JP2005225793A - Phosphine oxide compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new phosphine oxide compound useful as photopolymerization initiator useful in a visible light range. <P>SOLUTION: The phosphine oxide compound is represented by general formula (1) (R<SP>1</SP>is an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a cycloalkenyl or the like; R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>, R<SP>8</SP>and R<SP>9</SP>are each the same or different and are a hydrogen atom, a halogen atom, an alkyl, an alkenyl, an alkynyl or the like; X is a single bond, an oxygen atom, a sulfur atom, a substituted or nonsubstituted vinylene or the like). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel phosphine oxide compound useful as a photopolymerization initiator.

Photocuring technology is superior in terms of workability, economy, and hygiene, uses less organic solvents than thermal curing methods, and is attracting attention as an environmentally friendly technology that complies with volatile organic compound (VOC) regulations. Yes.
Photocuring is greatly influenced by the performance of the photopolymerization initiator. Conventionally, as one of the initiators, phosphine oxide has been used as a radical photopolymerization initiator (see, for example, Patent Document 1). When they are used as photopolymerization initiators, ultraviolet light (UV) is used as irradiation light, but phosphine oxide has been developed as a photoinitiator that can be cured with light in the visible light range, The depth of cure is also improved. (For example, refer to Patent Documents 2 and 3). Conventionally, the phosphine oxide used has a problem of colorability in which the yellow color derived from the initiator remains in the cured product.

Phosphine oxide is used for dental material applications (see, for example, Patent Document 4), and is also used for recording medium applications (for example, see Patent Document 5).
However, from the viewpoints of the harmful effects of ultraviolet light, photocuring of resins containing ultraviolet absorbers, and effective use of visible light emitting diode (LED) irradiators and inexpensive light sources such as sunlight, the visible light range is further increased. The development of a photopolymerization initiator that can be cured with light on the side is desired.

Further, in applications of dental materials and biomaterials, in addition to harmlessness of irradiation light, non-coloring property is desired as an aesthetic factor. For paints, inks, and adhesives, in addition to demands for excellent adhesion and adhesion, it is environmentally friendly with a large depth of cure, which can effectively use harmless and inexpensive light sources such as sunlight, and uses less organic solvents. There is a need for photopolymerization initiators.
European Patent Application No. 7508 JP-A-3-101686 JP-A-5-345790 Japanese Patent Laid-Open No. 61-130296 JP-A-1-102455

  An object of the present invention is to provide a novel phosphine oxide compound useful as a photopolymerization initiator usable in the visible light region.

The present invention provides the following [1] to [25].
[1] General formula (1)

(Wherein R ¹ represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, or substituted or unsubstituted aralkenyl. , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, a halogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, Alkyloxy, cycloalkyloxy, alkenyloxy, cycloalkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, aralkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl or substituted Or an unsubstituted ara It represents a Kenyir, together with ^{R 2, R 3, R 4} , R 5, R 6, R 7, adjacent two groups of two carbon atoms, each of which adjacent of R ⁸ and R ⁹ A hydrocarbon ring may be formed, and X is a single bond, oxygen atom, sulfur atom, substituted or unsubstituted vinylene, substituted or unsubstituted —NH, or unsubstituted phosphorus atom or substituted or unsubstituted silicon atom A phosphine oxide compound represented by:
[2] R ¹ is substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same Or, differently, a hydrogen atom, a halogen atom, alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein X is a single bond, [1].
[3] R ¹ is substituted or unsubstituted aryl, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and are each a hydrogen atom, halogen The phosphine oxide compound according to [1], which is an atom or alkyl, and X is a single bond.
[4] General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, and M represents an alkali metal. And general formula (3)

(Wherein R ¹ has the same meaning as described above, and Z represents a halogen atom or acyloxy), and is reacted with a carboxylic acid halide or carboxylic anhydride represented by the general formula (4)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), The obtained phosphine compound is oxidized, and is represented by the general formula (1)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .
[5] The method for producing a phosphine oxide compound according to claim 4, wherein the oxidation is an oxidation by reacting with a gas containing oxygen.
[6] General formula (4)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above).
[7] General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X and M are as defined above, and a general formula (3)

(Wherein R ¹ and Z have the same meanings as described above) and a carboxylic acid halide or a carboxylic acid anhydride represented by the general formula (4)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. .
[8] General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X and M are as defined above, and a general formula (5)

(Wherein R ¹ has the same meaning as described above) to react with the aldehyde represented by the general formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. And then oxidizing the resulting α-hydroxyphosphine compound to give a general formula (7)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine An oxide compound is obtained, and the α-hydroxyphosphine oxide compound is further oxidatively dehydrogenated.

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .
[9] The method for producing a phosphine oxide compound according to [8], wherein the oxidative dehydrogenation is oxidative dehydrogenation by reacting with a peroxide.
[10] The method for producing a phosphine oxide compound according to [9], wherein the peroxide is hydrogen peroxide or an organic hydroperoxide.
[11] The method for producing a phosphine oxide compound according to any one of [8] to [10], wherein the oxidative dehydrogenation is oxidative dehydrogenation performed in the presence of a catalyst.
[12] The method for producing a phosphine oxide compound according to [11], wherein the catalyst is a ruthenium catalyst.
[13] General formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. .
[14] General formula (7)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine oxide Compound.
[15] General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X and M are as defined above, and a general formula (5)

(Wherein R ¹ has the same meaning as described above), which is reacted with an aldehyde represented by the general formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. Manufacturing method.
[16] General formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. General formula (7), characterized in that

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine oxide Compound production method.
[17] The method for producing a hydroxyphosphine oxide compound according to [16], wherein the oxidation is an oxidation by treatment with a gas containing oxygen.
[18] General formula (4)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively). General formula (1) characterized by

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .
[19] General formula (7)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine oxide General formula (1) characterized by oxidative dehydrogenation of a compound

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .
[20] A photopolymerization initiator containing the phosphine oxide compound according to any one of [1] to [3].
[21] A photopolymerizable composition comprising the phosphine oxide compound according to any one of [1] to [3] and an unsaturated compound.
[22] A cured product obtained by curing the photopolymerizable composition according to [21].
[23] A paint containing the phosphine oxide compound according to any one of [1] to [3] and an unsaturated compound.
[24] A film obtained by curing an unsaturated compound by light irradiation in the presence of the phosphine oxide compound according to any one of [1] to [3].
[25] A plastic obtained by curing an unsaturated compound by light irradiation in the presence of the phosphine oxide compound according to any one of [1] to [3].

  Hereinafter, the phosphine oxide compound represented by the general formula (1) may be expressed as the compound (1). The phosphide compound represented by the general formula (2) may be expressed as the compound (2). The carboxylic acid halide represented by the general formula (3) may be expressed as a compound (3). The phosphine compound represented by the general formula (4) may be expressed as a compound (4). The aldehyde represented by the general formula (5) may be expressed as the compound (5). The α-hydroxyphosphine compound represented by the general formula (6) may be expressed as a compound (6). The α-hydroxyphosphine compound represented by the general formula (7) may be expressed as a compound (7).

  The present invention provides a novel phosphine oxide compound useful as a photopolymerization initiator that can be used in the visible light region.

