof - Google Patents

Abstract

A resist ink which can form a cured product excellent in acid resistance is provided. The resist ink contains a (meth)allyl-containing compound (A) having two or more (meth)allyl groups in one molecule, and a thiol compound having two or more mercapto groups in one molecule (B) And a polymerization initiator (C).

Description

Resistive ink and cured product thereof, protective film for line and manufacturing method thereof

The present invention relates to a resist ink and a cured product thereof, and a protective film for a line and a method of manufacturing the same.

In order to prevent oxidation, a copper wire used for a printed wiring board or the like is treated with a strong acid electroless tin plating solution and subjected to tin plating. Therefore, a resist (a cured product of a resist ink) which is resistant to a strongly acidic electroless tin plating solution is pursued. Although Patent Literatures 1 to 3 disclose a resist ink capable of forming a resist having an acid resistance, the resistance to a strongly acidic electroless tin plating solution cannot be said to be sufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 268067

[Patent Document 2] Japanese Patent Laid-Open Publication No. 24591, 2005

[Patent Document 3] Japanese Patent Gazette No. 3190251

Therefore, the present invention has been made to solve the problems of the above-described conventional techniques and to provide a resist ink capable of forming a cured product excellent in acid resistance. Moreover, the present invention also aims to provide a cured product excellent in acid resistance. Further, the present invention also provides a protective film for providing a line excellent in acid resistance and a method for producing the same.

In order to solve the above problems, one aspect of the present invention is as follows [1] to [14].

[1] A resist ink comprising a (meth)allyl-containing compound (A) having two or more (meth)allyl groups in one molecule and sulfur having two or more mercapto groups in one molecule The alcohol compound (B) and a polymerization initiator (C).

[2] The resist ink according to [1], wherein the (meth)allyl-containing compound (A) contains at least one selected from the group consisting of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. Constructed compound.

[3] The resist ink according to [1] or [2] wherein the (meth)allyl-containing compound (A) comprises at least one of an allyloxycarbonyl group and an N-allyl group. compound of.

[4] The resist ink according to any one of [1], wherein the (meth)allyl-containing compound (A) comprises at least an ester structure and an isocyanurate structure. A compound of one's construction.

[5] The resist ink according to [1], wherein the aforementioned (A) The allyl compound (A) comprises diallyl phthalate, diallyl isophthalate, diallyl terephthalate, 1,4-cyclohexanedicarboxylic acid At least one selected from the group consisting of allyl ester, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, and triallyl isocyanurate.

[6] The resist ink according to any one of [1], wherein the thiol compound (B) contains a compound having two or more secondary or tertiary sulfhydryl groups in one molecule.

[7] The resist ink according to [6], wherein the thiol compound (B) is 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol ruthenium (3-mercaptobutyrate) 1,3,5-glycol(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropane At least one selected from ginseng (3-mercaptobutyrate).

[8] The resist ink according to any one of [1] to [7], which further comprises a (meth)acrylonitrile group-containing compound (D).

[9] The resist ink according to [8], wherein the (meth)acrylonitrile group-containing compound (D) contains a compound having two or more (meth)acrylonium groups in one molecule.

[10] The resist ink according to [9], wherein the (meth)acrylonitrile group-containing compound (D) comprises an epoxy group (meth) acrylate or a (poly) ester (meth) acrylate. At least one selected from the group consisting of an ester, a (poly)carbonate (meth) acrylate, and a hydrogenated polybutadiene (meth) acrylate.

[11] The resistance described in any one of [8]~[10] In the agent ink, the (meth)acrylonitrile group-containing compound (D) contains a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure.

[12] The resist ink according to any one of [8], wherein the (meth)allyl-containing compound (A) has a (meth)allyl number relative to the aforementioned mercaptan. The ratio of the number of fluorenyl groups of the compound (B) (the number of allyl groups / the number of fluorenyl groups) is in the range of 0.25 or more and 4 or less, and the compound (A) containing a (meth)allyl group and the thiol compound (B) and containing When the total content of the methyl (meth) fluorenyl group (D) is 100 parts by mass, the content of the polymerization initiator (C) is 0.01 parts by mass or more and 10 parts by mass or less.

The resist ink according to any one of [8] to [12] wherein the (meth)allyl-containing compound (A) and the thiol compound (B) and the aforementioned ( When the total content of the (meth) fluorenyl group-containing compound (D) is 100 parts by mass, the content of the (meth) acrylonitrile-containing compound (D) is 10 parts by mass or more and 80 parts by mass or less.

[14] The resist ink according to any one of [1] to [13] wherein the polymerization initiator (C) comprises a compound which generates a polymerizable radical species by irradiation with an active energy ray.

[15] A cured product of the resist ink according to any one of [1] to [14].

[16] A protective film for a line containing the cured product described in [15].

[17] A method of manufacturing a protective film for a line, A coating step of distributing the resist ink described in [14] into a film shape on a substrate having a wiring, covering the wiring with the film of the resist ink, and coating the wiring on the film containing the resist ink In some fields or all fields of the field, an active energy ray which causes the polymerization initiator (C) to generate a wavelength of a polymerizable radical species, and a curing step of curing the resist ink to form a protective film of the above-mentioned line.

According to the present invention, it is possible to provide a cured film excellent in acid resistance and a protective film for wiring.

[Best Mode for Carrying Out the Invention]

An embodiment of the present invention will be described below. The resist ink of the present embodiment contains a (meth)allyl-containing compound (A) having two or more (meth)allyl groups in one molecule, and a thiol having two or more mercapto groups in one molecule. Compound (B) and a polymerization initiator (C).

The resist ink of the present embodiment can be easily cured in a short time by irradiation with an active energy ray or heat, and the cured product has excellent acid resistance. Therefore, the resist ink of the present embodiment is preferably used as a protective material for protecting an acidic liquid. For example, since the cured product of the resist ink of the present embodiment is sufficiently resistant to the acidic plating solution, it can be used as a resist (protection of the line) when the copper circuit used for a printed wiring board or the like is plated with an acidic plating solution. membrane). The electroless tin plating solution used for tin plating is particularly strong, but If the cured product of the resist ink of the present embodiment is resistant, it can be used as a resist when tin plating is performed using an electroless tin plating solution.

Further, the cured product of the resist ink of the present embodiment (protective film for the line) is excellent in adhesion to the substrate to be coated, and is excellent in moisture resistance and heat resistance, and further has a high degree of long-term insulation reliability.

Further, since the resist ink of the present embodiment is not required to be dissolved in a solvent, it can be made solvent-free, so that environmental pollution is less likely to occur.

Hereinafter, a resist ink according to an embodiment of the present invention, a cured product obtained by curing the resist ink, and a protective film for a line containing the cured product and a method for producing the same will be described in detail.

Moreover, the "(meth)acryloyl group" in the present specification means an acryloyl group and/or a methacryl fluorenyl group. Further, in the present specification, "(meth)allyl" means methallyl (i.e., 2-methyl-2-propenyl) and/or allyl (i.e., 2-propenyl). Further, "(meth)acrylate" means methacrylate and/or acrylate, and "(meth)acrylic" means methacrylic acid and/or acrylic acid.

[1] (meth)allyl-containing compound having two or more (meth)allyl groups in one molecule (A)

The (meth)allyl-containing compound (A) is a compound having two or more (meth)allyl groups in one molecule, and may be a monomer or an oligomer or a polymer, from the viewpoint of viscosity, A compound having a number average molecular weight of 200 or more and 20,000 or less is preferred. Further, the molecular weight of the oligomer or polymer in the present invention is, without particular limitation, by colloidal permeation chromatography. (GPC method) The number average molecular weight in terms of polystyrene (PS) measured. The detailed measurement conditions of the molecular weight are as follows.

The compound (a) having at least one structure selected from the group consisting of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in the molecule, and a non-cyclic ring, may be mentioned as the compound (A) containing a (meth)allyl group. Compound (a-2) of the formula.

The alicyclic structure may, for example, be an alicyclic ring having 3 to 6 carbon atoms, preferably a cyclohexane ring and a cycloheptane ring. The aromatic ring structure may, for example, be an aromatic ring having 6 to 10 carbon atoms, preferably a benzene ring or a naphthalene ring. The heterocyclic ring structure may, for example, be a three-membered to ten-membered ring having a nitrogen atom or an oxygen atom or a sulfur atom, for example, a pyridine ring, a triazine ring, a ring derived from cyanuric acid, and a heterocyanide derived from Acid ring and so on.

When the (meth)allyl group-containing compound (A) is a monomer, the compound (a-1) may, for example, be diallyl phthalate, diallyl isophthalate or p-phenylene. An allyloxycarbonyl-containing compound having an aromatic ring structure such as diallyl formate, triallyl trimellitate or tetraallyl pyromelliate or 1,2-cyclohexanedicarboxylate Diallyl acrylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, 1,2,4-cyclohexanetricarboxylic acid triene Propyl ester, tetraallyl 1,2,4,5-cyclohexanetetracarboxylate, diallyl 5-alkyl-substituted cyclohexane-1,4-dicarboxylate, 5-halo-substituted ring Diallyl hexane-1,4-dicarboxylate, diallyl 1,3-adamantane dicarboxylate, triallyl 1,3,5-adamantane tricarboxylate, hydrogenated bisphenol A Type of diallyl ether, hydrogenated dimer acid (carbon number 36 or 44 and having an alicyclic structure) diallyl ester, tricyclodecane dimethanol dicarboxylate, etc. having an alicyclic structure Allyloxycarbonyl-containing compound or isomeric cyanuric acid Allyl ester, triallyl cyanurate, diallyl monohydroxyethyl cyanurate, diallyl monohydroxyethyl isocyanurate, diallyl isocyanuric acid Ester, triallyl isocyanurate prepolymer, 1,3,5-triallylhexahydro-1,3,5-triazine, 1,3,4,6-tetraallyl An N-allyl-containing compound having a heterocyclic structure such as urea. Among these, as the compound (A) containing a (meth)allyl group, a compound having at least one of an ester structure and an isocyanurate structure is preferred.

