JP2019068062A - Resist ink, protective film of wiring, method for producing the same, semiconductor substrate, and method for producing protective film thereof - Google Patents

Abstract

To provide a resist ink which is capable of forming a cured product excellent in acid resistance and has excellent printability.SOLUTION: The 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; a polymerization initiator (C); and a thixotropic agent (D). The resist ink has a thixotropy index of 1.05 or more and 4.00 or less.SELECTED DRAWING: None

Description

  The present invention relates to a resist ink, a protective film of wiring and a method of manufacturing the same, a semiconductor substrate and a method of manufacturing the protective film.

  Copper wiring used for printed wiring boards and the like is treated with a strongly acidic electroless tin plating solution and tin plated to prevent oxidation. Therefore, a resist (cured product of resist ink) resistant to a strongly acidic electroless tin plating solution is required. Although the resist ink which can form the resist which has acid resistance in patent documents 1-3 is disclosed, the tolerance with respect to a strongly acidic electroless tin plating solution was not enough. Moreover, the improvement of the printability of resist ink was also desired.

Unexamined-Japanese-Patent No. 2003-268067 JP 2005-24591 A Patent No. 3190251

  Then, this invention solves the problem which the above prior art has, and makes it a subject to provide the resist ink which can form the hardened | cured material which is excellent in acid resistance, and has the outstanding printability. . Another object of the present invention is to provide a protective film of a wiring which is excellent in acid resistance and easy to manufacture, and a method of manufacturing the same. Another object of the present invention is to provide a method of manufacturing a semiconductor substrate and its protective film.

In order to solve the above-mentioned subject, one mode of the present invention is as [1]-[16] of the following.
[1] (meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule, thiol compound (B) having two or more mercapto groups in one molecule, and polymerization A resist ink containing an initiator (C) and a thixo agent (D), and having a thixotropy index of 1.05 or more and 4.00 or less.

[2] The content of the thixotropic agent (D) is 0.5 parts by mass or more when the total content of the (meth) allyl group-containing compound (A) and the thiol compound (B) is 100 parts by mass. The resist ink as described in [1] which is 9.0 mass parts or less.
[3] The resist ink according to [1] or [2], wherein the thixo agent (D) is a silica particle having an average particle diameter of 1 nm or more and 100 nm or less.
[4] The resist ink according to [3], wherein the silica particles are subjected to surface treatment with a surface treatment agent to have reactivity.

[5] 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 [1] to [4] Resist ink according to one item.
[6] The resist ink according to any one of [1] to [5], wherein the (meth) allyl group-containing compound (A) contains a compound having at least one of an ester structure and an isocyanurate structure.

[7] The resist ink according to any one of [1] to [6], wherein the thiol compound (B) contains a compound having two or more secondary or tertiary mercapto groups in one molecule.
[8] The resist ink according to any one of [1] to [7], further containing a (meth) acryloyl group-containing compound (E).
[9] The resist ink according to [8], wherein the (meth) acryloyl group-containing compound (E) contains a compound having two or more (meth) acryloyl groups in one molecule.
[10] The (meth) acryloyl group-containing compound (E) includes a compound having at least one structure selected from an isocyanurate structure, an alicyclic structure and an aromatic ring structure. The resist according to [8] or [9] ink.

[11] The ratio of the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) to the number of mercapto groups of the thiol compound (B) (number of allyl groups / number of mercapto groups) is 0. In the range of 25 to 4
Content of the said polymerization initiator (C) when content of the sum total of (meth) allyl group containing compound (A), a thiol compound (B), and (meth) acryloyl group containing compound (E) is 100 mass parts The resist ink as described in any one of [8]-[10] which is 0.01 mass part or more and 10 mass parts or less.

[12] The total content of the (meth) allyl group-containing compound (A), the thiol compound (B) and the (meth) acryloyl group-containing compound (E) is 100 parts by mass, The resist ink according to any one of [8] to [11], wherein a content of the (meth) acryloyl group-containing compound (E) is 10 parts by mass or more and 80 parts by mass or less.
[13] A protective film of a wiring containing a cured product of the resist ink according to any one of [1] to [12].
[14] A semiconductor substrate covered with a protective film containing a cured product of the resist ink according to any one of [1] to [12], wherein a wiring is formed on a portion not covered by the protective film. Semiconductor substrate.

[15] A coating step of arranging the resist ink according to any one of [1] to [12] in a film form on a substrate having a wiring, and covering the wiring with the film of the resist ink;
An active energy ray of a wavelength causing generation of a polymerizable radical species to the polymerization initiator (C) is irradiated to a partial region or the entire region including the region covering the wiring in the film of the resist ink, and the resist Curing the ink to form a protective film of the wiring;
Method of producing a protective film of wiring comprising:

[16] A coating step of arranging the resist ink according to any one of [1] to [12] in a film form on a semiconductor substrate to cover the semiconductor substrate with a film of the resist ink,
An active energy ray of a wavelength that causes the polymerization initiator (C) to generate a polymerizable radical species is applied to a partial region or the entire region of the film of the resist ink, and the resist ink is cured to thereby cure the semiconductor A curing step of forming a protective film of the substrate;
A method of manufacturing a protective film of a semiconductor substrate comprising:

  The resist ink of the present invention is capable of forming a cured product excellent in acid resistance and has excellent printability. The protective film of the wiring of the present invention is excellent in acid resistance and easy to manufacture. The method for producing a protective film of a wiring and the method for producing a protective film for a semiconductor substrate according to the present invention can easily produce a protective film excellent in acid resistance.

  One embodiment of the present invention will be described below. The resist ink according to the present embodiment includes a (meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule, and a thiol compound (two or more mercapto groups in one molecule) B), a polymerization initiator (C), and a thixo agent (D), and having a thixotropy index of 1.05 or more and 4.00 or less.

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

  In addition, since it is excellent in resistance to an acidic electrolytic copper plating solution and an electrolytic tin plating solution, for example, it is acidic to a metal oxide or metal such as indium tin oxide (ITO) used in the production of a photovoltaic cell. When performing electrolytic plating using the plating solution of the above, it can be used as a resist (protective film) for protecting a place where plating is unnecessary. The electrolytic copper plating solution used for copper plating and the electrolytic tin plating solution used for tin plating are particularly strongly acidic, but since they are resistant if they are cured products of the resist ink of this embodiment, It can also be used as a resist at the time of copper plating using an electrolytic copper plating solution or at the time of tin plating using an electrolytic tin plating solution.

Further, the resist ink of the present embodiment is excellent in printability because the thixotropy index is controlled to 1.05 or more and 4.00 or less by the thixo agent (D). Therefore, the cured product of the resist ink and the protective film of the wiring of the present embodiment can be easily manufactured using a printing method.
Furthermore, since the resist ink of the present embodiment is excellent in printability, the resist ink of the present embodiment is applied by a printing method only to a portion where wiring is unnecessary on a base material requiring protection from an acidic solution. By doing this, it is possible to construct the wiring by plating only on the part where the wiring is necessary.
In addition, in the resist ink of the present embodiment, the types of the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), and the thixo agent (D) may be appropriately selected, Excellent transparency is given. Therefore, excellent transparency can be imparted to the cured product of the resist ink of the present embodiment and the protective film of the wiring.

Further, the cured product of the resist ink of the present embodiment and the protective film of the wiring are excellent in adhesion to the substrate to be coated, and also excellent in moisture resistance and heat resistance, and further, long-term insulation reliability at a high level. It also has sex. Therefore, for example, when electrolytic plating is performed using a metal oxide or metal such as ITO, which is used to manufacture a photovoltaic cell, using an acidic plating solution, a resist for protecting a portion where plating is unnecessary ( It can be used as a protective film, and can also be used as a photovoltaic cell without removing the protective film.
Furthermore, since the resist ink of the present embodiment does not need to be dissolved in a solvent and can be solvent free, it is less likely 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 protective film of a wiring containing the cured product, and a method for producing the same will be described in detail. .
In the present specification, “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group. In addition, as used herein, "(meth) allyl" means methallyl (i.e. 2-methyl-2-propenyl) and / or allyl (i.e. 2-propenyl). Also, "(meth) acrylate" means methacrylate and / or acrylate, and "(meth) acrylic" 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, but excludes a (meth) acryloyl group-containing compound. The (meth) allyl group-containing compound (A) may be a monomer, an oligomer or a polymer, and is preferably a compound having a number average molecular weight of 200 or more and 20,000 or less from the viewpoint of viscosity. The compound is more preferably 550 or more and 10000 or less, and still more preferably 550 or more and 3000 or less. In addition, unless otherwise indicated, the molecular weight of the oligomer or polymer in this invention is a number average molecular weight of polystyrene (PS) conversion measured by the gel permeation chromatography method (GPC method). Detailed measurement conditions of the number average molecular weight are shown in Examples described later.

  In addition, in consideration of the balance between the curability at the time of light irradiation and the flexibility after curing, the iodine value of the mixture obtained by mixing all the compounds belonging to the (meth) allyl group-containing compound (A) is in the range of 20 to 70. It is preferably inside, and more preferably in the range of 20 or more and 50 or less. If the iodine value is in the range of 20 or more and 70 or less, the resist ink can be easily cured in a short time by irradiation of an active energy ray or heat. In addition, the iodine value described in the present specification is a value obtained by converting the amount of halogen (in units of g) to be reacted with 100 g of the target substance into the number of grams of iodine, and it is a method according to JIS K 0070 It can measure.