  In the definition of each group of the general formula, examples of the alkyl moiety in alkyl and alkoxy include, for example, a linear or branched alkyl group having 1 to 20, preferably 1 to 8 carbon atoms, or 3 to 8 carbon atoms. Specific examples include cyclic alkyl, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, 2-methylbutyl, tert-pentyl, hexyl, heptyl, octyl, nonyl. Decyl, dodecyl, undecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

  Examples of the alkenyl part of alkenyl and alkenyloxy include linear or branched alkenyl having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples include vinyl, allyl, propenyl, isopropenyl, butenyl, Examples include 2-methylallyl, pentenyl, hexenyl, heptenyl, octenyl, 1,3-butadienyl, 1,3-pentadienyl, 1,3,5-hexatrienyl and the like.

Examples of the alkynyl part of alkynyl and alkynyloxy include straight-chain or branched alkynyl having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, specifically, ethynyl, propynyl, butynyl, pentynyl, hexynyl, 1 , 3-butadiynyl, 1,3,5-hexatriynyl and the like.
Examples of cycloalkenyl include cycloalkenyl having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. Specific examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cyclooctenyl. , Cyclododecenyl, cyclododecatrienyl and the like.

Examples of the aryl moiety of aryl and aryloxy include phenyl, naphthyl, anthryl and the like.
Examples of the aralkyl moiety of aralkyl and aralkyloxy include aralkyl having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, and specifically include benzyl, phenethyl, phenylpropyl, naphthylmethyl and the like.

Examples of aralkenyl include aralkenyl having 8 to 30 carbon atoms, preferably 8 to 20 carbon atoms, and examples thereof include styryl and cinnamyl.
Examples of the aromatic heterocycle in heteroaryl and heteroaryloxy include, for example, a 5-membered or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, A bicyclic or tricyclic condensed 8-membered ring containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically a pyridine aromatic ring Ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, thiophene ring, Furan ring, thiazole ring, oxazole ring, indole ring, isoindole ring, indazole , Benzimidazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, purine ring, carbazole ring and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Carbonization formed by two adjacent substituents of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , each together with two adjacent carbon atoms Examples of the hydrogen ring include unsaturated hydrocarbon rings having 5 to 10 carbon atoms, and specific examples include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a benzene ring, and a naphthalene ring. .

  Examples of the substituent of aryl, heteroaryl, aralkyl, aralkenyl, vinylene, nitrogen atom, phosphorus atom, and silicon atom include, for example, the same or different 1 to 5 substituents, specifically, hydroxyl, carboxyl, halogen atom , Alkyl, alkoxy, nitro, and optionally substituted amino (examples of amino substituents include those described below as examples of amino substituents). The halogen atom, alkyl and the alkyl part of alkoxyl have the same meanings as described above.

Examples of the amino substituent include the same or different one or two substituents, specifically, alkyl, aralkyl, aryl and the like. Alkyl, aralkyl and aryl are as defined above.
Examples of the acyl moiety of acyloxy include formyl, acetyl, malonyl, benzoyl, cinnamoyl and the like.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium. Among them, lithium or sodium is preferable.
Compound (2) can be obtained from triarylphosphine or triarylphosphine oxide by a known method (Hoffmann, H., Chem. Ber., 1962, Vol. 95, p. 2563-2566, Bull. Chem. Soc. Jpn., 1991, Vol. 64, p. 3182-3184, etc.).

Compound (4) can be synthesized by reacting compound (2) with compound (3), preferably 0.5 to 10 equivalents, more preferably 0.8 to 2 equivalents.
In this case, the reaction temperature is preferably started from a low temperature such as −78 ° C. and gradually raised. In order to complete the reaction, the temperature may be raised or heated to reflux after the addition of the compound (3). .
The reaction solvent is not particularly limited as long as it can dissolve the substrate, but ether solvents such as tetrahydrofuran (THF), dialkyl ether, dioxane, ethylene glycol dialkyl ether, di (ethylene glycol) dialkyl ether are preferable. The amount used is 1 to a large excess (weight ratio) relative to the compound (3).
Compound (4) can be purified by a purification method (recrystallization, chromatography, etc.) generally used in organic synthetic chemistry, if necessary.
Compound (1) can be produced by oxidizing compound (4). As the oxidation method, oxidation with oxygen gas, peroxide oxidation, electrical oxidation, biological oxidation and the like can be used, and oxidation with oxygen gas or oxidation with peroxide is particularly preferable. When the compound (1) is oxidized using oxygen gas, the oxygen gas itself may be used. However, a gas containing oxygen, for example, air or an inert gas such as oxygen and nitrogen or argon or air is used. It is preferable to use a mixed gas or the like. In the oxidation by peroxide, examples of the peroxide include an aqueous hydrogen peroxide solution, perbenzoic acid, m-chloroperbenzoic acid, acetone oxide, t-butyl hydroperoxide, cumyl hydroperoxide, and the like. However, it is preferable to use an aqueous hydrogen peroxide solution.
Compound (1) can be purified by a purification method (recrystallization, chromatography, etc.) generally used in organic synthetic chemistry, if necessary.

Compound (6) is obtained by reacting compound (2) with compound (5), preferably 0.5 to 10 equivalents, more preferably 0.8 to 2 equivalents. The reaction temperature can be freely selected from the range of −80 to 200 ° C., but is generally carried out at room temperature, and if necessary to complete the reaction, the temperature is raised or refluxed after addition of compound (5). May be.
The reaction solvent is not particularly limited as long as it dissolves the substrate, but ether solvents such as THF, dialkyl ether, dioxane, ethylene glycol dialkyl ether, and di (ethylene glycol) dialkyl ether are preferable.
The reaction solution thus obtained is hydrolyzed to produce compound (6). The separation and purification can be easily performed by conventional means such as extraction, distillation, recrystallization, chromatography and the like.

Compound (7) can be synthesized by oxidizing compound (6). The oxidation reaction can be carried out by a method similar to the method for oxidizing the compound (2).
Compound (1) can be obtained by oxidative dehydrogenation of compound (7). As a method of oxidative dehydrogenation, for example, preferably 0.5 to 50 equivalents, more preferably 10 to 20 equivalents hydrogen peroxide or preferably 0.5 to 10 equivalents, more preferably 0.8 to 3 equivalents of organic hydro A method using a peroxide is preferred. Oxidative dehydrogenation is preferably carried out in the presence of a catalyst. As the catalyst, various kinds of catalysts containing metals can be used, for example, supported or unsupported metal platinum or metal palladium, platinum, palladium, ruthenium, vanadium, rhenium and other oxides and salts, olefins and arenes. Examples thereof include complexes of metals such as platinum, palladium, ruthenium, vanadium, rhenium and the like having organic ligands such as phosphine ligands, and among them, ruthenium oxides, salts or metal complexes are preferred. The amount of the catalyst used is preferably from 0.01 to 2 equivalents, particularly preferably from 0.1 to 0.5 equivalents, relative to compound (7).

