TW201829477A - Photo-base generator and photosensitive composition - Google Patents

Abstract

Provided are: a photo-base generator which upon reception of light, can efficiently generate an amine having high catalytic activity and which has no fear of metal corrosion; and a photosensitive composition containing the photo-base generator. The photo-base generator of the present invention is characterized by comprising an ammonium borate compound (A) represented by the general formula. [In the formula, R1 to R4 are each independently a C1-18 alkyl group, a phenyl group, or a naphthyl group, some of the hydrogen atoms of the phenyl or naphthyl group each having been optionally replaced with a C1-18 alkyl group, a C6-14 aryl group, etc.; R5 is a polyalkyleneoxy group, the terminal of the polyalkyleneoxy group being a hydrogen atom, a C1-4 alkyl group, or a phenyl group; R6 and R7 are each independently a methyl or ethyl group; Ar is a C6-14 aryl group; and Q is a divalent group through which the Ar is bonded to the cationic nitrogen atom.].

Description

Photobase generator and photosensitive composition

The present invention relates to a photobase generator which generates a base by light irradiation and a photosensitive composition containing the photobase generator. Further, in detail, there is a photobase generator and a photosensitive composition which are preferably used for production by using a base generated by light irradiation. a hardened material (for example, a coating agent or a coating material); or a product or member formed by patterning with poor solubility in an exposed portion or an unexposed portion in a developing solution (for example, an electronic component, an optical article, or an optical component forming material) , layer forming material or adhesive).

As a photobase generator which generates a base by exposure, a photobase generator which produces a primary or secondary amine, a strong base (a tertiary amine, a pKa of 8 to 11) or a superbase is known ( Various photobase generators such as a photobase generator such as 胍 or 脒, and a pKa of 11 to 13) (Patent Documents 1 to 7 and Non-Patent Literature 1 to Non-Patent Document 2).

However, the alkali generated by the photobase generator described in Patent Document 1 and Non-Patent Document 1 has a low basicity (pKa<8), and is not suitable as a catalyst for polymerization reaction or a catalyst for crosslinking reaction. Further, since the amine has an active hydrogen atom, if it is used in a polymerization reaction or a crosslinking reaction of an epoxide or an isocyanate, the reaction itself occurs, so that a large amount of photobase is required in order to carry out a sufficient reaction. Producing agent.

Further, the base generators of Patent Documents 2 to 5 and Non-Patent Document 2 have problems in that the activity as a light is low and the combined effect of the photosensitizer is also low, so that polymerization as an epoxide or an isocyanate is carried out. The photolatent alkali catalyst of the reaction or crosslinking reaction has low performance.

In addition, in the use of an adhesive, a sealant, a coating material, or a coating, a curable resin containing a compound having a highly reactive thiol group as a curing agent has been studied. Since the thiol has high reactivity, it can be hardened at a relatively low temperature, and can be stored in a single liquid by a combination with a photobase generator, and an alkali can be generated by irradiation of light or the like by the alkali contact. The effect of the medium is rapidly hardened (for example, refer to Patent Document 8). Under the circumstances, it is desirable to develop a photobase generator which sufficiently maintains the storage stability of a composition containing a highly reactive thiol compound and has catalytic activity for hardening, that is, compared to the former The photobase generator is a photobase generator excellent in stability and catalyst activity balance. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. 2005-107235 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2005-264156 (Patent Document 4) [Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-280785 (Patent Document 6) WO2005-014696 (Patent Document 7) WO2009-122664 (Patent Document 8) Japanese Patent Special Table 2005 -511536 [Non-Patent Document]

[Non-Patent Document 1] "Light Application Technology and Materials Encyclopedia Dictionary", Industrial Technology Service Center Co., Ltd., 2006, 130 pages [Non-Patent Document 2] "Photopolymer Science and Technology Magazine (J. Photopolym. Sci. Tech) .,)", vol. 19., NO.1(81)2006

[Problem to be Solved by the Invention] An object of the present invention is to provide a photobase generator which is capable of sensitizing light and efficiently producing an amine having high catalytic activity and having no metal corrosion, and provides the following Photosensitive composition containing the photobase generator and a highly reactive thiol group, and having excellent solubility with respect to resin and excellent storage stability as compared with the use of the conventional photobase generator Alkali generator. [Means for solving the problem]

The inventors of the present invention have diligently studied in order to solve the above problems, and as a result, have found a photobase generator having excellent characteristics. That is, the present invention is a photobase generator comprising an ammonium borate compound (A) represented by the following formula.

