WO2017170050A1 - Resist ink, cured product of same, protective film for wiring lines and method for producing protective film for wiring lines - Google Patents

Abstract

Provided is a resist ink which is capable of forming a cured product that has excellent acid resistance. This resist ink contains a (meth)allyl group-containing compound (A) having two or more (meth)allyl groups in one molecule, a thiol compound (B) having two or more mercapto groups in one molecule, and a polymerization initiator (C).

Description

Resist ink, cured product thereof, protective film for wiring, and manufacturing method thereof

The present invention relates to a resist ink, a cured product thereof, a protective film for wiring, and a manufacturing method thereof.

Copper wiring used for printed wiring boards and the like is treated with a strong acid electroless tin plating solution and tin-plated to prevent oxidation. Therefore, a resist (cured product of resist ink) having resistance to a strongly acidic electroless tin plating solution is required. Patent Documents 1 to 3 disclose resist inks that can form resists having acid resistance, but have not been sufficiently resistant to strongly acidic electroless tin plating solutions.

Japanese Patent Publication No. 268067 in 2003 Japanese Patent Publication No. 24591, 2005 Japanese Patent Gazette No. 3190251

Therefore, an object of the present invention is to provide a resist ink that can solve the above-described problems of the prior art and can form a cured product having excellent acid resistance. Another object of the present invention is to provide a cured product having excellent acid resistance. Furthermore, this invention makes it a subject to provide the protective film of the wiring excellent in acid resistance, and its manufacturing method.

In order to solve the above problems, one aspect of the present invention is as described in [1] to [14] below.
[1] A (meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule, a thiol compound (B) having two or more mercapto groups in one molecule, and polymerization Resist ink containing an initiator (C).
[2] The resist ink according to [1], wherein the (meth) allyl group-containing compound (A) includes a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure.
[3] The resist ink according to [1] or [2], wherein the (meth) allyl group-containing compound (A) includes a compound having at least one of an allyloxycarbonyl group and an N-allyl group.

[4] The resist ink according to any one of [1] to [3], wherein the (meth) allyl group-containing compound (A) includes a compound having at least one of an ester structure and an isocyanurate structure.
[5] The (meth) allyl group-containing compound (A) includes diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, 1,2- The resist ink according to [1], comprising at least one selected from diallyl cyclohexanedicarboxylate and triallyl isocyanurate.

[6] The resist ink according to any one of [1] to [5], wherein the thiol compound (B) includes a compound having two or more secondary or tertiary mercapto groups in one molecule.
[7] The thiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryl). Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and at least one selected from trimethylolpropane tris (3-mercaptobutyrate) [6] The resist ink described in 1.
[8] The resist ink according to any one of [1] to [7], further containing a (meth) acryloyl group-containing compound (D).

[9] The resist ink according to [8], wherein the (meth) acryloyl group-containing compound (D) includes a compound having two or more (meth) acryloyl groups in one molecule.
[10] The (meth) acryloyl group-containing compound (D) is selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate, and hydrogenated polybutadiene (meth) acrylate. [9] The resist ink according to [9].

[11] The compound (D) according to any one of [8] to [10], wherein the (meth) acryloyl group-containing compound (D) includes a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure. Resist ink.
[12] The ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) (number of allyl groups / number of mercapto groups) is 0. Within the range of 25 or more and 4 or less,
Content of the polymerization initiator (C) when the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass. The resist ink according to any one of [8] to [11], wherein is from 0.01 parts by weight to 10 parts by weight.

[13] When the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass, The resist ink according to any one of [8] to [12], wherein the content of the (meth) acryloyl group-containing compound (D) is from 10 parts by weight to 80 parts by weight.
[14] The resist ink according to any one of [1] to [13], wherein the polymerization initiator (C) includes a compound that generates a polymerizable radical species upon irradiation with active energy rays.
[15] A cured product of the resist ink according to any one of [1] to [14].
[16] A protective film for a wiring containing the cured product according to [15].

[17] A coating process in which the resist ink according to [14] is arranged in a film shape on a substrate having wiring, and the wiring is covered with the resist ink film;
The resist ink film is irradiated with active energy rays having a wavelength that generates a polymerizable radical species in the polymerization initiator (C) on a part or all of the region including the region covering the wiring in the resist ink film. A curing step of curing the ink to form a protective film for the wiring;
The manufacturing method of the protective film of wiring provided with this.

According to the present invention, a cured product excellent in acid resistance and a protective film for wiring can be provided.

An embodiment of the present invention will be described below. The resist ink of this embodiment includes a (meth) allyl group-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).

The resist ink of this embodiment can be easily cured in a short time by irradiation with active energy rays or heat, and the cured product has excellent acid resistance. Therefore, the resist ink of this embodiment can be used suitably as a protective material for acidic liquid protection. For example, the cured product of the resist ink of the present embodiment is sufficiently resistant to an acidic plating solution. Therefore, when plating a copper wiring used for a printed wiring board or the like with an acidic plating solution, the resist (wiring of the wiring) is used. It can be used as a protective film. Although the electroless tin plating solution used for tin plating is particularly strongly acidic, the cured product of the resist ink of this embodiment has resistance, so tin plating is performed using the electroless tin plating solution. It can also be used as a resist.

In addition, the cured product of the resist ink (wiring protective film) of the present embodiment has excellent adhesion to the substrate to be coated, as well as excellent moisture resistance and heat resistance, and has a long-term insulation at a high level. It also has reliability.
Furthermore, the resist ink of the present embodiment does not need to be dissolved in a solvent and can be made solvent-free, so that it is difficult to cause environmental pollution.

Hereinafter, a resist ink according to an embodiment of the present invention, a cured product obtained by curing the resist ink, a wiring protective film containing the cured product, and a manufacturing method thereof will be described in detail. .
In addition, the “(meth) acryloyl group” in the present specification means an acryloyl group and / or a methacryloyl group. In addition, as used herein, “(meth) allyl” means methallyl (ie, 2-methyl-2-propenyl) and / or allyl (ie, 2-propenyl). Further, “(meth) acrylate” means methacrylate and / or acrylate, and “(meth) acryl” means methacryl and / or acrylic.

[1] (Meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule
The (meth) allyl group-containing compound (A) is a compound having two or more (meth) allyl groups in one molecule, and may be a monomer, an oligomer or a polymer, From the viewpoint, a compound having a number average molecular weight of 200 or more and 20000 or less is preferable. In addition, unless otherwise indicated, the molecular weight of the oligomer or polymer in this invention is the number average molecular weight of polystyrene (PS) conversion measured by the gel permeation chromatography method (GPC method). Detailed measurement conditions of the molecular weight are shown in the examples described later.

Examples of the (meth) allyl group-containing compound (A) include a compound (a-1) having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in the molecule and an acyclic compound ( a-2).
Examples of the alicyclic structure include alicyclic rings having 3 to 6 carbon atoms, preferably a cyclohexane ring and a cycloheptane ring. Examples of the aromatic ring structure include aromatic rings having 6 to 10 carbon atoms, preferably a benzene ring and a naphthalene ring. Examples of the heterocyclic structure include a three-membered ring to a ten-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom, and examples thereof include a pyridine ring, a triazine ring, a ring derived from cyanuric acid, and a ring derived from isocyanuric acid.

When the (meth) allyl group-containing compound (A) is a monomer, examples of the compound (a-1) include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, and tetraallyl pyromellitic acid. Allyloxycarbonyl group-containing compounds having an aromatic ring structure, diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, triallyl 1,2,4-cyclohexanetricarboxylate 1,2,4,5-cyclohexanetetracarboxylic acid tetraallyl, 5-alkyl-substituted cyclohexane-1,4-dicarboxylic acid diallyl, 5-halogen-substituted cyclohexane-1,4-dicarboxylic acid diallyl, 1,3-adamantane dicarboxylic acid Diallyl 1,3,5-adamantanetricarboxylic acid triallyl, hydrogenated bisphenol A type diallyl ether, hydrogenated dimer acid (having 36 or 44 carbon atoms and having an alicyclic structure) diallyl, tricyclodecane dimethanol dicarboxylate diallyl Allyloxycarbonyl group-containing compounds having an alicyclic structure such as triallyl isocyanurate, triallyl cyanurate, diallyl monohydroxyethyl cyanurate, diallyl monohydroxyethyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate prepolymer, 1, Examples thereof include N-allyl group-containing compounds having a heterocyclic structure such as 3,5-triallylhexahydro-1,3,5-triazine and 1,3,4,6-tetraallylglycoluril. Among these, the (meth) allyl group-containing compound (A) is preferably a compound having at least one of an ester structure and an isocyanurate structure.

