JPWO2018074308A1 - Photobase generator and photosensitive composition - Google Patents

Abstract

Provided is a photobase generator capable of efficiently generating high catalytic activity amine by photosensitizing light, and having no concern about metal corrosion, and a photosensitive composition containing the photobase generator. The present invention is a photobase generator comprising an ammonium borate salt compound (A) represented by the following general formula. [Wherein, R 1 to R 4 are each independently an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group, and a part of hydrogen atoms of the phenyl group or naphthyl group is an alkyl having 1 to 18 carbon atoms. R5 may be a polyalkyleneoxy group, and the end of the polyalkyleneoxy group may be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R6 to R7 are each independently a methyl group or an ethyl group, Ar is an aryl group having 6 to 14 carbon atoms, and Q is a divalent group that bonds Ar to a cationic nitrogen atom. . ]

Description

The present invention relates to a photobase generator that generates a base by light irradiation and a photosensitive composition containing the photobase generator. More specifically, a material that is cured using a base generated by light irradiation (for example, a coating agent or a paint), or a product formed through patterning using a difference in solubility in a developer in an exposed area or an unexposed area, or The present invention relates to a photobase generator and a photosensitive composition that are suitably used for producing members (for example, electronic components, optical products, optical component forming materials, layer forming materials, or adhesives).

As a photobase generator that generates a base upon exposure, a photobase generator that generates a primary amine or a secondary amine, a strong base (tertiary amine, pKa 8 to 11), a super strong base (guanidine, amidine, etc.) Various photobase generators such as photobase generators (Patent Documents 1 to 7 and Non-Patent Documents 1 and 2) that generate pKa11 to 13) are known.

However, the photobase generators described in Patent Document 1 and Non-Patent Document 1 have low basicity of the generated base (pKa <8) and are not suitable as a catalyst for polymerization reaction or crosslinking reaction. In addition, since these amines have active hydrogen atoms, if they are used for polymerization reaction or crosslinking reaction of epoxides or isocyanates, they react with each other, so that a large amount of photobase generator is required to perform a sufficient reaction. There was a problem of becoming.

  Moreover, since the base generators of Patent Documents 2 to 5 and Non-Patent Document 2 have low activity for light and the combined use effect of the photosensitizer is low, the photolatency of polymerization reaction or crosslinking reaction of epoxide or isocyanate is low. The base catalyst has a problem that its performance is low.

By the way, in applications such as adhesives, sealants, paints and coatings, a curable resin using a compound containing a highly reactive thiol group as a curing agent has been studied. Because of the high reactivity of thiol, it can be cured at a relatively low temperature, and in combination with a photobase generator, it can be stored in a single solution, generating a base by irradiation with energy such as light, and the effect of its base catalyst Can be cured more quickly (see, for example, Patent Document 8).
Under such circumstances, a photobase generator having a catalytic activity for curing while maintaining sufficient storage stability of a composition comprising a highly reactive thiol compound, that is, a conventional photobase generator. However, development of a photobase generator excellent in the balance between stability and catalytic activity is desired.

Japanese Patent Laid-Open No. 10-7709 JP 2005-107235 A JP 2005-264156 A JP 2007-119766 A JP 2009-280785 A WO2005-014696 WO2009-122664 JP 2005-511536 Gazette

Encyclopedia of applied optical technology and materials, Industrial Technology Service Center Co., Ltd., 2006, p. 130 J.Photopolym.Sci.Tech., Vol.19., No.1 (81) 2006

The problem to be solved by the present invention is to provide a photobase generator that can efficiently generate amine having high catalytic activity by photosensitizing light, and has no concern about metal corrosion: and reaction with the photobase generator A photosensitive composition containing a highly functional thiol group, which contains a photobase generator that is more soluble in resins than the conventional photobase generator and has excellent storage stability. To provide things.

As a result of intensive studies to solve the above problems, the present inventors have found a photobase generator having excellent characteristics.
That is, this invention is a photobase generator characterized by including the ammonium borate salt compound (A) represented by the following general formula.