As the (meth) allyl group-containing compound (A), 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) a-2).
As said alicyclic structure, a C3-C10 alicyclic ring can be illustrated, Preferably they are a cyclohexane ring, a cycloheptane ring, an adamantane ring, and a tricyclodecane ring. As said aromatic ring structure, a C6-C10 aromatic ring can be illustrated, Preferably it is a benzene ring and a naphthalene ring. Examples of the heterocyclic structure include a three-membered to ten-membered ring having a nitrogen atom, an oxygen atom or a sulfur atom, and a pyridine ring, a triazine ring, a ring derived from cyanuric acid, a ring derived from isocyanuric acid, a derivative derived from glycoluric acid Can be exemplified.

  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 trimellitate, and tetraallyl pyromellitic acid. Aryloxy carbonyl 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 1,4,5-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, , 3,5-adamantane tricarboxylic acid triallyl, hydrogenated bisphenol A type diallyl ether, hydrogenated dimer acid (having 36 or 44 carbon atoms and having an alicyclic structure) diallyl, diallyl tricyclodecanedimethanoldicarboxylate, etc. Compounds having alicyclic structure, triallyl isocyanurate, triallyl cyanurate, diallyl monohydroxyethyl cyanurate, diallyl monohydroxyethyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate prepolymer, 1,3 N-allyl group-containing compounds having a heterocyclic structure such as 5-triallylhexahydro-1,3,5-triazine and 1,3,4,6-tetralyl glycoluril can be mentioned. Among these, as the (meth) allyl group-containing compound (A), a compound having at least one of an ester structure and an isocyanurate structure is preferable. Further, in consideration of the weather resistance of the cured product of the resist ink, a compound having at least one of an alicyclic structure and an isocyanurate structure is preferable.

  In addition, as the compound (a-1), a metallyloxycarbonyl group-containing compound having an aromatic ring structure such as dimethallyl phthalate, dimethallyl isophthalate, dimethallyl terephthalic acid, trimethallyl trimellitate, and tetramethallyl pyromellitic acid; Dimethallyl cyclohexanedicarboxylate, dimethallyl 1,3-cyclohexanedicarboxylate, dimethallyl 1,4-cyclohexanedicarboxylate, trimethallyl 1,2,4-cyclohexanedicarboxylate, tetramethallyl 1,2,4,5-cyclohexanetetracarboxylate, 5 -Alkyl substituted cyclohexane-1,4-dicarboxylic acid dimethallyl, 5-halogen substituted cyclohexane-1,4-dicarboxylic acid dimethallyl, 1,3-adamantane dicarboxylic acid dimethallyl, 1,3,5-adamantane Trimethallyl lithium carboxylate, 5-halogen substituted cyclohexane-1,4-dicarboxylic acid dimethallyl, hydrogenated dimer acid (having 36 or 44 carbon atoms and having an alicyclic structure) dimethallyl, tricyclodecane dimethanol dicarboxylic acid dimethallyl, etc. Compounds having an alicyclic structure, trimethallyl isocyanurate, trimethallyl cyanurate, 1,3,5-trimethallyl hexahydro-1,3,5-triazine, 1,3,4,6-tetra N- methallyl group containing compounds, such as methallyl glycoluryl, are mentioned.

  Furthermore, as the 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- Naphthalene dicarboxylic acid diallyl ether, 2,7-naphthalene dicarboxylic acid dimethallyl ether, diphenyl-m, m'-dicarboxylic acid diallyl ether, diphenyl-m, m'-dicarboxylic acid 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, Methylterephthalic acid diallyl ether, methylterephthalic acid dimethallyl ether, tetrachlorophthalic acid diallyl ether, tetrachlorophthalic acid dimethallyl ether, diallyl fluorene, dimethallyl fluorene, fluorene bisphenoxyethyl diallyl ether, fluorene bisphenoxyethyl dimethallyl ether, Allyls such as fluorene bisphenoxyethyl dimethallyl ether, fluorene bis phenoxyethyl dimethallyl ether, fluorene bisphenoxy bis methallyl ether Ether compounds, and the like.

  On the other hand, compounds having an allyl group and a methallyl group in one molecule can also be mentioned. As the compound (a-1), phthalic acid allyl methallyl ester, isophthalic acid allyl methallyl ester, trimellitic acid diallyl methallyl ester, trimellitic acid allyl dimethallyl ester, pyromellitic acid triallyl methallyl ester, pyromellitic acid diallyl dimethallyl 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 allyl methallyl ether, 2,7-naphthalene dicarboxylic acid allyl methallyl ether, diphenyl-m, m'-dicarboxylic acid allyl methallyl ether, diphenyl- , P'-dicarboxylic acid allyl methallyl ether, benzophenone-4, 4-dicarboxylic acid allyl methallyl ether, methyl terephthalate allylmethallyl ether, tetrachlorophthalic acid allyl methallyl ether, allyl methallyl fluorene, fluorene bis phenoxyethyl allyl methallyl ether, Compounds in which an allyl group and a methallyl group having an aromatic ring structure, such as fluorene bisphenoxalyl methallyl ether, coexist, allylmethallyl 1,4-cyclohexanedicarboxylate, allylmethallyl 1,3-cyclohexanedicarboxylate, 1,2,4-cyclohexanetricarboxylic acid Allyl dimethallyl acid 1,2,4 cyclohexane tricarboxylic acid diallyl methallyl, 1,2,4 cyclohexane tricarboxylic acid triaryl methallyl 1,2 4,5-Cyclohexanetetracarboxylic acid diallyldimethallyl, 1,2,4,5-cyclohexanetetracarboxylic acid allyltrimethallyl, 5-alkyl substituted cyclohexane-1,4-dicarboxylic acid allylmethallyl, 5-halogen substituted cyclohexane-1, Allyl methallyl 4-dicarboxylate, allyl methallyl 1,3-adamantanedicarboxylate, diallyl methallyl 1,3,5-adamantane tricarboxylate, allyl dimethallyl 1,3,5-adamantane tricarboxylate, hydrogenated dimer acid (number of carbon atoms is A compound having an alicyclic structure such as allyl methallyl, tricyclodecanedimethanol diaryl allyl dicarboxylic acid, and a compound having a methallyl group having an alicyclic structure and an allyl group, allyl methallyl monohydroxyethyl cyanurate, Diallyl methallyl isocyanurate, allyl dimethallyl isocyanurate, 1,5-diallyl-3-methallyl hexahydro-1,3,5-triazine, 1-allyl-3,5-dimethallyl hexahydro-1,3, N-methallyl such as 5-triazine, 1,3,4,6-methallyl triaryl glycoluril, 1,3,4,6-dimethallyl diaryl glycoluril, 1,3,4,6-trimethallyl allyl glycoluril, etc. The compound which the group and N-allyl group coexist is mentioned.

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

  From the viewpoint of the acid resistance of the cured product of the resist ink of the present embodiment, among the (meth) allyl group-containing compounds (A) described above, at least one selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure Compounds having one structure are preferable, and compounds having at least one structure selected from an aromatic ring structure and a heterocyclic structure are more preferable. From the viewpoint of durability, a compound having at least one structure selected from a chain aliphatic structure, an alicyclic structure, and a heterocyclic structure is preferable, and has at least one structure selected from an alicyclic structure and a heterocyclic structure. Compounds are more preferable, and compounds having a heterocyclic structure are more preferable. From the viewpoint of heat resistance, a compound having at least one structure selected from a chain aliphatic structure, an alicyclic structure, and a heterocyclic structure is preferable, and has at least one structure selected from an alicyclic structure and a heterocyclic structure. Compounds are more preferable, and compounds having a heterocyclic structure are more preferable.

  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 terminal and having a repeating unit in the molecule. For example, it is selected from transesterification between (meth) allyl ester compound of polybasic acid and polyhydric alcohol, alcohol such as monool and polyhydric alcohol containing (meth) allyl alcohol, and polybasic acid and polybasic acid anhydride Condensation reaction with at least one kind, transesterification reaction of polyol having repeating unit with (meth) allyl ester compound of polybasic acid, and alcohol such as monool containing (meth) allyl alcohol and polyol having repeating unit It is a compound produced | generated by various reaction of condensation reaction with at least 1 sort (s) chosen from polybasic acid and polybasic acid anhydride.

As the catalyst used for the above-mentioned transesterification, organometallic compounds are particularly preferable, and specific examples thereof include tetraisopropoxytitanium, tetra-n-butoxytitanium, dibutyltin oxide, dioctyltin oxide, acetylacetone hafnium, acetylacetone zirconium and the like. be able to.
As reaction temperature of the said transesterification, Preferably it is 100 to 230 degreeC, More preferably, it is 120 to 200 degreeC. In particular, in the case of using a solvent for the transesterification reaction, the boiling point may limit the reaction. In addition, it may be limited by the polyhydric alcohol used.

Furthermore, although it is not necessary to use a solvent in the said esterification (condensation) reaction, the solvent which does not inhibit transesterification can also be used as needed. Specifically, benzene, toluene, xylene, cyclohexane and the like can be mentioned. Among these, benzene and toluene are preferable.
As a specific example of (meth) allyl ester resin, the oligomer which has a structure represented by following formula (1), (2), (4) is mentioned, for example.

N pieces of R ¹ 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 12 carbon atoms, more preferably 4 to 10 carbon atoms) . R ² and R ³ each independently represent a hydrogen atom or a methyl group. Preferably, R ² and R ³ are both hydrogen atoms.

  In addition, (n + 1) X's in the formula (1) 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, and more preferably a phenylene group or a cyclohexylene group having no substituent. As a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, a sec-butyl group, an isobutyl group, a tert- butyl group is mentioned, for example.