Examples of the compound (a-1) include a metalyloxycarbonyl group-containing compound having an aromatic ring structure such as dimethallyl phthalate, dimethallyl isophthalate, dimethallyl terephthalate, trimethallyl trimellitic acid, tetramethallyl pyromellitic acid, -Dimethallyl cyclohexanedicarboxylate, dimethallyl 1,3-cyclohexanedicarboxylate, dimethallyl 1,4-cyclohexanedicarboxylate, trimethallyl 1,2,4-cyclohexanetricarboxylate, tetramethallyl 1,2,4,5-cyclohexanetetracarboxylate, 5 -Alkyl-substituted cyclohexane-1,4-dicarboxylate dimethallyl, 5-halogen-substituted cyclohexane-1,4-dicarboxylate dimethallyl, 1,3-adamantane dicarboxylate 1,3,5-adamanta Trimethallyl tricarboxylate, dimethallyl 5-halogen-substituted cyclohexane-1,4-dicarboxylate, hydrogenated dimer acid (having 36 or 44 carbon atoms and having an alicyclic structure) dimethallyl, dimethallyl tricyclodecane dimethanol dicarboxylate, etc. Compounds having a alicyclic structure such as trimethallyl isocyanurate, trimethallyl cyanurate, 1,3,5-trimethallylhexahydro-1,3,5-triazine, 1,3,4,6-tetra Examples thereof include N-methallyl group-containing compounds such as methallyl glycoluril.

Further, as compound (a-1), bisphenol A diallyl ether, bisphenol A dimethallyl ether, bisphenol S diallyl ether, bisphenol S dimethallyl ether, 1,4-naphthalenedicarboxylic acid diallyl ether, 1,4-naphthalenedicarboxylic acid Dimethallyl ether, 1,5-naphthalenedicarboxylic acid diallyl ether, 1,5-naphthalenedicarboxylic acid dimethallyl ether, 2,6-naphthalenedicarboxylic acid diallyl ether, 2,6-naphthalenedicarboxylic acid dimethallyl ether, 2,7- Naphthalenedicarboxylic acid diallyl ether, 2,7-naphthalenedicarboxylic acid dimethallyl ether, diphenyl-m, m′-dicarboxylic acid diallyl ether, diphenyl-m, m′-dimethallyl ether Diphenyl-p, p'-dicarboxylic acid diallyl ether, diphenyl-p, p'-dicarboxylic acid dimethallyl ether, benzophenone-4,4-dicarboxylic acid diallyl ether, benzophenone-4,4-dicarboxylic acid dimethallyl ether, Methyl terephthalic acid diallyl ether, methyl terephthalic acid dimethallyl ether, tetrachlorophthalic acid diallyl ether, tetrachlorophthalic acid dimethallyl ether, diallyl fluorene, dimethallyl fluorene, fluorene bisphenoxyethyl diallyl ether, fluorene bisphenoxyethyl dimethallyl ether, Aliene such as fluorene bisphenoxyethyl dimethallyl ether, fluorene bisphenoxyethyl dimethallyl ether, fluorene bisphenoxybismethallyl ether, etc. Ether compounds, and the like.

On the other hand, compounds having an allyl group and a methallyl group in one molecule are also included. Compound (a-1) includes allyl methallyl phthalate, allyl methallyl isophthalate, diallyl methallyl trimellitic acid, allyl dimethallyl trimellitic acid, triallyl methallyl pyromellitic acid, diallyl dimetall pyromellitic acid Ester, pyromellitic acid allyltrimethallyl ester, bisphenol A allylmethallyl ether, bisphenol S allylmethallyl ether, 1,4-naphthalenedicarboxylic acid allylmethallyl ether, 1,5-naphthalenedicarboxylic acid allylmethallyl ether, 2,6-naphthalenedicarboxylic acid Acid allylmethallyl ether, 2,7-naphthalenedicarboxylic acid allylmethallyl ether, diphenyl-m, m′-dicarboxylic acid allylmethallyl ether, diphenyl- , P'-dicarboxylic acid allyl methallyl ether, benzophenone-4,4-dicarboxylic acid allyl methallyl ether, methyl terephthalic acid allyl methallyl ether, tetrachlorophthalic acid allyl methallyl ether, allyl methallyl fluorene, fluorene bisphenoxyethyl allyl methallyl ether, Compounds having an aromatic ring structure such as fluorene bisphenoxyallyl methallyl ether and allyl groups, allyl methallyl 1,4-cyclohexanedicarboxylate, allyl methallyl 1,3-cyclohexanedicarboxylate, 1,2,4-cyclohexanetricarboxylic Allyl dimethallyl, 1,2,4-cyclohexanetricarboxylic acid diallylmethallyl, 1,2,4,5-cyclohexanetetracarboxylic acid triallylmethallyl, 1,2 4,5-cyclohexanetetracarboxylate diallyldimethallyl, 1,2,4,5-cyclohexanetetracarboxylate allyltrimethallyl, 5-alkyl-substituted cyclohexane-1,4-dicarboxylate allylmethallyl, 5-halogen-substituted cyclohexane-1, Allyl methallyl 4-dicarboxylate, allyl methallyl 1,3-adamantane dicarboxylate, diallyl methallyl 1,3,5-adamantane tricarboxylate, allyl dimethallyl 1,3,5-adamantane tricarboxylate, hydrogenated dimer acid (with carbon number) 36 or 44 having an alicyclic structure) allyl methallyl, a compound in which a methallyl group having an alicyclic structure and an allyl group, such as allyl methallyl dicyclohexanedimethanol dicarboxylate, allyl methallyl monohydroxyethyl cyanurate, Diallylmethallyl isocyanurate, allyldimethallyl isocyanurate, 1,5-diallyl-3-methallylhexahydro-1,3,5-triazine, 1-allyl-3,5-dimethallylhexahydro-1,3 N-methallyl such as 5-triazine, 1,3,4,6-methallyltriallylglycoluril, 1,3,4,6-dimethallyldiallylglycoluril, 1,3,4,6-trimethallylallylglycoluril And a compound in which a group and an N-allyl group coexist.

As the compound (a-2), diethylene glycol bis (allyl carbonate), tetraallyl 1,2,3,4-butanetetracarboxylate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl sebacate, diallyl dimer, Hydrogenated dimer acid diallyl, diallyl 1,12-dodecanedioate, diallyl maleate, diallyl itaconate, diethylene glycol bis (methallyl carbonate), tetramethallyl 1,2,3,4-butanetetracarboxylate, dimethallyl succinate, glutar Dimethallyl acid, dimethallyl adipate, dimethallyl sebacate, dimethallyl dimer, dimethallyl hydrogenated dimer, dimethallyl 1,12-dodecanedioate, dimethallyl maleate, dimethallyl itaconate, trimethylolpropane dimethallyl Ether, pentaerythritol methallyl ether, trimethylolpropane methallyl ether, pentaerythritol tetra methallyl ether can be exemplified.

In consideration of the physical properties such as acid resistance of the cured product of the resist ink of this embodiment, among these (meth) allyl group-containing compounds (A), the compound (a-1) is more preferable than the compound (a-2). The case is preferred, and the same applies when the (meth) allyl group-containing compound (A) is a monomer and when the (meth) allyl group-containing compound (A) described later is an oligomer.
In consideration of the reactivity (curability) of the resist ink, among these (meth) allyl group-containing compounds (A), compounds having at least one of an allyloxycarbonyl group and an N-allyl group are preferable.

Furthermore, considering both the physical properties such as acid resistance of the cured product of the resist ink of this embodiment and the reactivity of the resist ink, the compound (a-1) having at least one of an allyloxycarbonyl group and an N-allyl group Preferred are diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, and triallyl isocyanurate. .