[Chemical 1]

In the formula, 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 a hydrogen atom of a phenyl group or a naphthyl group may be an alkyl group having 1 to 18 carbon atoms or carbon. 6 to 14 of an aryl group, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or an aryloxy group represented by -OR ⁸ or a halogen atom, and R ⁸ is an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 The aryl group of ～14, R ⁵ is a polyalkyleneoxy group, the terminal of the polyalkyleneoxy group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ to R ⁷ are each independently a methyl group or Ethyl group, Ar is an aryl group having 6 to 14 carbon atoms, and Q is a divalent group in which Ar is bonded to a cationic nitrogen atom]

Furthermore, the present invention provides a photosensitive composition comprising the photobase generator described above, a compound (B) having two or more thiol groups in the molecule, and two or more and the thiol group. Reaction-based compound (C).

Further, the present invention is a cured body obtained by curing the photosensitive composition. [Effects of the Invention]

The photobase generator of the present invention can efficiently emit an amine having high catalytic activity by sensitizing light. Further, since the photobase generator of the present invention does not contain a halogen ion or the like as a counter anion, there is no possibility of metal corrosion. Further, since the photobase generator of the present invention does not have a basicity before the photosensitivity, even when the photobase generator is contained in the reactive composition, the storage stability of the reactive composition is not lowered. . Further, the photobase generator of the present invention is also stable with respect to heat, and it is difficult to generate an alkali even if it is heated without irradiating light. In addition, when the method for producing a cured product using the photosensitive composition of the present invention is used, it is possible to efficiently produce an amine having high catalytic activity by using the photobase generator and irradiating light, and it is efficient. Produce hardened materials.

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

The photobase generator refers to a person whose chemical structure is decomposed by light irradiation to produce a base (amine). The resulting base can be used as a catalyst for the hardening reaction of the epoxy resin, the hardening reaction of the polyimine resin, the urethanization reaction of the isocyanate with the polyol, and the crosslinking reaction of the acrylate.

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

[Chemical 2]

In the formula, 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 a hydrogen atom of a phenyl group or a naphthyl group may be an alkyl group having 1 to 18 carbon atoms or carbon. an aryl group having 6 to 14, nitro, hydroxy, cyano, -OR ⁸ alkoxy or aryloxy group represented by or a halogen atom, R ⁸ is alkyl having 1 to 6 carbon atoms or 8 The aryl group of ～14, R ⁵ is a polyalkyleneoxy group, the terminal of the polyalkyleneoxy group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ to R ⁷ are each independently a methyl group or Ethyl group, Ar is an aryl group having 6 to 14 carbon atoms, and Q is a divalent group in which Ar is bonded to a cationic nitrogen atom]

In the general formula, examples of the alkyl group having 1 to 18 carbon atoms in R ¹ to R ⁴ include a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl). , n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc., branched alkyl (isopropyl, isobutyl, second butyl, third) Butyl, isopentyl, neopentyl, third amyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl (cyclopropyl, cyclo) Butyl, cyclopentyl and cyclohexyl, etc.) and cross-linked cyclic alkyl groups (norbornyl, adamantyl and fluorenyl, etc.). Among these, a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group is preferred, and a linear alkyl group having 2 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, and a carbon number are preferred. 5 to 6 cycloalkyl groups.

In the formula, the phenyl or naphthyl group in R ¹ to R ⁴ may have a part of a hydrogen atom thereof, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group or a cyano group. The alkoxy group or aryloxy group represented by -OR ⁸ or a halogen atom is substituted, and the alkyl group having 1 to 18 carbon atoms is the same as those described above, and preferably the same.

