JP6959245B2 - Photobase generator and photosensitive composition - Google Patents

Description

The present invention relates to a photobase generator that generates a base by irradiation with light and a photosensitive composition containing the same. More specifically, a material that is cured by using a base generated by light irradiation (for example, a coating agent or a paint), or a product formed through patterning that utilizes the difference in solubility of exposed and unexposed areas in a developing solution. It relates to a photobase generator and a photosensitive composition preferably used for producing a member (for example, an electronic part, an optical product, a material for forming an optical part, a layer forming material or an adhesive).

As a photobase generator that generates a base by exposure, a photobase generator that generates a primary amine or a secondary amine, a strong base (tertiary amine, pKa8-11), a superstrong base (guanidine, amidin, etc.) , PKa11-13), and various photobase generators (Patent Documents 1 to 7, Non-Patent Documents 1 and 2, etc.) 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 catalysts for polymerization reaction or cross-linking reaction. In addition, since these amines have active hydrogen atoms, if they are used in the polymerization reaction or cross-linking reaction of epoxides and isocyanates, they will react by themselves, so a large amount of photobase generator is required to carry out a sufficient reaction. There was a problem of becoming.

Further, since the base generators of Patent Documents 2 to 5 and Non-Patent Document 2 have low activity against light and the combined effect of the photosensitizer is also low, the photopotency of the polymerization reaction and the cross-linking reaction of epoxide and isocyanate is low. As a base catalyst, it has a problem of low performance.

By the way, in applications such as adhesives, encapsulants, paints and coatings, curable resins using compounds containing highly reactive thiol groups as curing agents have been studied. Since thiol has high reactivity, it can be cured at a relatively low temperature. Furthermore, by combining it with a photobase generator, one-component storage is realized, and bases are generated by irradiation with energy such as light, and the effect of the base catalyst. (See, for example, Patent Document 8).
Under such circumstances, a photobase generator having catalytic activity for curing while maintaining sufficient storage stability of a composition containing a highly reactive thiol compound, that is, a conventional photobase generator. However, it is desired to develop a photobase generator having an excellent balance between stability and catalytic activity.

Japanese Unexamined Patent Publication No. 10-7709 Japanese Unexamined Patent Publication No. 2005-107235 Japanese Unexamined Patent Publication No. 2005-264156 Japanese Unexamined Patent Publication No. 2007-11976 JP-A-2009-280785 WO2005-014696 WO2009-122664 Japanese Patent Publication No. 2005-511536

Optical Application Technology / Materials Encyclopedia, 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 capable of efficiently generating an amine having high catalytic activity by sensitizing light and without fear of metal corrosion: and reaction with the photobase generator. A photosensitive composition containing a thiol group having high properties, which contains a photobase generator having excellent solubility in a resin and excellent storage stability as compared with the case of using a conventional photobase generator. To provide things.

As a result of diligent research to solve the above problems, the present inventors have found a photobase generator having excellent properties.
That is, the present invention is a photobase generator, which comprises an ammonium borate salt compound (A) represented by the following general formula.

[In the formula, R ^{1 to} R ⁴ are alkyl groups, phenyl groups or naphthyl groups having 1 to 18 carbon atoms independently of each other, and some of the hydrogen atoms of the phenyl group or naphthyl group have 1 to 18 carbon atoms. It may be substituted with an alkyl group, 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. It is an alkyl group having a number of 1 to 8 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. R ^{6 to} R ⁷ are independent of each other, 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 and a cationic nitrogen atom. It is a group. ]

Further, the present invention is photosensitive containing the above-mentioned photobase generator, a compound (B) having two or more thiol groups in the molecule, and a compound (C) having two or more groups reacting with the thiol group. It is a composition.

Further, the present invention is a cured product obtained by curing the above-mentioned photosensitive composition.

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

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

A photobase generator refers to an agent that generates a base (amine) by decomposing its chemical structure by light irradiation. The generated base can act as a catalyst for curing reaction of epoxy resin, curing reaction of polyimide resin, urethanization reaction of isocyanate and polyol, cross-linking reaction of acrylate and the like.