When the (meth) allyl group-containing compound (A) is an oligomer, examples of the (meth) allyl group-containing compound (A) include (meth) allyl ester resins. The (meth) allyl ester resin is a compound having a (meth) allyloxycarbonyl group at the molecular end and a repeating unit in the molecule. For example, transesterification reaction between a polybasic acid (meth) allyl ester compound and a polyhydric alcohol, an alcohol such as a monool or polyhydric alcohol containing (meth) allyl allyl alcohol, a polybasic acid and a polybasic acid anhydride Condensation reaction with at least one selected from the above, a transesterification reaction between a polyol having a repeating unit and a (meth) allyl ester compound of a polybasic acid, a monool containing (meth) allylallyl alcohol, a polyol having a repeating unit, etc. It is a compound produced | generated by various reaction of condensation reaction with at least 1 sort (s) chosen from the alcohol of this, a polybasic acid, and a polybasic acid anhydride.

As the catalyst used in the transesterification reaction, an organometallic compound is particularly preferable, and specific examples include tetraisopropoxy titanium, tetra-n-butoxy titanium, dibutyl tin oxide, dioctyl tin oxide, acetylacetone hafnium, acetylacetone zirconium and the like. be able to.
The reaction temperature for the transesterification reaction is preferably 100 ° C. or higher and 230 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower. In particular, when a solvent is used in the transesterification reaction, the boiling point may limit. In addition, the polyhydric alcohol used may be limited.

Furthermore, in the transesterification reaction, it is not necessary to use a solvent, but if necessary, a solvent that does not inhibit the transesterification reaction can also be used. Specific examples include benzene, toluene, xylene, cyclohexane and the like. Of these, benzene and toluene are preferred.
Specific examples of the (meth) allyl ester resin include, for example, oligomers having a structure represented by the following formulas (1), (2), and (4).

N R ^{1 s} in the formula (1) each independently represent a linear alkylene group or a branched alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). . R ² and R ³ each independently represent a hydrogen atom or a methyl group. Preferably, both R ² and R ³ are hydrogen atoms.

In the formula (1), (n + 1) Xs are each independently an organic group derived from a divalent carboxylic acid, preferably having an alkyl group having 1 to 4 carbon atoms as a substituent. It may be a phenylene group or a cyclohexylene group, more preferably a phenylene group or a cyclohexylene group having no substituent. Examples of the alkyl group having 1 to 4 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 phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but considering the ease of synthesis, the 1,3-position or 1-position , 4th position is preferred.
N in Formula (1) is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less, and 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 20000 or less, more preferably 800 or more and 18000 or less, and further preferably 1000 or more and 16000 or less.

In formula (2), (2m + 1) A's are each independently an organic group derived from a divalent carboxylic acid, preferably having an alkyl group having 1 to 4 carbon atoms as a substituent. A good phenylene group or cyclohexylene group, more preferably a phenylene group or cyclohexylene group having no substituent. Examples of the alkyl group having 1 to 4 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 phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but considering the ease of synthesis, the 1,3-position or 1-position , 4th position is preferred.

The m ^{R 4} in the formula (2) are each independently a hydrogen atom, 1 to 4 alkyl group having a carbon number (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec -Butyl group, isobutyl group, and tert-butyl group), or a group represented by the following formula (3). Moreover, R < ⁵ >, R < ⁷ > and m R < ⁶ > in Formula (2) show a hydrogen atom or a methyl group each independently. Preferably, R ⁵ , R ⁷ and m R ⁶ are all hydrogen atoms. A in the formula (3) is the same as in the oligomer represented by the formula (2), and R ⁸ represents 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, and 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 20000 or less, more preferably 500 or more and 18000 or less, and further preferably 700 or more and 16000 or less.

In formula (4), (q + 1) Z's are each independently an organic group derived from a divalent carboxylic acid, and preferably have an alkyl group having 1 to 4 carbon atoms as a substituent. A good phenylene group or cyclohexylene group, more preferably a phenylene group or cyclohexylene group having no substituent. Examples of the alkyl group having 1 to 4 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 a linear alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). Or a branched alkylene group is shown. Moreover, R < ¹⁰ > and R < ¹¹ > in Formula (4) shows a hydrogen atom or a methyl group each independently. Preferably, both R ¹⁰ and R ¹¹ are hydrogen atoms.
P in Formula (4) 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 Formula (4) is an integer of 5 or more and 50 or less, preferably 5 or more and 45 or less, and more preferably 5 or more and 40 or less. The molecular weight of the oligomer represented by formula (4) is preferably 300 or more and 20000 or less, more preferably 500 or more and 19000 or less, and further preferably 700 or more and 18000 or less.

Specific examples other than the (meth) allyl ester resin when the (meth) allyl group-containing compound (A) is an oligomer include polyene compounds derived from substituted or unsubstituted allyl alcohol, polyethylene glycol bis (allyl carbonate) Etc.
When the (meth) allyl group-containing compound (A) is a polymer, examples of the (meth) allyl group-containing compound (A) include compounds in which two or more allyl groups are introduced into the polymer skeleton. Examples of the polymer skeleton include a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamide skeleton, a polyimide skeleton, a polyoxyalkylene skeleton, and a polyphenylene skeleton.
Only one type of (meth) allyl group-containing compound (A) may be used alone, or two or more types may be used in combination.

Moreover, it is preferable that the iodine value of the mixture which mixed all the compounds which belong to the (meth) allyl group containing compound (A) used for the resist ink of this embodiment exists in the range of 20 or more and 240 or less. Preferably they are 30 or more and 210 or less. If 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 active energy rays or heat. The iodine value described in the present specification is a value obtained by converting the amount of halogen (unit: g) that reacts with 100 g of the target substance into grams of iodine.

[2] Thiol compound having two or more mercapto groups in one molecule (B)
The thiol compound (B) is not particularly limited as long as it is a compound having two or more mercapto groups in one molecule. Specific examples 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 6 in one molecule. And compounds having one mercapto group.

Examples of compounds having two mercapto groups in one molecule are butanediol bis (2-mercaptoacetate), hexanediol bis (2-mercaptoacetate), ethanediol bis (2-mercaptoacetate), butanediol bis. (2-mercaptoacetate), 2,2 '-(ethylenedithio) diethanethiol, ethylene glycol bis (3-mercapto-2-methylpropionate), propylene glycol bis (3-mercapto-2-methylpropionate) ), Diethylene glycol bis (3-mercapto-2-methylpropionate), butanediol bis (3-mercapto-2-methylpropionate), octanediol bis (3-mercapto-2-methylpropionate), bis (3-mercapto-2-methyl A compound having two primary mercapto groups in one molecule such as propyl) phthalate, 1,4-bis (3-mercaptobutyryloxy) 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-mercaptopropyl) Pionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate) , Diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), ethyl Glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercapto) Compounds having two secondary mercapto groups in one molecule such as valerate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2 -Mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), etc., compounds having two tertiary mercapto groups in one molecule be able to.

Examples of compounds having three mercapto groups in one molecule include trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3- Compounds having three primary mercapto groups in one molecule such as mercapto-2-methylpropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropio) Nate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (4-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), 1,3,5-tris (3- Mercaptobutyloxyethyl)- , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc., a compound having three secondary mercapto groups in one molecule, trimethylolpropane tris (2-mercaptoisobutyrate) And compounds having three tertiary mercapto groups per molecule.

Further, examples of compounds having four mercapto groups in one molecule include four ones in one molecule such as pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate). Compounds having a class mercapto group, dipentaerythritol hexakis (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercapto-2-propionate), pentaerythritol tetrakis (2-mercaptoisobutyrate), pentaerythritol tetrakis (4-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), etc. have four secondary mercapto groups in one molecule Compound or can be given the compound in one molecule such as pentaerythritol tetrakis (2-mercapto isobutyrate) having four tertiary mercapto group.

Further, examples of compounds having 6 mercapto groups in one molecule include six primary mercapto groups in one molecule such as dipentaerythritol hexakis (3-mercapto-2-methylpropionate). Dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoisobutyrate), dipentaerythritol hexa Compounds having six secondary mercapto groups in one molecule such as kiss (4-mercaptovalerate) and dipentaerythritol hexakis (3-mercaptovalerate), dipentaerythritol hexakis (2-mercaptoiso 6 tertiary mercaps of 1 molecule such as butyrate) It can be exemplified compounds having a group.

Among these thiol compounds (B), considering the acid resistance and pot life of the resist ink of the present embodiment, it has no primary mercapto group and the number of secondary mercapto groups and tertiary mercapto groups. The total number of the number is preferably 2 or more. For example, a compound having two secondary mercapto groups in one molecule, a compound having two tertiary mercapto groups in one molecule, a compound having three secondary mercapto groups in one molecule, A compound having three tertiary mercapto groups in one molecule, a compound having four secondary mercapto groups in one molecule, a compound having four tertiary mercapto groups in one molecule, and one molecule A compound having 6 secondary mercapto groups in it, a compound having 6 tertiary mercapto groups in one molecule, and the like are preferable.