Even when hydrogen peroxide is used as the compound (6), the compound (1) can be obtained directly.
The compound (1) of the present invention can be used as a photopolymerization initiator for unsaturated compounds.
The photopolymerization initiator of the present invention can be used in combination with a known initiator. Known photoinitiators include, for example, benzophenone, acetophenone derivatives, benzoin ethers, benzyl ketals, monoacylphosphine oxides, other bisacylphosphine oxides, peresters or titanocene-based photopolymerization initiators, and the like (1) You may use 0.001-20 weight% with respect to.

The photopolymerizable composition of the present invention contains compound (1) and an unsaturated compound.
The unsaturated compound used here has one or more carbon-carbon double bonds in the molecule. They are low molecular weight to medium / high molecular weight unsaturated compounds.
Among the low molecular weight unsaturated compounds, examples of monomers having one double bond in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, 2-hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkylstyrene, Examples thereof include halostyrene, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like. Here, (meth) acrylate represents acrylate and methacrylate. The following is expressed similarly.

  Examples of polyfunctional monomers having two or more double bonds in the molecule among the low molecular weight unsaturated compounds include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, and hexamethylene glycol diacrylate. Bisphenol A diacrylate, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, pentaerythritol divinyl ether, vinyl acrylate, divinylbenzene, divinyl succinate , Diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris (2-acryloylethyl) isocyanurate, divini Ether, triethylene glycol divinyl ether and the like.

Examples of the medium / high molecular weight unsaturated compound include epoxy acrylate, polyether acrylate, urethane acrylate, ester acrylate, and unsaturated polyester resin. Their preferred molecular weight is 500 to 10,000.
Since these medium / high molecular unsaturated compounds are usually highly viscous, they are preferably diluted with a low molecular weight unsaturated compound or a solvent and contained in the photopolymerizable composition of the present invention.

  In addition to the photopolymerization initiator, other additives can be added to the photopolymerizable composition of the present invention. Examples of these additives include polymerization inhibitors such as hydroquinone and sterically hindered phenol. Moreover, in order to prolong the shelf life in a dark room, a copper compound, a phosphorus compound, a quaternary ammonium compound, a hydroxylamine derivative, etc. can be added. In addition, paraffin or similar wax analogs that migrate to the surface at the beginning of the polymerization can be added to reduce oxygen damage during the polymerization. As light stabilizers, small amounts of UV absorbers such as benzotriazole, benzophenone, hydroxyphenyl-s-triazine or oxalanilide type can be added. Light stabilizers that do not absorb UV light such as sterically hindered amines (HALS) may be added. For example, photopolymerization is accelerated by adding amines such as triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone. This effect can be increased by adding benzophenone type aromatic ketones. Photopolymerization is further accelerated by the addition of a photosensitizer. The effect changes or broadens the spectral sensitivity. Examples of these are aromatic carbonyl compounds (eg benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives) and 3- (aroylmethylene) thiazolines. In addition, an optical brightener, a filler, a pigment, a dye, a wetting agent, a flow control agent, or the like can be added depending on the application. The addition amount is preferably 0.01 to 5% by weight in the photopolymerizable composition of the present invention.

The photopolymerization initiator of the present invention is particularly suitable for initiating curing of a polymerizable composition containing a substance that lowers transparency, such as a filler. The cured product obtained by curing the unsaturated compound using the photopolymerization initiator of the present invention is excellent in transparency.
In the photopolymerizable composition of the present invention, the compound (1) is preferably contained in an amount of 0.01 to 15% by weight, more preferably 0.2 to 5% by weight, based on the total solid content.

  The photopolymerizable composition of the present invention may be dissolved or dispersed in water depending on the structure of the unsaturated compound constituting the composition. Examples of unsaturated compounds used here include unsaturated compounds in which medium or high molecular weight unsaturated compounds such as epoxy acrylates, polyether acrylates, urethane acrylates, ester acrylates, and unsaturated polyester resins are dissolved or dispersed in water. Examples thereof include compounds and water-soluble monofunctional / polyfunctional monomers. As a method of water solubilization and water dispersion, an acidic group such as carboxylic acid or sulfonic acid is introduced into the molecule of the unsaturated compound and neutralized with an alkali to make it hydrophilic, or Although methods such as introducing a polyethylene glycol unit into the molecule to make it hydrophilic can be mentioned, the method is not limited to these.

  Further, there is a method of dispersing the composition in water using a known emulsifier without introducing a hydrophilic functional group into the molecule. Examples of the emulsifier include anionic, cationic and nonionic emulsifiers, and polymer emulsifiers. For example, anionic surfactants such as higher alcohol sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenol ether sulfate salts, polyoxyethylene alkyl phenol ethers, ethylene oxide propylene oxide block polymers, sorbitan derivatives Nonionic surfactants such as, for example, are not limited thereto.

  In the photopolymerizable composition of the present invention, as other additives, a dispersion aid, an emulsifier, an antioxidant, a light stabilizer, a dye, a pigment / filler (for example, talc, gypsum, silica, rutile, carbon black, Zinc oxide and iron oxide), extenders, matting agents, antifoaming agents, fluorescent agents, phosphorescent agents, luminescent agents, conductive agents, metal particles (gold particles, silver particles, copper particles, etc.), color materials, antibacterial agents (Titanium oxide, antibacterial organic compounds, etc.) and other auxiliary agents conventionally used in surface coating technology can be added. Examples of the dispersion aid include organic compounds containing a polar group, such as polyvinyl alcohol, polyvinyl pyrrolidone, and cellulose ether.

  The photopolymerizable composition of the present invention is cured by irradiation with sunlight, visible laser light, or UV light. Examples of preferred light sources are low, medium and high pressure mercury lamps, metal halogen lamps or laser light, whose maximum emission wavelength is in the range of 250-450 nm. When a combination with a photosensitizer is employed, relatively long wavelength light or laser light up to 600 nm can be used. The cured product can be used as a film, plastic or the like.

  The photopolymerizable composition of the present invention comprises printing ink, varnish, white paint for wood or metal, paint composition for paper, wood, metal or plastic, pigmented paint, building finish paint, road sign paint, visible light Paints with curable UV absorbers, transparent or colored aqueous dispersion paints, civil engineering and building materials, road repair agents, heavy-duty anticorrosion paints, cold district paints, fluorescent paints, luminescent paints, lining materials, sealing materials, sealants , Plastic materials, fluorescent plastics, luminous plastics, stereolithography materials, micropart materials, molecular device materials, photo-curable packaging / container materials, printing inks, printing plate manufacturing, screen printing mask manufacturing, printed matter, Label printing, package printing, beverage pack printing, business form printing, card printing, photo reproduction process, photo developing material, image recording process, optical recording Materials, Dental Filling Materials, Dental Adhesives, Medical Adhesives, Organ Duplicates, Gibbs Materials, Nail Art Products, Design Design, Design Design, Small Equipment Model Creation, Simulation Model Creation , Optical markking agents, adhesives, biomaterials, biological / herbal medicine packaging materials, etching agents for printed electronic circuits, resist materials, color filter materials, film materials, conductive films, antireflection films, surface coating materials, for liquid crystals Sealant, prism sheet, solder stop mask, optical molding material, solar cell material, optical switch, optical circuit material, photodetector, semiconductor sealant, coating or encapsulation of electronic components, plant cultivation material, tree repair material, Greenhouse materials, photodegradable plastics, antibacterial plastics, sheet materials, composite materials (eg composites of glass fiber and other auxiliaries) Materials, etc.), optical adhesives, refractive index adjusting agents, potting agents, spectacle lenses, optical materials including lenses and prisms, optical communication materials, optical fiber paints, sports equipment, toys, automotive parts, automotive repair putty, It can be used as a ship part, an aircraft part, or a space material.