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

[In the formula, R ^{1 to} R ⁴ are alkyl groups, phenyl groups or naphthyl groups having 1 to 18 carbon atoms independently of each other, and some of the hydrogen atoms of the phenyl group or naphthyl group have 1 to 18 carbon atoms. It may be substituted with an alkyl group, 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. It is an alkyl group having a number of 1 to 8 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. R ^{6 to} R ⁷ are independent of each other, 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 and a cationic nitrogen atom. It is a group. ]

In the general formula, ^{the alkyl groups having 1 to 18 carbon atoms in R 1 to} R ⁴ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl). , N-dodecyl, n-tetradecyl, n-hexadecyl and 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, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and crosslinked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.).
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, and 5 carbon atoms. ~ 6 cycloalkyl groups.

In the general formula, the ^{phenyl group or naphthyl group in R 1 to} R ⁴ has an alkyl group having 1 to 18 carbon atoms as a part of its hydrogen atom, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, and a cyano group. It may be substituted with an alkoxy group or an aryloxy group represented by −OR ⁸ or a halogen atom, and the alkyl group having 1 to 18 carbon atoms is the same as that described above, and the preferred one is also the same. Is.

Among the above substituents, examples of the aryl group having 6 to 14 carbon atoms (excluding the carbon number of the substituent below) include a monocyclic aryl group (phenyl, etc.) and a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl). , Anthraquinolyl, fluorenyl and naphthoquinolyl, etc.) and aromatic heterocyclic hydrocarbon groups (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and other monocyclic heterocycles; and indrill, benzofuranyl, isobenzofuranyl , Benzothenyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantranyl, phenoxadinyl, phenoxatyynyl, chromanyl, isochromanyl, cumarinyl, dibenzothienyl, xanthonyl. A furanyl isocondensate polycyclic heterocycle) can be mentioned.
Of these, phenyl, naphthyl, anthracenyl, phenanthrenyl, anthracinolyl, xanthenyl, thianthrenyl, phenoxatyynyl, chromanyl, isochromanyl, coumarinyl, xanthonyl and thioxanthonyl are preferred, and phenyl, naphthyl, anthracenyl and phenanthrenyl are more preferred.

In the above-mentioned substituent ^{, R 8} of the alkoxy group represented by ^{−OR 8} includes an alkyl group having 1 to 8 carbon atoms, and specifically, among the above-mentioned alkyl groups, an alkyl group having 1 to 8 carbon atoms is used. Can be mentioned.

In the above-mentioned substituent ^{, R 8} of the aryloxy group represented by ^{−OR 8} includes an aryl group having 6 to 14 carbon atoms, and specifically, the above-mentioned aryl group having 6 to 14 carbon atoms.

Alkoxy groups 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-. Methylbutoxy and the like can be mentioned.
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, an alkoxy group such as methoxy, ethoxy, n-butoxy, an aryloxy group such as phenoxy and naphthoxy, an arylthio group such as methylthio, ethylthio, butylthioalkylthio group, phenylthio and naphthylthio, Fluorine atom, chlorine atom and bromine atom are preferable.

In the formula, it refers to those added alkylene oxide having 2 to 4 carbon atoms is 2 moles or more to the polyalkyleneoxy group in R ^5, the type of alkylene group, appended may be the same or different, Specific examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, and mixed adducts thereof. The number of added moles is preferably 2 to 10 mol, more preferably 2 to 5 mol, from the viewpoint of the molecular weight of the generated base.
Further, 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 an alkyl group having 1 to 4 carbon atoms among the above-mentioned alkyl groups.