Further, examples of the compound (a-1) include dimethyl allyl phthalate, dimethyl allyl isophthalate, dimethyl allyl terephthalate, and benzene. a methacryloxycarbonyloxy group-containing compound having an aromatic ring structure such as trimethyl allyl triacetate or tetramethyl allyl ester of pyromellitic acid or 1,2-cyclohexanedicarboxylic acid Methyl allyl ester, 1,3-cyclohexanedicarboxylic acid dimethylallyl ester, 1,4-cyclohexanedicarboxylic acid dimethylallyl ester, 1,2,4-ring Trimethylallyl hexane tricarboxylate, tetramethylallyl 1,2,4,5-cyclohexanetetracarboxylic acid, 5-alkyl-substituted cyclohexane-1,4-dicarboxylate Acid dimethyl allyl ester, 5-halogen substituted cyclohexane-1,4-dicarboxylic acid dimethylallyl ester, 1,3-adamantane dicarboxylic acid dimethylallyl ester, 1 , 3,5-adamantane tricarboxylic acid trimethylallyl ester, 5-halogen substituted cyclohexane-1,4-dicarboxylic acid dimethylallyl ester, hydrogenated dimer acid (carbon number 36 Or a methacrylate-containing oxycarbonyl group having an alicyclic structure, such as an alicyclic structure) dimethyl allylate, tricyclodecane dimethanol dicarboxyl dimethyl allylate, or the like a compound or trimethylallyl isocyanurate, trimethylallyl cyanurate, 1,3,5-trimethylallylhexahydro-1,3,5-tri An N-methylallyl-containing compound such as azine or 1,3,4,6-tetramethylallyl glycoluril.

Further, examples of the compound (a-1) include bisphenol A diallyl ether, bisphenol A dimethyl allyl ether, bisphenol S diallyl ether, and bisphenol S dimethyl allylate. Ether, 1,4-naphthalene dicarboxylic acid diallyl ether, 1,4-naphthalene dicarboxylic acid dimethyl allyl ether, 1,5-naphthalene dicarboxylic acid diallyl ether, 1,5 -naphthalene dicarboxylic acid dimethylallyl ether, 2,6-naphthalene dicarboxylic acid diallyl ether, 2,6-naphthalene dicarboxylic acid dimethylallyl ether, 2,7-naphthalene dicarboxyl Acid diallyl ether, 2,7-naphthalene dicarboxylic acid dimethylallyl ether, diphenyl-m,m'-dicarboxylic acid diallyl ether, diphenyl-m,m'- Dicarboxylic acid dimethyl allyl ether, diphenyl-p,p'-dicarboxylic acid diallyl ether, diphenyl-p,p'-dicarboxylic acid dimethylallyl ether, two Benzophenone-4,4-dicarboxylic acid diallyl ether, benzophenone-4,4-dicarboxylic acid dimethylallyl ether, methyl terephthalate diallyl ether, A Dimethyl allyl ether terephthalate, diallyl ether tetrachlorophthalate, dimethyl allyl ether tetrachlorobenzene, diallyl hydrazine, dimethylallyl hydrazine , bis-phenoxyethyl diallyl ether, bis-bisphenoxy Dimethyl allyl ether, quinone bisphenoxyethyl dimethyl allyl ether, quinone bisphenoxyethyl dimethyl allyl ether, quinone bisphenoxy bismethyl allyl ether An allyl ether compound or the like.

On the other hand, for example, a compound having an allyl group and a methallyl group in one molecule can also be mentioned. The compound (a-1) may, for example, be allylic methyl allyl phthalate, allyl methallyl isophthalate or diallyl methallyl trimellitate. Base ester, allyl dimethyl allyl trimellitate, triallyl methyl allyl ester of pyromellitic acid, diallyl dimethyl allyl ester of pyromellitic acid, Allyl trimethyl allyl ester of pyromellitic acid, bisphenol A allyl methyl allyl ether, bisphenol S allyl Methyl allyl ether, 1,4-naphthalene dicarboxylate allyl methyl allyl ether, 1,5-naphthalene dicarboxylate allyl methyl allyl ether, 2,6-naphthalene dicarboxylate Acid allyl methyl allyl ether, 2,7-naphthalene dicarboxylate allyl methyl allyl ether, diphenyl-m, m'-dicarboxylic acid allyl methyl allyl ether , diphenyl-p,p'-dicarboxylic acid allyl methyl allyl ether, benzophenone-4,4-dicarboxylic acid allyl methyl allyl ether, methyl p-phenylene Allyl methyl allyl ether, allyl methyl allyl ether, allyl methallyl oxime, bis bis oxyethyl allyl methyl ally a compound having a methallyl group and an allyl group having an aromatic ring structure, such as an ether or a bisphenoxyallylmethylallyl ether, or a 1,4-cyclohexanedicarboxylic acid allyl group Methyl allyl ester, 1,3-cyclohexanedicarboxylic acid allyl methallyl ester, 1,2,4-cyclohexanetricarboxylic acid allyl dimethylallyl ester, 1,2,4-cyclohexanetricarboxylic acid diallylallyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid triallylmethylallyl ester, 1, 2,4,5-cyclohexanetetracarboxylic acid diallyldimethylene Propyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid allyl trimethylallyl ester, 5-alkyl substituted cyclohexane-1,4-dicarboxylic acid allyl methyl Allyl ester, 5-halo substituted cyclohexane-1,4-dicarboxylic acid allyl methyl allyl ester, 1,3-adamantane dicarboxylic acid allyl methyl allyl ester, 1 , 3,5-adamantane tricarboxylic acid diallyl methallyl ester, 1,3,5-adamantane tricarboxylic acid allyl dimethylallyl ester, hydrogenated dimer acid (carbon number Methyl allylate having an alicyclic structure, such as allyl methyl allyl ester of 36 or 44 and having an alicyclic structure, allyl methallyl ester of tricyclodecane dimethanol dicarboxylate a compound in which the group and the allyl group coexist or allyl methallyl monohydroxyethyl cyanurate, diallyl methallyl isocyanurate, allyl dimethylallyl Isocyanurate, 1,5- Diallyl-3-methylallylhexahydro-1,3,5-triazine, 1-allyl-3,5-dimethylallylhexahydro-1,3,5-tri Pyrazine, 1,3,4,6-methylallyl triallyl glycoluril, 1,3,4,6-dimethylallyl diallyl glycoluril, 1,3,4,6 a compound in which N-methylallyl group such as trimethylallylallyl glycoluril coexists with N-allyl.

Examples of the compound (a-2) include diethylene glycol bis(allyl carbonate), 1,2,3,4-butanetetracarboxylic acid tetraallyl ester, and diallyl succinate. Diallyl glutarate, diallyl adipate, diallyl sebacate, diallyl dimerate, diallyl dimerate, 1,12-dodecanedioic acid Diallyl ester, diallyl maleate, diallyl iconate, diethylene glycol bis(methallyl carbonate), 1,2,3,4-butane tetracarboxylic acid Methyl allyl ester, dimethyl allyl succinate, dimethyl allyl glutarate, dimethyl allyl adipate, dimethyl allyl sebacate, Dimethyl allyl dimerate, dimethyl allyl hydrogen dimerate, dimethyl allyl 1,12-dodecanedioate, dimethyl allyl maleate , dimethyl allyl ester of itaconic acid, trimethylolpropane dimethyl allyl ether, pentaerythritol trimethyl allyl ether, trimethylolpropane trimethyl allyl ether, pentaerythritol tetramethyl Allyl ether and the like.

In consideration of physical properties such as acid resistance of the cured product of the resist ink of the present embodiment, in the (meth)allyl-containing compound (A), the compound (a-1) is a compound (a-2). Preferably, when the (meth)allyl-containing compound (A) is a monomer, and the (meth)allyl-containing compound (A) described later is an oligomer, the same applies.

Moreover, if the reactivity (hardenability) of the resist ink is considered, etc. In the compound (A) containing a (meth)allyl group, a compound having at least one of an allyloxycarbonyl group and an N-allyl group is preferred.

Further, in consideration of both the physical properties such as acid resistance of the cured product of the resist ink of the embodiment and the reactivity of the resist ink, a compound having at least one of an allyloxycarbonyl group and an N-allyl group is used ( A-1) is preferred, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,4-cyclohexanedicarboxylate, 1 Further, diallyl 3-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, and triallyl isocyanurate are particularly preferred.

When the (meth)allyl-containing compound (A) is an oligomer, the (meth)allyl-containing compound (A) may, for example, be a (meth)allyl ester resin. The (meth)allyl ester resin refers to a compound having a (meth)allyloxycarbonyl group at the terminal of the molecule and having a repeating unit in the molecule. For example, a transesterification reaction of a (meth)allyl ester compound of a polybasic acid with a polyhydric alcohol, an alcohol containing a (meth)allyl allyl alcohol-containing unit alcohol or a polyhydric alcohol, and a polybasic acid and a polybasic acid anhydride are selected. At least one condensation reaction, a transesterification reaction of a repeating unit polyol with a (meth)allyl ester compound of a polybasic acid, and a unit alcohol containing (meth)allyl allyl alcohol or A compound produced by various reactions of a condensation reaction of an alcohol such as a repeating unit of a polyhydric alcohol and at least one selected from a polybasic acid and a polybasic acid anhydride.

The catalyst used in the transesterification reaction is particularly preferably an organometallic compound, and specific examples thereof include titanium tetraisopropoxide, tetra-n-butoxytitanium, dibutyltin oxide, and dioctyltin oxide. Acetylacetone Bismuth, acetonitrile, zirconium, etc.