The position at which the phenylene group or the cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of 1, 2, 3, 1, or 1, but in view of easiness of synthesis, the 1, 3 or 1 position. , 4th is preferable.
N in the 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 200 or more and 20000 or less, more preferably 550 or more and 10000 or less, and still more preferably 550 or more and 3000 or less.

The (2m + 1) A in the formula (2) 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 is preferably a phenylene group or a cyclohexylene group, more preferably a phenylene group or a cyclohexylene group having no substituent. As a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, a sec-butyl group, an isobutyl group, a tert- butyl group is mentioned, for example.
The position at which the phenylene group or the cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of 1, 2, 3, 1, or 1, but in view of easiness of synthesis, the 1, 3 or 1 position. , 4th is preferable.

M R ⁴ in the formula (2) are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec) -Butyl group, isobutyl group, tert-butyl group may be mentioned) or a group represented by the following formula (3). Further, R ⁵ , R ⁷ and m R ⁶ in the formula (2) each independently represent a hydrogen atom or a methyl group. Preferably, R ⁵ , R ⁷ and m R ⁶ are all hydrogen atoms. A in Formula (3) is the same as that of the oligomer represented by Formula (2), R < ⁸ > shows a hydrogen atom or a methyl group. Preferably, R ⁸ is a hydrogen atom.

  In the formula (2), m is an integer of 3 to 70, preferably an integer of 4 to 60, and more preferably an integer of 4 to 50. The molecular weight of the oligomer represented by Formula (2) is preferably 200 or more and 20000 or less, more preferably 550 or more and 10000 or less, and still more preferably 550 or more and 3000 or less.

  (Q + 1) Z in the formula (4) 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 is preferably a phenylene group or a cyclohexylene group, more preferably a phenylene group or a cyclohexylene group having no substituent. As a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, a sec-butyl group, an isobutyl group, a tert- butyl group is mentioned, for example.

[(P + 1) × q] pieces of R ⁹ in the formula (4) each independently represent a linear alkylene group having 1 to 36 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 4 to 10 carbon atoms) Or a branched alkylene group. Further, R ¹⁰ and R ¹¹ in the formula (4) each independently represent a hydrogen atom or a methyl group. Preferably, R ¹⁰ and R ¹¹ are both hydrogen atoms.
P in the formula (4) is an integer of 1 or more and 10 or less, preferably 1 or more and 9 or less, and 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 200 or more and 20000 or less, more preferably 550 or more and 10000 or less, and still more preferably 550 or more and 3000 or less.

Specific examples other than (meth) allyl ester resin when (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.
As the (meth) allyl group-containing compound (A), only one type may be used alone, or two or more types may be used in combination.

[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, and a compound having two or more (meth) allyl groups in one molecule The compound which contains meta) acryloyl group is excluded. Specific examples of the thiol compound (B) 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 compounds having 6 mercapto groups in one molecule.

  Examples of compounds having two mercapto groups in one molecule include 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-methyl propionate), butanediol bis (3-mercapto-2-methyl propionate), octanediol bis (3-mercapto-2-methyl propionate), bis (3-mercapto-2-methyl Compounds having two primary mercapto groups in one molecule, such as ropyl 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-Mercaptobutylate), octanediol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptoproto) (Onate), 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), ethylene Glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate) Compounds having two secondary mercapto groups in one molecule, such as ethylene glycol bis (2-mercapto isobutyrate), propylene glycol bis (2-mercapto isobutyrate), diethylene glycol bis (2- Mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate) and the like compounds having two tertiary mercapto groups in one molecule Can.

  Moreover, as an example of the compound which has three mercapto groups in 1 molecule, trimethylolpropane tris (2-mercapto acetate), trimethylol propane tris (3-mercapto propionate), trimethylol propane tris (3- 3- Compounds having three primary mercapto groups in one molecule, such as mercapto-2-methyl propionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropio) Salts), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (4-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), 1,3,5-tris (3-mercapto) Mercaptobutyloxyethyl) -1 Compounds having three secondary mercapto groups in one molecule, such as 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and trimethylolpropane tris (2-mercaptoisobutyrate) Compounds having three tertiary mercapto groups in one molecule, and the like.

  Furthermore, examples of compounds having four mercapto groups in one molecule include four in one molecule such as pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate). Class of compounds having a 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. having four secondary mercapto groups in one molecule Gobutsu and can be given the compound in one molecule such as pentaerythritol tetrakis (2-mercapto isobutyrate) having four tertiary mercapto group.

  Furthermore, as an example of a compound having six mercapto groups in one molecule, six primary mercapto groups in one molecule such as dipentaerythritol hexakis (3-mercapto-2-methyl propionate) are exemplified. Compounds having the formula: dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoisobutyrate), dipentaerythritol hexakis 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 mercapto of 1 molecule such as butyrate) It can be exemplified compounds having a.

  Among these thiol compounds (B), in consideration of the acid resistance and the pot life of the resist ink of this embodiment, the number of secondary mercapto groups and the number of secondary mercapto groups and the tertiary mercapto group do not have a primary mercapto group. Preferred are compounds in which the total number of is 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, Compound having three tertiary mercapto groups in one molecule, compound having four secondary mercapto groups in one molecule, compound having four tertiary mercapto groups in one molecule, one molecule A compound having six secondary mercapto groups, a compound having six 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) More preferred are 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and trimethylolpropane-tris (3-mercaptobutyrate).

When all the mercapto groups possessed by the thiol compound (B) are bonded to a secondary carbon atom or a tertiary carbon atom (that is, all the mercapto groups are secondary mercapto groups or tertiary mercapto groups) And the pot life and storage stability of the resist ink are excellent.
As the thiol compound (B), one type may be used alone, or two or more types may be used in combination. 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 as a commercial product. Among the secondary thiols which contain two or more mercapto groups in one molecule and which are easily available as commercial products, 1,4-bis (3-mercaptobutyryloxy) butane (a product of Showa Denko KK) Name Karenz MT (trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT (trade name) 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 Kalenz MT (trade name) NR1 manufactured by Showa Denko KK), trimethylolpropane tris (3-mercapto) Butyrate (trade name TPMB manufactured by Showa Denko KK) and the like.

  The preferable content of the thiol compound (B) in the resist ink of the present embodiment is the ratio of the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) to the number of mercapto groups of the thiol compound (B) Can be represented. That is, the ratio of the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) to the number of mercapto groups of the thiol compound (B) (number of allyl groups / number of mercapto groups) is the curability and acid resistance It is preferable to be in the range of 0.25 or more and 4.00 or less, more preferably in the range of 0.50 or more and 3.00 or less, and in the range of 0.67 or more and 2.33 or less from the viewpoint of the property More preferably, it is within. The content of the (meth) allyl group-containing compound (A) and the thiol compound (B) in the resist ink may be determined so as to obtain such a ratio.

  The number of (meth) allyl groups in 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) The number of mercapto groups in the thiol compound (B) means the sum (number of moles) of the number of mercapto groups in all compounds belonging to the thiol compound (B).

  In addition, you may mix | blend mercapto group containing compounds other than a thiol compound (B) with the resist ink of this embodiment if it is quantity of the range which does not impair the effect of invention. 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 the mercapto group-containing compounds including the thiol compound (B) from the viewpoint of maintenance of curability, acid resistance, etc. It is preferable that it is the following.

[3] Polymerization initiator (C)
The polymerization initiator (C) includes a photopolymerization initiator and a thermal polymerization initiator, but radical radicals are 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 promotes the initiation of the polymerization initiator. For example, the polymerization initiator described in Japanese Patent No. 5302688 can be used. As the polymerization initiator (C), one type may be used alone, or two or more types may be used in combination in an arbitrary ratio.

  The photopolymerization initiator and the thermal polymerization initiator may be used alone, but from the viewpoint of retention of the printing shape of the resist ink when printing is performed using the resist ink, the polymerization initiator (C) may be used. Preferably, a photoinitiator is included. In the case of performing polymerization such that curing by irradiation of active energy rays and thermal curing are performed in combination, a photopolymerization initiator and a thermal polymerization initiator can be used in combination.

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

  Further, as a photopolymerization initiator sensitive to irradiation of visible light or ultraviolet light, benzophenone such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-trimethylsilyl benzophenone or the like There may also be mentioned derivatives thereof and benzoin such as benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin isopropyl ether or derivatives thereof.

  Furthermore, methylphenyl glyoxylate, benzoin dimethyl ketal, ethyl (2,4,6-trimethyl benzoyl) phenyl phosphinate (eg, Irgacure TPO manufactured by BASF Corp.) as a photopolymerization initiator sensitive to irradiation of visible light or ultraviolet light. -L) and the like, and also bisacylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and bis (2,6-dichlorobenzoyl) -phenyl phosphine oxide; Acyl phosphine oxide compounds such as 2,4,6-trimethyl benzoyl-diphenyl phosphine oxide and 2,4,6- trimethoxy benzoyl diphenyl phosphine oxide can also be mentioned.

  Particularly preferable photopolymerization initiators include diphenyl-2,4,6-trimethylbenzoyl phosphine oxide, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- (4-isopropenylphenyl) -2-methyl Propan-1-one and its oligomers, 2,4,6-trimethyl benzophenone, and mixtures thereof, LAMBERTI S. p. The product name "ESACURE KTO 46" manufactured by company A can be preferably used.

  Furthermore, as a photopolymerization initiator sensitive to irradiation of visible light or ultraviolet light, bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrole-1) [I] phenyl] titanium compounds such as titanium, etc., thioxanthones such as 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, methyl phenyl glyoxylate, benzoin dimethyl ketal, p-dimethylaminobenzoic acid isoamyl And ethyl p-dimethylaminobenzoate.