In the above-mentioned substituent, examples of the aryl group having 6 to 14 carbon atoms (excluding the carbon number of the substituents below) include a monocyclic aryl group (such as a phenyl group) and a condensed polycyclic aryl group (naphthalene). Alkyl, fluorenyl, phenanthryl, fluorenyl, fluorenyl and naphthyl fluorenyl, and aromatic heterocyclic hydrocarbon groups (thienyl, furyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, Monocyclic heterocyclic ring such as pyrimidinyl or pyrazinyl; and fluorenyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothiophenyl, quinolyl, isoquinolinyl, quin Porphyrin group, quinazolinyl, oxazolyl, acridinyl, phenothiazine, cyanozinyl, xanthenyl, thiophene, phenoxazinyl, phenothiaphthyl, benzodihydropyran a condensed polycyclic heterocyclic ring such as a benzoylhydropyranyl group, a coumarin group, a dibenzothiophenyl group, a xanthonone group, a thioxanthone group or a dibenzofuranyl group. Among these, preferred are phenyl, naphthyl, anthryl, phenanthryl, anthracenyl, xanthenyl, thionyl, phenothiaphthyl, benzohydropyranyl, isobenzodihydroperazine A thiol group, a coumarin group, a xanthone group, a thioxanthone group, and more preferably a phenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group.

In the above-mentioned substituent, R ⁸ of the alkoxy group represented by -OR ⁸ may, for example, be an alkyl group having 1 to 8 carbon atoms. Specifically, the alkyl group may include an alkyl group having 1 to 8 carbon atoms. base.

In the above-mentioned substituent, R ⁸ of the aryloxy group represented by -OR ⁸ may, for example, be an aryl group having 6 to 14 carbon atoms, and specific examples thereof include the aryl group having 6 to 14 carbon atoms.

Examples of the alkoxy group represented by -OR ⁸ include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, and a third butoxy group. Pentyloxy, isopentyloxy, neopentyloxy, 2-methylbutoxy and the like. Examples of the aryloxy group represented by -OR ⁸ include a phenoxy group and a naphthyloxy group. 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 a methoxy group, an ethoxy group or a n-butoxy group, an aryloxy group such as a phenoxy group or a naphthyloxy group, or the like is preferable. An arylthio group such as a thio group, an ethylthio group, a butylthioalkylthio group, a phenylthio group or a naphthylthio group; a fluorine atom, a chlorine atom or a bromine atom;

In the formula, the polyalkyleneoxy group in R ⁵ is an alkoxy group having 2 to 4 carbon atoms or more, and the type of the alkylene group to be added may be the same. Specific examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, or a mixed adduct thereof. Further, the molar number of addition is preferably from 2 mol to 10 mol, and more preferably from 2 mol to 5 mol, from the viewpoint of the molecular weight of the alkali to be produced. Further, it is preferred that the oxygen atom at the terminal of the alkoxy 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 in the alkyl group.

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

In the formula, Ar is an aryl group having 6 to 14 carbon atoms, and is preferably the same as those described above.

In the formula, Q is a divalent group in which the Ar is bonded to a cationic nitrogen atom, and examples thereof include an alkylene group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms which may have a substituent. a group having a carbon number of 6 to 14 in an extended aryl group. Among them, a C1-C8 alkylene group which may have a substituent is preferable, and a C1-C8 alkylene group which is unsubstituted, substituted with an oxo group or a phenyl group is preferable. Specific examples of preferred Q include a methylene group, an ethylidene group, a phenylmethylene group, a propyl group, a butyl group, a dimethylmethylene group, a diethylmethylene group, and a hexane. -1,1-diyl, octane-1,1-diyl, cyclohexane-1,1-diyl, 2-oxo-extended ethyl, 2-oxo-1,1-dimethyl Ethyl, 2-oxo-1,1-dimethoxyethyl and the like are extended. From the viewpoint of easiness in starting the raw materials, etc., it is preferably a methylene group, an ethyl group, a phenylmethylene group or a 2-oxo-extended ethyl group. Specific examples of the preferred ammonium borate compound (A) include the following compounds. These ammonium borate compound (A) may be used alone or in combination of two or more.

[Chemical 3]

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 having two or more groups reactive with the thiol group (C) ).