  When the photopolymerizable composition of the present invention is used for coating formation, for example, dipping, brushing, spraying or roll coating can be applied. The film thickness of the coating and the substrate at this time are selected according to the application field. For example, examples of suitable substrates for recording photographic information are polyester, cellulose acetate films, or resin-coated paper. The painted substrate for offset printing plates is specially treated aluminum and the painted substrate for producing printed circuits is a copper clad laminate. The film thickness of the photographic material and the offset printing plate is usually 0.5 to 10 μm.

  In the printing ink field, since the polymerization time of the binder greatly affects the production rate of the recording product, a photopolymerizable composition that can be rapidly polymerized and cured is required. For the photocurable printing ink, the speed of curing is particularly important in offset printing. The photopolymerizable composition of the present invention has a high curing speed and an excellent curing depth, and is suitable for producing a printing plate for flexographic printing or letterpress printing. In this field, a mixture of soluble linear polyamide or styrene butadiene rubber and a photopolymerizable monomer such as acrylamide or acrylate and a photoinitiator is used. Films and plates made with these mixtures are irradiated through the negative or positive of the original print, after which the unexposed portions are eluted with a suitable solvent. Development is then carried out in an organic solvent or in an aqueous alkaline medium to form a printing plate.

  Other fields of application of the photopolymerizable composition of the present invention include, for example, metal coatings for sheet, tube, bottle or bottle lids. Other examples include resin coatings for coating PVC floors or walls. In the paper field, for example, labels, cards, record jackets, CD / DVD jackets, milk packs, beverage packs, paper cups, cup noodle containers, calendars, posters, business forms, colorless covers on record jackets or book covers. can give.

The photopolymerizable composition of the present invention can also be applied to image or information carrier production. The photopolymerizable composition is usually applied to a substrate to form a coating film, and then irradiated with light through a photomask, and the non-irradiated surface is treated with a solvent and removed (developed). Images or information carriers can be made.
The photopolymerizable composition of the present invention can form a coating film also by electrodeposition on a metal. The portion irradiated with light of the coating film becomes insoluble because it becomes a crosslinked polymer, and remains on the substrate. When this remaining portion is appropriately stained, a visible image is formed. When the substrate is a vapor-deposited metal coating, the metal can be removed from the non-irradiated surface by etching after light irradiation and development, or the film thickness can be increased by galvanization. A printed electronic circuit board can be produced as described above.

The photopolymerization initiator of the present invention has high reactivity. Moreover, the coating surface after photopolymerization shows a favorable gloss value. The photopolymerization initiators of the present invention are particularly suitable for initiating the curing of white paints and can cure thick coating films so that they can be used for the production of printing plates and composite materials.
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Synthesis of 9- (2,4,6-trimethylbenzoyl) -9-oxo-9-phosphafluorene (Compound 1-1):
To a flask equipped with a reflux condenser, 9-phenyl-9-phosphafluorene (650 mg, 2.5 mmol), tetrahydrofuran (7.5 mL) and lithium metal (45 mg, 15 mg) were added, and the mixture was stirred at room temperature for 3 hours under an argon atmosphere. did. The reaction solution was transferred to a flask with a reflux condenser (argon atmosphere, at room temperature), tert-butyl chloride (0.27 mL, 2.5 mmol) was added, and the mixture was heated with stirring at 60 ° C. for 10 minutes, and cooled to room temperature. The mixture was added dropwise to a flask (argon atmosphere) containing a solution of 2,4,6-trimethylbenzoyl chloride (460 mg, 2.5 mmol) in tetrahydrofuran (7.5 mL) cooled to −78 ° C. Thereafter, the reaction mixture was stirred at −78 ° C. for 15 minutes, blown with oxygen gas (1 atm), stirred for 1 hour, and then returned to room temperature. After the reaction mixture was concentrated, the residue was diluted with 5 mL of dichloromethane and separated and purified by silica gel column chromatography (n-hexane, then ether). The ether eluate was concentrated, the residue was recrystallized from a dichloromethane / n-hexane solvent, and the crystals were collected by filtration. The obtained crystals were dried under reduced pressure to obtain Compound 1-1 in a yield of 54% (430 mg).

¹ H NMR (CDCl ₃ ): δ 2.10 (s, 6H), 2.24 (s, 3H), 6.85 (s, 2H), 7.23 (dt, J = 3.69, 7.57 Hz) , 2H), 7.64 (t, J = 7.57 Hz, 2H), 7.75 (dd, J = 7.57, 8.01 Hz, 2H), 7.88 (dd, J = 2.93, 7.57 Hz, 2H).
¹³ C NMR (CDCl ₃ ): δ 21.65, 25.56, 121.19, 130.02 (d, J = 10.94 Hz), 129.10, 130.03 (d, J = 97.44 Hz), 131.09 (d, J = 9.32 Hz), 134.59, 134.64 (d, J = 11.77 Hz), 137.15 (d, J = 43.000 Hz), 140.75, 143.04 (D, J = 21.13 Hz), 216.22 (d, J = 73.06 Hz).
³¹ P NMR (CDCl ₃ ): δ + 29.12.
IR (KBr, cm ⁻¹ ): n = 2973.7, 1608.3, 1438.6, 1176.4, 717.4, 570.8.
Elemental _analysis: C _{22 H} 19 _{O 2} Calculated as P: C, 76.29; H, 5.33; O, 9.24. Found: C, 76.12; H, 5.64; O, 9.09.

Synthesis of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2):
The reaction was concentrated in the same manner as in Example 1 except that p-toluoyl chloride was used in place of 2,4,6-trimethylbenzoyl chloride. The residue was diluted with 5 mL of dichloromethane, and then separated and purified by silica gel column chromatography (ether / n-hexane = 5: 1). The residue obtained by concentrating the eluate was recrystallized from a dichloromethane / n-hexane solvent, and the crystals were collected by filtration. The obtained crystals were dried under reduced pressure to obtain Compound 1-2 in a yield of 52% (413 mg).

¹ H NMR (CDCl ₃ , ppm): δ 2.49 (s, 3H) 7.34-7.37 (m, 2H), 7.36 (d, J = 7.74 Hz, 2H), 7.48 ( dt, J = 0.98, 7.47 Hz, 2H), 7.74 (dd, J = 4.85, 7.47 Hz, 2H), 7.92 (d, J = 7.74 Hz, 2H), 8 .01 (dd, J = 2.11, 8.18 Hz, 2H).
¹³ C NMR (CDCl ₃ , ppm): δ 23.82, 121.78, 128.07 (d, J = 7.77 Hz), 128.96 (d, J = 8.98 Hz), 129.31, 129. 82, 130.46 (d, J = 28.56 Hz), 131.58 (d, J = 19.62 Hz), 135.99, 137.51 (d, J = 36.3 Hz), 144.48 ( d, J = 79.78 Hz), 210.35 (d.J = 71.53 Hz).
³¹ P NMR (CDCl ₃ , ppm): δ + 17.11.
IR (KBr, cm ^-1 ): n = 2929.3, 1641.3, 1598.7, 1174.4, 746.3.
FAB-MS m / z (relative intensity): 519 [8%, (M + C ₁₂ H ₉ PO) ⁺ ], 319 [43%, (M + H) ⁺ ], 119 (100%, C ₁₂ H ₉ PO ⁺ ).