  In addition, a compound generally referred to as a photopolymerization accelerator (for example, p-dimethylaminobenzoic acid isoamyl acid) which has an excellent promoting function for a hydrogen abstraction type photopolymerization initiator (for example, benzophenone type, thioxanthone type) (P-dimethylaminoethyl benzoate) is also defined in the present invention as being included in the photopolymerization initiator.

  Among these photopolymerization initiators, acyl phosphine oxide compounds, bisacyl phosphine 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, 1-hydroxycyclohexyl phenyl ketone is preferable, 2,4,6- More preferred are trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone.

Next, although the kind of thermal polymerization initiator is not particularly limited, for example, peroxide type polymerization initiators such as organic peroxides, azo compounds, persulfates, redox type polymerization initiators, etc. are mentioned Be
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, cumylperoxy neodecanoate and the like. Furthermore, as a peroxide type polymerization initiator, dibenzoyl peroxide, t-butyl permaleate, di-t, t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, t-butyl hydro Peroxide etc. are mentioned.

Moreover, as an azo compound, 2, 2'- azobis (4-methoxy- 2,4- dimethyl valeronitrile), 2, 2'- azo bis (2, 4- dimethyl valeronitrile) etc. are mentioned.
Moreover, as a redox type polymerization initiator, the combination of a persulfate and sodium bisulfite, the combination of a peroxide and sodium ascorbate etc. are mentioned, for example. Examples of persulfates include potassium persulfate and ammonium persulfate.

  The content of the polymerization initiator (C) in the resist ink of the present embodiment is the content of components which do not contribute to the reaction of the polymerization initiator (C) and the non-reactive solvent, inorganic filler, etc. It is preferable that content of a polymerization initiator (C) at the time of making the quantity which deducted be 100 mass parts is 0.01 mass part or more and 10 mass parts or less, and is 0.1 mass part or more and 10 mass parts or less The content is more preferably 0.3 to 7 parts by mass, and particularly preferably 0.4 to 3 parts by mass. 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 is increased.

  For example, when the resist ink of the present embodiment comprises the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), and the thixo agent (D), the (meth) allyl group The content of the polymerization initiator (C) when the content of the total of the contained 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 More preferably, it is 0.1 parts by mass to 10 parts by mass, still more preferably 0.3 parts by mass to 7 parts by mass, and most preferably 0.4 parts by mass to 5 parts by mass. preferable.

  Also, for example, the resist ink of the present embodiment includes the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), the thixo agent (D), and the (meth) acryloyl group-containing compound described later When it consists of a compound (E), when the content of the sum total of a (meth) allyl group containing compound (A), a thiol compound (B), and a (meth) acryloyl group containing compound (E) is 100 mass parts The content of the polymerization initiator (C) 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, 0.3 parts by mass or more It is more preferably 7 parts by mass or less, and most preferably 0.4 parts by mass or more and 5 parts by mass or less.

[4] Thixo agent (D)
The resist ink of the present embodiment is controlled to have a thixotropy index (thixo index) of 1.05 or more and 4.00 or less by containing the thixotropic agent (D). Thereby, the resist ink of this embodiment is excellent in printability. In order to make the printability of the resist ink more excellent, the thixotropy index is more preferably 1.05 or more and 3.70 or less, and still more preferably 1.10 or more and 3.50 or less. In addition, a thixotropy index is a value measured by the method as described in the Example mentioned later.

  The content of the thixo agent (D) in the resist ink of this embodiment is not particularly limited as long as the thixotropy index can be 1.05 or more and 4.00 or less, but the (meth) allyl group-containing compound ( When the content of the total of A) and the thiol compound (B) is 100 parts by mass, the content of the thixotropic agent (D) is preferably 0.5 parts by mass or more and 10.0 parts by mass or less. More preferably, it is 0 parts by mass or more and 8.5 parts by mass or less. If the content of the thixotropic agent (D) is within the above numerical range, the printability is good, and the shape of the printed portion is easily stabilized.

The type of thixotropic agent (D) is not particularly limited, and any thixotropic agent such as an inorganic thixotropic agent or an organic thixotropic agent can be used.
Examples of inorganic thixotropic agents include silica (SiO ₂ ) such as fumed silica represented by Aerosil (trademark), alumina (Al ₂ O ₃ ), titania (TiO ₂ ) and 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) ), lead lanthanum zirconate titanate (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 silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), calcium sulfate (CaSO _4), zinc oxide (ZnO), titanium Examples include magnesium oxide (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon, hydrotalcite and the like. These thixotropic agents (D) can be used singly or in combination of two or more. Among the above-mentioned thixo agents (D), silica and hydrotalcite are preferred, and silica is particularly preferred.

  As the silica, silica particles having an average particle diameter of 1 nm or more and 100 nm or less can be suitably used. When the average particle size of the silica particles is 1 nm or more, a significant increase in the viscosity of the resist ink can be suppressed, and therefore, in addition to the fact that the content of the silica particles in the resist ink is not easily restricted, the silica particles in the resist ink The dispersibility and heat resistance of the cured product obtained by curing the resist ink tends to be sufficient. In addition, when the average particle diameter of the silica particles is 100 nm or less, the transparency of the cured product of the resist ink tends to be sufficient.

  The average particle diameter of the silica particles is more preferably 5 nm or more and 50 nm or less, and still more preferably 5 nm or more and 40 nm or less, from the balance between the viscosity of the resist ink and the transparency of the cured product. In addition, the average particle diameter of the silica particle is 100 silica particles optionally observed from the particle image observed by observing the silica particle with a high resolution transmission electron microscope (for example, H-9000 type manufactured by Hitachi, Ltd.) An image can be selected and determined as a number average particle diameter by a known image data statistical processing method.

The silica particles may be subjected to surface treatment with a surface treatment agent having an ethylenic double bond to be reactive. By this, it is possible to improve the transparency when the resist ink is cured. Although the kind of said surface treatment agent is not specifically limited, The silane compound represented by following formula (5) can be used. The silica particle to which the surface treatment with the silane compound represented by following formula (5) was given is a (meth) allyl group containing compound (A), a thiol compound (B), a (meth) acryloyl group containing compound (E) It has the reactivity which causes reactions such as radical polymerization and ene-thiol reaction. R ²¹ in the formula (5) represents a hydrogen atom or a methyl group, R ²² represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ²³ represents a hydrogen atom or 1 to 10 carbon atoms Indicates a hydrocarbon group. Moreover, s in Formula (5) is an integer of 1-6, and r is an integer of 0-2.

When r is 2, two R ²² may be the same or different. When r is 1 or 0, a plurality of R ²³ may be the same or different.
From the viewpoint of reduction in viscosity of the resist ink and storage stability, preferred R ²² is a methyl group, preferred R ²³ is an alkyl group having 1 to 3 carbon atoms (more preferably a methyl group), and preferred s is 3 and preferably r is 0.
When the silane compound of the formula (5) bonded to the surface of the silica particles cures a resist ink, the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group described later By reacting with the containing compound (E), the dispersibility of the silica particles is improved, and the transparency of the cured product is improved.

  As the silane compound of the formula (5), for example, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldiethylmethoxysilane, γ-acryloxypropylethyldimethoxysilane, γ- Acryloxypropyltrimethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxypropyldiethylethoxysilane, γ-acryloxypropylethyldiethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldiethylmethoxysilane, γ-methacrylo Xypropylethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldiethylethoxysilane, γ-methacryloxypropylethyldi Ethoxysilane, (gamma)-methacryloxypropyl triethoxysilane, etc. are mentioned.

  Among these silane compounds, γ-acryloxypropyldimethylmethoxysilane, γ- from the viewpoints of the transparency of the cured product of the resist ink, the prevention of aggregation of the silica particles in the resist ink, and the improvement of the storage stability of the resist ink. Acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferred. One of these silane compounds may be used alone, or two or more of these silane compounds may be used in combination.

  The amount of the silane compound used in the surface treatment of the silica particles is usually 0.5 parts by mass or more and 25 parts by mass or less, preferably 1.0 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the silica particles. And more preferably 1.5 parts by mass or more and 15.0 parts by mass or less. When the amount of the silane compound used is 0.5 parts by mass or more, the viscosity of the resist ink does not become too high and the viscosity tends to be appropriate. In addition, the dispersibility of the silica particles in the resist ink is good, and gelation hardly occurs. On the other hand, if the amount of the silane compound used is 25 parts by mass or less, reaction between the silica particles is less likely to occur during surface treatment, so aggregation and gelation are less likely to occur. In addition, when using the silica particle disperse | distributed to the organic solvent for surface treatment, the mass of a silica particle points out the mass of only a silica particle, and an organic solvent is not included.

Hydrotalcite, which is one of preferable inorganic thixotropic agents, is a kind of naturally occurring clay mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O etc., and is a layered inorganic compound It is. Further, hydrotalcite, for _{example, Mg 1-x Al x (} OH) 2 (CO 3) x / 2 · mH 2 O , etc. can be obtained in the synthesis. That is, hydrotalcite is a Mg / Al layered compound, and anions such as chloride ion (Cl ⁻ ) and / or sulfate ion (SO ₄ ²⁻ ) are fixed by ion exchange with the carbonate group in the interlayer. Can be Using this function, it is possible to capture chloride ions (Cl ⁻ ) and sulfate ions (SO ₄ ²⁻ ) that cause migration of copper and tin, and improve insulation reliability. Examples of commercial products of hydrotalcite include STABIACE HT-1, STABIACE HT-7, STABIACE HT-P of Sakai Chemical Co., Ltd., DHT-4A, DHT-4A2, DHT-4C, etc. of Kyowa Chemical Industry Co., Ltd. Can be 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. For example, fatty acid amide based thixotropic agents and ethyl cellulose based thixotropic agents can be mentioned. Fatty acid amide-based thixotropic agents and ethyl cellulose-based thixotropic agents can be readily obtained as commercial products.
Examples of commercially available fatty acid amide-based thixotropic agents include Disparon (trademark) 6500, Disparon (trademark) 6650, Disparon (trademark) 6700 and the like manufactured by Kushimoto Chemical Co., Ltd. Further, as a commercially available ethylcellulose-based thixotropic agent, ETHOCEL (trademark) 45, ETHOCEL (trademark) 100, ETHOCEL (trademark) 200 and the like manufactured by Dow Chemical Co., Ltd. can be mentioned.