Examples of the compound (B) having two or more thiol groups in the molecule of the present invention include trimethylolpropane tris(3-mercaptopropionate) and trimethylolpropane tris(3-mercaptobutylate). Acid ester), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tetraethylene glycol bis(3-mercaptopropionate), ethylene glycol dithioacetate, 1,4-butanediol dithioacetate, trimethylolpropane trithioacetate, pentaerythritol tetrathioacetate, bis(2-mercaptoethyl)ether, 1,4-butane Mercaptan, 1,5-diamidino-3-thiopentane, 2,2'-(ethylidene dithio)diethanethiol, 1,8-dimercapto-3,6-dioxooctane , 1,4-benzenedithiol, 1,3-benzenedithiol, 1,5-naphthalenedithiol, 1,3,5-trimercaptomethylbenzene, 4,4'-thiodi Phenyl mercaptan, 1,3,5-trimethylmethyl-2,4,6-trimethylbenzene, 2,4,6-trimethyl-s-triazine, 2-dibutylamino-4,6 -dimercapto-s-triazine, tris-[(3-mercaptopropoxy)-ethyl]-isocyanurate, trimethylolethane tris(3-mercaptobutyrate), tri-[ (3-mercaptobutyloxy)-ethyl]-isocyanurate, dipentaerythritol hexa-3-mercaptopropionate, and the like. These compounds (B) may be used alone or in combination of two or more.

The compound (C) having two or more groups reactive with the thiol group in the present invention is used together with the compound (B), and a basic compound produced from a photobase generator by energy irradiation using light or the like. Catalyst is carried out, and the crosslinking reaction and the polymerization reaction are rapidly carried out. The compound (C) in the present invention includes 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 a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and an alicyclic epoxy resin. In addition to these, a phenol novolak type epoxy resin, a heterocyclic-containing epoxy resin, a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, an aliphatic epoxy resin, and a snail may be used. Ring epoxy resin, etc. 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, etc.) with epichlorohydrin, or Polymerization of an epoxy group obtained by a reaction of a compound having two or more carboxyl groups and derivatives thereof (for example, an aliphatic polycarboxylic acid, an aromatic polycarboxylic acid, and a derivative thereof) with epichlorohydrin Ester compound and the like. The cyclic thio group-containing compound (C-2) is one in which an oxygen atom of the epoxy compound is substituted with a sulfur atom, and for example, the epoxy compound described above and a thiocyanate or thiourea as a vulcanizing agent can be used. The reaction is obtained (for example, refer to "J. Polym. Sci. Polym. Phys.", 17, 329 (1979), "J. Org. Chem.," 26, 3467 (1961)). As the isocyanato group-containing compound (C-3), a compound which has been used in a polyurethane or a polyisocyanurate or the like from the prior art can be used. Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified substances (for example, carbodiimide modification, allophanate modification, urea reform). Quality, biuret modification, isocyanurate modification, oxazolidinone modification, etc.), isocyanate terminal prepolymer, and the like. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate or 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI) or 2,6-toluene diisocyanate. , crude TDI, Methane diphenyl Diisocyanate (MDI) or diphenylmethane-4,4'-diisocyanate, polymethylene polyphenylisocyanate (crude MDI), Naphthyl-1,5-diisocyanate, triphenylmethane-4,4',4''-triisocyanate, and the like. Examples of the aliphatic isocyanate include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4-cyclohexyl diisocyanate. 2,4-trimethylhexamethylene diisocyanate or the like. Examples of the alicyclic polyisocyanate include xylylene diisocyanate and tetramethyl xylylene diisocyanate. Examples of the modified polyisocyanate include carbodiimide modified MDI, sucrose modified TDI, and castor oil modified MDI. These compounds (C) may be used alone or in combination of two or more.

The compounding amount of the compound (B) and the compound (C) in the present invention is the thiol equivalent of the compound (B) to be formulated, and the epoxy equivalent, the cyclic thio group equivalent or the equivalent of the compound (C) to be formulated. The ratio of the total equivalent of the cyanate group equivalent is (B): (C) = 1.0: 0.5 to 3.0, more preferably 1.0: 0.7 to 2.0, most preferably 1.0: 0.8 to 1.3. By blending in the above range, a good cured product can be obtained.

The amount of the compound (A) to be used as the photobase generator in the present invention is 0.05% by weight to 30% by weight, preferably 0.1% by weight 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 higher sensitivity to light than the conventional photobase generator, it can obtain sufficient effects even when used alone, but it can also be used in combination with other photosensitizers.