The reaction temperature of the transesterification reaction is preferably 100 ° C or more and 230 ° C or less, more preferably 120 ° C or more and 200 ° C or less. In particular, when a solvent is used for the transesterification reaction, there is a case where it is limited by its boiling point. Also, there are cases where the use of the polyol is limited.

Further, in the above transesterification reaction, a solvent may not be used, but a solvent which does not inhibit the transesterification reaction may be used as necessary. Specific examples thereof include benzene, toluene, xylene, cyclohexane, and the like. Among them, benzene and toluene are preferred.

Specific examples of the (meth) allyl ester resin include oligomers having a structure represented by the following formulas (1), (2), and (4).

In the formula (1), n of R ^{1 's} each independently represent a linear alkyl group or a branched alkyl group having 1 or more and 36 or less (preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less). Further, R ² and R ³ each independently represent a hydrogen atom or a methyl group. Preferably, both R ² and R ³ are a hydrogen atom.

Further, (n+1) X in the formula (1) are each independently an organic group derived from a divalent carboxylic acid, and preferably a phenyl group which may have an alkyl group having 1 or more and 4 or less carbon atoms as a substituent. Or a cyclohexyl group, and preferably a phenyl or a cyclohexyl group having no substituent. An alkyl group having a carbon number of 1 or more and 4 or less The surface may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group.

The position at which the phenyl or exocyclohexyl group is bonded to the adjacent carbonyl carbon may be any one of 1, 2, 1, 3, and 1, 4, but if the ease of synthesis is considered, 1, 3 or 1 4 is better.

n in the formula (1) is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less, more preferably 1 or more and 15 or less. The molecular weight of the oligomer represented by the formula (1) is preferably 300 or more and 20,000 or less, more preferably 800 or more and 18,000 or less, still more preferably 1,000 or more and 16,000 or less.

(2m+1) A in the formula (2) are each independently, and are an organic group derived from a divalent carboxylic acid, preferably a phenyl group or a stretching group which may have an alkyl group having 1 or more and 4 or less carbon atoms as a substituent. The cyclohexyl group is more preferably a phenyl group or a cyclohexyl group having no substituent. Examples of the alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.

The position at which the phenyl or exocyclohexyl group is bonded to the adjacent carbonyl carbon may be any one of 1, 2, 1, 3, and 1, 4, but if the ease of synthesis is considered, 1, 3 or 1, 4 are preferred.

Each of m R ⁴ in the formula (2) is independently a hydrogen atom and an alkyl group having 1 or more and 4 or less carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group). , isobutyl, tert-butyl.), or a group represented by the following formula (3). Further, R ⁵ , R ⁷ and m R ⁶ in the formula (2) are each independently a hydrogen atom or a methyl group. Preferably, R ⁵ , R ⁷ and m R ^{6 are} all hydrogen atoms. In the case where the A in the formula (3) is the same as the oligomer represented by the formula (2), R ⁸ is a hydrogen atom or a methyl group. Preferably, R ⁸ is a hydrogen atom.

m in the formula (2) is an integer of 3 or more and 70 or less, preferably 4 or more and 60 or less, more preferably 4 or more and 50 or less. The molecular weight of the oligomer represented by the formula (2) is preferably 300 or more and 20,000 or less, more preferably 500 or more and 18,000 or less, and still more preferably 700 or more and 16,000 or less.

In the formula (4), (q+1) Z are each independently and are an organic group derived from a divalent carboxylic acid, and preferably have a carbon number of 1 or more and 4 or less. The alkyl group as a substituent is a phenyl or cyclohexyl group, and more preferably a phenyl group or a cyclohexyl group having no substituent. Examples of the alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.

[(p+1)×q] R ⁹ in the formula (4) are each independently, and represent a straight-chain alkylene having a carbon number of 1 or more and 36 or less (preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less). A base or a branched alkyl group. Further, in the formula (4), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group. Preferably, both R ¹⁰ and R ¹¹ are a hydrogen atom.

In the formula (4), p is an integer of 1 or more and 10 or less, preferably 1 or more and 9 or less, more preferably 1 or more and 8 or less. q in the formula (4) is an integer of 5 or more and 50 or less, preferably 5 or more and 45 or less, more preferably 5 or more and 40 or less. The molecular weight of the oligomer represented by the formula (4) is preferably 300 or more and 20,000 or less, more preferably 500 or more and 19,000 or less, still more preferably 700 or more and 18,000 or less.

Specific examples other than the (meth)allyl ester resin in the case where the (meth)allyl group-containing compound (A) is an oligomer may, for example, be a polycondensation derived from a substituted or unsubstituted allyl alcohol. An olefin compound, polyethylene glycol bis(allyl carbonate) or the like.

When the (meth)allyl group-containing compound (A) is a polymer, the (meth)allyl group-containing compound (A) may, for example, be a compound in which two or more allyl groups are introduced into a polymer skeleton. . The polymer skeleton may, for example, be a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamine skeleton, a polyamidene skeleton, a polyoxyalkylene skeleton, or a polyphenylene skeleton. frame.

The (meth)allyl-containing compound (A) may be used alone or in combination of two or more kinds.

Further, the iodine value of the mixture of all the compounds of the (meth)allyl-containing compound (A) used in the resist ink of the present embodiment is preferably in the range of 20 or more and 240 or less. It is 30 or more and 210 or less. When the iodine value is in the range of 20 or more and 240 or less, the resist ink can be easily cured in a short time by irradiation with an active energy ray or heat. Further, the iodine value described in the present specification means a value obtained by converting the amount of halogen (unit: g) reacted with 100 g of the target substance into the gramm of iodine.

[2] a thiol compound having two or more mercapto groups in one molecule (B)

The thiol compound (B) is not particularly limited as long as it has two or more mercapto groups in one molecule. Specific examples thereof include a compound having two mercapto groups in one molecule, a compound having three mercapto groups in one molecule, a compound having four mercapto groups in one molecule, and a compound having six mercapto groups in one molecule.

Examples of the compound having two mercapto groups in one molecule include, for example, butanediol bis(2-mercaptoacetate), hexanediol bis(2-mercaptoacetate), and ethanediol bis(2- Mercaptoacetate), butanediol bis(2-mercaptoacetate), 2,2'-(ethylenedithio)diethanethiol, ethylene glycol bis(3-mercapto-2-methylpropionic acid Ester), propylene glycol bis(3-mercapto-2-methylpropionate), diethylene glycol bis(3-mercapto-2-methylpropionate), butanediol bis(3-mercapto-2-yl) Propionate), octanediol bis(3-mercapto-2-methyl a compound having two primary sulfhydryl groups or a 1,4-bis(3-mercaptobutyloxy) group in one molecule such as propionate or bis(3-mercapto-2-methylpropyl) phthalate Butane, bis(1-mercaptoethyl) phthalate, bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, ethylene glycol bis ( 3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol Bis(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), dibutyl Alcohol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), two Ethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), ethylene glycol bis(4-mercaptovalerate) Ester), propylene glycol bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis (4- Mevalonate, ethylene glycol bis(3-mercaptovalerate), Propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate a compound having two secondary sulfhydryl groups in one molecule, or ethylene glycol bis(2-mercaptoisobutyrate), propylene glycol bis(2-mercaptoisobutyrate), diethylene glycol bis(2-fluorenyl) A compound having two tertiary sulfhydryl groups in one molecule such as isobutyrate), butanediol bis(2-mercaptoisobutyrate) or octanediol bis(2-mercaptoisobutyrate).

Further, examples of the compound having three mercapto groups in one molecule include, for example, trimethylolpropane ginseng (2-mercaptoacetate) and trishydroxyl a compound having three primary sulfhydryl groups or trimethylolpropane in one molecule of propane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (3-mercapto-2-methylpropionate) Reference (3-mercaptobutyrate), trimethylolpropane ginseng (2-mercaptopropionate), trimethylolpropane ginseng (2-mercaptopropionate), trimethylolpropane ginseng (4-mercapto) Valerate), trimethylolpropane ginseng (3-mercaptovalerate), 1,3,5-gin (3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 3, 6 (1H, 3H, 5H)-trione or the like having 3 fluorenyl compounds or 1 molecule of trimethylolpropane ginsyl (2-mercaptoisobutyrate) A compound of the third order thiol group.

Further, examples of the compound having four mercapto groups in one molecule include, for example, pentaerythritol bismuth (2-mercaptoacetate), pentaerythritol lanthanum (3-mercaptopropionate), and the like, and one of the first-order fluorenyl groups in one molecule. Compound or dipentaerythritol tert-(3-mercaptobutyrate), pentaerythritol bismuth (2-mercaptopropionate), pentaerythritol bismuth (3-mercapto-2-propionate), pentaerythritol bismuth (2-mercaptoisobutyrate) a compound having four secondary sulfhydryl groups or pentaerythritol ruthenium (2-mercaptoisobutyrate) in one molecule such as pentaerythritol oxime (4-mercapto valerate) or pentaerythritol lanthanum (3-mercapto valerate) A compound having four tertiary sulfhydryl groups in one molecule.

Further, examples of the compound having six mercapto groups in one molecule include, for example, a compound having six primary sulfhydryl groups or dipentaerythritol in one molecule such as dipentaerythritol tert-(3-mercapto-2-methylpropionate). Terephthalic acid (3-mercaptobutyrate), dipentaerythritol tert-(2-mercaptopropionate), dipentaerythritol tert-(2-mercaptoisobutyrate), dipentaerythritol tert-(pentyl valerate), dipentaerythritol (3-mercaptovalerate) and the like in one molecule A compound having six secondary sulfhydryl groups or a compound having two tertiary sulfhydryl groups, such as dipentaerythritol tertiary (2-mercaptoisobutyrate), or the like.