Synthesis of 9- (p-anisoyl) -9-oxo-9-phosphafluorene (Compound 1-3):
Compound 1-3 was obtained at 7% (0.60 g) in the same manner as in Example 1 except that p-anisoyl chloride was used in place of 2,4,6-trimethylbenzoyl chloride.

¹ H NMR (CDCl ₃ , ppm): δ 3.82 (s, 3H), 7.01 (d, J = 8.67 Hz, 2H), 7.33 (ddt, J = 1.07, 3.17, 7.43 Hz, 2H), 7.44 (dt, J = 1.19, 7.43 Hz, 2H), 7.72 (dd, J = 4.71, 7.43 Hz, 2H), 7.89 (d , J = 7.43 Hz, 2H), 8.07-8.17 (m, 2H).
¹³ C NMR (CDCl ₃ , ppm): δ 56.12, 114.35, 121.71, 128.31 (d, J = 7.77 Hz), 129.55, 131.51 (d, J = 9.74 Hz) ), 131.78 (d, J = 19.70 Hz), 133.32 (d, J = 47.93 Hz), 136.54 (d, J = 1.43 Hz), 144.26 (d, J = 2) .34 Hz), 164.39, 208.73 (d, J = 37.59 Hz).
³¹ P NMR (CDCl ₃ , ppm): δ + 15.86.
IR (KBr, cm ⁻¹ ): n = 3073.9, 2838.7, 1596.8, 1504.2, 1186.0.

Synthesis of 9- (2,6-dimethoxybenzoyl) -9-oxo-9-phosphafluorene (Compound 1-4):
Compound 1-4 was obtained at 46% (4.1 g) in the same manner as in Example 1 except that 2,6-dimethoxybenzoyl chloride was used in place of 2,4,6-trimethylbenzoyl chloride.

¹ H NMR (CDCl ₃ , ppm): δ 3.83 (s, 6H), 6.53 (d, J = 8.40 Hz, 2H), 7.31 (t, J = 8.40 Hz, 1H), 7 .28-7.44 (m, 2H), 7.59 (dt, J = 1.23, 8.22 Hz, 2H), 7.76-7.80 (m, 2H), 7.85 (d, J = 8.22 Hz, 2H).
¹³ C NMR (CDCl ₃ , ppm): δ 56.71, 104.72, 117.26 (d, J = 9.89 Hz), 129.67 (d, J = 11.25 Hz), 131.15 (d, J = 10.03 Hz), 131.20 (d, J = 98.80 Hz), 133.79, 134.30 (d, J = 2.05 Hz), 143.36 (d, J = 20.30 Hz), 158.48, 209.42 (d, J = 84.53 Hz).
³¹ P NMR (CDCl ₃ , ppm): δ + 25.92.

IR (KBr, cm ⁻¹ ): n = 3066.2, 2834.8, 1687.9, 1592.9, 1207.2.

Synthesis of 9- (1-naphthoyl) -9-oxo-9-phosphafluorene (Compound 1-5):
Compound 1-5 was obtained in the same manner as in Example 1 except that 1-naphthoyl chloride was used in place of 2,4,6-trimethylbenzoyl chloride.

¹ H NMR (CDCl ₃ , ppm): δ 7.23 (d, J = 3.12 Hz, 1H), 7.27 (d, J = 1.25 Hz, 1H), 7.31 (d, J = 1. 08 Hz, 1H), 7.34 (dt, J = 3.03, 11.95 Hz, 2H), 7.40-7.48 (m, 2H), 7.56 (dd, J = 4.57, 7 .38 Hz, 2H), 7.68 (t, J = 7.45 Hz, 1H), 7.85 (d, J = 8.22 Hz, 2H), 7.89 (d, J = 7.82 Hz, 1H) 8.02 (dd, J = 5.96, 8.28 Hz, 1H), 8.45-8.49 (m, 2H).

IR (KBr, cm ⁻¹ ): n = 1641.1, 1216.0.

Synthesis of 9- (2,4,6-trimethylbenzoyl) -9-oxo-9-phosphafluorene (Compound 1-1):
Into the flask was added 349 mg (1.0 mmol) of 9- (hydroxy-2,4,6-trimethylbenzyl) -9-oxo-9-phosphafluorene, acetone (5 mL), 2.1 mg (0.01 mmol) of ruthenium trichloride. In addition, a t-butyl alcohol solution (0.23 mL) of t-butyl hydroperoxide (2.0 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 45 minutes, and the mixture was separated and purified by silica gel column chromatography (n-hexane followed by ether). The ether eluate was concentrated, the residue was recrystallized from a dichloromethane / n-hexane solvent, and the crystals were collected by filtration. The obtained crystal was dried under reduced pressure to obtain Compound 1-1.

Synthesis of 9- (2,4,6-trimethylbenzoyl) -9-phosphafluorene (Compound 4-1):
To a flask equipped with a reflux condenser, 9-phenyl-9-phosphafluorene (650 mg, 2.5 mmol), tetrahydrofuran (7.5 mL) and lithium metal (45 mg, 15 mg) were added, and the mixture was stirred at room temperature for 3 hours under an argon atmosphere. did. The reaction solution was transferred to a flask with a reflux condenser (argon atmosphere, at room temperature), tert-butyl chloride (0.27 mL, 2.5 mmol) was added, and the mixture was heated with stirring at 60 ° C. for 10 minutes, and cooled to room temperature. The mixture was added dropwise to a flask (argon atmosphere) containing a solution of 2,4,6-trimethylbenzoyl chloride (460 mg, 2.5 mmol) in tetrahydrofuran (7.5 mL) cooled to −78 ° C. The reaction solution was concentrated, 50 mL of ether was added and stirred, insoluble matter was filtered off, and the filtrate was dried to obtain a compound 4-1 as a highly viscous liquid.

¹ H NMR (CDCl ₃ , ppm): δ 1.78 (s, 6H), 2.26 (s, 3H), 6.71 (s, 2H), 7.27 (ddt, J = 1.05, 3 .13, 7.48 Hz, 2H), 7.41-7.47 (m, 4H), 7.86 (dd, J = 1.05, 7.48 Hz, 2H).
IR (KBr, cm ⁻¹ ): n = 2917.8, 1654.6, 846.6, 750.2.