As the thiol compound (B), in particular, 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane-tris (3-mercaptobutyrate) are more preferred.

When all mercapto groups of the thiol compound (B) are bonded to a secondary carbon atom or a tertiary carbon atom (that is, all mercapto groups are secondary mercapto groups or tertiary mercapto groups) And) the resist ink pot life and storage stability are excellent.
A thiol compound (B) may be used individually by 1 type, and may use 2 or more types together. 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 this embodiment.

The thiol compound (B) can also be easily obtained as a commercial product. Among secondary thiols containing two or more mercapto groups in one molecule, commercially available products include 1,4-bis (3-mercaptobutyryloxy) butane (a product manufactured by Showa Denko KK). Name Karenz MT (trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT (trademark) PE1 manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyryloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name Karenz MT (trademark) NR1 manufactured by Showa Denko KK), trimethylolpropane tris (3-mercapto Butyrate) (trade name TPMB manufactured by Showa Denko KK) and the like.

The preferred content of the thiol compound (B) in the resist ink of this embodiment is the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B). Can be represented. That is, the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) (number of allyl groups / number of mercapto groups) is determined by curability and acid resistance. From the viewpoint of safety, it is preferably in the range of 0.25 to 4, and more preferably in the range of 0.67 to 2.33. The contents of the (meth) allyl group-containing compound (A) and the thiol compound (B) in the resist ink may be determined so as to achieve such a ratio.

In addition, the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) is the total number of (meth) allyl groups of all the compounds belonging to the (meth) allyl group-containing compound (A) (moles). The number of mercapto groups in the thiol compound (B) means the total number (in moles) of mercapto groups in all the compounds belonging to the thiol compound (B).

In addition, as long as the amount does not impair the effects of the invention, a mercapto group-containing compound other than the thiol compound (B) may be added to the resist ink of the present embodiment. However, the blending amount of the mercapto group-containing compound other than the thiol compound (B) is 20% by mass of the content of all mercapto group-containing compounds including the thiol compound (B) from the viewpoint of maintaining curability and acid resistance. The following is preferable.

[3] Polymerization initiator (C)
The polymerization initiator (C) includes a photopolymerization initiator and a thermal polymerization initiator. The radical polymerization radical is generated by active energy rays and / or heat to polymerize the (meth) allyl group-containing compound (A). Any compound can be used as long as it is a compound that promotes initiation of the polymerization. For example, a polymerization initiator described in Japanese Patent No. 5302688 can be used. A polymerization initiator (C) may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

The photopolymerization initiator and the thermal polymerization initiator may each be used alone, but from the viewpoint of maintaining the printed shape of the resist ink when printing is performed using the resist ink, the polymerization initiator (C) includes It is preferable that a photopolymerization initiator is included. In addition, when performing superposition | polymerization which uses together hardening by irradiation of an active energy ray, and thermosetting, a photoinitiator and a thermal-polymerization initiator can be used together.

The type of the photopolymerization initiator is not particularly limited as long as it is a polymerization initiator that is sensitive to the irradiated active energy rays. Active energy rays include near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, γ rays, electron rays and other electromagnetic waves and particle rays, but as photopolymerization initiators that are sensitive to irradiation with visible rays or ultraviolet rays. Acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, Darocur 1173 manufactured by BASF) and the like, and derivatives thereof.

Further, as a photopolymerization initiator sensitive to irradiation with visible light or ultraviolet light, benzophenone such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-trimethylsilylbenzophenone or the like Examples thereof include benzoin such as benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzoin isopropyl ether or derivatives thereof.

Furthermore, methylphenylglyoxylate, benzoin dimethyl ketal, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate (for example, Irgacure TPO manufactured by BASF) is used as a photopolymerization initiator that is sensitive to irradiation with visible light or ultraviolet light. -L), and bisacylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -phenylphosphine oxide; Examples thereof include acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide.

Particularly preferred photopolymerization initiators include diphenyl-2,4,6-trimethylbenzoylphosphine oxide, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- (4-isopropenylphenyl) -2-methyl. Propan-1-one and its oligomer, 2,4,6-trimethylbenzophenone, and a mixture thereof, LAMBERTI S.P. p. The product name “ESACURE KTO 46” manufactured by Company A can be preferably used.

Further, bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrole-1-) is used as a photopolymerization initiator that is sensitive to irradiation with visible light or ultraviolet light. Yl) phenyl] titanium, thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, methylphenylglyoxylate, benzoin dimethyl ketal, isoamyl p-dimethylaminobenzoate And ethyl p-dimethylaminobenzoate.

A compound generally called a photopolymerization accelerator (for example, isoamyl p-dimethylaminobenzoate) having an excellent accelerating function with respect to a hydrogen abstraction type photopolymerization initiator (eg, benzophenone series, thioxanthone series). , Ethyl p-dimethylaminobenzoate) is also defined as being included in the photopolymerization initiator in the present invention.

Among these photopolymerization initiators, acylphosphine oxide compounds, bisacylphosphine oxide compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl -2-Methylamino-1- (4-morpholinophenyl) butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone are preferred, 2,4,6- Trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, and 1-hydroxycyclohexyl phenyl ketone are more preferable.

Next, the type of thermal polymerization initiator is not particularly limited, and examples thereof include peroxide polymerization initiators such as organic peroxides, azo compounds, persulfates, and redox polymerization initiators. It is done.
As the organic peroxide, for example, dialkyl peroxide, acyl peroxide, hydroperoxide, ketone peroxide, peroxy ester, and the like can be used. Specific examples thereof include diisobutyryl peroxide and cumyl peroxyneodecanoate. Further, peroxide-based polymerization initiators include dibenzoyl peroxide, t-butyl permaleate, di-t, t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, and t-butyl hydro gen. A peroxide etc. are mentioned.

Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile).
Examples of the redox polymerization initiator include a combination of persulfate and sodium bisulfite, a combination of 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 this embodiment is the content of components that do not contribute to the reaction such as the polymerizable initiator (C) and the non-reactive solvent or inorganic filler from the total amount of the resist ink. The content of the polymerization initiator (C) is preferably 0.01 parts by weight or more and 10 parts by weight or less when the amount obtained by subtracting 100 parts by weight is 100 parts by weight. More preferably, it is 0.3 to 7 parts by mass, and particularly preferably 0.4 to 3 parts by mass. If content of a polymerization initiator (C) is in said numerical range, while being able to obtain sufficient hardening rate, the mechanical strength of hardened | cured material becomes high.

For example, when the resist ink of this embodiment is composed of a (meth) allyl group-containing compound (A), a thiol compound (B), and a polymerization initiator (C), the (meth) allyl group-containing compound (A) and When the total content of the thiol compound (B) is 100 parts by mass, the content of the polymerization initiator (C) 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 comprises a (meth) allyl group-containing compound (A), a thiol compound (B), a polymerization initiator (C), and a (meth) acryloyl group-containing compound (D) described later. In this case, the polymerization initiator (C) when the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass. The content of is preferably 0.01 parts by mass or more and 10 parts by mass or less.

[4] (Meth) acryloyl group-containing compound (D)
The resist ink of this embodiment may further contain a (meth) acryloyl group-containing compound (D).
The (meth) acryloyl group-containing compound (D) is not particularly limited as long as it is a compound containing a (meth) acryloyl group, but examples thereof include epoxy (meth) acrylate, (poly) ester (meta) ) Acrylate, (poly) carbonate (meth) acrylate, hydrogenated polybutadiene (meth) acrylate, (poly) ether (meth) acrylate, (poly) urethane (meth) acrylate, and the like.

Among these, epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate, and hydrogenated polybutadiene (meth) acrylate are preferable, and epoxy (meth) acrylate, (poly ) Carbonate (meth) acrylate, more preferably epoxy (meth) acrylate.

The (meth) acryloyl group-containing compound (D) is preferably a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure in the molecule. Furthermore, the (meth) acryloyl group-containing compound (D) is preferably a compound having two or more (meth) acryloyl groups from the viewpoint of curability of the resist ink.
Epoxy (meth) acrylate means all compounds obtained by reacting an epoxy resin having an epoxy group with a monocarboxylic acid having a (meth) acryloyl group. The epoxy resin is preferably a compound having two or more epoxy groups in one molecule, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin. Bisphenol type epoxy resins such as hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin.