[Wherein, R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group, and a part of hydrogen atoms of the phenyl group or naphthyl group is 1 to 18 carbon atoms. Or an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by —OR ⁸ or an aryloxy group, or a halogen atom, and R ⁸ is carbon. An alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R ⁵ is a polyalkyleneoxy group, and the terminal of the polyalkyleneoxy group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and a, R ⁶ to R ⁷ independently of one another are methyl or ethyl, Ar is an aryl group having 6 to 14 carbon atoms, Q is a divalent coupling the Ar and cationic nitrogen atom It is. ]

Furthermore, the present invention is a photosensitivity containing the photobase generator described above, a compound (B) having two or more thiol groups in the molecule, and a compound (C) having two or more groups that react with the thiol group. It is a composition.

  Furthermore, this invention is a hardening body obtained by hardening | curing the said photosensitive composition.

The photobase generator of the present invention can generate amine having high catalytic activity efficiently by exposing light.
Moreover, since the photobase generator of the present invention does not contain a halogen ion or the like as a counter anion, there is no concern about metal corrosion.
In addition, since the photobase generator of the present invention is not basic before exposure, even if it is contained in the reactive composition, the storage stability of the reactive composition is not reduced.
Moreover, the photobase generator of the present invention is stable against heat, and it is difficult to generate a base even when heated unless it is irradiated with light.
In addition, according to the method for producing a cured product using the photosensitive composition of the present invention, by using the above photobase generator, by irradiating with light, an amine having high catalytic activity can be efficiently generated, A cured product can be produced efficiently.

  Hereinafter, embodiments of the present invention will be described in detail.

The photobase generator is a compound that decomposes its chemical structure upon irradiation with light and generates a base (amine). The generated base can act as a catalyst for epoxy resin curing reaction, polyimide resin curing reaction, isocyanate and polyol urethanization reaction, acrylate crosslinking reaction, and the like.

The photobase generator of the present invention contains an ammonium borate salt compound (A) represented by the following general formula.

[Wherein, R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group, and a part of hydrogen atoms of the phenyl group or naphthyl group is 1 to 18 carbon atoms. Or an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by —OR ⁸ or an aryloxy group, or a halogen atom, and R ⁸ is carbon. An alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R ⁵ is a polyalkyleneoxy group, and the terminal of the polyalkyleneoxy group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and a, R ⁶ to R ⁷ independently of one another are methyl or ethyl, Ar is an aryl group having 6 to 14 carbon atoms, Q is a divalent coupling the Ar and cationic nitrogen atom It is. ]

In the general formula, the alkyl group having 1 to 18 carbon atoms in R ^{1 to} R ⁴ is a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl). , N-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1 , 1,3,3-tetramethylbutyl), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridged cyclic alkyl groups (such as norbornyl, adamantyl and pinanyl).
Of these, preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, more preferably a linear alkyl group having 2 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or 5 carbon atoms. ˜6 cycloalkyl groups.

In the general formula, a phenyl group or a naphthyl group in R ^{1 to} R ⁴ is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, An alkoxy group or aryloxy group represented by —OR ⁸ or a halogen atom may be substituted, and the alkyl group having 1 to 18 carbon atoms is the same as described above, and the preferable ones are also the same. It is.

In the above substituent, the aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents) includes a monocyclic aryl group (such as phenyl) and a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl). Monocyclic heterocycles such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl; and indolyl, benzofuranyl, isobenzofuranyl , Benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathiinyl, chromanyl, i Chromanyl, coumarinyl, dibenzothienyl, Kisantoniru, Chiokisantoniru, dibenzofuranyl, etc. fused polycyclic heterocyclic ring).
Of these, preferred are phenyl, naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, xanthenyl, thianthenyl, phenoxathiinyl, chromanyl, isochromanyl, coumarinyl, xanthonyl, thioxanthonyl, and more preferred are phenyl, naphthyl, anthracenyl, and phenanthrenyl.

In the above substituent, R ⁸ of the alkoxy group represented by —OR ⁸ includes an alkyl group having 1 to 8 carbon atoms. Specifically, among the above alkyl groups, an alkyl group having 1 to 8 carbon atoms is used. Can be mentioned.