Synthesis of 9- [hydroxy (2,4,6-trimethylphenyl) methyl] -9-phosphafluorene (Compound 6-1):
9-Phenyl-9-phosphafluorene (6.50 g, 25 mmol), tetrahydrofuran (75 mL) and lithium metal (0.45 g, 0.15 g-atom) were added to a flask equipped with a reflux condenser, and an argon atmosphere at room temperature. For 3 hours. The reaction solution was transferred to a flask with a reflux condenser (argon atmosphere, at room temperature), t-butyl chloride (2.7 mL, 25 mmol) was added, and the mixture was heated and stirred at 60 ° C. for 10 minutes, and cooled to room temperature. 2,4,6-Trimethylbenzaldehyde (3.70 g, 25 mmol) was added dropwise to the mixture. The reaction mixture was then stirred at room temperature for 15 minutes, the reaction was concentrated at room temperature until the amount was about 15 mL, and saturated aqueous ammonium chloride (25 mL) and 200 mL of ether were added. The ether layer was separated, washed with water, dried, and concentrated to dryness to obtain Compound 6-1 as a highly viscous liquid.

¹ H NMR (CDCl ₃ , ppm): δ 2.26 (s, 6H), 2.31 (s, 3H), 5.65 (s, 1H), 6.36 (d, J = 3.65 Hz, 1H ), 7.08 (s, 2H), 7.39 (dt, J = 7.41, 2H), 7.52 (t, J = 7.41, 2H), 7.85 (dd, J = 5) .89, 7.41 Hz, 2H), 7.9 (d, J = 7.41, 2H).
IR (KBr, cm ⁻¹ ): n = 3399.9, 1417.4, 740.5.

Synthesis of 9- [hydroxy (2,4,6-trimethylphenyl) methyl] -9-oxo-9-phosphafluorene (Compound 7-1):
9-Phenyl-9-phosphafluorene (6.50 g, 25 mmol), tetrahydrofuran (75 mL) and lithium metal (0.45 g, 0.15 g) were added to a flask equipped with a reflux condenser, and the mixture was added under argon atmosphere at room temperature. Stir for hours. The reaction solution was transferred to a flask with a reflux condenser (argon atmosphere, at room temperature), t-butyl chloride (2.7 mL, 25 mmol) was added, and the mixture was heated and stirred at 60 ° C. for 10 minutes, and cooled to room temperature. 2,4,6-Trimethylbenzaldehyde (3.70 g, 25 mmol) was added dropwise to the mixture. The reaction mixture was then stirred at room temperature for 15 minutes and saturated aqueous ammonium chloride (25 mL) was added. The mixture was poured into 3 wt% aqueous hydrogen peroxide (300 mL) and the resulting solid was collected by filtration. The solid was recrystallized from dichloromethane / n-hexane solvent, and the crystals were collected by filtration. The obtained crystals were dried under reduced pressure to obtain 9- [hydroxy (2,4,6-trimethylphenyl) methyl] -9-oxo-9-phosphafluorene (Compound 7-1) in a yield of 83% (7.00 g). ).

¹ H NMR (CDCl ₃ ): δ = 1.60 (br s, 3H), 2.32 (s, 3H), 3.01 (br s, 3H), 3.37-3.43 (m, 1H ), 5.22-5.26 (m, 1H), 6.63 (brs, 1H), 6.88 (t, J = 7.83 Hz, 1H), 6.89 (brs, 1H), 7.12-7.14 (m, 1H), 7.45-7.46 (m, 1H), 7.51 (t, J = 7.83 Hz, 1H), 7.61 (t, J = 7 .56 Hz, 1H), 7.78 (m, 2H), 7.98 (t, J = 7.56 Hz, 1H).
³¹ P NMR (CDCl ₃ ): δ = + 40.06.
IR (KBr, cm ⁻¹ ): n = 3270.6, 1191.7.

Synthesis of 9- [hydroxy (p-tolyl) methyl] -9-oxo-9-phosphafluorene (Compound 7-2):
9-Phenyl-9-phosphafluorene (650 mg, 2.5 mmol), tetrahydrofuran (75 mL) and lithium metal (45 mg, 15 mg) were added to a flask equipped with a reflux condenser, and the mixture was stirred at room temperature for 3 hours under an argon atmosphere. The reaction solution was transferred to a flask with a reflux condenser (argon atmosphere, at room temperature), tert-butyl chloride (0.27 mL, 2.5 mmol) was added, and the mixture was heated with stirring at 60 ° C. for 10 minutes, and cooled to room temperature. P-Tolualdehyde (300 mg, 2.5 mmol) was added dropwise to the mixture. The reaction mixture was then stirred at room temperature for 15 minutes and saturated aqueous ammonium chloride (2.5 mL) was added. The mixture was poured into 3 wt% aqueous hydrogen peroxide (30 mL) and the resulting solid was collected by filtration. The solid was recrystallized from a dichloromethane / n-hexane solvent, and the crystals were collected by filtration. The obtained crystals were dried under reduced pressure to obtain 9- [hydroxy (p-tolyl) methyl] -9-oxo-9-phosphafluorene (Compound 7-2) in a yield of 84% (672 mg).

¹ H NMR (CDCl ₃ ): δ = 2.28 (s, 3H), 4.28 (br s, 1H), 5.23 (d, J = 3.49 Hz, 1H), 6.97 (d, J = 8.15 Hz, 2H), 7.03 (dd, J = 1.69, 8.15 Hz, 2H), 7.28-7.32 (m, 1H), 7.33-7.41 (m , 1H), 7.53-7.57 (m, 3H), 7.58-7.70 (m, 2H), 7.78 (t, J = 8.01 Hz, 1H).
¹³ C NMR (CDCl ₃ ): δ = 21.59, 74.31 (d, J = 78.85 Hz) 121.38 (d, J = 9.82 Hz), 127.25 (d, J = 4.78 Hz) ), 128.98 (d, J = 99.84 Hz), 129.02 (d, J = 2.16 Hz), 129.19 (d, J = 22.60 Hz), 131.12 (d, J = 14) 48 Hz), 133.93, 138.20, 142.24 (d, J = 12.1 Hz), 142.52 (d, J = 12.31 Hz).
³¹ P NMR (CDCl ₃ ): δ = + 41.76.
IR (KBr, cm ⁻¹ ): n = 2973.7, 1608.3, 1438.6, 1176.4, 717.4, 570.8.

Elemental _analysis: C _{22 H} 19 _{O 2} Calculated as P: C, 74.99; H, 5.35; O, 10.04. Found: C, 75.23; H, 5.46; O, 9.80.

Example of Film Preparation by Ultraviolet Light Curing Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts are mixed and photopolymerized composition Manufactured. A solution prepared by dissolving 1 part of 9- (2,4,6-trimethylbenzoyl) -9-oxo-9-phosphafluorene (compound 1-1) in 50 parts of methylene chloride was added to this composition and stirred. The composition was applied onto a glass plate using a 1 mm bar coater and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Subsequently, the coated glass plate was exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high-pressure mercury lamp, 400 mJ, 80 W / cm ² , belt speed 5 m / min). The resulting coating film was checked for touch of the degree of cure and yellowness measurement (YI). The results are shown in Table 1.

Example of Film Preparation by Ultraviolet Light Curing Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts are mixed and photopolymerized composition Manufactured. A solution prepared by dissolving 1 part of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) in 50 parts of methylene chloride was added to this composition and stirred. The composition was applied onto a glass plate using a 1 mm bar coater and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Subsequently, the coated glass plate was exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high-pressure mercury lamp, 400 mJ, 80 W / cm ² , belt speed 5 m / min). The obtained coating film was checked for finger touch and measured for yellowness (YI). The results are shown in Table 1.