In the thiol compound (B), in consideration of the acid resistance and the operable period of the resist ink of the present embodiment, the total number of the fluorenyl group and the fluorenyl group having no fluorenyl group and having two fluorenyl groups is two. The above compounds are preferred. For example, a compound having two fluorenyl groups in one molecule, a compound having two fluorenyl groups in one molecule, a compound having three fluorenyl groups in one molecule, and a compound having three fluorenyl groups in one molecule, A compound having four sulfhydryl groups in one molecule, a compound having four fluorenyl groups in one molecule, a compound having six fluorenyl groups in one molecule, and a compound having six fluorenyl groups in one molecule are preferred. .

In terms of the thiol compound (B), especially 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol ruthenium (3-mercaptobutyrate), 1,3,5-gin (3-mercaptobutylate) More preferably, oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropane-gin (3-mercaptobutyrate).

If all of the mercapto groups of the thiol compound (B) are bonded to the second-order carbon atom or the third-order carbon atom (that is, all of the mercapto groups are a 2- or a mercapto group), the operable period of the resist ink or The preservation stability becomes excellent.

The thiol compound (B) may be used alone or in combination of two or more. In addition, the molecular weight of the thiol compound (B) is not particularly limited, but is preferably 200 or more and 1000 or less from the viewpoint of improving the acid resistance of the cured product of the resist ink of the present embodiment.

The thiol compound (B) can also be easily obtained from commercial products. In the case of a second-stage thiol having two or more thiol groups in one molecule, it is easy to be obtained as a commercial product, and 1,4-bis(3-mercaptobutyl fluorenyloxy) butane (made by Showa Denko Co., Ltd.) The product name is KarenzMT (trademark) BD1), pentaerythritol oxime (3-mercaptobutyrate) (trade name: KarenzMT (trademark) PE1, manufactured by Showa Denko Co., Ltd.), 1,3,5-gin (3-mercaptobutyloxy) -1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT (trademark) NR1, manufactured by Showa Denko Co., Ltd.), trimethylolpropane ginseng ( 3-mercaptobutyrate) (trade name: TPMB, manufactured by Showa Denko Co., Ltd.).

The preferred content of the thiol compound (B) in the resist ink of the present embodiment may include the (meth)allyl number of the (meth)allyl compound (A) and the thiol compound (B). The ratio of the base of the 表示 is expressed. That is, the ratio of the (meth)allyl number of the (meth)allyl group-containing compound (A) to the number of thiol groups of the thiol compound (B) (allyl number / fluorenyl group), from hardenability and acid resistance The viewpoint of properties is preferably in the range of 0.25 or more and 4 or less, more preferably in the range of 0.67 or more and 2.33 or less. The content of the (meth)allyl-containing compound (A) and the thiol compound (B) in the resist ink may be determined in such a ratio.

Further, the (meth)allyl number of the (meth)allyl-containing compound (A) means the (meth)allyl number of all the compounds belonging to the (meth)allyl-containing compound (A). The total number (molar number) of the thiol compound (B) means the total number of thiol groups (moles) of all the compounds belonging to the thiol compound (B).

Further, the resist ink of the present embodiment can be blended with a mercapto group-containing compound other than the thiol compound (B), without impairing the range of the effects of the invention. However, the amount of the thiol group-containing compound other than the thiol compound (B) is 20% by mass based on the content of the thiol group-containing compound containing the thiol compound (B) from the viewpoint of maintaining curability and acid resistance. The following is better.

[3] Polymerization initiator (C)

The polymerization initiator (C) has a photopolymerization initiator and a thermal polymerization initiator, but generates a radical polymerizable radical by an active energy ray and/or heat to promote a (meth) olefin. A compound starting from the polymerization of the propyl compound (A) can be used. For example, a polymerization initiator described in Patent No. 5302688 can be used. The polymerization initiator (C) may be used singly or in combination of two or more kinds in any ratio.

The photopolymerization initiator and the thermal polymerization initiator may be used singly, and the polymerization initiator (C) contains a photopolymerization initiator from the viewpoint of maintaining the printing shape of the resist ink when printing with a resist ink. It is better. Further, in the polymerization in which curing by hardening and thermosetting by irradiation with an active energy ray is carried out, a photopolymerization initiator and a thermal polymerization initiator may be used in combination.

The type of the photopolymerization initiator is a polymerization initiator which is an active energy ray for induction irradiation, and is not particularly limited. Examples of the active energy ray include electromagnetic waves, particle lines such as near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, gamma rays, and electron beams, and photopolymerization initiators that induce visible light rays or ultraviolet rays. Acetophenone, diethoxybenzene An acetophenone or a derivative thereof such as a ketone or 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, Darocur 1173 manufactured by BASF Corporation).

Further, in terms of a photopolymerization initiator which induces irradiation with visible light or ultraviolet rays, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-double may also be mentioned. a benzophenone or a derivative thereof such as (diethylamino)benzophenone or 4-trimethyldecyl benzophenone or benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl A benzoin or a derivative thereof of an ether, benzoin isopropyl ether or the like.

Further, examples of the photopolymerization initiator which induces irradiation with visible light or ultraviolet rays include, for example, methylphenylglyoxylic acid, benzoin dimethyl ketal, and ethyl (2,4,6-trimethylbenzhydrazide). Phenylphosphonate (for example, Irgacure TPO-L manufactured by BASF Corporation), and the like, and bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, bis (2) a bis-decylphosphine oxide compound such as 6-dichlorobenzhydryl)-phenylphosphine oxide or 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, 2,4 a fluorenylphosphine oxide compound such as 6-trimethoxybenzylidene-diphenylphosphine oxide.

In terms of a photopolymerization initiator, for example, diphenyl-2,4,6-trimethylbenzimidylphosphine oxide, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1-( 4-isopropenylphenyl)-2-methylpropan-1-one and its oligomer, 2,4,6-trimethylbenzophenone, LAMBERTI SpA, a mixture of such a mixture The product name is "ESACURE KTO 46".

Further, in terms of a photopolymerization initiator which induces irradiation with visible light or ultraviolet rays, for example, bis(η5-2,4-cyclopentadiene-1- a ferrocene compound such as bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium or 2,4-diethylthioxanthone or 2-isopropyl Thioxanthone or methylphenylglyoxylic acid, benzoin dimethyl ketal, p-dimethylamino benzoic acid isoamyl ester, p-dimethyl thioxanthone, 2-chlorothioxanthone Ethyl benzoic acid ethyl ester and the like.

Further, a photo-polymerization initiator (for example, a benzophenone-based or a thioxanthone-based) which has an excellent hydrogen-promoting function is generally called a photopolymerization accelerator (for example, p-dimethylamino benzoin). Acid isoamyl ester, p-dimethylamino benzoic acid ethyl ester) is also defined as the photopolymerization initiator included in the present invention.

Among these photopolymerization initiators, a mercaptophosphine oxide compound, a bis-decylphosphine oxide compound, 2-methyl-1-[4-(methylthio)phenyl]-2-? Olinone propan-1-one, 2-benzyl-2-methylamino-1-(4-morpholinophenyl)butanone-1, 2,2-dimethoxy-1,2-di Phenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone is preferred, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, 2,4,6-trimethoxy Benzopyridyl-diphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone are more preferred.

The type of the thermal polymerization initiator is not particularly limited, and examples thereof include a peroxide-based polymerization initiator such as an organic peroxide, an azo compound, a persulfate, and a redox polymerization initiator.

As the organic peroxide, for example, a dialkyl peroxide, a mercapto peroxide, a hydroperoxide, a ketone peroxide, a peroxyester or the like can be used. Specific examples thereof include diisobutyl decyl peroxide and cumyl peroxy neodecanoate. Further, in terms of a peroxide polymerization initiator, For example, benzhydryl peroxide, t-butyl peroxy maleate, di-t, t-hexyl peroxide, t-hexylperoxy-2-ethylhexanoate, t - Butyl hydroperoxide and the like.

Further, examples of the azo compound include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (2,4-di). Methyl valeronitrile) and the like.

Further, examples of the redox polymerization initiator include a combination of a persulfate and sodium hydrogen sulfite, a combination of a peroxide and sodium ascorbate, and the like. Examples of the persulfate include potassium persulfate and ammonium persulfate.

The content of the polymerization initiator (C) in the resist ink of the present embodiment is such that the polymerization initiator (C) and the non-reactive solvent or inorganic filler are not reacted from the total amount of the resist ink. The content of the polymerization initiator (C) when the amount of the component of the reaction is 100 parts by mass is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more. It is more preferably 7 parts by mass or less, more preferably 0.4 parts by mass or more and 3 parts by mass or less. When the content of the polymerization initiator (C) is within the above numerical range, a sufficient curing rate can be obtained and the mechanical strength of the cured product becomes high.

For example, when the resist ink of the present embodiment is composed of a (meth)allyl-containing compound (A), a thiol compound (B), and a polymerization initiator (C), it contains a (meth)allyl group. The content of the polymerization initiator (C) when the total content of the compound (A) and the thiol compound (B) is 100 parts by mass is preferably 0.01 parts by mass or more and 10 parts by mass or less.

Further, for example, the resist ink of the present embodiment contains (meth)allyl When the compound (A), the thiol compound (B), the polymerization initiator (C), and the (meth)acryloyl group-containing compound (D) described later are composed of a compound containing a (meth)allyl group, (A) When the total content of the thiol compound (B) and the (meth)acrylonitrile group-containing compound (D) is 100 parts by mass, the content of the polymerization initiator (C) is 0.01 parts by mass or more and 10 parts by mass. The following is better.

[4] Compound containing (meth) acrylonitrile group (D)

The resist ink of the present embodiment may further contain a compound (D) containing a (meth) acrylonitrile group.

The compound (D) containing a (meth) acrylonitrile group is not particularly limited as long as it is a compound containing a (meth) acryl fluorenyl group, and examples thereof include an epoxy group (meth) acrylate and (poly). Ester (meth) acrylate, (poly) carbonate (meth) acrylate, hydrogenated polybutadiene (meth) acrylate, (poly) ether (meth) acrylate, (poly) urethane Ester (meth) acrylate and the like.