As the other photosensitizer, a sensitizer or the like which is known (Japanese Patent Laid-Open No. Hei 11-279212, and Japanese Patent Laid-Open No. Hei 09-183960, etc.) can be used, and examples thereof include benzoquinone {1,4-benzoquinone, 1 , 2-benzoquinone, etc.; naphthoquinone {1,4-naphthoquinone, 1,2-naphthoquinone, etc.; 蒽醌{2-methylhydrazine, 2-ethylhydrazine, etc.}; 蒽{蒽, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-di Propyloxypurine, etc.; hydrazine; 1,2-benzopyrene; anthracene; fused tetraphenyl; anthracene; thioxanthone {thioxanthone, 2-methylthiaxanone, 2-ethylsulfide Anthrone, 2-chlorothiazepinone, 2-isopropylthioxanthone, and 2,4-diethylthiaxanthone, etc.; phenothiazine {phthylazine, N-methylphutizine , N-ethyl phenothiazine, N-phenyl phenothiazine, etc.; xanthone; 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-benzene Propane-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzylidene-4'-methyldiphenyl sulfide, etc.; carbazole {N- Carbazole, N- ethyl carbazole, and poly-N- vinylcarbazole -N- glycidyl carbazole}; {1,4-dimethoxy And 1,4-di-α-methylbenzyloxy 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 sensitizer such as naphthoquinone, benzophenone, thioxanthone, anthraquinone or thioxanthone is used, a high sensitizing effect can be obtained. Therefore, it is better. The blending amount of the other photosensitizer is 0.01 equivalent to 10 equivalents, preferably 0.1 equivalents to 5 equivalents, and more preferably 0,5, based on the molar number of the compound (A) to be formulated. Equal amount ~ 2 equal amount. If the amount of the photosensitizer is too large, energy such as light that has been irradiated does not reach the bottom of the bottom, resulting in unevenness in hardenability.

The ammonium borate compound (A) which is a photobase generator of the present invention can be produced by a known method. An example is shown by the following chemical reaction formula. By directly reacting the compound (H) substituted with the substituent (Z) corresponding to the substituents Ar and Q of the target compound (A) with the amine substituted with the substituent R ⁵ to the substituent R ⁷ or the solvent The reaction is carried out to obtain a cationic intermediate having Z ^- as a relative anion. The target photobase generator can be obtained by anion exchange of the cationic intermediate with a metal borate having a substituent corresponding to the target photobase generator in an organic solvent or water.

[Chemical 4]

Wherein R ¹ to R ⁷ , Q and Ar are the same as the above formula, Z is a leaving group, Z ⁻ is a relative anion formed by detachment, and M ⁺ is a metal cation]

As the leaving group (Z), it contains a halogen atom (such as a chlorine atom and a bromine atom), a sulfomethoxy group (trifluoromethylsulfonyloxy group, 4-methylphenylsulfonyloxy group, and methylsulfonyloxy group). Et.) and anthraceneoxy (ethoxylated and trifluoromethylcarbonyloxy, etc.). Among these, a halogen atom and a sulfomethoxy group are preferable from the viewpoint of easiness 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 (such as tetrahydrofuran and dioxane), chlorine solvents (such as chloroform and dichloromethane), and alcohols (methanol, ethanol, and the like). Isopropanol, etc.), ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), nitrile (acetonitrile, etc.) and polar organic solvents (dimethyl sulfoxide, dimethylformamide, and N- Methylpyrrolidone, etc.). These solvents may be used singly or in combination of two or more.

The reaction temperature (°C) of the compound (H) and the amine as a raw material of the cationic intermediate is preferably from -10 to 100, more preferably from 0 to 80. It is preferred to dissolve the compound (G) in an organic solvent and to add an amine thereto. The method of adding the amine may be dropwise addition, or may be diluted with an organic solvent and then added dropwise.

The compound (H) can be produced by a known method. In the case of halogenating (preferably bromination) the α-position carbon substituted by an aromatic ring group in the compound (H), a method using halogen (preferably bromine) or N-using a radical generator is used. The method of bromobutylimine is simple and preferred (4th edition of Experimental Chemistry Lecture 19, Japanese Society of Chemistry, p422).