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

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

In the general formula, Q is a divalent group that bonds Ar and a cationic nitrogen atom, and may have a substituent, an alkylene group having 1 to 18 carbon atoms, and an alkenylene group having 2 to 18 carbon atoms. , A group selected from an arylene group having 6 to 14 carbon atoms can be mentioned. Of these, an alkylene group having 1 to 8 carbon atoms which may have a substituent is preferable, and an unsubstituted, oxo group, or a phenyl group substituted alkylene group having 1 to 8 carbon atoms 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 Examples thereof include −oxo-ethylene, 2-oxo-1,1-dimethylethylene, 2-oxo1,1-dimethoxyethylene and the like.
Methylene, ethylene, phenylmethylene, and 2-oxo-ethylene are more preferable from the viewpoint of easy availability of raw materials.
Specific examples of the preferable ammonium borate salt compound (A) include the following compounds. These ammonium borate salt compounds (A) can be used alone or in combination of two or more.

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

Examples of the compound (B) having two or more thiol groups in the molecule of the present invention include trimethylolpropanthris (3-mercaptopropionate), trimethylolpropanetris (3-mercaptobutyrate), and pentaerythritol tetrakis (3-mercaptopropionate). 3-Mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tetraethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, Trimethylol Propanetristhioglycolate, Pentaeristol tetrakisthioglycolate, Di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,5-dimercapto-3-thiapentane, 2,2'-(ethylenedithio) ) Dietanethiol, 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-dibutyl Amino-4,6-dimercapto-s-triazine, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, trimethylolethanetris (3-mercaptobutyrate), tris-[(3-mercaptobutylyl) Oxy) -ethyl] -isocyanurate, dipentaerythritol hexa-3-mercaptopropionate and the like can be mentioned.
These compounds (B) can be used alone or in admixture of two or more.

The compound (C) having two or more groups that react with the thiol group in the present invention is used together with the above compound (B), and is catalyzed by a base compound generated from a photobase generator by irradiation with light or other energy to rapidly crosslink. The 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 isocyanato group-containing compound (C-3).

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

The compounding 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 compounded to the epoxy equivalent, episulfide equivalent or isocyanato equivalent of the compound (C) to be compounded. As a result, (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. It is in the range of 3. A good cured product can be obtained by blending in this range.

The blending amount of the compound (A), which is a photobase generator in the present invention, is 0.05 to 30% by weight, preferably 0.1 to 20% by weight, based on the total weight of the compound (B) and the compound (C). %.

Since the photobase generator of the present invention has improved sensitivity to light as compared with the conventional photobase generator, a sufficient effect can be obtained by itself, but it may be used in combination with other photosensitizers.

As other photosensitizers, known sensitizers (Japanese Patent Laid-Open No. 11-279212, JP-A-09-183960, etc.) can be used, and benzoquinone {1,4-benzoquinone, 1,2-benzoquinone, etc.} can be used. Naphthalene {1,4-naphthoquinone, 1,2-naphthoquinone, etc.}; Anthracene {2-methylanthracene, 2-ethylanthracene, etc.}; Anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, etc.} , 9,10-Diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronen; thioxanthone {thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone}; phenothracene {phenothracene, N-methylphenothracene, N-ethylphenothracene, N-phenylphenothracene, etc.}; Naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol, etc.}; Ketone {dimethoxyacetophenone, diethoxyacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone and 4-benzoyl-4'-methyldiphenylsulfide, etc.}; Carbazole {N-phenylcarbazole, etc.} , N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; chrycene {1,4-dimethoxychrycene and 1,4-di-α-methylbenzyloxychrycene, etc.}; , 9-Hythracene, 9-hydroxy-10-methoxyphenthracene, 9-hydroxy-10-ethoxyphenthracene, etc.} and the like.
In particular, from the viewpoint of electron acceptability, a high sensitizing effect can be obtained when a naphthoquinone-based, benzophenone-based, xanthone-based, anthraquinone-based, or thioxanthone-based sensitizer is used, which is preferable.
The amount of the other photosensitizer to be blended is 0.01 to 10 equal to the number of moles of the compound (A) to be blended, preferably 0.1 to 5 equal, and more preferably 0.5 to 2. Equal amount. If there is too much photosensitizer, the energy such as the irradiated 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 by the following chemical reaction formula. Having substituents Ar and Q corresponding to the desired compound (A), a compound leaving group (Z) is substituted with (H), and amine substituents R ⁵ to R ⁷ is substituted directly or in a solvent By reacting ^{, a cation intermediate having Z −} as a counter anion is obtained. The desired photobase generator can be obtained by exchanging anions between this cation intermediate and a borate metal salt having a substituent corresponding to the target photobase generator in an organic solvent or water.