[5] (Meth) Acryloyl Group-Containing Compound (E)
The resist ink of the present embodiment may further contain a (meth) acryloyl group-containing compound (E).
The (meth) acryloyl group-containing compound (E) is not particularly limited as long as it is a compound containing a (meth) acryloyl group, but is preferably a compound containing a (meth) acryloyloxy group, and the molecule It is more preferable that the compound is a compound having at least one structure selected from an isocyanurate structure, an alicyclic structure and an aromatic ring structure.
Further, the (meth) acryloyl group-containing compound (E) is preferably a compound having two or more (meth) acryloyl groups in one molecule from the viewpoint of the curability of the resist ink, and It is more preferable that it is a compound which has 2 or more of acryloyloxy group.

Furthermore, the (meth) acryloyl group-containing compound (E) may be a monomer, an oligomer or a polymer, but from the viewpoint of viscosity, it is a compound having a number average molecular weight of 150 or more and 1,500 or less. Is preferred.
As a preferable compound in case a (meth) acryloyl-group containing compound (E) is an oligomer, an epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate etc. are mentioned, for example Can.

  The epoxy (meth) acrylate means the general compound formed by making the epoxy resin which has an epoxy group, and the monocarboxylic acid which has a (meth) acryloyl group react. The epoxy resin is preferably a compound having two or more epoxy groups in one molecule. Specifically, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin And 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 Novolak epoxy resins such as group-containing novolac epoxy resins and brominated phenol novolac epoxy resins can also be mentioned.

In addition, bifunctional compounds such as phenol aralkyl type epoxy resin (generally called epoxidized ziloc resin), diglycidyl ether of resorcin, diglycidyl ether of hydroquinone, diglycidyl ether of catechol, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc. Type epoxy resin, triglycidyl cissocyanurate, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolac type epoxy resin (phenol nucleus is connected by bismethylene group) Epoxidized polyhydric phenol resin), methoxy group-containing phenol aralkyl resin, and the like.
Among the above-mentioned epoxy resins, hydrogenated bisphenol A epoxy resins, hydrogenated bisphenol F epoxy resins, and triglycidyl cissocyanurate are preferable from the viewpoint of weather resistance.

Next, (poly) ester (meth) acrylate means a compound having one or more ester bonds other than the (meth) acryloyloxy group and having one or more (meth) acrylate groups.
Specifically as (poly) ester (meth) acrylate, (meth) acrylate of (poly) ester polyol which uses 1, 4- cyclohexane dicyl carbonic acid, 1, 3- cyclohexane dicyl carbonic acid as a dibasic acid Or (meth) acrylate of (poly) ester polyol using tricyclo ^{[5,2,1,0 (2,6)] decanedimethanol} or 1,4-cyclohexanedimethanol as a diol component, or tris [N- Mention may be made of (meth) acrylates of (poly) ester polyols using (2-hydroxyethyl) isocyanurate and a diol as a polyol component.

Next, (poly) carbonate (meth) acrylate means a compound having one or more carbonate groups and having two or more (meth) acrylate groups. Specifically, (meth) acrylates of (poly) carbonate diols which use 1,4-cyclohexanedimethanol and other diols as raw materials, tricyclo ^{[5,2,1,0 (2,6)]} decanedimethanol and the like (Meth) acrylates of (poly) carbonate diols starting from other diols, and (meth) acrylates of (poly) carbonate polyols starting from tris [N- (2-hydroxyethyl)] isocyanurate and other diols Etc. can be mentioned.

Next, as a preferable compound when the (meth) acryloyl group-containing compound (E) is a monomer, for example, tris [N- (2-acryloyloxyethyl)] isocyanurate, tris [N- (2-methacryloyloxy) Ethyl)] isocyanurate, bis [N- (2-acryloyloxyethyl)]-N- (2-methacryloyloxyethyl) isocyanurate, bis [N- (2-methacryloyloxyethyl)]-N- (2-acryloylyl) Oxyethyl) isocyanurate, bis [N- (2-acryloyloxyethyl)]-N- (2-hydroxyethyl) isocyanurate, bis [N- (2-methacryloyloxyethyl)]-N- (2-hydroxyethyl ) isocyanurate, tricyclo ^{[5,2,1,0 (2,6)]} Dekanjime Nord diacrylate, tricyclo ^{[5,2,1,0 (2,6)]} decanedimethanol dimethacrylate, 1,4-cyclohexane dimethanol diacrylate, 1,4-cyclohexane dimethanol dimethacrylate, hydrogenated bisphenol A di Acrylate, hydrogenated bisphenol A dimethacrylate, hydrogenated bisphenol F diacrylate, hydrogenated bisphenol F dimethacrylate and the like can be mentioned.

Among these, tris [N- (2-acryloyloxyethyl)] isocyanurate, tris [N- (2-methacryloyloxyethyl)] isocyanurate, bis [N- (2-acryloyloxyethyl)]-N- (2-hydroxyethyl) isocyanurate, bis [N- (2-methacryloyloxyethyl)]-N- (2-hydroxyethyl) isocyanurate, tricyclo ^[ 5,2,1,0 ^(2,6)] decanediyl More preferred are methanol diacrylate and tricyclo ^{[5,2,1,0 (2,6)] decanedimethanol} dimethacrylate, and tris [N- (2-acryloyloxyethyl)] isocyanurate and bis [N- (2) -(Acryloyloxyethyl)]-N- (2-hydroxyethyl) isocyanurate is further preferred .

  When the resist ink of the present embodiment contains the (meth) acryloyl group-containing compound (E), 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 (E) is 100 parts by mass, the (meth) acryloyl group thereof The content of the compound (E) is preferably 10 parts by mass to 80 parts by mass, more preferably 15 parts by mass to 60 parts by mass, and further preferably 15 parts by mass to 55 parts by mass More preferable. When the content of the (meth) acryloyl group-containing compound (E) is within the above range, the mechanical physical properties improving effect of the cured product by the compounding of the (meth) acryloyl group-containing compound (E) is sufficiently expressed, and It is difficult to increase the volume shrinkage rate at the time of curing of the resist ink.

[6] Polymerization Inhibitor The resist ink of the present embodiment may contain a polymerization inhibitor, if necessary, in order to suppress radical polymerization during storage and improve storage stability. The type of 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- 4- Methoxynaphthalene, 1,4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, 1,4-dihydroxy-2-methylnaphthalene, pyrogallol, methylhydroquinone, tertiary butyl hydroquinone, 4-methoxyphenol, N-Nitroso-N-phenylhydroxyamine aluminum And the like.

Among these polymerization inhibitors, methylhydroquinone, pyrogallol and tertiary butylhydroquinone are preferable, particularly from the viewpoint of storage stability of resist ink.
One of these polymerization inhibitors may be used alone, or two or more thereof may be used in combination.

  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) and the thiol compound (B) The total content of 100 parts by mass (when the resist ink of the present embodiment contains the (meth) acryloyl group-containing compound (E), the (meth) allyl group-containing compound (A) and the thiol compound (B) The content of the polymerization inhibitor when the total content with the (meth) acryloyl group-containing compound (E) is 100 parts by mass) is preferably less than 0.5 parts by mass, and 0.0001 parts by mass or more More preferably, it is 0.3 parts by mass or less.

[7] Antioxidant The resist ink of the present embodiment may contain an antioxidant, if necessary, in order to suppress coloring of the cured product of the resist ink at high temperature. The type of 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- (5,5) 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. One of these antioxidants may be used alone, or two or more thereof may be used in combination.

  Among these antioxidants, tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine- from the viewpoint of suppression of coloration of the cured product of the resist ink under high temperature. Preferred is 2,4,6- (1H, 3H, 5H) -trione, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  The content of the antioxidant in the resist ink of the present embodiment is not particularly limited, but from the viewpoint of suppressing the coloration of the cured product of the resist ink at high temperature, the (meth) allyl group-containing compound (A) 100 parts by mass of the total content of (A) and the thiol compound (B) ((meth) allyl group-containing compound (A) when the resist ink of this embodiment contains a (meth) acryloyl group-containing compound (E) The content of the antioxidant is preferably less than 3.0 parts by mass when the total content of 100 parts by mass of the thiol compound (B) and the (meth) acryloyl group-containing compound (E) is 100 parts by mass) More preferably, it is 0.1 parts by mass or more and 2.50 parts by mass or less.

[8] Other Components that can be Added to Resist Ink The resist ink of the present embodiment is a (meth) allyl group-containing compound (A), a thiol compound (B), a polymerization initiator (C), and a thixo agent (D) In addition to containing, the (meth) acryloyl group containing compound (E) which is an optional component, a polymerization inhibitor, and an antioxidant may be contained, and also within the range which does not impair the object of the present invention If there is, it may contain other ingredients.