Example of Film Preparation by Ultraviolet Light Curing Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts are mixed to form a photopolymerization composition. The thing was manufactured. To this composition was added a solution prepared by dissolving 1 part of 9- (p-anisoyl) -9-oxo-9-phosphafluorene (compound 1-3) in 50 parts of methylene chloride and stirred. The composition was applied onto a glass plate using a 1 mm bar coater and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Subsequently, the coated glass plate was exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high-pressure mercury lamp, 400 mJ, 80 W / cm ² , belt speed 5 m / min). The obtained coating film was checked for finger touch and measured for yellowness (YI). The results are shown in Table 1.

Example of Film Preparation by Ultraviolet Light Curing Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts are mixed to form a photopolymerization composition. The thing was manufactured. To this composition was added a solution prepared by dissolving 1 part of 9- (2,6-dimethoxybenzoyl) -9-oxo-9-phosphafluorene (compound 1-4) in 50 parts of methylene chloride and stirred. The composition was applied onto a glass plate using a 1 mm bar coater and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. The coated glass plate was then exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high-pressure mercury lamp, 400 mJ, 80 W / cm ² , belt speed 5 m / min). The obtained coating film was checked for finger touch and measured for yellowness (YI). The results are shown in Table 1.
Comparative Example 1: Preparation Example of Film by Ultraviolet Light Curing Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts were mixed. A photopolymerization composition was produced. A solution prepared by dissolving 1 part of lucillin TPO (MAPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF) in 50 parts of methylene chloride was added to this composition and stirred. The composition was applied onto a glass plate using a 1 mm bar coater, and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Subsequently, the coated glass plate was exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high-pressure mercury lamp, 400 mJ, 80 W / cm ² , belt speed 5 m / min). The obtained coating film was checked for finger touch of the degree of cure and measured for yellowness. The results are shown in Table 1.
Comparative Example 2: Preparation Example of Film by UV Light Curing Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts, TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts were mixed. A photopolymerization composition was produced. A solution prepared by dissolving 1 part of Irgacure 819 (BAPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by Ciba Special Chemicals) in 50 parts of methylene chloride was added to this composition and stirred. The composition was applied onto a glass plate using a 1 mm bar coater, and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Subsequently, the coated glass plate was exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high-pressure mercury lamp, 400 mJ, 80 W / cm ² , belt speed 5 m / min). The obtained coating film was checked for finger touch of the degree of cure and measured for yellowness. The results are shown in Table 1.

Confirmation of the touch of the degree of cure is represented by ○ for complete cure, Δ for semi-cured, and × for uncured.
Yellowness is measured using a color difference meter (SZ-Sigma 80, Nippon Denshoku Industries Co., Ltd.), and a sample with an average film thickness of 0.31 ± 0.02 mm (average film thickness at any 5 points in the transmission path) is obtained. Using, the yellowness (YI) of the film was measured three times and the average value was recorded.
In the table, the resin composition and the amount of initiator added represent parts by weight. The same applies to the following tables.

Cured product adjustment example 1 by visible light curing
A photopolymerization composition was prepared by mixing 60 parts of Evecril 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) and 40 parts of TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB). To this composition was added a solution prepared by dissolving 2 parts of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) in 50 parts of methylene chloride and stirred. The composition was applied onto a glass plate using a 1 mm bar coater and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Next, the coated glass plate is covered with aluminum foil, and a dental visible light irradiator (Eliper Free Light, 3M Espe, 400 mW / cm ² , 440 to 490 nm) is placed at a height of 3 mm for 8 minutes (40 (Second × 12 times). The resulting coating film was checked for finger touch of the degree of cure. The results are shown in Table 2.

Cured product adjustment example 2 by visible light curing
9- (p-Toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) Instead of 2 parts, 9- (p-anisoyl) -9-oxo-9-phosphafluorene (Compound 1-3) ) A film was obtained in the same manner as in Example 15 except that 2 parts were used. The resulting film was checked for finger touch of the degree of cure. The results are shown in Table 2.

Cured product adjustment example 3 by visible light curing
9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) instead of 2 parts 9- (2,6-dimethoxybenzoyl) -9-oxo-9-phosphafluorene (compound 1-4) A film was obtained in the same manner as in Example 15 except that 2 parts were used. The resulting film was checked for finger touch of the degree of cure. The results are shown in Table 2.
Comparative example 3: Cured material adjustment example 4 by visible light curing
9 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (MAPO: Lucillin TPO, manufactured by BASF) instead of 2 parts of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) The same procedure as in Example 15 was carried out except that was used. Touch confirmation of the degree of cure of the obtained film was performed. The results are shown in Table 2.
Comparative example 4: Cured material adjustment example 5 by visible light curing
9- (p-Toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) Instead of 2 parts, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BAPO: Irgacure 819, Ciba Special) The same procedure as in Example 15 was performed except that 2 parts of Chemicals) were used. The resulting film was checked for finger touch of the degree of cure. The results are shown in Table 2.

  Confirmation of the touch of the degree of cure is represented by ○ for complete cure, Δ for semi-cured, and × for uncured.

Example 1 of film preparation by solar curing
A photopolymerization composition was prepared by mixing 60 parts of Evecril 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) and 40 parts of TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB). To this composition was added a solution prepared by dissolving 2 parts of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (Compound 1-3) in 50 parts of methylene chloride and stirred. The composition was applied onto a glass plate using a 1 mm bar coater and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Next, the coated glass plate was left for 5 hours under outdoor sunlight (sunny weather, temperature 10 ° C., 10:00 to 15:00). The resulting film was checked for finger touch of the degree of cure and measured for yellowness (YI). The results are shown in Table 3.

Example 2 of film preparation by solar curing
9- (p-Toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) Instead of 2 parts, 9- (p-anisoyl) -9-oxo-9-phosphafluorene (Compound 1-3) ) A film was obtained in the same manner as in Example 18 except that 2 parts were used. The resulting film was checked for finger touch of the degree of cure and measured for yellowness (YI). The results are shown in Table 3.

Preparation Example 3 of Film by Solar Curing
9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) instead of 2 parts 9- (2,6-dimethoxybenzoyl) -9-oxo-9-phosphafluorene (compound 1-4) A film was obtained in the same manner as in Example 18 except that 2 parts were used. The resulting film was checked for finger touch of the degree of cure and measured for yellowness (YI). The results are shown in Table 3.
Comparative Example 5: Film preparation example 4 by solar curing
9 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (MAPO: Lucillin TPO, manufactured by BASF) instead of 2 parts of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) The same procedure as in Example 18 was carried out except that was used. Touch confirmation of the degree of cure of the obtained film was performed. The results are shown in Table 3.
Comparative Example 6: Film Preparation Example 5 by Solar Curing
9- (p-Toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) Instead of 2 parts, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BAPO: Irgacure 819, Ciba Special) The same procedure as in Example 18 was carried out except that 2 parts of Chemicals) were used. The resulting film was checked for finger touch of the degree of cure and measured for yellowness (YI). The results are shown in Table 3.