In the above substituent, R ⁸ of the aryloxy group represented by —OR ⁸ includes an aryl group having 6 to 14 carbon atoms, specifically, the above aryl group having 6 to 14 carbon atoms.

Examples of the alkoxy group represented by —OR ⁸ include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2- Examples include methylbutoxy.
Examples of the aryloxy group represented by —OR ⁸ include phenoxy and naphthoxy.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among these substituents, from the viewpoint of solvent solubility of the salt, alkoxy groups such as methoxy, ethoxy, n-butoxy, aryloxy groups such as phenoxy, naphthoxy, methylthio, ethylthio, butylthioalkylthio groups, arylthio groups such as phenylthio, naphthylthio, A fluorine atom, a chlorine atom and a bromine atom are preferred.

In the general formula, the polyalkyleneoxy group in R ⁵ refers to a group in which 2 to 4 moles of alkylene oxide having 2 to 4 carbon atoms has been added, and the types of alkyleneoxy groups added may be the same or different, Specific examples include polyethylene oxide, polypropylene oxide, polybutylene oxide, and mixed adducts thereof. The number of added moles is preferably 2 to 10 moles and more preferably 2 to 5 moles from the viewpoint of the molecular weight of the generated base.
Furthermore, it is preferable that the oxygen atom at the terminal of the polyalkyleneoxy group is substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Specific examples of the alkyl group having 1 to 4 carbon atoms include alkyl groups having 1 to 4 carbon atoms among the above alkyl groups.

In the general formula, R ^{6 to} R ⁷ are a methyl group or an ethyl group.

In the general formula, Ar is an aryl group having 6 to 14 carbon atoms, which is the same as described above, and preferred ones are also the same.

In the general formula, Q is a divalent group that bonds the Ar and the cationic nitrogen atom, and may have a substituent, a C1-C18 alkylene group, a C2-C18 alkenylene group. And groups selected from arylene groups having 6 to 14 carbon atoms. Among these, an alkylene group having 1 to 8 carbon atoms which may have a substituent is preferable, and an alkylene group having 1 to 8 carbon atoms substituted with an unsubstituted, oxo group or phenyl group is more preferable.
Specific examples of preferable Q include methylene, ethylene, phenylmethylene, propylene, butylene, dimethylmethylene, diethylmethylene, hexane-1,1-diyl, octane-1,1-diyl, cyclohexane-1,1-diyl, 2 -Oxo-ethylene, 2-oxo-1,1-dimethylethylene, 2-oxo1,1-dimethoxyethylene and the like.
From the viewpoint of easy availability of raw materials, methylene, ethylene, phenylmethylene, and 2-oxo-ethylene are more preferable.
Specific examples of the preferred ammonium borate salt compound (A) include the following compounds. These ammonium borate salt compounds (A) can be used alone or in admixture of two or more.

The photosensitive composition of the present invention contains the photobase generator, a compound (B) having two or more thiol groups in the molecule, and a compound (C) having two or more groups that react with the thiol group. .

Examples of the compound (B) having two or more thiol groups in the molecule of the present invention include trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis ( 3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tetraethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,5-dimercapto-3-thiapentane, 2,2 ′-(ethi N-dithio) diethanethiol, 1,8-dimercapto-3,6-dioxaoctane, 1,4-benzenedimethanethiol, 1,3-benzenedimethanethiol, 1,5-naphthalenedithiol, 1,3,5 -Trimercaptomethylbenzene, 4,4'-thiodibenzenethiol, 1,3,5-trimercaptomethyl-2,4,6-trimethylbenzene, 2,4,6-trimercapto-s-triazine, 2- Dibutylamino-4,6-dimercapto-s-triazine, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, trimethylolethanetris (3-mercaptobutyrate), tris-[(3-mercaptobuty Ryloxy) -ethyl] -isocyanurate, dipentaerythritol hexa-3-mercapto Ropioneto, and the like.
These compounds (B) can be used alone or in admixture of two or more.