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

The reaction of the boron compound with the organometallic compound is -80 ° C to 100 ° C, preferably -50 ° C to 50 ° C, most preferably -30 ° C to 30 ° C. As the organic solvent to be used, a hydrocarbon (hexane, heptane, toluene, xylene, etc.), a cyclic ether (such as tetrahydrofuran or dioxane), or a chlorine solvent (such as chloroform or dichloromethane) can be preferably used. .

The metal borate salt obtained is preferably an alkali metal salt from the viewpoint of stability or solubility. In the case of carrying out the reaction using a Grenadi reagent, it is preferred to add sodium hydrogencarbonate, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide or the like during or after the reaction. Perform metal exchange.

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

The photobase generator obtained in the above manner, that is, the ammonium borate compound (A), may be isolated from an organic solvent and then purified. The separation from the organic solvent can be carried out by directly adding (or after concentrating) a poor solvent to the organic solvent solution containing the photobase generator and precipitating the photobase generator. Here, the poor solvent to be used includes a chain ether (such as diethyl ether and dipropyl ether), an ester (such as ethyl acetate or butyl acetate), an aliphatic hydrocarbon (such as hexane and cyclohexane), and a fragrance. Group hydrocarbons (toluene and xylene, etc.).

In the case where the compound (A) is an oil, the oil which is contained in the oil can be distilled off by separating the oily substance from the organic solvent solution, thereby obtaining the light as the present invention. An ammonium borate compound (A) of a base generator. On the other hand, when the compound (A) is a solid, the organic solvent contained in the solid can be distilled off by separating the precipitated solid from the organic solvent solution, thereby obtaining photobase generation as the present invention. Ammonium borate compound (A).

The purification can be carried out by recrystallization (a method of using a difference in solubility due to cooling, a method of adding a poor solvent and precipitation, and a combination of the methods). Further, when the photobase generator is an oil (in the case where crystallization is not performed), it can be purified by a method of washing the oil with water or a poor solvent.

The photosensitive composition of the present invention may optionally contain a solvent or the like. Examples of the solvent include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone). , esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether acetate, propylene glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, and 1,3,5-trimethylbenzene) Etc.), alcohols (methanol, ethanol, n-propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran and 1,8-eucalyptol, etc.). Further, as the glycidyl ether such as phenyl glycidyl ether or methyl glycidyl ether having one glycidyl group in the molecule, and an alkylene oxide such as oxetane, styrene oxide or cyclohexene oxide, Solvent. Further, the glycidyl ethers and alkylene oxides are referred to as 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 from 0% by weight to 99% by weight, more preferably from 3% by weight to 95% by weight, even more preferably from 5% by weight to 90% by weight based on the total mass of the photosensitive resin composition. %.

In order to control the appearance or physical properties of the cured product of the photosensitive composition, the photosensitive composition of the present invention may optionally contain other additives which are generally used. A pigment such as an inorganic pigment or an organic pigment, a coloring agent such as a dye, a dispersing agent, metal oxide particles, and metal particles are contained. The photosensitive composition of the present invention may further contain an adhesion imparting agent, an antifoaming agent, a leveling agent, a thixotropic agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant, an ultraviolet absorber, etc., depending on the purpose of use. .

The photobase generator of the present invention can be applied to a latent alkali catalyst (a catalyst which does not have a catalytic action before irradiation of light but exhibits an action of a base catalyst by light irradiation), and the like, and can be used as a base reactivity. The compound, for example, a curing catalyst of a photosensitive resin composition is used, and when light is irradiated, it is preferable to use a curing catalyst as a photosensitive resin composition to be cured. For example, a photosensitive resin composition containing a base resin which promotes hardening by alkali, a photobase generator of the present invention, and an optional solvent and/or an additive can be easily formed. Since the photosensitive resin composition contains the photobase generator of the present invention, it is excellent in curability as well as excellent in storage stability. In other words, the photosensitive resin composition containing the photobase generator of the present invention is irradiated with light to generate an alkali, and the curing reaction is accelerated to obtain a cured product. Therefore, as a method for producing the cured product, it is preferred to include a step of generating a base by irradiating light to the photobase generator of the present invention. Further, it is also possible to perform heating as needed during the hardening reaction.