Confirmation of the touch of the degree of cure is represented by ○ for complete cure, Δ for semi-cured, and × for uncured.
Yellowness is measured using a color difference meter (SZ-Sigma 80, Nippon Denshoku Industries Co., Ltd.), and a sample with an average film thickness of 0.31 ± 0.02 mm (average film thickness at any 5 points in the transmission path) is obtained. Using, the yellowness (YI) of the film was measured three times and the average value was recorded.

Preparation example 1 of thick film cured product by UV light curing
Evecryl 600 (Ebecryl 600, bisphenol A type basic epoxy acrylate, manufactured by Daicel UCB) 60 parts TMPTA (trimethylolpropane triacrylate, manufactured by Daicel UCB) 40 parts A photopolymerization composition was produced. To this composition was added a solution prepared by dissolving 0.5 part of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (Compound 1-2) in 50 parts of methylene chloride and stirred. The mixture was poured into an aluminum cup so that the liquid level was 2.7 cm from the bottom, and dried in a vacuum dryer at 50 ° C. for 1 hour under light shielding. Next, the cup was exposed to light by passing it once through an ultraviolet curing light source device (manufactured by I-Graphics, metal halide and high pressure mercury lamp, 400 mJ, 80 W / cm 2, belt speed 5 m / min) to obtain a thick film cured product. . The cup was opened, the degree of cure was visually confirmed, and the thickness of the cured product was measured. The results are shown in Table 4.

Preparation example 2 of thick film cured product by ultraviolet light curing
9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) instead of 0.5 parts 9- (p-anisoyyl) -9-oxo-9-phosphafluorene (compound 1) -3) A thick film cured product was obtained in the same manner as in Example 21 except that 0.5 part was used. The degree of cure was confirmed and the thickness of the cured product was measured. The results are shown in Table 4.

Preparation example 3 of thick film cured product by ultraviolet light curing
9- (2,6-Dimethoxybenzoyl) -9-oxo-9-phosphafluorene instead of 0.5 part of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) A thick film cured product was obtained in the same manner as in Example 21 except that 0.5 part of (Compound 1-4) was used. The degree of cure was confirmed and the thickness of the cured product was measured. The results are shown in Table 4.
Comparative example 7: Preparation example 4 of thick film cured product by ultraviolet light curing
9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) instead of 0.5 part 2,4,6-trimethylbenzoyldiphenylphosphine oxide (MAPO: Lucillin TPO, manufactured by BASF) A thick film cured product was obtained in the same manner as in Example 21 except that 0.5 part was used. The degree of cure was confirmed and the thickness of the cured product was measured. The results are shown in Table 4.
Comparative example 8: Preparation example 5 of thick film cured product by ultraviolet light curing
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BAPO: Irgacure 819) instead of 0.5 part of 9- (p-toluoyl) -9-oxo-9-phosphafluorene (compound 1-2) A thick film cured product was obtained in the same manner as in Example 21 except that 0.5 part of Ciba Special Chemicals was used. The degree of cure was confirmed and the thickness of the cured product was measured. The results are shown in Table 4.

Confirmation of the touch of the degree of cure is represented by ○ for complete cure, Δ for semi-cured, and × for uncured.
For film thickness measurement, the uncured resin was wiped clean, the thickness of the cured product from the surface was measured at 5 points using calipers, and the average value was recorded.

The present invention provides a novel phosphine oxide compound useful as a photopolymerization initiator that can be used in the visible light region.

Claims (25)

General formula (1)

(Wherein R ¹ represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, or substituted or unsubstituted aralkenyl. , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, a halogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, Alkyloxy, cycloalkyloxy, alkenyloxy, cycloalkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, aralkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl or substituted Or an unsubstituted ara It represents a Kenyir, together with ^{R 2, R 3, R 4} , R 5, R 6, R 7, adjacent two groups of two carbon atoms, each of which adjacent of R ⁸ and R ⁹ May form a hydrocarbon ring, X is a single bond, oxygen atom, sulfur atom, substituted or unsubstituted vinylene, substituted or unsubstituted —NH, substituted or unsubstituted phosphorus atom or substituted or unsubstituted silicon A phosphine oxide compound represented by: R ¹ is substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different, respectively. The phosphine oxide compound according to claim 1, wherein X is a single bond, hydrogen atom, halogen atom, alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R ¹ is substituted or unsubstituted aryl, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different, and each represents a hydrogen atom, a halogen atom or an alkyl The phosphine oxide compound according to claim 1, wherein X is a single bond. General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, and M represents an alkali metal. And general formula (3)

(Wherein R ¹ has the same meaning as described above, and Z represents a halogen atom or acyloxy), and is reacted with a carboxylic acid halide or carboxylic anhydride represented by the general formula (4)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), The obtained phosphine compound is oxidized, and is represented by the general formula (1)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .   The method for producing a phosphine oxide compound according to claim 4, wherein the oxidation is an oxidation by treating with a gas containing oxygen. General formula (4)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above). General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X and M are as defined above, and a general formula (3)

(Wherein R ¹ and Z have the same meanings as described above) and a carboxylic acid halide or a carboxylic acid anhydride represented by the general formula (4)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. . General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X and M are as defined above, and a general formula (5)

(Wherein R ¹ has the same meaning as described above) to react with the aldehyde represented by the general formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. And then oxidizing the resulting α-hydroxyphosphine compound to give a general formula (7)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine An oxide compound is obtained, and the α-hydroxyphosphine oxide compound is further oxidatively dehydrogenated.

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .   The method for producing a phosphine oxide compound according to claim 8, wherein the oxidative dehydrogenation is oxidative dehydrogenation by reacting with a peroxide.   The method for producing a phosphine oxide compound according to claim 9, wherein the peroxide is hydrogen peroxide or an organic hydroperoxide.   The method for producing a phosphine oxide compound according to any one of claims 8 to 10, wherein the oxidative dehydrogenation is oxidative dehydrogenation performed in the presence of a catalyst.   The method for producing a phosphine oxide compound according to claim 11, wherein the catalyst is a ruthenium catalyst. General formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. . General formula (7)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine oxide Compound. General formula (2)

Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X and M are as defined above, and a general formula (5)

(Wherein R ¹ has the same meaning as described above), which is reacted with an aldehyde represented by the general formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. Manufacturing method. General formula (6)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively. General formula (7), characterized in that

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine oxide Compound production method.   The method for producing an α-hydroxyphosphine oxide compound according to claim 16, wherein the oxidation is an oxidation by reacting with a gas containing oxygen. General formula (4)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above, respectively). General formula (1) characterized by

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), . General formula (7)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above) α-hydroxyphosphine oxide General formula (1) characterized by oxidative dehydrogenation of a compound

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are as defined above), .   The photoinitiator containing the phosphine oxide compound in any one of Claims 1-3.   The photopolymerizable composition containing the phosphine oxide compound and unsaturated compound in any one of Claims 1-3.   A cured product obtained by curing the photopolymerizable composition according to claim 21.   The coating material containing the phosphine oxide compound and unsaturated compound in any one of Claims 1-3.   The film obtained by hardening an unsaturated compound by light irradiation in presence of the phosphine oxide compound in any one of Claims 1-3. The plastic obtained by hardening an unsaturated compound by light irradiation in presence of the phosphine oxide compound in any one of Claims 1-3.