The compound (C) having two or more groups capable of reacting with the thiol group in the present invention is used together with the compound (B), and is rapidly cross-linked catalyzed by a base compound generated from a photobase generator upon irradiation with light energy. Reaction and polymerization reaction proceed.
Examples of the compound (C) in the present invention include an epoxy group-containing compound (C-1), an episulfide group-containing compound (C-2), and an isocyanate group-containing compound (C-3).

Examples of the epoxy group-containing compound (C-1) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and alicyclic epoxy resins. In addition to these, a phenol novolac type epoxy resin, a heterocyclic epoxy resin, a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, an aliphatic epoxy resin, a spiro ring-containing epoxy resin, and the like can also be used.
In addition to the above, an epoxy resin obtained by the reaction of a compound having two or more hydroxyl groups in the molecule (for example, polyether polyol or aliphatic polyol) and epichlorohydrin, or two or more carboxyl groups in the molecule In addition, a polyester compound containing an epoxy group obtained by a reaction between a compound having a derivative thereof and a derivative thereof (for example, an aliphatic polycarboxylic acid, an aromatic polycarboxylic acid and a derivative thereof) and epichlorohydrin can be used as well. .
The episulfide group-containing compound (C-2) is obtained by replacing the oxygen atom of the epoxy compound with a sulfur atom, and is obtained by reacting, for example, the epoxy compound described above with a thiocyanate or thiourea as a sulfiding agent. (See, for example, J. Polym. Sci. Polym. Phys., 17,329 (1979), J. Org. Chem., 26, 3467 (1961)).
As the isocyanate group-containing compound (C-3), compounds conventionally used for polyurethane or polyisocyanurate can be used. Examples of such polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified products thereof (for example, carbodiimide modification, allophanate modification, urea modification, burette modification, isocyanate modification). (Nuarate modification, oxazolidone modification, etc.), isocyanate group-terminated prepolymers and the like.
Aromatic polyisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), crude TDI, diphenylmethane-2,4'- or 4,4′-diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, etc. Is mentioned.
Aliphatic isocyanates include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexylene diisocyanate, 2,2,4-trimethyl. Examples include hexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include xylylene diisocyanate and tetramethylxylylene diisocyanate. Examples of the modified polyisocyanate include carbodiimide-modified MDI, sucrose-modified TDI, castor oil-modified MDI, and the like.
These compounds (C) can be used alone or in admixture of two or more.

The blending amount of the compound (B) and the compound (C) in the present invention is the ratio of the total thiol equivalent of the compound (B) to be blended and the total equivalent of the epoxy equivalent, episulfide equivalent or isocyanate equivalent of the compound (C) to be blended. (B) :( C) = 1.0: 0.5 to 3.0, more preferably 1.0: 0.7 to 2.0, and most preferably 1.0: 0.8 to 1. 3 range. By blending in this range, a good cured product can be obtained.

As a compounding quantity of the compound (A) which is a photobase generator in this invention, it is 0.05-30 weight% with respect to the total weight of a compound (B) and a compound (C), Preferably it is 0.1-20 weight %.

The photobase generator of the present invention has sufficient sensitivity to light compared to conventional photobase generators, so that a sufficient effect can be obtained alone, but it may be used in combination with other photosensitizers.

As other photosensitizers, known sensitizers (JP-A Nos. 11-279212 and 09-183960) can be used, and benzoquinone {1,4-benzoquinone, 1,2-benzoquinone, etc.} Naphthoquinone {1,4-naphthoquinone, 1,2-naphthoquinone, etc.]; anthraquinone {2-methylanthraquinone, 2-ethylanthraquinone, etc.}; anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene , 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxone Phenthiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine, etc.}; xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol and the like}; ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone and 4-benzoyl-4'-methyldiphenyl sulfide etc.}; carbazole {N-phenylcarbazo , N-ethylcarbazole, poly-N-vinylcarbazole and N-glycidylcarbazole etc.}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene etc.}; phenanthrene {9- Hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.}.
In particular, from the viewpoint of electron acceptability, when a naphthoquinone, benzophenone, xanthone, anthraquinone, or thioxanthone sensitizer is used, a high sensitization effect is obtained, which is preferable.
The compounding amount of the other photosensitizer is 0.01 to 10 equivalents, preferably 0.1 to 5 equivalents, more preferably 0.5 to 2 based on the number of moles of the compound (A) to be compounded. Is equal. If there is too much photosensitizer, the irradiated energy such as light may not reach the bottom, which causes variations in curability.