Also, ortho-cresol novolac epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, bisphenol A novolac epoxy resin, brominated phenol novolac epoxy resin, alkylphenol novolac epoxy resin, bisphenol S novolac epoxy resin, methoxy Examples also include novolak type epoxy resins such as group-containing novolak type epoxy resins and brominated phenol novolac type epoxy resins.

Others are bifunctional such as phenol aralkyl type epoxy resin (commonly known as epoxidized xyloc resin), resorcin diglycidyl ether, hydroquinone diglycidyl ether, catechol diglycidyl ether, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc. Type epoxy resin, triglycidyl isocyanurate, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolak type epoxy resin (phenolic nucleus linked by bismethylene group) Epoxidized polyhydric phenol resins), methoxy group-containing phenol aralkyl resins, and the like.

Epoxy (meth) acrylate can also be easily obtained as a commercial product. Examples of commercially available epoxy (meth) acrylates include VR-77 manufactured by Showa Denko KK, Epoxy ester 40EM, Epoxy ester 30002M, Epoxy ester 3002A, Epoxy ester 3000MK, and Epoxy ester 3000A manufactured by Kyoeisha Chemical Co., Ltd. , EBECRYL600, EBECRYL648, EBECRYL3700, etc. manufactured by Daicel Ornex Co., Ltd. can be mentioned.

Next, (poly) ester (meth) acrylate means a compound having at least one ester bond other than a (meth) acryloyloxy group and having at least one (meth) acrylate group.
(Poly) ester (meth) acrylate can also be easily obtained as a commercial item. Examples of commercially available (poly) ester (meth) acrylates include EBECRYL450, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL846, EBECRYL851 and EBECRYL8551, EBECRYL851 and EBECRYL851. .

Next, (poly) carbonate (meth) acrylate means a compound having one or more carbonate groups and one or more (meth) acrylate groups.
Synthesis methods of (poly) carbonate (meth) acrylate include dehydrochlorination reaction of (meth) acrylic acid chloride and polycarbonate polyol, direct dehydration reaction of (meth) acrylic acid and (poly) carbonate polyol, (meth) A transesterification reaction between a lower alkyl ester of acrylic acid and a (poly) carbonate polyol is used.
(Poly) carbonate (meth) acrylate can also be easily obtained as a commercial product. Examples of the commercially available (poly) carbonate (meth) acrylate include a compound represented by the following formula (5), which is a polycarbonate diol diacrylate manufactured by Ube Industries, Ltd. In the formula (5), k is an integer of 1 or more.

Next, hydrogenated polybutadiene (meth) acrylate means a compound having a hydrogenated polybutadiene structure and a (meth) acrylate structure in the molecule.
As a synthesis method of hydrogenated polybutadiene (meth) acrylate, esterification reaction of hydrogenated polybutadiene polyol and (meth) acrylic acid, transesterification reaction of hydrogenated polybutadiene polyol and (meth) acrylic acid ester, hydrogenated polybutadiene polyol and An addition reaction of isocyanato group-containing (meth) acrylate, an addition reaction of hydrogenated polybutadiene polyol, polyisocyanate, and alcoholic hydroxyl group-containing (meth) acrylate is preferably used.

Hydrogenated polybutadiene (meth) acrylate can also be easily obtained as a commercial product. Examples of the commercially available hydrogenated polybutadiene (meth) acrylate include NISSO-PB TEAI-1000 manufactured by Nippon Soda Co., Ltd., which is an adduct of hydrogenated polybutadiene polyol, polyisocyanate, and alcoholic hydroxyl group-containing acrylate, hydrogenated polybutadiene. Examples thereof include SPBDA-S30 manufactured by Osaka Organic Chemical Industry Co., Ltd., which is a diacrylate.

Among hydrogenated polybutadiene (meth) acrylates, esterified products of hydrogenated polybutadiene polyols having no urethane bond and (meth) acrylic acid, or transesterification products of hydrogenated polybutadiene polyol and (meth) acrylic esters Is preferred.
Next, (poly) ether (meth) acrylate means a compound having at least one ether bond and having at least one (meth) acrylate group in the molecule, such as polyethylene glycol diacrylate, polypropylene. Examples include glycol diacrylate and polytetramethylene glycol diacrylate.

Next, (poly) urethane (meth) acrylate means a compound having one or more urethane bonds in the molecule and having one or more (meth) acrylate groups. For example, polyol, polyisocyanate and hydroxyl A compound obtained by performing a polyaddition reaction using a group-containing (meth) acrylate as an essential raw material, or a compound obtained by performing a polyaddition reaction using a polyol and an isocyanate group-containing (meth) acrylate as an essential raw material Can be mentioned.
The number average molecular weight of the (meth) acryloyl group-containing compound (D) is not limited, but is preferably 400 or more and more preferably 600 or more from the viewpoint of acid resistance.

When the resist ink of this embodiment contains a (meth) acryloyl group-containing compound (D), the content is preferably as follows from the viewpoint of acid resistance. That is, when the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass, the (meth) acryloyl group The content of the containing compound (D) is preferably 10 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, and 40 parts by mass or more and 70 parts by mass or less. Further preferred. When the content of the acryloyl group-containing compound (D) is within the above range, the effect of improving the mechanical properties of the cured product by the blending of the (meth) acryloyl group-containing compound (D) is sufficiently expressed, and the resist ink Volume shrinkage during curing is difficult to increase.

[5] Polymerization inhibitor The resist ink of the present embodiment may contain a polymerization inhibitor as necessary in order to suppress radical polymerization during storage and improve storage stability. The type of the polymerization inhibitor is not particularly limited. For example, 4-methoxy-1-naphthol, 1,4-dimethoxynaphthalene, 1,4-dihydroxynaphthalene, 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-naphthol, 1,4-dihydroxy-2-methylnaphthalene, pyrogallol, methylhydroquinone, tertiary butylhydroquinone, 4-methoxyphenol, N-nitroso-N-phenylhydroxyamine aluminium And the like.
Among these polymerization inhibitors, methylhydroquinone, pyrogallol, and tertiary butylhydroquinone are particularly preferred from the viewpoint of the storage stability of the resist ink.
These polymerization inhibitors may be used individually by 1 type, and may be used in combination of 2 or more type.

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

[6] Antioxidant The resist ink of the present embodiment may contain an antioxidant as necessary in order to suppress coloring of the cured product of the resist ink at a high temperature. The type of the antioxidant is not particularly limited. For example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [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-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine , 4,6- (1H, 3H, 5H) -trione, tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 4,4 ′, 4 ″-(1-methylpropanyl-3-ylidene) tris (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) propionyloxy] -1,1-dimethylethyl} -2 , 4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene And the like. These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these antioxidants, tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine- is used from the viewpoint of suppressing coloring of a cured resist ink at high temperature. 2,4,6- (1H, 3H, 5H) -trione, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) prothionate are preferred.

The content of the antioxidant in the resist ink of the present embodiment is not particularly limited. From the viewpoint of suppressing coloring of the cured product of the resist ink at a high temperature, the (meth) allyl group-containing compound (A) And 100 parts by mass of the total content of the thiol compound (B) (when the resist ink of this embodiment contains the (meth) acryloyl group-containing compound (D), the (meth) allyl group-containing compound (A) The total content of the thiol compound (B) and the (meth) acryloyl group-containing compound (D) is preferably 100 parts by mass), and the content of the antioxidant is preferably less than 0.1 parts by mass. More preferably, it is 0.0001 parts by mass or more and 0.05 parts by mass or less.

[7] Other components that can be added to the resist ink The resist ink of this embodiment contains the (meth) allyl group-containing compound (A), the thiol compound (B), and the polymerization initiator (C). In addition, the (meth) acryloyl group-containing compound (D), a polymerization inhibitor, and an antioxidant, which are optional components, may be contained, and other components as long as the purpose of the present invention is not impaired. May be contained.
Moreover, the resist ink of this embodiment does not need to contain a solvent as another component, and may contain a solvent, but it is preferable not to contain a solvent.
Furthermore, the resist ink of this embodiment may contain a thixotropic agent, a tackifier, etc. as other components. The type of 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 fumed silica (SiO ₂ ) represented by Aerosil (trademark), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia ( ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), titanium zirconate titanate, lead lanthanum (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)} , It Rear-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), calcium sulfate (CaSO _4), zinc oxide (ZnO), titanate Examples thereof include magnesium (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C), and hydrotalcite. These can be used individually by 1 type or in combination of 2 or more types. Moreover, it is preferable to include at least one selected from silica fine particles and hydrotalcite fine particles among the above.