In addition to the photosensitive composition of the present invention, the photobase generator of the present invention can be used without any limitation as long as it is a photocurable resin which is cured by an alkali. For example, it can also be used for a curable acrylic resin {acrylic monomer and/or acrylic oligomer and a curing agent (thiol, malonate, acetamidine, etc.)}, polyoxyalkylene (hardening to form a poly A siloxane, a polyimine resin, and a resin described in Patent Document 3.

In addition to commonly used high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and high-power metal halide lamps, the photobase generator of the present invention (see, for example, "ultraviolet (UV)" electron beam (EB) hardening technology. In addition to the latest trends, radiation curing (radtech) research, CMC publication, 138 pages, 2006), it can be used for light emitting diode (LED) ultraviolet irradiation devices or EB lines, excimer thunder, depending on the application. Laser light irradiation devices such as an emitter and an Ar laser. [Examples]

Hereinafter, the present invention will be further illustrated by the examples, but the invention is not intended to be limited thereto. In addition, unless otherwise indicated, the % means 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 dimethylaminoethoxyethanol 16 was added dropwise thereto. g, stirring at 60 °C. After 6 hours, the disappearance of the starting material was confirmed by High Performance Liquid Chromatograph (HPLC) to obtain a 20% chloroform solution of the intermediate (CA-1 chloride). (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 to the chamber. Stir for 3 hours under temperature. The organic layer was washed 5 times with 100 g of ion-exchanged water. The organic layer was concentrated, and the solvent was evaporated, and then the residue was recrystallized from methanol to give a white solid. The white solid was confirmed to be Compound A-1 by ¹ H-nuclear magnetic resonance (NMR).

[Chemical 5]

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 set as (1-bromoethyl)benzene 23 g, and A 21% chloroform solution of the intermediate (CA-2 chloride) was obtained. (2) Synthesis of Compound A-2 The same operation as in Production Example 1 was carried out to obtain a white solid. The white solid was confirmed to be Compound A-2 by ¹ H-NMR.

[Chemical 6]

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 used as 30 g of diphenylbromomethane to obtain an intermediate. 23% chloroform solution of (CA-3 chloride). (2) Synthesis of Compound A-3 In Production Example 1, except that 25 g of sodium tetraphenylborate and 250 g of ion-exchanged water were used as 300 g of a 10% aqueous solution of lithium butyltriphenylborate, and Production Example 1 was carried out. The same operation gave a white solid. The white solid was confirmed to be Compound A-3 by ¹ H-NMR.

[Chemistry 7]

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

[化8]

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

[Chemistry 9]

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

[化10]

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

[11]

Example 1 to Example 6, Comparative Example 1 to Comparative Example 5 [Preparation of photosensitive composition] Compound (A), compound (B), compound (C) and sensitizer (D) as a photobase generator The photosensitive compositions of the present invention [Examples 1 to 6] and the comparative photosensitive compositions [Comparative Examples 1 to 5] were prepared by uniformly mixing. The types of raw materials used are shown below. [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 synthesized in Production Example 3 ( A-3) A-4: Compound (A-4) synthesized in Production Example 4 A'-1: Comparative compound (H-1) synthesized in Production Example 1 A'-2: Comparatively synthesized in Production Example 2 Compound (H-2) A'-3: Comparative compound (H-3) synthesized in Production Example 3 B-1: Pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by Aldrich) B-2 : pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko) C-1: Epikote 828 (manufactured by Mitsubishi Chemical Corporation) D-1: 2-isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.) [Solubility of Photobase Generator] The solubility of the photobase generator (Compound A and Comparative Compound A') was evaluated by evaluating the appearance of the photosensitive composition by the following criteria. The results are shown in Table 1. Appearance evaluation: ○ Uniform transparency △ Slightly blurred × Precipitated [Photocurability] The obtained photosensitive composition was applied onto a glass substrate (76 mm × 52 mm) using an applicator (40 μm), and then transported. The UV irradiation device (Eye Graphics Co., Ltd., ECS-151U) was exposed to produce a base, which was immediately placed on a hot plate heated to 80 ° C, and the viscosity of the coated surface was measured. The time until it disappears. The results are shown in Table 1. In addition, when the obtained photosensitive composition was not irradiated with light and heated to 80 ° C, it was not cured for 60 minutes or longer. Evaluation of photocurability: ◎ Hardened within 10 seconds. ○ Hardens within 1 minute. △ Hardens within 10 minutes. × Hardens within 60 minutes. ×× does not harden for more than 60 minutes. [Storage stability at room temperature] The obtained photosensitive composition was stored in a brown bottle, and it was confirmed that the composition of the examples and the composition of the comparative example were stored at room temperature for 30 days or more until the fluidity disappeared. stability.