The ammonium borate salt compound (A) which is the photobase generator of the present invention can be produced by a known method. An example is shown in the following chemical reaction formula. A compound (H) substituted with a leaving group (Z) having substituents Ar and Q corresponding to the target compound (A) and an amine substituted with substituents R ^{5 to} R ⁷ are directly or in a solvent. by reacting, Z ^- obtain a cationic intermediates with the counter anion. The target photobase generator can be obtained by anion exchange between this cation intermediate and a borate metal salt having a substituent corresponding to the target photobase generator in an organic solvent or water.

[Wherein R ^{1 to} R ⁷ , Q and Ar are the same as those in the above general formula, Z is a leaving group, Z ⁻ is a counter anion generated by elimination, and M ⁺ is a metal cation] . ]

  Examples of the leaving group (Z) include a halogen atom (such as a chlorine atom and a bromine atom), a sulfonyloxy group (such as trifluoromethylsulfonyloxy, 4-methylphenylsulfonyloxy and methylsulfonyloxy), and an acyloxy (acetoxy and trifluoromethyl). Carbonyloxy and the like). Of these, a halogen atom and a sulfonyloxy group are preferred from the viewpoint of ease of production.

  As the solvent, water or an organic solvent can be used. Organic solvents include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran, dioxane, etc.), chlorinated solvents (chloroform, dichloromethane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones ( Acetone, methyl ethyl ketone and methyl isobutyl ketone), nitriles (acetonitrile, etc.) and polar organic solvents (dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, etc.). These solvents may be used alone or in combination of two or more.

  The reaction temperature (° C.) between the compound (H) as a raw material of the cation intermediate and the amine is preferably −10 to 100, more preferably 0 to 80. It is preferable to dissolve the compound (G) in an organic solvent and add an amine thereto. The amine may be added dropwise or may be added dropwise after dilution with an organic solvent.

The compound (H) can be produced by a known method. Among the compounds (H), when the α-position carbon substituted with an aromatic ring group is halogenated (preferably brominated), a method using a halogen (preferably bromine) or N-bromosuccinimide combined with a radical generator is used. The method was simple and preferred (4th edition, Experimental Chemistry Course 19 edited by the Chemical Society of Japan, p422).

  A borate metal salt which is an anionic component is obtained by using a known method (for example, Journal of Polymer Science: Part A: Polymer Chemistry, vol 34, 2817 (1996) or the like) and alkyl or aryl organometallic compound and alkyl or aryl. It can be obtained by reacting a boron compound or a boron halide compound in an organic solvent. As the organometallic compound to be used, lithium compounds such as alkyl lithium and aryl lithium, and magnesium compounds (Grignard reagent) such as alkyl magnesium halide and aryl magnesium halide are preferably used.

The reaction between the boron compound and the organometallic compound is −80 ° C. to 100 ° C., preferably −50 ° C. to 50 ° C., and most preferably −30 ° C. to 30 ° C. As the organic solvent to be used, hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran, dioxane, etc.), and chlorinated solvents (chloroform, dichloromethane, etc.) are preferably used.

  The borate metal salt obtained above is preferably an alkali metal salt from the viewpoint of stability and solubility. In the case of reacting with a Grignard reagent, it is preferable to perform metal exchange during or after the reaction by adding sodium hydrogen carbonate, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide or the like.

Anion exchange is performed by mixing the borate metal salt obtained above with an organic solvent or an aqueous solution containing an intermediate.
The anion exchange may be carried out after the intermediate is obtained, or the intermediate may be isolated and purified and then dissolved in an organic solvent again to carry out the anion exchange.