Moreover, the resist ink of the present embodiment may not contain a solvent as another component, or may contain a solvent, but preferably does not contain a solvent.
Furthermore, the resist ink of the present embodiment may contain a tackifier and the like as other components.
The tackifier is a substance to be mixed with a polymer compound typified by an elastomer having rubber elasticity to have an adhesive function. Tackifiers are much smaller in molecular weight than polymer compounds represented by elastomers, and are generally compounds of oligomer regions with molecular weights of several hundred to several thousand, in the glassy state at room temperature, and rubber elastic in itself. Have the property of not showing

  As tackifiers, petroleum resin tackifiers, terpene resin tackifiers, rosin resin tackifiers, coumarone indene resin tackifiers, styrene resin tackifiers and the like can generally be used. As petroleum resin tackifiers, aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, hydrogenated products thereof, etc. And modified products of The synthetic petroleum resin may be C5 system or C9 system. 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. Rosin-based resin tackifiers include gum rosin, tall oil rosin, rosin such as wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as polymerized rosin, maleated rosin, rosin glycerin ester, hydrogenated rosin ester And rosin esters such as hydrogenated rosin glycerin esters. These rosin resins have polar groups. One of these tackifiers may be used alone, or two or more thereof may be used in combination.

  Furthermore, the resist ink of the present embodiment may contain an antifoaming agent as another component. The type of antifoaming agent is not particularly limited, and specific examples thereof include BYK-077 and BYK-1794 manufactured by Big Chemie Japan Co., Ltd., SN deformer 470 manufactured by San Nopco Co., Ltd., manufactured by GE Toshiba Silicone Co., Ltd. Silicone antifoaming agents such as TSA 750 S, silicone oil SH-203 manufactured by Toray Dow Corning Co., Ltd., and acrylic polymer systems such as DAPPO SN-348, DAPPO SN-354, DAPPO SN-368 manufactured by SAN NOPCO Ltd. Agents, and acetylene diol antifoaming agents such as Surfynol DF-110D and Surfynol DF-37 manufactured by Nisshin Chemical Industry Co., Ltd., and fluorine-containing silicone antifoaming agents such as FA-630 manufactured by Shin-Etsu Chemical Co., Ltd. And the like.

[9] Preparation of Resist Ink The resist ink of the present embodiment may be used together with the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), and the thixotropic agent (D) as necessary. The (meth) acryloyl group-containing compound (E), a polymerization inhibitor, an antioxidant, and other components can be appropriately mixed and prepared.

Furthermore, the content of the polymerization initiator (C) is 0.01 parts by mass or more when the amount obtained by subtracting the content of the polymerization initiator (C) from the amount of the entire resist ink of this embodiment is 100 parts by mass. It is good to mix so that it may become in the range below a mass part.
The preparation method of 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 thixo agent (D), (meta ) Any method may be used as long as it is capable of mixing and dispersing the respective ingredients of the resist ink including the acryloyl group-containing compound (E). 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, can, plastic cup, aluminum cup and the like, and is kneaded with a stirring rod, spatula or the like.
(B) Knead each raw material with a double helical ribbon blade, a gate blade or the like.
(C) The raw materials are kneaded by a planetary mixer.
(D) Knead each raw material with a bead mill.
(E) Knead each raw material with a triple roll.
(F) The raw materials are kneaded by an extruder type kneading extruder.
(G) Knead each raw material with a rotation / revolution mixer.

The addition and mixing of the respective raw materials can be performed in any order, and all the raw materials may be added simultaneously or sequentially.
When using the polymerization initiator (C), the treatment before curing, such as handling and mixing of the above-mentioned respective materials, active energy ray illumination through a filter for removing light of the absorption wavelength that the photopolymerization initiator decomposes It can be carried out under conditions in which the polymerization initiator (C) does not act before curing treatment, such as under irradiation with no active energy ray or below the temperature at which the thermal polymerization initiator acts.
Moreover, when using hardened | cured material of the resist ink of this embodiment as a protective film of fine patterns, such as wiring, the screen-printing method is preferably used for printing of resist ink.

[10] Cured Product of Resist Ink and Hardening Method The resist ink is cured by irradiating the resist ink of the present embodiment with active energy rays or by heating, and a cured product is obtained. Examples of the active energy ray used for curing include near infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, electromagnetic waves such as X rays, γ rays and electron rays, and particle rays, but since inexpensive devices can be used, ultraviolet rays and And / or visible light is preferred.
Various light sources can be used as a light source for curing the resist ink of the present embodiment with ultraviolet light or visible light. Examples include black lights, UV-LED lamps, high pressure mercury lamps, pressurized mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, and halogen lamps.

  Here, with black light, a near-ultraviolet light emitting phosphor is attached to a special outer tube glass cut with visible light and ultraviolet light of a wavelength of 300 nm or less, and only near ultraviolet light of a wavelength of 300 nm to 430 nm (peak around 350 nm) Is a lamp that emits Moreover, a UV-LED lamp is a lamp | ramp which used the light emitting diode which emits an ultraviolet-ray. Among these light sources, high pressure mercury lamps and metal halide lamps are preferred from the viewpoint of curability. Also, in view of economy such as running cost, an LED lamp (UV-LED lamp) is preferable.

The irradiation dose of the active energy ray may be an amount sufficient to cure the resist ink of the present embodiment, and may be the composition of the resist ink of the present embodiment, the amount used, the thickness, the shape of the cured product to be formed, etc. It 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 dose of 3000 mJ / cm ² or less can be employed. In addition, the measurement wavelength of said exposure amount is 365 nm.

  The coating (coating) method in the case of coating the resist ink of this embodiment, for example on a base material and forming a coating film is not specifically 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, reverse roll, air blade, knife belt coater, floating knife , Knife over roll, knife on blanket and the like. Moreover, the method using an inkjet printer, a screen printer, etc. can also be mentioned.

  When a cured product of resist ink is used as a protective film of a fine pattern such as wiring, a method using a screen printing machine is preferable from the viewpoint of being able to control the printing pattern with high accuracy. Moreover, when obtaining the hardened | cured material of the shape holding the printing pattern shape and using it as a protective film of fine patterns, such as wiring, as above-mentioned, a polymerization initiator (C) should contain a photoinitiator. Is preferred.

Next, a protective film of a wiring containing a cured product of the resist ink of the present embodiment and a method of manufacturing the same will be described. The method of manufacturing the protective film of the wiring of the present embodiment includes the following coating step and curing step.
The covering step is a step of arranging a resist ink in a film shape by, for example, a printing method on a substrate having a wiring (for example, a printed wiring substrate) and covering the wiring with a film of the resist ink.
The resist ink film may be disposed on the entire surface of the substrate, or may be disposed on part of the surface if it can cover the wiring. Further, 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, from the viewpoint of controlling the shape pattern of the resist ink film which is a printed matter, the screen printing method is preferable.

  Further, in the curing step, a partial region or the entire region including the region covering the wiring in the resist ink film is irradiated with active energy rays of a wavelength that causes the polymerization initiator (C) to generate a polymerizable radical species. In the step of curing the resist ink in the area irradiated with the active energy ray, a protective film of the wiring is formed.

Examples of the active energy ray used in the curing step include near infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, electromagnetic waves such as X rays, γ rays and electron rays, and particle rays, but ultraviolet rays and visible rays are preferable, and ultraviolet rays Is more preferred. The light source of ultraviolet light and visible light is not particularly limited. 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 and a halogen lamp 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. Within this range, uncured parts are less likely to remain, and excessive energy consumption can be avoided. In addition, the measurement wavelength of said exposure amount is 365 nm.

  Moreover, when using together a photoinitiator and a thermal-polymerization initiator as a polymerization initiator (C), the curing process by heating can be performed after the curing process by irradiation of an active energy ray. The heating temperature (heat curing temperature) in the curing step by heating varies depending on the cleavage temperature of the thermal polymerization initiator, but is preferably 80 ° C. or more and 170 ° C. or less. Although the heating time (heat curing time) in the curing step by heating is the same, it is preferably 5 minutes to 3 hours, and more preferably 10 minutes to 2 hours.

The thickness of the protective film of the present embodiment may be appropriately set according to the application of the protective film, but is preferably 0.1 μm to 30 μm, more preferably 1 μm to 20 μm, and still more preferably 2 μm to 15 μm. Moreover, the protective film of this embodiment may also contain components other than the hardened | cured material of the resist ink of this embodiment as needed.
When the cured product of the resist ink of the present embodiment is used as a protective film of wiring, a thickness of 50 μm on a glass substrate EAGLE XG (dimension: 5 cm × 8 cm, thickness: 0.7 mm) manufactured by Corning Japan Ltd. The transmittance of light with a wavelength of 300 nm is at least 20%, the transmittance of light with a wavelength of 400 nm is at least 90%, and the transmittance of light with a wavelength of 500 nm is at least 95% Is preferred. It is preferable that the light transmittance of the cured product is as described above, because light of a wavelength used for power generation by a single crystal silicon solar cell or a polycrystalline silicon solar cell can sufficiently reach the silicon surface. In addition, said transmittance | permeability is the value which measured the transmittance | permeability of glass substrate EAGLE XG (dimension: 5 cm x 8 cm, thickness: 0.7 mm) as a reference (100%).

[11] Use of Resist Ink Although the use of the resist ink of the present embodiment is not particularly limited, for example, as described above, it can be used for the production of a printed wiring board, and a solar power generation cell It can be preferably used in order to form a protective film in the case of forming electrode wiring by a plating method at the time of manufacture.