Hydrotalcite is a kind of a naturally occurring clay mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O and the like, and is a layered inorganic compound. Further, hydrotalcite, for example, can be obtained by combining the _{Mg1-xAlx (OH) 2 (} CO 3) x / 2 · mH 2 O , and the like. That is, hydrotalcite is an Mg / Al-based layered compound, and anions such as chloride ions (Cl ⁻ ) and / or sulfate ions (SO ₄ ²⁻ ) are fixed by ion exchange with carbonate groups between layers. Can be By using this function, chloride ions (Cl ⁻ ) and sulfate ions (SO ₄ ²⁻ ) that cause migration of copper and tin can be captured, and the insulation reliability can be improved. Examples of commercially available hydrotalcite include STABIACE HT-1, STABIACE HT-7 and STABIACE HT-P from Sakai Chemical Co., Ltd., DHT-4A, DHT-4A2, and DHT-4C from Kyowa Chemical Industry Co., Ltd. Is mentioned.

As the organic thixotropic agent, fine particles of a heat-resistant resin having an amide bond, an imide bond, an ester bond or an ether bond are preferable. Examples include fatty acid amide thixotropic agents and ethyl cellulose thixotropic agents. The fatty acid amide thixotropic agent and the ethyl cellulose type thixotropic agent can also be easily obtained as commercial products.

Examples of commercially available fatty acid amide thixotropic agents include Disparon (trademark) 6500, Disparon (trademark) 6650, Disparon (trademark) 6700 and the like manufactured by Enomoto Kasei Co., Ltd. Examples of commercially available ethylcellulose thixotropic agents include ETHOCEL ™ 45, ETHOCEL ™ 100, and ETHOCEL ™ 200 manufactured by Dow Chemical Company.

The tackifier is a substance that is added to a polymer compound typified by an elastomer having rubber elasticity to give an adhesive function. Tackifiers are much smaller in molecular weight than high molecular compounds typified by elastomers, and are generally compounds in the oligomer range with molecular weights of several hundred to several thousand. They are glassy at room temperature, and themselves are rubber elastic. It has the property of not showing.

As the tackifier, a petroleum resin tackifier, a terpene resin tackifier, a rosin resin tackifier, a coumarone indene resin tackifier, a styrene resin tackifier, or the like can be generally used. Examples of petroleum resin tackifiers include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and hydrogenated products thereof. Of the modified product. The synthetic petroleum resin may be C5 or C9. Examples of the terpene resin tackifier include β-pinene resin, α-pinene resin, terpene-phenol resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. Many of these terpene resins are resins having no polar group. Examples of rosin resin tackifiers include rosins such as gum rosin, tall oil rosin and wood rosin, modified rosins such as hydrogenated rosin, disproportionated rosin, polymerized rosin and maleated rosin, rosin glycerin ester and hydrogenated rosin ester. And rosin esters such as hydrogenated rosin glycerin ester. These rosin resins have polar groups. These tackifiers may be used individually by 1 type, and may be used in combination of 2 or more type.

Furthermore, the resist ink of this embodiment may contain an antifoaming agent as another component. The type of antifoaming agent is not particularly limited, and specific examples include BYK-077 manufactured by Big Chemie Japan, SN deformer 470 manufactured by San Nopco, TSA750S manufactured by GE Toshiba Silicone, Toray Silicone antifoaming agents such as silicone oil SH-203 manufactured by Dow Corning Co., Ltd., acrylic polymer antifoaming agents such as Dappo SN-348, Dappo SN-354, and Dappo SN-368 manufactured by San Nopco Co., Ltd. Examples include acetylenic diol defoamers such as Surfynol DF-110D and Surfynol DF-37 manufactured by Shin Chemical Co., Ltd., and fluorine-containing silicone defoamers such as FA-630 manufactured by Shin-Etsu Chemical Co., Ltd. be able to.

[8] Preparation of resist ink The resist ink of the present embodiment comprises a (meth) acryloyl group as necessary together with a (meth) allyl group-containing compound (A), a thiol compound (B), and a polymerization initiator (C). The compound (D), the polymerization inhibitor, the antioxidant, and other components can be appropriately mixed and prepared.

Furthermore, when the amount obtained by subtracting the content of the polymerization initiator (C) from the total amount of the resist ink of this embodiment 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. It is good to mix so that it may become in the range below a mass part.
The method for preparing the resist ink of the present embodiment is not particularly limited, and the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), the (meth) acryloyl group-containing compound ( Any method may be used as long as it can mix and disperse each raw material of resist ink including D). Examples of the method of mixing and dispersing include the following methods.

(A) Each raw material is put into a container such as a glass beaker, a can, a plastic cup, or an aluminum cup and kneaded with a stirring rod, a spatula, or the like.
(B) Each raw material is kneaded with a double helical ribbon blade, a gate blade, or the like.
(C) Each raw material is kneaded with a planetary mixer.
(D) Each raw material is kneaded by a bead mill.
(E) Each raw material is kneaded with three rolls.
(F) Each raw material is kneaded by an extruder-type kneading extruder.
(G) Each raw material is kneaded by a rotating / revolving mixer.

The addition and mixing of each raw material can be performed in an arbitrary order, and all the raw materials may be added simultaneously or sequentially.
When using the polymerization initiator (C), active energy ray illumination is performed through a filter that removes light having an absorption wavelength at which the photopolymerization initiator decomposes during the pre-curing treatment such as handling and mixing of the above raw materials. It can be carried out under conditions where the polymerization initiator (C) does not act before the curing treatment, such as under or without irradiation with active energy rays, or under a temperature at which the thermal polymerization initiator acts.
Moreover, when using the hardened | cured material of resist ink of this embodiment as a protective film of fine patterns, such as wiring, a screen printing method is used preferably for printing of resist ink.

[9] Cured product of resist ink and curing method The resist ink is cured by irradiating the resist ink of the present embodiment with active energy rays or heating, and a cured product is obtained. Active energy rays used at the time of curing include near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, γ-rays, electromagnetic waves such as electron rays, and particle rays, but since inexpensive devices can be used, ultraviolet rays and Visible light is preferred.
Various light sources can be used as the light source for curing the resist ink of the present embodiment with ultraviolet rays or visible rays. Examples thereof include a black light, a UV-LED lamp, a high-pressure mercury lamp, a pressurized mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a halogen lamp.

Here, black light is a near-ultraviolet light having a wavelength of 300 nm or more and 430 nm or less (peak 350 nm) only when a near-ultraviolet phosphor is applied to a special outer glass cut from visible light and ultraviolet light having a wavelength of 300 nm or less. It is a lamp that radiates. The UV-LED lamp is a lamp using a light emitting diode that emits ultraviolet rays. Among these light sources, a high-pressure mercury lamp and a metal halide lamp are preferable from the viewpoint of curability. In consideration of economics such as running cost, an LED lamp (UV-LED lamp) is preferable.

The irradiation amount of the active energy ray may be an amount sufficient to cure the resist ink of this embodiment, and the composition, usage amount, thickness, shape of the cured product to be formed, etc. of the resist ink of this embodiment. Can be selected accordingly. For example, when ultraviolet rays are radiated onto the coating film formed by coating the resist ink of the present embodiment is preferably 100 mJ / cm ² or more 5000 mJ / cm ² or less of the exposure amount, and more preferably 300 mJ / cm ² or more An exposure amount of 3000 mJ / cm ² or less can be employed. In addition, the measurement wavelength of said exposure amount is 365 nm.

The application (coating) method in the case where the resist ink of the present embodiment is applied onto a substrate to form a coating film is not particularly limited. For example, in addition to spray method and dip method, natural coater, curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater, curtain coater, kiss roll, squeeze roll, reverse roll, air blade, knife belt coater, floating knife , A method using a knife over roll, a knife on blanket or the like. Moreover, the method using an inkjet printer, a screen printer, etc. can also be mentioned.