  The ammonium borate salt compound (A), which is a photobase generator obtained as described above, may be purified after being separated from the organic solvent. Separation from the organic solvent can be carried out by adding a poor solvent directly to the organic solvent solution containing the photobase generator (or after concentration) to precipitate the photobase generator. Examples of the poor solvent used here include chain ethers (such as diethyl ether and dipropyl ether), esters (such as ethyl acetate and butyl acetate), aliphatic hydrocarbons (such as hexane and cyclohexane), and aromatic hydrocarbons (toluene and Xylene and the like).

  When the compound (A) is an oily substance, the precipitated oily substance is separated from the organic solvent solution, and further the organic solvent contained in the oily substance is distilled off, whereby the ammonium borate salt compound which is the photobase generator of the present invention is obtained. (A) can be obtained. On the other hand, when the compound (A) is a solid, the precipitated solid is separated from the organic solvent solution, and further, the organic solvent contained in the solid is distilled off, whereby the ammonium borate salt compound which is the photobase generator of the present invention. (A) can be obtained.

  Purification can be performed by recrystallization (a method using a difference in solubility due to cooling, a method of adding a poor solvent to precipitate, and a combination thereof). Further, when the photobase generator is an oily substance (when it is not crystallized), it can be purified by a method of washing the oily substance with water or a poor solvent.

The photosensitive composition of this invention can contain a solvent etc. as needed.
Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran) And 1,8-cineole).
Further, glycidyl ethers such as phenyl glycidyl ether and methyl glycidyl ether having one glycidyl group in the molecule, and alkylene oxides such as oxetane, styrene oxide, and cyclohexene oxide can be used as a solvent. These glycidyl ethers and alkylene oxides are called reactive diluents.
These may be used alone or in combination of two or more.
The content of the solvent in the photosensitive composition is preferably 0 to 99% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight based on the total weight of the photosensitive resin composition. It is.

  The photosensitive composition of the present invention may contain other additives that are generally used to control the appearance and physical properties of the cured product of the photosensitive composition as necessary. Examples include pigments such as inorganic pigments and organic pigments, colorants such as dyes, dispersants, metal oxide particles, and metal particles. The photosensitive composition of the present invention is further provided with an adhesion imparting agent, an antifoaming agent, a leveling agent, a thixotropic property imparting agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant, and an ultraviolet absorber according to the purpose of use. An agent etc. can be contained.

The photobase generator of the present invention can be applied to a latent base catalyst (a catalyst that does not have a catalytic action before irradiation with light, but develops an action of a basic catalyst by light irradiation), etc. For example, it can be used as a curing catalyst for a photosensitive resin composition, and is suitable as a curing catalyst for a photosensitive resin composition that cures when irradiated with light. For example, it is possible to easily constitute a photosensitive resin composition comprising a basic resin that accelerates curing with a base, the photobase generator of the present invention, and, if necessary, a solvent and / or an additive. Since such a photosensitive resin composition contains the photobase generator of the present invention, it is excellent not only in storage stability but also in curability. That is, a cured product can be obtained by generating a base by irradiating light to the photosensitive resin composition containing the photobase generator of the present invention to promote the curing reaction. Therefore, as a manufacturing method of such hardened | cured material, it is preferable to include the process of generating a base by irradiating light with respect to the photobase generator of this invention. In addition, you may heat as needed in the case of hardening reaction.

The photobase generator of the present invention can be used without limitation as long as it is a photocurable resin that is cured by a base in addition to the photosensitive composition of the present invention. For example, curable acrylic resins {acrylic monomers and / or acrylic oligomers and curing agents (such as thiols, malonic esters and acetylacetonates)}, polysiloxanes (cured to cross-linked polysiloxanes), polyimide resins, and patents The resin described in Document 3 can also be used.

The photobase generator of the present invention includes commonly used high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, high-power metal halide lamps and the like (for example, the latest trends in UV / EB curing technology, edited by Radtech Research Group, CMC Publishing) 138, 2006), and an LED ultraviolet irradiation device, an EB line, an excimer laser, an Ar laser, or the like can be used depending on the application.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not intending to be limited to this. Unless otherwise specified, “%” means “% by weight”.