  When using it for manufacture of the cell for solar power generation, after coating the resist ink of this embodiment in film form with a printing method on a partial area | region among the main surfaces of a semiconductor substrate, and forming a resist ink layer, The resist ink layer is irradiated with active energy rays to cure the resist ink, and an insulating layer made of a cured product of the resist ink is formed on the main surface of the semiconductor substrate. Then, plating is performed using the insulating layer as a mask to form an electrode or wiring connected to the exposed surface of the semiconductor substrate exposed from the insulating layer to obtain a photovoltaic cell. The insulating layer after plating may be removed from the semiconductor substrate or may be left on the semiconductor substrate without being removed.

  Moreover, after apply | coating the resist ink of this embodiment to a base material, and hardening it, it is also possible to peel hardened | cured material as needed. For example, if an acidic group such as a carboxy group is present in the structure of the (meth) acryloyl group-containing compound (E), the resist ink is cured and then dipped in a basic solution to obtain a resist ink from the substrate surface. It is also possible to peel off the cured product of

  Examples of the basic solution include aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous potassium carbonate solution, aqueous sodium carbonate solution and the like. The basic aqueous solution is preferably heated from the viewpoint of shortening the time for peeling the cured product of the resist ink. As heating conditions, 20 degreeC or more and 90 degrees C or less are preferable, and 30 degreeC or more and 90 degrees C or less are more preferable. If it is this temperature range, the operation | work of a peeling process can be performed efficiently and temperature control is also easy.

When the cured product of the resist ink is peeled using a basic aqueous solution as a peeling liquid, the acid value of the resist ink is preferably 20 mgKOH / g or more and 150 mgKOH / g or less. If the acid value of the resist ink is within the above range, the cured product of the resist ink can be easily peeled off from the substrate by a basic aqueous solution, and it is possible to have good resistance to the plating solution. The effect is played.
The present embodiment shows an example of the present invention, and the present invention is not limited to the present embodiment. In addition, various changes or improvements can be added to this embodiment, and a form added with such changes or improvements can be included in the present invention.

  The present invention will be described in more detail with reference to the following Examples and Comparative Examples. (Meth) allyl group-containing compound (A), thiol compound (B), polymerization initiator (C), thixo agent (D), (meth) acryloyl group-containing compound (E), and various raw materials of antifoam agent It mixed by this roll, and prepared the resist ink of Examples 1-8 and Comparative Examples 1-3. The various raw materials used for preparation of resist ink are demonstrated below.

(I) (meth) allyl group-containing compound (A)
(I-1) Synthesis of Allyl Ester Resin (a) As a (meth) allyl group-containing compound (A), an allyl ester resin (a) manufactured by the following method was used.
In a 2-neck three-neck flask equipped with a distillation apparatus, 631 g of 1,4-cyclohexanedicarboxylic acid diallyl ester, 208 g of neopentyl glycol, 12 g of tris (2-hydroxyethyl) isocyanurate and 0.92 g of dioctyl tin oxide are introduced It heated at 180 degreeC under airflow. The allyl alcohol thus produced was distilled off stepwise while reducing the pressure to obtain allyl ester resin (a).

The iodine value of the allyl ester resin (a) measured by the method according to JIS K 0070 was 36.
Gas chromatography GC-14B (detector: hydrogen flame ionization detector, column: Agilent J & W GC column, grade name DB-1, manufactured by Shimadzu Corporation), temperature condition: after holding at 70 ° C for 2 minutes, at a speed of 20 ° C / min When the allyl ester resin (a) was analyzed using a temperature rise and maintained at 280 ° C. for 2 minutes, the allyl ester resin (a) contained 3.4% by mass of diallyl 1,4-cyclohexanedicarboxylate .

(I-2) Synthesis of allyl ester resin (b) In a 2-neck three-necked flask equipped with a distillation apparatus, 1, 5-cyclohexanedicarboxylic acid diallyl ester 532 g, 1, 9-nonanediol 258 g, tris (2-hydroxyethyl) 12 g of isocyanurate and 0.92 g of dioctyltin oxide were charged, and heated at 180 ° C. in a nitrogen stream. The resulting allyl alcohol was distilled off stepwise while reducing pressure to obtain allyl ester resin (b).

The iodine value of the allyl ester resin (b) measured by the method according to JIS K 0070 was 36.
Gas chromatography GC-14B (detector: hydrogen flame ionization detector, column: Agilent J & W GC column, grade name DB-1, manufactured by Shimadzu Corporation), temperature condition: after holding at 70 ° C for 2 minutes, at a speed of 20 ° C / min The allyl ester resin (b) was analyzed using an elevated temperature and maintained at 280 ° C. for 2 minutes), and it was found that the allyl ester resin (b) contained 3.1% by mass of diallyl 1,4-cyclohexanedicarboxylate .

(I-3) Synthesis of allyl ester resin (c) In a 2-neck three-necked flask equipped with a distillation apparatus, 588 g of 1,4-cyclohexanedicarboxylic acid diallyl ester, 74 g of 1,9-nonanediol, 2,4-diethyl- 74 g of 1,5-pentanediol, 95 g of neopentyl glycol, 12 g of tris (2-hydroxyethyl) isocyanurate, and 0.92 g of dioctyl tin oxide were charged, and heated at 180 ° C. in a nitrogen stream. The allyl alcohol thus produced was distilled off stepwise while reducing the pressure to obtain allyl ester resin (c).

The iodine value of the allyl ester resin (c) measured by the method according to JIS K 0070 was 36.
Gas chromatography GC-14B (detector: hydrogen flame ionization detector, column: Agilent J & W GC column, grade name DB-1, manufactured by Shimadzu Corporation), temperature condition: after holding at 70 ° C for 2 minutes, at a speed of 20 ° C / min The allyl ester resin (c) was analyzed using an elevated temperature and maintained at 280 ° C. for 2 minutes), and it was found that the allyl ester resin (c) contained 2.9% by mass of diallyl 1,4-cyclohexanedicarboxylate .

(Ii) Thiol compound (B)
The following compounds were used as a thiol compound (B).
(Ii-1) Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Kalores MT (registered trademark) PE1 manufactured by Showa Denko KK, molecular weight 545, number of mercapto groups of 4)
(Ii-2) Pentaerythritol tetrakis (3-mercaptopropionate) (trade name PEMP manufactured by Sakai Chemical Industry Co., Ltd., molecular weight 489, number of mercapto groups 4)

(Iii) Polymerization initiator (C)
As the polymerization initiator (C), diphenyl-2,4,6-trimethyl benzoyl phosphine oxide, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropane LAMBERTI S., which is a mixture of -1-one and its oligomers and 2,4,6-trimethylbenzophenone. p. The product name "ESACURE KTO 46" manufactured by company A was used.

(Iv) (meth) acryloyl group-containing compound (E)
The following compounds were used as the (meth) acryloyl group-containing compound (E).
(Iv-1) Isocyanuric acid EO modified diacrylate and triacrylate (Alonix M-315 manufactured by Toagosei Co., Ltd.)
(Iv-2) dimethylol-tricyclodecane diacrylate (DCP-A manufactured by Kyoeisha Chemical Co., Ltd.)
(Iv-3) Epoxy acrylate having a bisphenol A type framework (VR-77 manufactured by Showa Denko KK)

(V) Thixotropic agent (D)
As the thixotropic agent (D), silica particles having an average particle diameter of 12 nm or titanium oxide particles having an average particle diameter of 14 nm were used. Specifically, the following three compounds (v-1), (v-2) and (v-3) were used as the thixo agent (D).

(V-1) Fumed titanium oxide whose surface is modified with an alkylsilane group (Aeroxide (registered trademark) NKT 90, manufactured by Nippon Aerosil Co., Ltd., average particle diameter 14 nm)
(V-2) Fumed silica whose surface is modified with an octylsilane group (Aerosil (registered trademark) R 805 manufactured by Nippon Aerosil Co., Ltd., average particle diameter 12 nm)
(V-3) Fumed silica whose surface is modified with a methacryloyloxysilane group (Aerosil (registered trademark) R 711, manufactured by Nippon Aerosil Co., Ltd., average particle diameter 12 nm)

(Vi) Antifoamer As an antifoamer, an antifoamer BYK-1794 manufactured by Big Chemie Japan Co., Ltd. and an antifoamer polyflow No. 4 manufactured by Kyoeisha Chemical Co., Ltd. 77 was used.
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 of GPC are as shown below.

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

  The (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), the thixo agent (D), the (meth) acryloyl group-containing compound (E), and the antifoaming agent are shown in Table 1 The resist ink was prepared by mixing with the mass ratio shown (the unit of the numerical values shown in Table 1 is mass part) and kneading using a three-roll. Then, the thixotropy and printability of these resist inks, and the acid resistance (resistance to an electrolytic tin plating solution) and transparency of a cured product of the resist ink were evaluated. The method of each evaluation test is described below, and the evaluation results are shown in Table 1. In Table 1, “the functional group number ratio of (A) / (B)” is the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) relative to the number of mercapto groups of the thiol compound (B) Ratio (number of (meth) allyl groups / number of mercapto groups) is shown.

<Evaluation of Thixotropy of Resist Ink>
The thixotropy index of the resist ink was measured using a Brookfield cone / plate viscometer (model: DV-II + Pro, spindle model: CPE-52). And loaded resist ink of approximately 0.5mL viscometer, temperature 25.0 ° C., the viscosity was measured each at a rotational speed 0.5 min ^-1 and 5min ^-1, measured from the start of measurement after 7 minutes The measured viscosity value was taken as the measured value. Then, to calculate the percentage obtained by dividing the measured value of a rotational speed 0.5 min ^-1 measured value of a rotational speed 5.0min ^-1.