Among these, epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate, hydrogenated polybutadiene (meth) acrylate are More preferably, it is an epoxy (meth) acrylate, (poly) carbonate (meth) acrylate, and further preferably an epoxy (meth) acrylate.

Further, the (meth)acrylonitrile group-containing compound (D) is preferably a compound having at least one structure selected from the group consisting of an alicyclic structure and an aromatic ring structure in the molecule. Further, a compound containing a (meth) acrylonitrile group (D) From the viewpoint of the curability of the resist ink, a compound having two or more (meth) acrylonitrile groups is preferred.

The epoxy group (meth) acrylate means all compounds obtained by reacting an epoxy group having an epoxy group with a monocarboxylic acid having a (meth) acryl fluorenyl group. The epoxy resin is preferably a compound having two or more epoxy groups in one molecule, and specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol. AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol AD type epoxy resin, tetrabromobisphenol A type epoxy A bisphenol type epoxy resin such as a resin.

Further, for example, an o-cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a naphthol novolac type epoxy resin, a bisphenol A novolac type epoxy resin, a brominated phenol novolak type ring may be mentioned. Novolac type ring of oxygen resin, alkylphenol novolak type epoxy resin, bisphenol S novolak type epoxy resin, methoxy novolak type epoxy resin, brominated phenol novolak type epoxy resin Oxygen resin.

Other examples include phenol aralkyl type epoxy resins (known as epoxides of neophenolic resin (xylok)), diglycidyl ether of resorcinol, diglycidyl ether of hydroquinone, and children. Bifunctional epoxy resin such as diglycidyl ether, biphenyl type epoxy resin or tetramethylbiphenyl type epoxy resin, or triglycidyl isocyanurate or triphenylmethane type ring Oxygen resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolac type epoxy resin (multiple phenolic core-linked nucleus Epoxide of phenolic resin), methoxy group Phenol aralkyl resin and the like.

Epoxy (meth) acrylates are also readily available in commercial products. For example, VR-77 manufactured by Showa Denko Co., Ltd., or epoxy ester 40EM, epoxy ester 30002M, epoxy ester 3002A, epoxy ester manufactured by Kyoei Kogyo Co., Ltd., may be used as a commercially available epoxy group (meth) acrylate. 3000MK, epoxy ester 3000A or EBECRYL 600, EBECRYL 648, EBECRYL 3700 manufactured by Daicel ‧ Allnex AG.

Next, the (poly)ester (meth) acrylate refers to a compound having one or more ester bonds other than a (meth) acryloyloxy group and having one or more (meth) acrylate groups.

(Poly)ester (meth) acrylate is also commercially available. For the (poly)ester (meth) acrylate of the commercial product, for example, EBECRYL450, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL846, EBECRYL851, EBECRYL852, EBECRYL853, EBECRYL1870, EBECRYL884, EBECRYL885, etc., manufactured by Daicel ‧ Allnex Co., Ltd. .

Next, (poly)carbonate (meth) acrylate means a compound having one or more carbonate groups and having one or more (meth) acrylate groups.

For the synthesis of (poly)carbonate (meth) acrylate, dehydrochlorination of a chloride of (meth)acrylic acid with a polycarbonate polyol, (meth)acrylic acid and (poly)carbonate polyol can be used. Direct dehydration A transesterification reaction of a lower alkyl ester of (meth)acrylic acid with a (poly)carbonate polyol.

(Poly)carbonate (meth) acrylate is also commercially available. In the case of the (poly)carbonate (meth) acrylate of the commercially available product, a compound represented by the following formula (5), such as a polycarbonate diol diacrylate manufactured by Ube Industries, Ltd., may be mentioned. In the formula (5), k is an integer of 1 or more.

Next, the hydrogenated polybutadiene (meth) acrylate is a compound having a hydrogenated polybutadiene structure and a (meth) acrylate structure in the molecule.

For the synthesis of hydrogenated polybutadiene (meth) acrylate, it is preferred to use an esterification reaction of a hydrogenated polybutadiene polyol with (meth)acrylic acid, hydrogenated polybutadiene polyols and (meth) acrylates. Transesterification reaction, addition reaction of hydrogenated polybutadiene polyol with isocyanato-containing (meth) acrylate, hydrogenation of polybutadiene polyol with polyisocyanate and alcoholic hydroxyl group (methyl) Addition reaction of acrylate, and the like.

Hydrogenated polybutadiene (meth) acrylate is also readily available in commercial products. The hydrogenated polybutadiene (meth) acrylate of the commercial product may, for example, be a hydrogenated polybutadiene polyol, a polyisocyanate, and an alcoholic property. NISSO-PB TEAI-1000 manufactured by Japan Caoda Co., Ltd., SPBDA-S30 manufactured by Osaka Organic Chemical Industry Co., Ltd., hydrogenated polybutadiene diacrylate, etc.

In hydrogenated polybutadiene (meth) acrylate, a hydrogenated polybutadiene polyol having no urethane bond and an esterified or hydrogenated polybutadiene polyol with (meth)acrylic acid ( A transesterification reaction of a methyl acrylate is preferred.

Next, the (poly)ether (meth) acrylate is a compound having one or more ether bonds in the molecule and having one or more (meth) acrylate groups, and examples thereof include polyethylene glycol diacrylate and poly Propylene glycol diacrylate, polytetramethylene glycol diacrylate, and the like.

Next, the (poly)urethane (meth) acrylate is a compound having one or more urethane bonds in the molecule and having one or more (meth) acrylate groups, for example, A compound obtained by performing a polyaddition reaction between a polyhydric alcohol, a polyisocyanate, a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing (meth) acrylate, or a polyol and an isocyanato group-containing (meth) acrylate as essential raw materials. A compound obtained by a polyaddition reaction.

The number average molecular weight of the (meth)acrylonitrile group-containing compound (D) is not particularly limited, and is preferably 400 or more, and more preferably 600 or more from the viewpoint of acid resistance.

When the resist ink of the present embodiment contains the (meth)acryl fluorenyl group-containing compound (D), the content thereof is preferably from the viewpoint of acid resistance. That is, the compound (A) containing a (meth)allyl group is combined with a thiol. When the total content of the compound (B) and the (meth)acrylonitrile group-containing compound (D) is 100 parts by mass, the content of the (meth)acrylonitrile group-containing compound (D) is 10 parts by mass or more and 80%. The mass part is preferably 5% or less, more preferably 70 parts by mass or less, more preferably 40 parts by mass or more and 70 parts by mass or less. When the content of the propylene group-containing compound (D) is within the above range, the mechanical property improving effect of the cured product obtained by the combination of the (meth)acryl fluorenyl group-containing compound (D) is sufficiently expressed and hindered. The volume shrinkage rate at the time of hardening of the ink is not easily increased.

[5] Polymerization inhibitor

The resist ink of the present embodiment can improve the storage stability in order to suppress radical polymerization during storage, and may contain a polymerization inhibitor as necessary. The type of the polymerization inhibitor is not particularly limited, and examples thereof include 4-methoxy-1-naphthol, 1,4-dimethoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-2-methyl. 1-naphthol, 4-methoxy-3-methyl-1-naphthol, 1,4-dimethoxy-2-methylnaphthalene, 1,2-dihydroxynaphthalene, 1,2- Dihydroxy-4-methoxynaphthalene, 1,3-dihydroxy-4-methoxynaphthalene, 1,4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthalene Phenol, 1,4-dihydroxy-2-methylnaphthalene, pyrogallol, methylhydroquinone, tert-butylhydroquinone, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine Aluminum and so on.

Among these polymerization inhibitors, methylhydroquinone, pyrogallol, and t-butylhydroquinone are preferred from the viewpoint of storage stability of the resist ink.

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

The content of the polymerization inhibitor in the resist ink of the present embodiment The amount is not particularly limited, and the total content of the (meth)allyl-containing compound (A) and the thiol compound (B) is 100 parts by mass from the viewpoint of storage stability of the resist ink (the resist of the present embodiment) When the ink contains the (meth)acrylonitrile group-containing compound (D), the (meth)allyl group-containing compound (A) and the thiol compound (B) and the (meth)acrylonitrile group-containing compound ( The content of the polymerization inhibitor in the case where the total content of D) is 100 parts by mass or less is preferably less than 0.1 part by mass, more preferably 0.0001 part by mass or more and 0.05 part by mass or less.

[6] Antioxidants

The resist ink of the present embodiment may contain an antioxidant in order to suppress the coloration of the cured product of the resist ink at a high temperature. The kind of the antioxidant is not particularly limited, and examples thereof include pentaerythritol 肆 [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl-3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propionate, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thio group Divinyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,6-bis(octylthiomethyl)-o-cresol, 2, 4-bis[(dodecylthio)methyl]-6-methylphenol, 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, ginseng (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-three Pyrazine-2,4,6-(1H,3H,5H)-trione, 4,4',4"-(1-methylpropanyl-3-fork) ginseng (6-tert-butyl-m- Cresol), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis{2-[3-(3-tert-butyl- 4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethyl Ethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-paran (3,5-di-tert-butyl-4-hydroxyphenylmethyl )-2,4,6-trimethylbenzene and the like. These antioxidants may be used alone or in combination of two or more.

Among these antioxidants, from the viewpoint of suppressing the coloration of the cured product of the resist ink at a high temperature, ginseng (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-three Preferably, azine-2,4,6-(1H,3H,5H)-trione or octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is preferred.