Production Example 1 Synthesis of Compound A-1 (1) Synthesis of Intermediate (CA-1 Chloride) 21 g of benzyl bromide was dissolved in 150 g of chloroform, and 16 g of dimethylaminoethoxyethanol was added dropwise thereto and stirred at 60 ° C. . Six hours later, disappearance of the raw materials was confirmed by HPLC, and a 20% chloroform solution of the intermediate (CA-1 chloride) was obtained.
(2) Synthesis of Compound A-1 25 g of sodium tetraphenylborate and 250 g of ion-exchanged water were added to 100 g of a 20% chloroform solution of the intermediate (CA-1 chloride) obtained in (1), and the mixture was stirred at room temperature for 3 hours. Stir. The organic layer was washed 5 times with 100 g of ion exchange water. The organic layer was concentrated and the solvent was evaporated, and the residue was recrystallized from methanol to obtain a white solid. It was confirmed by ¹ H-NMR that this white solid was Compound A-1.

Production Example 2 Synthesis of Compound A-2 (1) Synthesis of Intermediate (CA-2 Chloride) In Production Example 1, 21 g of benzyl bromide was changed to 23 g of (1-bromoethyl) benzene, and the intermediate (CA-2 chloride) was synthesized. 21% chloroform solution was obtained.
(2) Synthesis of Compound A-2 The same operation as in Production Example 1 was performed to obtain a white solid. ¹ H-NMR confirmed that the white solid was compound A-2.

Production Example 3 Synthesis of Compound A-3 (1) Synthesis of Intermediate (CA-3 Chloride) In Production Example 1, 21 g of benzyl bromide was changed to 30 g of diphenylbromomethane to obtain 23 of intermediate (CA-3 chloride). % Chloroform solution was obtained.
(2) Synthesis of Compound A-3 The same operation as in Production Example 1 was performed except that 25 g of sodium tetraphenylborate and 250 g of ion-exchanged water were changed to 300 g of 10% aqueous solution of lithium butyltriphenylborate in Production Example 1, and white A solid was obtained. This white solid was confirmed to be compound A-3 by ¹ H-NMR.

Production Example 4 Synthesis of Compound A-4 (1) Synthesis of Intermediate (CA-4 Bromide) In Production Example 1, 16 g of dimethylaminoethoxyethanol was 15 g of phenyldimethylamine and 21 g of benzyl bromide was triethylene glycol 2-bromoethyl. A 24% chloroform solution of the intermediate (CA-2 bromide) was obtained using 32 g of methyl ether.
(2) Synthesis of Compound A-4 The same operation as in Production Example 1 was performed to obtain a white solid. ¹ H-NMR confirmed that the white solid was compound A-4.

Comparative Production Example 1 Synthesis of Compound H-1 Synthesis was performed according to the method described in Example 1 except that 11 g of dimethylaminoethanol was used instead of dimethylaminoethoxyethanol.

Comparative Production Example 2 Synthesis of Compound H-2 Synthesis was performed according to the method described in Example 1 except that 22 g of tributylamine was used instead of dimethylaminoethoxyethanol in Example 1.

Comparative Production Example 3 Synthesis of Compound H-3 According to the method described in Example 1, except that 40 g of tris [2- (2-methoxyethoxy) ethyl] amine was used instead of dimethylaminoethoxyethanol in Example 1. Synthesized.