In the case of using a cured product of resist ink as a protective film for fine patterns such as wiring, a method using a screen printer is preferable because the printing pattern can be accurately controlled. In addition, when a cured product having a shape retaining the printed pattern shape is obtained and used as a protective film for fine patterns such as wiring, the polymerization initiator (C) includes a photopolymerization initiator as described above. Is preferred.

Next, a protective film for a wiring containing a cured product of the resist ink of this embodiment and a method for manufacturing the same will be described. The manufacturing method of the protective film of wiring of this embodiment is provided with the following coating processes and hardening processes.
The covering step is a step in which a resist ink is provided in a film shape by a printing method, for example, on a substrate having wiring (for example, a printed wiring board), and the wiring is covered with a resist ink film.

The resist ink film may be disposed on the entire surface of the substrate, or may be disposed on a part of the surface as long as the wiring can be covered. The printing method is not particularly limited, and examples thereof include a screen printing method, a roll coater method, a spray method, and a curtain coater method. However, the screen printing method is preferable from the viewpoint of controlling the shape pattern of the resist ink film as a printed matter.

In the curing step, a part or all of the region including the region covering the wiring in the resist ink film is irradiated with active energy rays having a wavelength that generates a polymerizable radical species in the polymerization initiator (C). In this step, the resist ink in the region irradiated with the active energy ray is cured to form a protective film for the wiring.

Examples of active energy rays used in the curing step include near infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, γ rays, electron rays and other electromagnetic waves and particle rays, but ultraviolet rays and visible rays are preferable, and ultraviolet rays are preferred. Is more preferable. The light source of ultraviolet light and visible light is not particularly limited, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, a halogen lamp, or the like can be used. UV during this, the dose of visible light, varies depending on the composition or the like of the resist ink may be a 100 mJ / cm ² or more 5000 mJ / cm ² within the following ranges. In addition, the measurement wavelength of said exposure amount is 365 nm.

Further, when a photopolymerization initiator and a thermal polymerization initiator are used in combination as the polymerization initiator (C), a curing step by heating can be performed after the curing step by irradiation with active energy rays. The heating temperature (thermosetting temperature) in the curing step by heating varies depending on the cleavage temperature of the thermal polymerization initiator, but is preferably 80 ° C. or higher and 170 ° C. or lower. The heating time (thermal curing time) in the curing step by heating is the same, but 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 this embodiment may be appropriately set according to the use of the protective film, but is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 20 μm or less, and further preferably 2 μm or more and 15 μm or less. Moreover, the protective film of this embodiment may contain other components other than the hardened | cured material of the resist ink of this embodiment as needed.
In addition, this embodiment shows an example of this invention and this invention is not limited to this embodiment. In addition, various changes or improvements can be added to the present embodiment, and forms to which such changes or improvements are added can also be included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Examples 1 to 11 and Comparative Examples were prepared by mixing various raw materials of (meth) allyl group-containing compound (A), thiol compound (B), polymerization initiator (C), and (meth) acryloyl group-containing compound (D). 1 to 4 resist inks were prepared. Various raw materials used for preparing the resist ink will be described below.

(I) (Meth) allyl group-containing compound (A)
The following seven compounds (i-1) to (i-7) were used as the (meth) allyl group-containing compound (A).
(I-1) Allyl ester resin A (iodine value 77.1) produced in Production Example 1 described later
(I-2) Allyl ester resin B (iodine value 148.3) produced in Production Example 2 described later
(I-3) Allyl ester resin C (iodine value 75.0) produced in Production Example 3 described later
(I-4) Allyl ester resin D (iodine value 141.6) produced in Production Example 4 described later
(I-5) triallyl isocyanurate (the number of allyl groups is 3, the iodine value is 306)
(I-6) Diallyl terephthalate (number of allyl groups, iodine value 206.1)
(I-7) Diallyl 1,4-cyclohexanedicarboxylate (trade name H-DATP manufactured by Showa Denko KK, number of allyl groups, iodine number 201.2)

(Ii) Thiol compound (B)
The following three compounds (ii-1) to (ii-3) were used as the thiol compound (B).
(Ii-1) Pentaerythritol-tetrakis (3-mercaptobutyrate) (trade name Karenz MT (trademark) PE1, manufactured by Showa Denko KK, molecular weight 545, number of mercapto groups 4)
(Ii-2) 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko KK) Trade name Karenz MT (trademark) NR1, molecular weight 568, number of mercapto groups 3)
(Ii-3) Pentaerythritol-tetrakis (3-mercaptopropionate) (trade name PEMP, molecular weight 489, number 4 of mercapto group, manufactured by Sakai Chemical Industry Co., Ltd.)

(Iii) Polymerization initiator (C)
The following three compounds (iii-1) to (iii-3) were used as the polymerization initiator (C).
(Iii-1) 2,4,6-trimethylbenzoylphosphine oxide (a mixture of ESACURE KTO46, a polymer having an α-hydroxyketone group and a benzophenone derivative manufactured by DKSH Japan)
(Iii-2) Ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate (Irgacure TPO-L manufactured by BASF)
(Iii-3) 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173 manufactured by BASF)

(Iv) (Meth) acryloyl group-containing compound (D)
The following four compounds (iv-1) to (iv-4) were used as the (meth) acryloyl group-containing compound (D).
(Iv-1) Epoxy acrylate having bisphenol A type skeleton (VR77 manufactured by Showa Denko KK)
(Iv-2) Polyester acrylate having a bisphenol A-type skeleton (Ebecryl 812 manufactured by Daicel Ornex Co., Ltd.)
(Iv-3) Urethane acrylate A produced in Production Example 5 described later
(Iv-4) Dipentaerythritol hexaacrylate (DPHA manufactured by Daicel Ornex Co., Ltd., molecular weight 524, number of acryloyloxy groups 6)

The following production examples 1 to 5 show production methods of the above-mentioned allyl ester resins A to D and urethane acrylate A.
[Production Example 1: Production of allyl ester resin A]
500 g diallyl terephthalate, 101 g propylene glycol and 0.5 g dibutyltin oxide are put into a 2 L three-necked flask equipped with a distillation apparatus and heated at 180 ° C. in a nitrogen stream to distill allyl alcohol produced. Left.
When about 90 g of allyl alcohol was distilled, the pressure inside the reaction system was reduced to 1.3 kPa to increase the distillation rate of allyl alcohol. After distillation of the theoretical amount of allyl alcohol, the remaining diallyl terephthalate is removed from the allyl ester resin A by further heating for 1 hour and holding at a temperature of 190 ° C. and a pressure of 0.13 kPa for an additional hour, so that 445 g Allyl ester resin A was obtained. The iodine value of allyl ester resin A measured by a method based on JIS K 0070 was 77.

Allyl ester resin A was analyzed using a gas chromatography GC-14B (detector: hydrogen flame ionization detector, column: OV-17 (0.5 m), temperature condition: 160 ° C. constant) manufactured by Shimadzu Corporation. The allyl ester resin A contained 1% by mass of diallyl terephthalate, and the remaining 99% by mass was a transesterification product (allyl ester oligomer) of diallyl terephthalate and propylene glycol.

[Production Example 2: Production of allyl ester resin B]
699 g of allyl ester resin B was obtained in the same manner as in Production Example 1 except that the amount of diallyl terephthalate used was changed to 739 g and the amount of propylene glycol used was changed to 76 g. The iodine value of allyl ester resin B measured by a method according to JIS K 0070 was 145.
When the allyl ester resin B was analyzed in the same manner as in Production Example 1, the allyl ester resin B contained 35% by mass of diallyl terephthalate. The remaining 65% by mass was a transesterification product (allyl ester oligomer) of diallyl terephthalate and propylene glycol.

[Production Example 3: Production of allyl ester resin C]
452 g of allyl ester resin C was obtained in the same manner as in Production Example 1 except that 505 g of diallyl 1,4-cyclohexanedicarboxylate was used instead of 500 g of diallyl terephthalate. The iodine value of allyl ester resin C measured by a method based on JIS K 0070 was 75.0.
When the allyl ester resin C was analyzed in the same manner as in Production Example 1, the allyl ester resin C contained 2% by mass of diallyl 1,4-cyclohexanedicarboxylate. The remaining 98% by mass was a transesterification product (allyl ester oligomer) of diallyl 1,4-cyclohexanedicarboxylate and 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 diallyl 1,4-cyclohexanedicarboxylate was changed to 757 g and the amount of propylene glycol was changed to 76 g. The iodine value of allyl ester resin D measured by a method based on JIS K 0070 was 141.6.
Further, when allyl ester resin D was analyzed in the same manner as in Production Example 1, allyl ester resin D contained 35% by mass of diallyl 1,4-cyclohexanedicarboxylate. The remaining 65% by mass was a transesterification product (allyl ester oligomer) of diallyl 1,4-cyclohexanedicarboxylate and propylene glycol.