The content of the antioxidant in the resist ink of the present embodiment is not particularly limited, and the (meth)allyl-containing compound (A) and the thiol compound (from the viewpoint of suppressing the coloration of the cured product of the resist ink at a high temperature) The total content of B) is 100 parts by mass (when the resist ink of the present embodiment contains the (meth) acrylonitrile-containing compound (D), the (meth)allyl-containing compound (A) and the thiol are used. The content of the antioxidant when the total content of the compound (B) and the (meth)acrylonitrile group-containing compound (D) is 100 parts by mass is preferably less than 0.1 part by mass, and more preferably 0.0001 part by mass or more and 0.05 part by mass or less. Better.

[7] Other ingredients that can be added to the resist ink

The resist ink of the present embodiment may contain a (meth)allyl-containing compound (A), a thiol compound (B), and a polymerization initiator (C), and may contain an optional component (methyl group). The propylene group-based compound (D), the polymerization inhibitor, and the antioxidant may further contain other components within the range not impairing the object of the present invention.

Further, the resist ink of the present embodiment may contain no solvent or a solvent as the other component, but it is preferably a solvent.

Further, the resist ink of the present embodiment may contain a thixotropic agent, an adhesion-imparting agent, or the like as another component. The type of the thixotropic agent is not particularly limited, and any thixotropic agent such as an inorganic thixotropic agent or an organic thixotropic agent can be used.

Examples of the inorganic thixotropic agent include, for example, cerium (SiO ₂ ) represented by AEROSIL (trademark), alumina (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), cerium oxide (Ta ₂ O ₅ ), and oxidation. Zirconium (ZrO ₂ ), cerium nitride (Si ₃ N ₄ ), barium titanate (BaO‧TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO‧TiO ₂ ), lead zirconate titanate (PZT) ), zirconate titanate, barium lead (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO‧Al ₂ O ₃ ), mullite (3Al ₂ O ₃ ‧2SiO ₂ ), cordierite (2MgO‧2Al ₂ O ₃ ‧5SiO ₂ ), talc (3MgO‧4SiO ₂ ‧H ₂ O), aluminum titanate (TiO2-Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ -ZrO ₂ ), barium strontium silicate (BaO‧8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO‧TiO ₂ ), sulfuric acid Barium (BaSO ₄ ), organic bentonite, carbon (C), and magnesite. These may be used alone or in combination of two or more. Further, it is preferable that at least one selected from the group consisting of cerium oxide microparticles and magnesite particles is used.

Further, the magnesite is a naturally occurring clay mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ‧4H ₂ O or the like, and is a layered inorganic compound. Further, the magnesite may be obtained by, for example, synthesizing Mg1-xAlx(OH) ₂ (CO ₃ )x/2‧mH ₂ O or the like. In other words, the magnesite is a Mg/Al layered compound, and chloride ions (Cl ⁻ ) and/or sulfate ions (SO ₄ ^2- ) can be exchanged by ion exchange with the carbonate groups existing between the layers. Anion immobilization. Using this function, the chloride ion (Cl ^- ) or sulfate ion (SO ₄ ^2- ) which is the cause of copper or tin migration can be captured, and the insulation reliability can be improved. As a commercial item of the magnesite, for example, STABIACE HT-1, STABIACE HT-7, STABIACE HT-P of 堺Chem Chemical Co., Ltd. or DHT-4A, DHT-4A2, DHT- of Kyowa Chemical Industry Co., Ltd. 4C and so on.

In the case of the organic thixotropic agent, fine particles of a heat resistant resin having a guanamine bond, an oxime bond, an ester bond or an ether bond are preferred. For example, a fatty amide-based thixotropic agent or an ethyl cellulose-based thixotropic agent can be mentioned. Fatty amide-type thixotropic agents and ethyl cellulose-based thixotropic agents are also commercially available.

For example, DISPARLON (trademark) 6500, DISPARLON (trademark) 6650, DISPARLON (trademark) 6700, etc., manufactured by Kanemoto Kasei Co., Ltd., may be mentioned as a fatty amide-based thixotropic agent. Moreover, ETHOCEL (trademark) 45, ETHOCEL (trademark) 100, ETHOCEL (trademark) 200, etc. by the Dow Chemical Co., Ltd. are mentioned, for example, the ethyl cellulose type thixotropic agent of the commercial item.

The adhesion-imparting agent refers to a substance having an adhesive function in combination with a polymer compound typified by an elastomer having rubber elasticity. The adhesion-imparting agent has a molecular weight much smaller than that of a polymer compound represented by an elastomer, and is generally a compound in the field of oligomers having a molecular weight of several hundreds to several thousands, and is in a glass state at room temperature, and has itself Not showing rubber elasticity nature.

For the adhesion-imparting agent, a petroleum-based resin adhesion-imparting agent, a terpene-based resin adhesion-imparting agent, a rosin-based resin adhesion-imparting agent, a coumarone-rubber resin adhesion-imparting agent, a styrene-based resin adhesion-imparting agent, and the like can be generally used. Examples of the petroleum-based resin adhesion-imparting agent include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic-aromatic copolymerized petroleum resin, an alicyclic petroleum resin, a dicyclopentadiene resin, and the like. A modified product of a hydride or the like. The synthetic petroleum resin may be a C5 system or a C9 system. Examples of the terpene-based resin adhesion-imparting agent include a β-pinene resin, an α-pinene resin, a terpene-phenol resin, an aromatic modified terpene resin, and a hydrogenated terpene resin. Most of these terpene-based resins are resins which do not have a polar group. Examples of the rosin-based resin adhesion-imparting agent include modified rosin or rosin glyceride such as rosin, tall oil rosin, wood rosin, rosin or hydrogenated rosin, uneven rosin, polymerized rosin, maleated rosin, and the like. A rosin ester such as hydrogenated rosin ester or hydrogenated rosin glyceride. These rosin-based resins are those having a polar group. These adhesion-imparting agents may be used alone or in combination of two or more.

Further, the resist ink of the present embodiment may contain an antifoaming agent as another component. The type of the antifoaming agent is not particularly limited, and specific examples thereof include BYK-077 manufactured by BYK Japan Co., Ltd., SNDEFOAMER 470 manufactured by Sannopco Co., Ltd., TSA750S manufactured by GE Toshiba Ketone Co., Ltd., and Dow Corning Toray Co., Ltd. Anthrone-based antifoaming agent such as SH-203 or DAPPO SN-348, DAPPO SN-354, DAPPO SN-368, etc. manufactured by Sannopco Co., Ltd. Acrylic acid-based defoaming agent or acetylene glycol-based antifoaming agent such as SURFYNOL DF-110D and SURFYNOL DF-37 manufactured by Nissin Chemical Industry Co., Ltd., or FA-630 manufactured by Shin-Etsu Chemical Co., Ltd. An anthraquinone defoamer or the like.

[8] Modulation of resist ink

The resist ink of the present embodiment can contain a (meth)allyl-containing compound (A), a thiol compound (B), and a polymerization initiator (C), and a necessary (meth) propylene-containing compound. The thiol compound (D), a polymerization inhibitor, an antioxidant, and other components are suitably mixed to prepare.

Further, the content of the polymerization initiator (C) when the amount of the polymerization initiator (C) is less than 100 parts by mass from the total amount of the resist ink of the embodiment is 0.01 parts by mass or more and 10 parts by mass. Mix in the range below.

The method for preparing the resist ink of the present embodiment is not particularly limited, and the compound (A) containing a (meth)allyl group, the thiol compound (B), a polymerization initiator (C), and the like may be contained. The method of mixing and dispersing each raw material of the resist ink of the compound (D) of the acrylonitrile group may be used. Examples of the method of mixing and dispersing include the following methods.

(A) Put each raw material into a container of a glass beaker, a can, a plastic cup, an aluminum cup, etc., and knead it with a stirring bar, a spatula, etc.

(B) Each raw material is kneaded by a double spiral wing, a door wing or the like.

(c) Each raw material was kneaded by a planetary mixer.

(D) Each raw material was kneaded by a bead mill.

(e) Each raw material was kneaded in three rolls.

Each of the raw materials was kneaded in an extruder-type kneading extruder.

(g) Each raw material was kneaded by a self-rotating ‧ revolution mixer.

The addition and mixing of each raw material can be carried out in any order, and all the raw materials can be added simultaneously or sequentially.

When the polymerization initiator (C) is used, the treatment before curing such as the operation and mixing of the above respective raw materials can be performed by the active energy ray of the filter of the absorption wavelength light which is decomposed by the photopolymerization initiator. The polymerization initiator (C) is not used until the active energy ray is not irradiated or the thermal polymerization initiator is subjected to a curing treatment or the like.

Further, when the cured product of the resist ink of the present embodiment is used as a protective film of a fine pattern such as a line, the printing of the resist ink is preferably screen printing.

[9] Hardener and hardening method of resist ink

By irradiating the resist ink of the present embodiment with an active energy ray or heating, the resist ink is cured to obtain a cured product. Examples of the active energy ray used for curing include electromagnetic waves and particle lines such as near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, γ-rays, and electron beams. However, ultraviolet rays and/or ultraviolet rays can be used. Visible light is preferred.

Various types of light sources can be used in the case of curing the resist ink of the present embodiment by ultraviolet rays or visible rays. For example, black light, UV-LED lamps, high pressure mercury lamps, pressurized mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, halogen lamps.

Here, the black light refers to a lamp in which a special outer tube glass that shields visible light rays from ultraviolet rays having a wavelength of 300 nm or less is coated with a near-ultraviolet light-emitting phosphor, and emits only near-ultraviolet light having a wavelength of 300 nm or more and 430 nm or less (near the peak of 350 nm). Further, the UV-LED lamp refers to a lamp using a light-emitting diode that emits ultraviolet rays. Among these light sources, high-pressure mercury lamps and metal halide lamps are preferred from the viewpoint of hardenability. Also, considering the economics of operating costs, etc., LED lights (UV-LED lights) are preferred.