Examples 1-6, Comparative Examples 1-5
[Preparation of photosensitive composition]
Compound (A), compound (B), compound (C) and sensitizer (D), which are photobase generators, are uniformly mixed, and the photosensitive composition of the present invention [Examples 1 to 6] and comparative photosensitivity are used. Composition [Comparative Examples 1 to 5] was prepared. The types of raw materials used are shown below.
[Raw materials used]
A-1: Compound (A-1) synthesized in Production Example 1
A-2: Compound synthesized in Production Example 2 (A-2)
A-3: Compound synthesized in Production Example 3 (A-3)
A-4: Compound (A-4) synthesized in Production Example 4
A′-1: Compound (H-1) synthesized in Comparative Production Example 1
A′-2: Compound (H-2) synthesized in Comparative Production Example 2
A′-3: Compound (H-3) synthesized in Comparative Production Example 3
B-1: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Aldrich)
B-2: Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko)
C-1: Epicoat 828 (Mitsubishi Chemical)
D-1: 2-Isopropylthioxanthone (manufactured by Tokyo Chemical Industry)
[Solubility of photobase generator]
As the solubility evaluation of the photobase generator (Compound A and Comparative Compound A ′), the appearance of the photosensitive composition was evaluated according to the following criteria. The results are shown in Table 1.
Appearance evaluation:
○ Uniformly transparent △ Slightly fogged x Precipitated
[Photocurability]
After apply | coating the obtained photosensitive composition to a glass substrate (76 mm x 52 mm) using an applicator (40 micrometers), it exposes with a belt conveyor type UV irradiation apparatus (Eye Graphics Co., Ltd., ECS-151U). A base was generated, and then immediately placed on a hot plate heated to 80 ° C., and the time until tack on the coated surface disappeared was measured. The results are shown in Table 1. Even when the obtained photosensitive composition was heated to 80 ° C. without light irradiation, it was not cured for 60 minutes or more.
Photocurability evaluation:
◎ Cured within 10 seconds.
○ Cured within 1 minute.
△ Cured within 10 minutes.
X Cured within 60 minutes.
XX Does not cure for more than 60 minutes.
[Room temperature storage stability]
The obtained photosensitive composition was stored in a brown bottle and the period until the fluidity disappeared was confirmed. As a result, the room temperature storage stability of 30 days or more was confirmed for both the composition of the example and the composition of the comparative example. .

From the results shown in Table 1, the photosensitive composition using the photobase generator of the present invention is more sensitive than the photosensitive composition using the comparative photobase generator, and has solubility and composition in the resin. It turns out that it is useful as a photosensitive composition excellent in the storage stability of a thing.

The base generator of the present invention uses a base generated by light irradiation, paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, anti-touch coating, optical fiber, etc.), Adhesive tape backside treatment agent, release coating material for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental materials (dental compound, dental composite) ink, inkjet ink , Positive resist (formation of connection terminals and wiring patterns for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist film, liquid resist, negative resist (semiconductor elements and transparent electrodes for FPD (ITO, IZO, GZO) ) Surface protective film, interlayer insulating film, permanent film material such as planarization film), MEMS resist, positive photosensitive material, negative Photosensitive materials, various adhesives (various electronic component temporary fixing agents, HDD adhesives, pickup lens adhesives, FPD functional film adhesives (deflecting plates, antireflection films, etc.), circuit forming and semiconductors Insulating film for sealing, anisotropic conductive adhesive (ACA), film (ACF), paste (ACP), etc.) resin for holography, FPD material (color filter, black matrix, partition material, photospacer, rib, liquid crystal Alignment films, FPD sealants, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, flip chips, COF, etc. Chip sealing material, package sealing material such as CSP or BGA, optical semiconductor (LED) sealing material, optical waveguide material, nanoimprint material, photofabrication, Suitably used in fine micro-stereolithography material or the like.

Claims (5)

A photobase generator comprising an ammonium borate salt compound (A) represented by the following general formula.

[Wherein, R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group, and a part of hydrogen atoms of the phenyl group or naphthyl group is 1 to 18 carbon atoms. Or an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by —OR ⁸ or an aryloxy group, or a halogen atom, and R ⁸ is carbon. An alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R ⁵ is a polyalkyleneoxy group, and the terminal of the polyalkyleneoxy group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and a, R ⁶ to R ⁷ independently of one another are methyl or ethyl, Ar is an aryl group having 6 to 14 carbon atoms, Q is a divalent coupling the Ar and cationic nitrogen atom It is. ] The photobase generator according to claim 1, wherein Q in the general formula is an alkylene group having 1 to 8 carbon atoms. Photosensitivity containing the photobase generator according to claim 1 or 2, the compound (B) having two or more thiol groups in the molecule, and the compound (C) having two or more groups that react with the thiol group. Composition. The compound (C) is selected from the group consisting of an epoxy group-containing compound (C-1), an episulfide group-containing compound (C-2), and an isocyanate group-containing compound (C-3). Photosensitive composition. A cured product obtained by curing the photosensitive composition according to claim 1.