[Production Example 5: Production of urethane acrylate A]
In a reaction vessel having a capacity of 1 L equipped with a stirrer, a thermometer, and a condenser, 475 g of polyester polyol HOKOKUOL (registered trademark) HT-110 (hydroxyl value: 112.2 mgKOH / g) manufactured by Toyokuni Oil Co., Ltd. and 2,2- 3.7 g of bis (hydroxymethyl) butyric acid was added, and the internal temperature of the reaction vessel was raised to 130 ° C. using an oil bath while stirring with a stirrer.

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 completion of the dropwise addition of isophorone diisocyanate, the internal temperature of the reaction vessel was maintained at 120 ° C. while continuing stirring, and the reaction was continued for 7 hours. Then, after the internal temperature of the reaction vessel was lowered to 80 ° C. while continuing the stirring, 0.7 g of hydroquinone monomethyl ether and 0.3 g of dioctyltin dilaurate were introduced into the reaction vessel, and then 2 made by Nippon Shokubai Co., Ltd. -116.12 g (1.0 mol) of hydroxyethyl acrylate was added dropwise over 1 hour. During this time, the internal temperature of the reaction vessel was maintained within the range of 80 ° C. or higher and 90 ° C. or lower.

After completion of the dropwise addition of 2-hydroxyethyl acrylate, the reaction was continued at 80 ° C. for 3 hours. Thereafter, the infrared absorption spectrum of the reaction product was measured. When it was confirmed in the infrared absorption spectrum that the absorption of the isocyanato group had disappeared, the reaction was terminated and urethane acrylate A was obtained.
In addition, the molecular weight of the oligomer or polymer in each Example and a comparative example is the number average molecular weight of polystyrene conversion measured by GPC method. The measurement conditions for GPC are as follows.

Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804 x 3 (in series)
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: JASCO Corporation RI-2031Plus
Temperature: 40.0 ° C
Sample volume: Sample loop 100 μL
Sample concentration: 0.1% by mass

Resist ink is prepared by mixing the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), and the (meth) acryloyl group-containing compound (D) at a mass ratio shown in Table 1. Was prepared. In Table 1, “(A) / (B) functional group number ratio” is the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B). (Number of (meth) allyl groups / number of mercapto groups).
Moreover, in Table 1, "mass ratio of (D)" is the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D). When it is 100 parts by mass, the content of the (meth) acryloyl group-containing compound (D) is shown.

Next, the acid resistance of the cured resist inks of Examples 1 to 11 and Comparative Examples 1 to 4 with respect to the electroless tin plating solution was evaluated as follows. The results are shown in Table 1.
A resist ink was applied in a film shape of 50 μm in thickness with a bar coater to the central part 5 cm × 8 cm of one side of a copper / polyimide laminated substrate (Esperflex manufactured by Sumitomo Metal Mining Co., Ltd.) cut into a rectangle of 8 cm × 11 cm. . Then, the resist ink film was cured by irradiating UV light with an exposure amount of ² J / cm ² using a conveyor type UV irradiator ECS-4011GX (high pressure mercury lamp) manufactured by IGraphics Co., Ltd. A test body having a protective film made of a cured product was obtained. In addition, the measurement wavelength of said exposure amount is 365 nm.

The obtained specimen was washed with an aqueous sulfuric acid solution having a concentration of 5% by 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, half of the protective film made of a resist ink cured product was not immersed in the electroless tin plating solution so that a portion not subjected to the plating treatment could be observed. The test specimen was taken out from the electroless tin plating solution, washed with warm water repeatedly, and then subjected to a eutectic treatment at 120 ° C. for 90 minutes with a blow type constant temperature dryer. And about this test body, the following 3 points | pieces were evaluated.

<Evaluation of peeling of protective film>
The presence or absence of peeling of the protective film from the substrate was visually observed, and the case where the protective film was not peeled was evaluated as “A”, and the case where the protective film was peeled was evaluated as “C”.
<Evaluation of plating penetration>
Using a microscope VHX-900 manufactured by Keyence Co., Ltd., it was observed whether or not plating was embedded between the protective film and copper. Then, “A” was evaluated for those that did not sink, “B” for those that were submerged but less than 1 mm, and “C” for those that submerged 1 mm or more.

<Evaluation of coloring of protective film>
The change in the color of the protective film is visually observed, and “A” indicates that there is no discoloration compared with that before immersion in the electroless tin plating solution. Although it became dark, it was evaluated as “B” when there was no color unevenness, and as “C” when discoloration occurred in the spotted pattern as compared with before immersion in the electroless tin plating solution.

As can be seen from the results shown in Table 1, in the cured resist inks of Examples 1 to 11, the resist ink was a (meth) allyl group-containing compound (A), a thiol compound (B), and a polymerization initiator (C). Therefore, even when immersed in a strongly acidic electroless tin plating solution, peeling of the protective film, penetration of the plating, and coloring of the protective film hardly occurred.
In contrast, the cured resist inks of Comparative Examples 1 to 4 have acid resistance because the resist ink does not contain at least one of the (meth) allyl group-containing compound (A) and the thiol compound (B). It was insufficient. For this reason, when immersed in a strongly acidic electroless tin plating solution, the protective film peeled off, and evaluation of the penetration of the plating and coloring of the protective film could not be performed.

Claims (17)

1. A (meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule, a thiol compound (B) having two or more mercapto groups in one molecule, a polymerization initiator ( C), and a resist ink containing.
2. The resist ink according to claim 1, wherein the (meth) allyl group-containing compound (A) includes a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure.
3. The resist ink according to claim 1 or 2, wherein the (meth) allyl group-containing compound (A) includes a compound having at least one of an allyloxycarbonyl group and an N-allyl group.
4. The resist ink according to any one of claims 1 to 3, wherein the (meth) allyl group-containing compound (A) includes a compound having at least one of an ester structure and an isocyanurate structure.
5. The (meth) allyl group-containing compound (A) includes diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, 1,2-cyclohexanedicarboxylic acid The resist ink according to claim 1, comprising at least one selected from diallyl and triallyl isocyanurate.
6. The resist ink according to any one of claims 1 to 5, wherein the thiol compound (B) includes a compound having two or more secondary or tertiary mercapto groups in one molecule.
7. The thiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) The at least one selected from -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane tris (3-mercaptobutyrate) Resist ink.
8. The resist ink according to any one of claims 1 to 7, further comprising a (meth) acryloyl group-containing compound (D).
9. The resist ink according to claim 8, wherein the (meth) acryloyl group-containing compound (D) includes a compound having two or more (meth) acryloyl groups in one molecule.
10. The (meth) acryloyl group-containing compound (D) is at least one selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate, and hydrogenated polybutadiene (meth) acrylate. The resist ink according to claim 9 containing one.
11. The resist ink according to any one of claims 8 to 10, wherein the (meth) acryloyl group-containing compound (D) includes a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure.
12. The ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) (number of allyl groups / number of mercapto groups) is 0.25 or more and 4 Within the following range,
    Content of the polymerization initiator (C) when the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass. The resist ink according to any one of claims 8 to 11, which has a content of 0.01 to 10 parts by mass.
13. When the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass, the (meth) of them The resist ink according to any one of claims 8 to 12, wherein the content of the acryloyl group-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 claims 1 to 13, wherein the polymerization initiator (C) includes a compound that generates a polymerizable radical species upon irradiation with active energy rays.
15. The cured product of the resist ink according to any one of claims 1 to 14.
16. A protective film for a wiring containing the cured product according to claim 15.
17. A coating step in which the resist ink according to claim 14 is arranged in a film form on a substrate having wiring, and the wiring is covered with the resist ink film;
    The resist ink film is irradiated with active energy rays having a wavelength that generates a polymerizable radical species in the polymerization initiator (C) on a part or all of the region including the region covering the wiring in the resist ink film. A curing step of curing the ink to form a protective film for the wiring;
    The manufacturing method of the protective film of wiring provided with this.