[Table 1]

According to the results of Table 1, it is understood that the photosensitive composition using the photobase generator of the present invention has high sensitivity as compared with the photosensitive composition using the comparative photobase generator, and is useful as a solubility to a resin and a composition. It is useful as a photosensitive composition excellent in storage stability. [Industrial availability]

The alkali generating agent of the present invention is preferably used for a coating material, a coating agent, various coating materials (hard coating, pollution-resistant coating material, anti-fog coating material, touch-resistant coating material, etc.) by using an alkali generated by light irradiation. (such as an optical fiber), a backing agent for a pressure-sensitive adhesive tape, a release sheet for a viscous label (release paper, a release plastic film, a release metal foil, etc.), a printing plate, a dental material (dental preparation, Connection terminals for electronic components such as dental composites, inks, inkjet inks, and positive resists (circuit boards, chip scale packages (CSP), and microelectro mechanical systems (MEMS) components) a wiring pattern, etc.), a resist film, a liquid resist, a negative resist (a semiconductor element, and a transparent electrode for a flat panel display (FPD) (Indium Tin Oxide (ITO), ZnO, such as indium Zinc Oxide (IZO), zinc gallium (Gallium Zinc Oxide (GZO)), surface protection film, interlayer insulating film, and permanent film material such as planarization film, etc. A resist, a positive photosensitive material, a negative photosensitive material, various adhesives (a temporary fixing agent for various electronic components, an adhesive for a hard disk drive (HDD), an adhesive for an imaging lens, An adhesive film for a functional film (such as a deflecting plate or an antireflection film) for FPD, an insulating film for circuit formation, a semiconductor sealing, an anisotropic conductive adhesive (ACA), a film (ACF), or a paste (ACP). , resin for holography, FPD material (color filter, black matrix, partition material, photoresist spacer, flange, alignment film for liquid crystal, sealant for FPD, etc.), optical member, molding material (for building materials) , optical parts, lenses), casting materials, putty, glass fiber impregnating agent, filler, sealing material, flip chip, COF and other wafer sealing materials, CSP or BGA packaging sealing materials, optical semiconductor (LED) sealing materials, Optical waveguide materials, nanoimprint materials, optical materials, and materials for micro-light shaping.

no

no

Claims (5)

A photobase generator comprising a boronic acid ammonium salt compound (A) represented by the following formula, In the formula, 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 a hydrogen atom of a phenyl group or a naphthyl group may be an alkyl group having 1 to 18 carbon atoms and a carbon number. 6 to 14 of an aryl group, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or an aryloxy group represented by -OR ⁸ or a halogen atom, and R ⁸ is an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 to 6 An aryl group of 14 wherein R ⁵ is a polyalkyleneoxy group, the terminal of the polyalkyleneoxy group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ to R ⁷ are each independently methyl or B. Further, Ar is an aryl group having 6 to 14 carbon atoms, and Q is a divalent group in which Ar is bonded to a cationic nitrogen atom. The photobase generator according to claim 1, wherein Q in the formula is an alkylene group having 1 to 8 carbon atoms. A photosensitive composition comprising: a photobase generator as described in claim 1 or 2, a compound (B) having two or more thiol groups in a molecule, and having two or more The thiol group-reactive group compound (C). The photosensitive composition according to any one of claims 1 to 3, wherein the compound (C) is selected from the group consisting of an epoxy group-containing compound (C-1) and an epoxy group-containing compound (C). -2) and a group of compounds (C-3) containing isocyanate groups. A hardened body obtained by curing the photosensitive composition according to any one of claims 1 to 4 of the invention.