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

Leaving groups (Z) include halogen atoms (chlorine atom, bromine atom, etc.), sulfonyloxy groups (trifluoromethylsulfonyloxy, 4-methylphenylsulfonyloxy, methylsulfonyloxy, etc.) and asyloxy (acetoxy and trifluoromethyl, etc.). Carbonyloxy, etc.) is included. Of these, halogen atoms and sulfonyloxy groups are preferable from the viewpoint of ease of production and the like.

As the solvent, water or an organic solvent can be used. Examples of the organic solvent include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahexyl, dioxane, etc.), chlorine-based solvents (chloroform, dichloromethane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones (methanol, ethanol, isopropyl alcohol, etc.), ketones ( Includes acetone, methyl ethyl ketone and methyl isobutyl ketone, etc.), nitriles (acetriform, 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), which is a raw material for the cationic intermediate, and the amine is preferably −10 to 100, and more preferably 0 to 80. It is preferable to dissolve the compound (G) in an organic solvent and add an amine to the compound (G). The amine may be added dropwise, or it may be diluted with an organic solvent and then added dropwise.

The compound (H) can be produced by a known method. Of the compound (H), when the α-position carbon substituted with the aromatic ring group is halogenated (preferably brominated), a method using a halogen (preferably bromine) or N-bromosuccinimide using a radical generator in combination is used. The method used is simple and preferable (4th Edition Experimental Chemistry Course 19 Japan Chemical Society, p422).

Boron metal salts, which are anionic components, can be prepared by using a known method (for example, Journal of Polymer Science: Part A: Polymer Chemistry, vol34, 2817 (1996), etc. can be referred to) with alkyl or aryl organometallic compounds and alkyl or aryl. It is obtained by reacting a boron compound or a boron halide compound in an organic solvent. As the organometallic compound to be used, a lithium compound such as alkyllithium or aryllithium, or a magnesium compound (grinyard reagent) such as alkylmagnesium halide or arylmagnesium halide is 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 chlorine-based 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. When the reaction is carried out with a greeninal reagent, it is preferable to add sodium hydrogen carbonate, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide and the like during or after the reaction to perform metal exchange.

The anion exchange is carried out by mixing the borate metal salt obtained above with an organic solvent or an aqueous solution containing an intermediate.
The intermediate may be obtained and then the anion exchange may be carried out, 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 the photobase generator obtained as described above, may be purified after being separated from the organic solvent. Separation from the organic solvent can be performed by directly (or after concentrating) the organic solvent solution containing the photobase generator and adding a poor solvent to precipitate the photobase generator. Examples of the poor solvent used here include chain ethers (diethyl ether, dipropyl ether, etc.), esters (ethyl acetate, butyl acetate, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), and aromatic hydrocarbons (toluene and cyclohexane, etc.). Xylene, etc.) is included.

When the compound (A) is an oil, the precipitated oil is separated from the organic solvent solution, and the organic solvent contained in the oil is distilled off to distill off the ammonium borate salt compound which is the photobase generator of the present invention. (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 the organic solvent contained in the solid is distilled off to distill off the ammonium borate salt compound which is the photobase generator of the present invention. (A) can be obtained.

Purification can be carried out by recrystallization (a method utilizing the difference in solubility due to cooling, a method of adding a poor solvent for precipitation, and a combination thereof). When the photobase generator is an oil (when it does not crystallize), the oil can be purified by washing with water or a poor solvent.

The photosensitive composition of the present invention may contain a solvent or the like, if necessary.
As the solvent, 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, etc.) Acetates and propylene glycol alkyl ether acetates, etc.), aromatic hydrocarbons (toluene, xylene, mesityrene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalol, citronellol, etc.) and ethers (tetralol, etc.) And 1,8-cineol, etc.).
Further, a glycidyl ether such as phenylglycidyl ether and methyl glycidyl ether having one glycidyl group in the molecule and an alkylene oxide 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. Is.

The photosensitive composition of the present invention may contain other commonly used additives as necessary for controlling the appearance and physical properties of the cured product of the photosensitive composition. Pigments such as inorganic pigments and organic pigments, colorants such as dyes, dispersants, metal oxide particles, metal particles and the like are included. The photosensitive composition of the present invention further has an adhesiveness-imparting agent, a defoaming agent, a leveling agent, a thixotropic property-imparting agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant and an ultraviolet absorbing agent, depending on the intended use. It can contain agents and the like.

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 being irradiated with light but exhibits the action of a base catalyst by light irradiation) or the like, and is a base-reactive compound. 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, a photosensitive resin composition containing a basic resin whose curing is promoted by a base, a photobase generator of the present invention, and, if necessary, a solvent and / or an additive can be easily constructed. 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, by irradiating the photosensitive resin composition containing the photobase generator of the present invention with light, a base can be generated to accelerate the curing reaction, and a cured product can be obtained. Therefore, as a method for producing such a cured product, it is preferable to include a step of generating a base by irradiating the photobase generator of the present invention with light. In addition, in the case of a curing reaction, it may be heated if necessary.

In addition to the photosensitive composition of the present invention, 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. For example, curable acrylic resins {acrylic monomers and / or acrylic oligomers and curing agents (thiol, malonic acid ester, acetylacetonate, etc.)}, polysiloxanes (cured to cross-linked polysiloxanes), polyimide resins, and patents. The resins described in Document 3 can also be used.

The photobase generator of the present invention includes commonly used high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, etc. (for example, the latest trends in UV / EB curing technology, edited by Radtech Study Group, CMC Publishing). In addition to (see p. 138, 2006), an LED ultraviolet irradiation device, a laser light irradiation device such as an EB line, an excimer laser, or an Ar laser can be used depending on the application.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not intended to be limited thereto. 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, 16 g of dimethylaminoethoxyethanol was added dropwise thereto, and the mixture was stirred at 60 ° C. .. After 6 hours, the disappearance of the raw material was confirmed by HPLC, and a 20% chloroform solution of the intermediate (CA-1 chloride) was obtained.
(2) Synthesis of Compound A-1 To 100 g of a 20% chloroform solution of the intermediate (CA-1 chloride) obtained in (1), 25 g of sodium tetraphenylborate and 250 g of ion-exchanged water were added, and the mixture was added to room temperature for 3 hours. Stirred. The organic layer was washed 5 times with 100 g of ion-exchanged water. After concentrating the organic layer and evaporating the solvent, the residue was recrystallized from methanol to obtain a white solid. ¹ 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 converted to 23 g of (1-bromoethyl) benzene, and an intermediate (CA-2 chloride) was used. ) Was obtained as a 21% chloroform solution.
(2) Synthesis of Compound A-2 The same operation as in Production Example 1 was carried out to obtain a white solid. ¹ It was confirmed by 1 H-NMR that this 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 is 30 g of diphenylbromomethane, and 23 of the intermediate (CA-3 chloride). % Chloroform solution was obtained.
(2) Synthesis of Compound A-3 The same operation as in Production Example 1 was carried out except that 25 g of sodium tetraphenylborate and 250 g of ion-exchanged water were added to 300 g of a 10% lithium butyltriphenylborate aqueous solution in Production Example 1, and the mixture was white. Obtained a solid. ¹ It was confirmed by 1 H-NMR that this white solid was compound A-3.

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

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

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 to obtain the photosensitive composition of the present invention [Examples 1 to 6] and comparative photosensitivity. Sex compositions [Comparative Examples 1 to 5] were 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 (A-2) synthesized in Production Example 2
A-3: Compound (A-3) synthesized in Production Example 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) (made by Aldrich)
B-2: Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko)
C-1: Epicoat 828 (manufactured by Mitsubishi Chemical Corporation)
D-1: 2-Isopropylthioxanthone (manufactured by Tokyo Kasei)
[Solubility of photobase generator]
As an evaluation of the solubility 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:
○ Uniform transparency △ Slightly smeared × with precipitation
[Photo-curing]
The obtained photosensitive composition was applied to a glass substrate (76 mm × 52 mm) using an applicator (40 μm), and then exposed to a belt conveyor type UV irradiation device (Eye Graphics Co., Ltd., ECS-151U). The base was generated and immediately placed on a hot plate heated to 80 ° C., and the time until the 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 did not cure for 60 minutes or more.
Photocurability evaluation:
◎ Curing within 10 seconds.
○ Cures within 1 minute.
△ Cures within 10 minutes.
× Cures within 60 minutes.
XX Does not cure for more than 60 minutes.
[Room temperature storage stability]
When the obtained photosensitive composition was stored in a brown bottle and the period until the fluidity disappeared was confirmed, both the composition of Example and the composition of Comparative Example were confirmed to have room temperature storage stability of 30 days or more. ..

From the results in Table 1, the photosensitive composition using the photobase generator of the present invention has higher sensitivity than the photosensitive composition using the photobase generator for comparison, and has solubility and composition in a resin. It can be seen that it is useful as a photosensitive composition having excellent storage stability.

The base generator of the present invention utilizes a base generated by light irradiation to paint, a coating agent, various coating materials (hard coat, stain-resistant coating material, anti-fog coating material, touch-resistant coating material, optical fiber, etc.), Adhesive tape back treatment agent, adhesive label release sheet (release paper, release plastic film, release metal foil, etc.) release coating material, printing board, dental material (dental formulation, dental composite) ink, inkjet ink , Positive type resist (connection terminal for manufacturing electronic parts such as circuit board, CSP, MEMS element, wiring pattern formation, etc.), resist film, liquid resist, negative type resist (semiconductor element and transparent electrode for FPD (ITO, IZO, GZO) ), Etc. surface protective film, interlayer insulating film, permanent film material such as flattening film, etc.), MEMS resist, positive photosensitive material, negative photosensitive material, various adhesives (temporary fixing agents for various electronic parts, etc.) HDD adhesives, pickup lens adhesives, FPD functional films (deflection plates, antireflection films, etc.) adhesives, circuit forming and semiconductor encapsulation insulating films, anisotropic conductive adhesives (ACA), Film (ACF), paste (ACP), etc.), holographic resin, FPD material (color filter, black matrix, partition material, photo spacer, rib, liquid crystal alignment film, FPD sealant, etc.), optical member, molding material (For building materials, optical parts, lenses), casting materials, putties, glass fiber impregnants, sealing materials, sealing materials, flip chips, chip encapsulants such as COF, encapsulants for packages such as CSP or BGA , Optical semiconductor (LED) encapsulant, optical waveguide material, nanoimprint material, optical molding material, micro optical molding material and the like.

Claims (4)

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

[In the formula, R ^{1 to} R ⁴ are alkyl groups, phenyl groups or naphthyl groups having 1 to 18 carbon atoms independently of each other, and some of the hydrogen atoms of the phenyl group or naphthyl group have 1 to 18 carbon atoms. It may be substituted with an alkyl group, 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. It is an alkyl group having a number of 1 to 8 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. R ^{6 to} R ⁷ are independent of each other, 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 and a cationic nitrogen atom. It is an alkylene group having 1 to 8 carbon atoms. ] A photosensitive composition containing the photobase generator according to claim 1 , 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 groups. .. The photosensitivity according to claim 1 or 2 , wherein the compound (C) is selected from the group of the epoxy group-containing compound (C-1), the episulfide group-containing compound (C-2) and the isocyanato group-containing compound (C-3). Composition. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 3.