The irradiation amount of the active energy ray may be a sufficient amount to cure the resist ink of the present embodiment, and may be selected in accordance with the composition, the amount of use, the thickness, the shape of the formed cured product, and the like of the resist ink of the present embodiment. For example, when the coating film formed by applying the resist ink of the present embodiment is irradiated with ultraviolet rays, it is preferable to use an exposure amount of 100 mJ/cm ² or more and 5000 mJ/cm ² or less, more preferably 300 mJ/cm ² or more and 3000 mJ. Exposure amount below /cm ² . Further, the measurement wavelength of the above exposure amount was 365 nm.

The coating (coating) method when the resist ink of the present embodiment is applied to, for example, a substrate to form a coating film is not particularly limited. For example, a spray method or a dipping method may be, for example, a natural coating, a curtain coater, a slant coater, a gravure coater, a micro gravure coater, a die coater, or a curtain coat. A cloth machine, a contact roll, a squeeze roll, a reverse roll, an air knife, a knife coater, a float knife, a roll lining blade, a method with a knife layer, and the like. Moreover, a method using an inkjet printer, a screen printing machine, etc. is mentioned, for example.

When the cured product of the resist ink is used as a protective film of a fine pattern such as a line, it is preferable to use a screen printing machine from the viewpoint of precisely controlling the printing pattern. Moreover, a shape that maintains the shape of the printed pattern is obtained When the cured product is used as a protective film of a fine pattern such as a wiring, as described above, the polymerization initiator (C) preferably contains a photopolymerization initiator.

Next, a protective film containing a cured product of the resist ink of the present embodiment and a method for producing the same will be described. The method for producing a protective film for a line according to the present embodiment includes the following coating step and curing step.

The coating step is a step of arranging the resist ink on a substrate having a wiring (for example, a printed wiring substrate) by, for example, a printing method, and coating the wiring with a film of the resist ink.

The film of the resist ink can be disposed on the entire surface of the substrate, and can be covered on one of the faces under the coverable line. Further, the printing method is not particularly limited, and examples thereof include screen printing, a roll coater method, a spray method, and a curtain coater method. However, it is preferable to use screen printing from the viewpoint of the shape pattern of the film which controls the resist ink of the printed matter.

Further, the hardening step is to irradiate the active energy ray at a wavelength at which the polymerization initiator (C) generates a polymerizable radical species in a partial field or a whole field in which the film of the resist ink is contained in the coated circuit. The step of hardening the resist ink in the field of energy rays to form a protective film for the line.

Examples of the active energy ray used in the hardening step include electromagnetic waves and particle beams such as near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, γ-rays, and electron beams, but ultraviolet rays and visible rays are preferred, and ultraviolet rays are more preferable. good. The light source of the ultraviolet ray and the visible ray is not particularly limited, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, a halogen lamp, or the like can be used. The amount of irradiation of ultraviolet rays and visible rays at this time varies depending on the composition of the resist ink, etc., but may be in the range of 100 mJ/cm ² or more and 5000 mJ/cm ² or less. Further, the measurement wavelength of the above exposure amount was 365 nm.

Further, when a photopolymerization initiator and a thermal polymerization initiator are used together as the polymerization initiator (C), a heating hardening step may be performed after the hardening step of irradiation of the active energy ray. The heating temperature (thermosetting temperature) in the hardening step of heating varies depending on the cracking temperature of the thermal polymerization initiator, but is preferably 80 ° C or more and 170 ° C or less. The heating time (thermal curing time) in the hardening step of heating is also the same, but it is preferably 5 minutes or longer and 3 hours or shorter, more preferably 10 minutes or longer and 2 hours or shorter.

The thickness of the protective film of the present embodiment can be appropriately set in accordance with the use of the protective film, and is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 20 μm or less, and still more preferably 2 μm or more and 15 μm or less. Further, the protective film of the present embodiment may contain other components than the cured product of the resist ink of the present embodiment as necessary.

Further, the present embodiment is an example of the present invention, but the present invention is not limited to the embodiment. Further, various modifications and improvements can be made to the embodiment, and various modifications and improvements are also included in the invention.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. Compound of (meth)allyl-containing compound (A), thiol compound (B), polymerization initiator (C), and (meth)acryloyl group The various materials of the material (D) were mixed, and the resist inks of Examples 1 to 11 and Comparative Examples 1 to 4 were prepared. Various materials used for the preparation of the resist ink are as described below.

(i) a compound containing (meth)allyl (A)

For the compound (A) containing a (meth)allyl group, the following seven compounds (i-1) to (i-7) were used.

(i-1) Allyl ester resin A produced in Production Example 1 to be described later (iodine price 77.1)

(i-2) Allyl ester resin B produced in Production Example 2 to be described later (iodine value 148.3)

(i-3) Allyl Ester Resin C (Iodine Price 75.0) produced in Production Example 3 to be described later

(i-4) Allyl ester resin D produced in Production Example 4 to be described later (iodine value: 141.6)

(i-5) triallyl isocyanurate (allyl number 3, iodine value 306)

(i-6) diallyl terephthalate (allyl number 2, iodine value 206.1)

(i-7) Diallyl 1,4-cyclohexanedicarboxylate (trade name H-DATP, allyl number 2, iodine price 201.2, manufactured by Showa Denko Co., Ltd.)

(ii) thiol compound (B)

For the thiol compound (B), the following three compounds are used (ii- 1)~(ii-3).

(ii-1) Pentaerythritol-indole (3-mercaptobutyrate) (trade name: Karenz MT (trademark) PE1, molecular weight 545, 巯 base number 4, manufactured by Showa Denko Co., Ltd.)

(ii-2) 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Showa Denko The product name of the company is KarenzMT (trademark) NR1, molecular weight 568, 巯 base number 3)

(ii-3) pentaerythritol-indole (3-mercaptopropionate) (trade name PEMP, molecular weight 489, fluorenyl number 4, manufactured by Sigma Chemical Industry Co., Ltd.)

(iii) polymerization initiator (C)

For the polymerization initiator (C), the following three compounds (iii-1) to (iii-3) were used.

(iii-1) 2,4,6-trimethylbenzimidylphosphine oxide (ESACURE KTO46 manufactured by DKSH JAPAN Co., Ltd., a mixture of a polymer having an α-hydroxyketone group and a benzophenone derivative)

(iii-2) Ethyl (2,4,6-trimethylbenzylidene)phenylphosphonate (Irgacure TPO-L manufactured by BASF Corporation)

(iii-3) 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173 by BASF)

(iv) a compound containing a (meth) acrylonitrile group (D)

For the compound (D) containing a (meth) acrylonitrile group, the following four compounds (iv-1) to (iv-4) were used.

(iv-1) Epoxy acrylate having a bisphenol A type skeleton (VR77 manufactured by Showa Denko Co., Ltd.)

(iv-2) Polyester acrylate having a bisphenol A type skeleton (Ebecryl 812 manufactured by Daicel Allnex Co., Ltd.)

(iv-3) Urethane acrylate A produced in Production Example 5 to be described later

(iv-4) Dipentaerythritol hexaacrylate (DPHA, molecular weight 524, propylene fluorenyloxy group 6 manufactured by Daicel Allnex Co., Ltd.)

The following Production Examples 1 to 5 are the production methods of the above allyl ester resins A to D and urethane acrylate A.

[Production Example 1: Production of Allyl Ester Resin A]

In a 2 L three-necked flask equipped with a distillation apparatus, 500 g of diallyl terephthalate, 101 g of propylene glycol, and 0.5 g of dibutyltin oxide were charged, and the mixture was heated at 180 ° C under a nitrogen stream to distill off the produced allyl alcohol. .

When the allyl alcohol was distilled off to about 90 g, the inside of the reaction system was reduced to 1.3 kPa to increase the distillation rate of the allyl alcohol. The theoretical amount of allyl alcohol was distilled off and then heated for 1 hour, and maintained at a temperature of 190 ° C and a pressure of 0.13 kPa for further 1 hour to remove the remaining diallyl terephthalate from the allyl ester resin A to obtain 445 g. Allyl ester resin A. The iodine value of the allyl ester resin A measured according to the JIS K 0070 method was 77.

Gas chromatograph GC-14B manufactured by Shimadzu Corporation, a joint-stock company (detector: hydrogen hydride ionization detector, column: OV-17 (0.5 m), temperature condition: 160 ° C), analysis of allyl ester resin A, allyl ester resin A containing 1% by mass of diallyl terephthalate, and the remaining 99% by mass of terephthalic acid A transesterification reaction of a diallyl ester with propylene glycol (allyl ester oligomer).

[Production Example 2: Production of allyl ester resin B]

In the same manner as in Production Example 1, except that the amount of use of diallyl terephthalate was changed to 739 g and the amount of propylene glycol used was changed to 76 g, 699 g of allyl ester resin B was obtained. The iodine value of allyl ester resin B measured according to the method of JIS K 0070 was 145.

In the same manner as in Production Example 1, allyl ester resin B was analyzed, and allyl ester resin B contained 35% by mass of diallyl terephthalate. The remaining 65 mass% is a transesterification reaction (allyl ester oligomer) of diallyl terephthalate with propylene glycol.

[Production Example 3: Production of allyl ester resin C]

In the same manner as in Production Example 1, except that 500 g of diallyl terephthalate was used instead of propylene carbonate 1,4-cyclohexanedicarboxylate, 452 g of allyl ester resin C was obtained. The iodine value of the allyl ester resin C measured according to the method of JIS K 0070 was 75.0.

In the same manner as in Production Example 1, allyl ester resin C was analyzed, and allyl ester resin C contained 2% by mass of diallyl 1,4-cyclohexanedicarboxylate. The remaining 98% by mass is a transesterification reaction (allyl ester oligomer) of diallyl 1,4-cyclohexanedicarboxylate with propylene glycol.

[Production Example 4: Production of allyl ester resin D]

717 g of allyl ester resin D was obtained in the same manner as in Production Example 3 except that the amount of use of diallyl 1,4-cyclohexanedicarboxylate was changed to 757 g, and the amount of propylene glycol used was changed to 76 g. The iodine value of the allyl ester resin D measured according to the method of JIS K 0070 was 141.6.

Further, in the same manner as in Production Example 1, allyl ester resin D was analyzed, and allyl ester resin D contained 3 mass% of diallyl 1,4-cyclohexanedicarboxylate. The remaining 65 mass% is a transesterification reaction (allyl ester oligomer) of diallyl 1,4-cyclohexanedicarboxylate with propylene glycol.

[Production Example 5: Production of urethane acrylate A]

A polyester polyol HOKOKUOL (registered trademark) HT-110 (hydroxyl price: 112.2 mgKOH/g) 475 g and 2,2 manufactured by the company of the company was supplied to a reaction vessel equipped with a stirring device, a thermometer, and a condenser. - 3.7 g of bis(hydroxymethyl)butyric acid, and the internal temperature of the reaction vessel was raised to 130 ° C using an oil bath while stirring with a stirring apparatus.

Thereafter, 222.29 g (1.0 mol) of isophorone diisocyanate (trade name: IPDI) manufactured by Evonik JAPAN Co., Ltd. was dropped into the reaction vessel over 30 minutes. After the completion of the dropwise addition of isophorone diisocyanate, the internal temperature of the reaction vessel was maintained at 120 ° C while stirring was continued, and the reaction was continued for 7 hours. Then, while stirring, the internal temperature of the reaction vessel was lowered to 80 ° C, and then hydroquinone monomethyl ether 0.7 g and dioctyltin dilaurate were added. 0.3 g of the solution was placed in a reaction vessel, and then 116.12 g (1.0 mol) of 2-hydroxyethyl acrylate manufactured by Nippon Shokubai Co., Ltd. was dropped for 1 hour. During this period, the internal temperature of the reaction vessel was maintained in the range of 80 ° C to 90 ° C.

After the dropwise addition of 2-hydroxyethyl acrylate was completed, the reaction was continued at 80 ° C for 3 hours. Thereafter, the infrared absorption spectrum of the reaction product was measured. It was confirmed in the infrared absorption spectrum that the absorption of the isocyanato group disappeared, and the reaction was completed to obtain the urethane acrylate A.

Further, the molecular weight of the oligomer or polymer in each of the examples and the comparative examples is a polystyrene-equivalent number average molecular weight measured by a GPC method. The measurement conditions of GPC are as follows.

Device name: HPLC unit HSS-2000 manufactured by Japan Seiko Co., Ltd.

Column: Shodex column LF-804×3 (series)

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus, manufactured by JASCO Corporation

Temperature: 40.0 ° C

Sample quantity: 100 μL of sample loop

Sample concentration: 0.1% by mass

The (meth)allyl-containing compound (A), the thiol compound (B), the polymerization initiator (C), and the (meth)acrylonitrile-containing compound (D) are as shown in Table 1. The resist ink is prepared by mixing. In Table 1, "(A)/(B) functional group ratio" is (meth)-containing The ratio of the (meth)allyl number of the propyl compound (A) to the thiol group of the thiol compound (B) ((meth)allyl number / fluorenyl number).

Further, in Table 1, "mass ratio of (D)" is a compound (A) containing a (meth)allyl group, a thiol compound (B), and a compound (D) containing a (meth)acryl fluorenyl group. The content of the compound (D) containing a (meth) acrylonitrile group in a total amount of 100 parts by mass.

Next, the cured products of the resist inks of Examples 1 to 11 and Comparative Examples 1 to 4 were evaluated for acid resistance of the electroless tin plating solution as follows. The results are shown in Table 1.

In a single-sided central portion of 5 cm × 8 cm of a copper/polyimine laminated substrate (S'PERFLEX manufactured by Sumitomo Metal Mining Co., Ltd.) having a rectangular shape of 8 cm × 11 cm, the resist ink was applied as a bar coater. A film having a thickness of 50 μm. Next, the film of the resist ink was cured by irradiating UV light of an exposure amount of ² J/cm ² using a conveyor belt type UV irradiator ECS-4011GX (high-pressure mercury lamp) manufactured by EYE GRAPHICS Co., Ltd. to obtain hardening by a resist ink. A test body of a protective film composed of the object. Further, the measurement wavelength of the above exposure amount was 365 nm.

The obtained test body was washed with a sulfuric acid aqueous solution having a concentration of 5 mass%, and then immersed in an electroless tin plating solution 580M12Z manufactured by Ishihara Chemical Co., Ltd. at 60 ° C for 4 minutes. At this time, in order to observe that the plating treatment portion was not applied, half of the protective film composed of the cured product of the resist ink was not immersed in the electroless tin plating solution. The test body was taken out from the electroless tin plating solution, washed repeatedly with warm water, and then subjected to eutectic treatment at 120 ° C for 90 minutes in a forced air type constant temperature dryer. Next, the test body was subjected to the following three evaluations.

<Evaluation of peeling of protective film>

The protective film was visually observed for peeling from the substrate, and the peeling of the protective film was "A", and the peeling of the protective film was "C".

<Evaluation of plating sneak>

Using a microscope VHX-900 manufactured by the company's Keyence, observe whether there is plating penetration between the protective film and the copper. For those who do not sneak into "A", those who sneak into but not reach 1mm are "B", and those who sneak into 1mm or more are "C".

<Evaluation of Protective Film Coloring>

By visually observing the change in the color of the protective film, compared with before the immersion in the electroless tin plating solution, the colorlessness is "A", and the color becomes thicker but the colorlessness is unevener than the non-electrolytic tin plating solution before the immersion. "Compared with that before the immersion of the electroless tin plating solution, the person who produces the mottled pattern discoloration is "C".

As is clear from the results of Table 1, the cured products of the resist inks of Examples 1 to 11 because the resist ink contains the (meth)allyl-containing compound (A), the thiol compound (B), and the polymerization initiator. (C) is excellent in acid resistance, and even if it is immersed in a strongly acidic electroless tin plating solution, peeling of the protective film, immersion of plating, and coloration of the protective film hardly occur.

On the other hand, in the cured product of the resist ink of Comparative Examples 1 to 4, since the resist ink does not contain at least one of the (meth)allyl-containing compound (A) and the thiol compound (B), it is resistant to acid. Insufficient. Therefore, the immersion in the strongly acidic electroless tin plating solution causes peeling of the protective film, and the immersion of the plating and the coloration of the protective film cannot be evaluated.

Claims (15)

A resist ink characterized by containing a (meth)allyl-containing compound (A) having two or more (meth)allyl groups in one molecule, and having two or more mercapto groups in one molecule. a thiol compound (B), a polymerization initiator (C), and a (meth) propylene group-containing compound (D), wherein the (meth)allyl-containing compound (A) and the sulfur are When the total content of the alcohol compound (B) and the (meth)acrylonitrile group-containing compound (D) is 100 parts by mass, the content of the (meth)acrylonitrile group-containing compound (D) is 10 mass. More than 80 parts by mass or less. The resist ink according to claim 1, wherein the (meth)allyl-containing compound (A) comprises a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. . The resist ink according to claim 1 or 2, wherein the (meth)allyl-containing compound (A) comprises a compound having at least one of an allyloxycarbonyl group and an N-allyl group. The resist ink according to claim 1 or 2, wherein the (meth)allyl-containing compound (A) comprises a compound having a structure of at least one of an ester structure and an isocyanurate structure. The resist ink according to claim 1, wherein the (meth)allyl-containing compound (A) comprises diallyl phthalate, diallyl isophthalate, or terephthalic acid. Diallyl ester, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, And at least one selected from triallyl isocyanurate. The resist ink according to claim 1 or claim 2, wherein the thiol compound (B) comprises a compound having two or more quaternary or tertiary sulfhydryl groups in one molecule. The resist ink according to claim 6, wherein the thiol compound (B) is 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol ruthenium (3-mercaptobutyrate), 1, 3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropane ginseng (3 At least one selected from - mercaptobutyrate. The resist ink according to claim 1 or claim 2, wherein the (meth)acrylonitrile group-containing compound (D) contains a compound having two or more (meth)acrylonium groups in one molecule. The resist ink according to claim 8, wherein the (meth)acrylonitrile group-containing compound (D) comprises an epoxy group (meth) acrylate or a (poly) ester (meth) acrylate, Poly)carbonate (methyl) At least one selected from the group consisting of acrylates and hydrogenated polybutadiene (meth) acrylates. The resist ink according to claim 1 or claim 2, wherein the (meth)acrylonitrile group-containing compound (D) comprises a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure. The resist ink according to claim 1 or claim 2, wherein the (meth)allyl group of the (meth)allyl group-containing compound (A) has a thiol group number relative to the thiol compound (B) The ratio (allyl number / fluorenyl group) is in the range of 0.25 or more and 4 or less, and the (meth)allyl group-containing compound (A) and the thiol compound (B) and the (meth)acryl-containing group are contained. When the total content of the compound (D) is 100 parts by mass, the content of the polymerization initiator (C) is 0.01 parts by mass or more and 10 parts by mass or less. The resist ink according to claim 1 or claim 2, wherein the polymerization initiator (C) comprises a compound which generates a polymerizable radical species by irradiation with an active energy ray. A cured product of the resist ink according to any one of claims 1 to 12. A protective film for a line, characterized by the content of claim 13 Hardened material. A method for producing a protective film for a line, comprising: disposing the resist ink described in any one of claims 1 to 12 as a film on a substrate having a line; The coating step of the film coating and the active energy ray of the wavelength at which the polymerization initiator (C) generates a polymerizable radical species is irradiated in a partial field or a whole field in the field of coating the above-mentioned circuit in the film containing the above-mentioned resist ink. And a hardening step of curing the resist ink to form a protective film of the above-mentioned wiring.