<Evaluation of acid resistance of cured product>
Next, the acid resistance of the cured products of the resist inks of Examples 1 to 8 and Comparative Examples 1 to 3 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 50 μm thick film with a bar coater on the central part 5 cm × 8 cm on 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 is irradiated with 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 I-Graphics Co., Ltd. to cure the resist ink film. The test body which has a protective film which consists of hardened | cured material was obtained. In addition, the measurement wavelength of said exposure amount is 365 nm.

  The obtained test body was washed with a 5% by mass aqueous sulfuric acid solution, and then immersed in 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 the cured product of the resist ink was not immersed in the electroless tin plating solution so that the portion not subjected to the plating treatment could be observed. The test body was taken out of the electroless tin plating solution and repeatedly washed with warm water, and then subjected to eutectic treatment at 120 ° C. for 90 minutes with a blast constant-temperature dryer. And the following two points evaluated about this test body.

<Evaluation of peeling of protective film>
The presence or absence of peeling of the protective film from the substrate was visually observed, and those with no peeling of the protective film were evaluated as “A”, and those with peeling of the protective film were evaluated as “C”.
<Evaluation of the penetration of plating>
Using a microscope VHX-900 manufactured by Keyence Corporation, it was observed whether or not plating was buried between the protective film and copper. Then, those with no penetration were evaluated as "A", those with penetration but having less than 1 mm were evaluated as "B", and those with 1 mm or more with penetration were evaluated as "C".

  As can be seen from the results shown in Table 1, in the cured products of the resist inks of Examples 1 to 8 and Comparative Example 1, the resist ink contains (meth) allyl group-containing compound (A), thiol compound (B), and polymerization initiation Since the agent (C) is contained, it is excellent in acid resistance, and peeling of the protective film and penetration of plating hardly occurred even if it was immersed in a strongly acidic electroless tin plating solution.

<Evaluation of printability of resist ink>
Next, the printability of the resist ink of Examples 1-8 and Comparative Examples 1-3 was evaluated as follows. The results are shown in Table 1.
The resist ink was printed using the screen printing plate on the surface of the n-type single crystal silicon substrate in which the uneven structure called the texture was formed in the single side | surface. Printing was carried out under an environment of a temperature of 23 ° C. and a humidity of 65%, and the temperature of the resist ink was also adjusted to 23 ° C. The printing conditions were a squeegee speed of 50 mm / sec, a scraper pressure of 0.2 MPa, a squeegee pressure of 0.24 MPa, and a clearance of 3.9 mm. The angle of the squeegee was set at 80 °. As the squeegee, a micro squeegee with a squeegee hardness of 80 (manufactured by Micro Tech Co., Ltd.) was used.

  As a printing machine, a screen printer MT-650 manufactured by Micro Tech Co., Ltd. was used. The screen printing plate was a combination plate, and a printing plate HSC-500-19-25T (wire diameter: 19 μm, total thickness: 25 μm) manufactured by Sonocom Inc. was used. The emulsion type of the screen printing plate was G95C, and the thickness of the emulsion was 5 μm. The shape of the screen printing plate is a rectangular shape of 650 mm wide and 550 mm long, and the resist ink transmitting portion and the resist ink non transmitting portion (the portion where the wiring is formed by the later plating) are formed in the following design. ing.

  That is, a plurality of strip-like resist ink non-transmissive portions each having a width of 100 μm and a length of 50 mm are formed on the screen printing plate. All resist ink non-transmissive portions extend in parallel with each other and at equal intervals in the longitudinal direction, and the resist ink non-transmissive portions are striped. All parts other than the resist ink non-permeable part are resist ink permeable parts. The printing direction is the longitudinal direction (direction along the longitudinal direction of the strip-like resist ink non-transmissive portion).

Then, 30 seconds after the start of printing, using a conveyor-type UV irradiator ECS-4011GX (high pressure mercury lamp) manufactured by Eyegraphics, Inc., a silicon substrate is irradiated with UV light (measurement wavelength 365 nm) at a dose of 1 J / cm ² The above resist ink was irradiated. Thereby, the resist ink was cured and a cured film (protective film) was formed. Since the resist ink is not applied to the portion of the surface of the silicon substrate corresponding to the resist ink non-transmissive portion of the screen printing plate, the protective film has an opening. Therefore, the printability of the resist ink was evaluated by the width of the opening. The width of the opening is measured by observation with a microscope, and the printability of the resist ink is “A” for 60 μm or more, “B” for 30 μm or more and less than 60 μm, and “C” for less than 30 μm. evaluated.

  As can be seen from the results shown in Table 1, the resist inks of Examples 1 to 8 have the thixotropy index controlled within the range of 1.05 or more and 4.00 or less by the thixo agent (D), so the printability is shown It was excellent. On the other hand, since the resist ink of Comparative Example 1 does not contain the thixo agent (D) and the thixotropy index is outside the range of 1.05 or more and 4.00 or less, the printability is insufficient. The

<Evaluation of transparency of cured product>
Next, the transparency of the resist inks of Examples 1 to 8 and Comparative Examples 1 to 3 was evaluated as follows. The results are shown in Table 1.
Resist ink was coated on a 50 μm thick film using a bar coater on the central part (size: 4 cm × 6 cm) of one side of a glass substrate EAGLE XG (dimension: 5 cm × 8 cm, thickness: 0.7 mm) manufactured by Corning Japan Ltd. Apply to Then, using a conveyor-type UV irradiator ECS-4011GX (high pressure mercury lamp) manufactured by I-Graphics Co., Ltd., the resist ink film is irradiated with UV light of an exposure amount of 1 J / cm ² to be cured, A test sample having a 50 μm thick protective film made of a cured product is obtained.

The transmittance of the obtained test sample is measured using an ultraviolet-visible near-infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation to evaluate the transparency of the cured product. In that case, the glass substrate used for preparation of a test sample was used as a reference. The transmittance at each wavelength of 300 nm, 400 nm and 500 nm was measured, and the results are shown in Table 1.
As seen from the results shown in Table 1, the cured products of the resist inks of Examples 1 to 8 had high transmittance to light of any wavelength and had excellent transparency. . On the other hand, the cured products of the resist inks of Comparative Examples 1 to 3 had low transmittance to light of a part of the wavelengths and insufficient transparency.

Claims (16)

  (Meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule, thiol compound (B) having two or more mercapto groups in one molecule, polymerization initiator ( C) and a thixo agent (D), and the resist ink whose thixotropy index is 1.05 or more and 4.00 or less.   When the content of the total of the (meth) allyl group-containing compound (A) and the thiol compound (B) is 100 parts by mass, the content of the thixo agent (D) is 0.5 parts by mass or more and 9.0 The resist ink according to claim 1, which is at most parts by mass.   The resist ink according to claim 1 or 2, wherein the thixotropic agent (D) is a silica particle having an average particle diameter of 1 nm or more and 100 nm or less.   The resist ink according to claim 3, wherein the silica particles are subjected to surface treatment with a surface treatment agent and have reactivity.   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, according to any one of claims 1 to 4. Resist ink.   The resist ink according to any one of claims 1 to 5, wherein the (meth) allyl group-containing compound (A) contains a compound having at least one of an ester structure and an isocyanurate structure.   The resist ink according to any one of claims 1 to 6, wherein the thiol compound (B) contains a compound having two or more secondary or tertiary mercapto groups in one molecule.   The resist ink according to any one of claims 1 to 7, further comprising a (meth) acryloyl group-containing compound (E).   The resist ink according to claim 8, wherein the (meth) acryloyl group-containing compound (E) contains a compound having two or more (meth) acryloyl groups in one molecule.   The resist ink according to claim 8 or 9, wherein the (meth) acryloyl group-containing compound (E) contains a compound having at least one structure selected from an isocyanurate structure, an alicyclic structure and an aromatic ring structure. The ratio of the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) to the number of mercapto groups of the thiol compound (B) (number of allyl groups / number of mercapto groups) is 0.25 or more Within the following range,
Content of the said polymerization initiator (C) when content of the sum total of (meth) allyl group containing compound (A), a thiol compound (B), and (meth) acryloyl group containing compound (E) is 100 mass parts Is 0.01 parts by mass or more and 10 parts by mass or less, The resist ink according to any one of claims 8 to 10.   When the total content of the (meth) allyl group-containing compound (A), the thiol compound (B) and the (meth) acryloyl group-containing compound (E) is 100 parts by mass, the (meth) of them The content of the acryloyl group-containing compound (E) is 10 parts by mass or more and 80 parts by mass or less, The resist ink according to any one of claims 8 to 11.   The protective film of the wiring containing the hardened | cured material of the resist ink as described in any one of Claims 1-12.   It is a semiconductor substrate covered with the protective film containing the hardened | cured material of the resist ink as described in any one of Claims 1-12, Comprising: The semiconductor substrate which has wiring in the part which is not covered by the said protective film. A step of arranging the resist ink according to any one of claims 1 to 12 in a film form on a substrate having a wire, and covering the wire with the film of the resist ink;
An active energy ray of a wavelength causing generation of a polymerizable radical species to the polymerization initiator (C) is irradiated to a partial region or the entire region including the region covering the wiring in the film of the resist ink, and the resist Curing the ink to form a protective film of the wiring;
Method of producing a protective film of wiring comprising: Covering the semiconductor substrate with a film of the resist ink by arranging the resist ink according to any one of claims 1 to 12 in a film shape on the semiconductor substrate;
An active energy ray of a wavelength that causes the polymerization initiator (C) to generate a polymerizable radical species is applied to a partial region or the entire region of the film of the resist ink, and the resist ink is cured to thereby cure the semiconductor A curing step of forming a protective film of the substrate;
A method of manufacturing a protective film of a semiconductor substrate comprising: