JP2021128259A - Photosensitive composition - Google Patents

Abstract

To provide a photosensitive composition which contains a high concentration of a filler with a high light blocking effect like a dental material while having excellent curability for a light source in the visible light region, and which has an excellent color tone of a cured product.SOLUTION: A photosensitive composition contains, as essential components, (A) a diaryliodonium salt represented by general formula (1), (Ar1)2I+ [ (R1)(R2)(R3)(R4)Ga]-, (B) a sensitizer, (C) a radical-polymerizable compound, and (D) a filler.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive composition that is exposed to light in the visible region and cured. More specifically, it is a photosensitive composition that is cured by irradiating it with visible light, and is used, for example, for coating agents, paints, lithographic printing plates, dental materials (dental formulations, dental composites), and the like. Further, the present invention relates to a product or member (for example, an electronic component, an optical product, a material for forming an optical component, a layer forming material or an adhesive) formed through patterning utilizing the difference in solubility of an exposed portion and an unexposed portion in a developing solution. The present invention relates to a photosensitive composition suitably used for producing (agents, etc.).

The range of application of UV curing technology, which cures a liquid substance by irradiation with ultraviolet rays (UV), is expanding from the viewpoint of workability (fast curing) and low VOC, such as coating agents, paints, and printing inks.
Generally, the photosensitive composition comprises a photopolymerization initiator and a sensitizer, a radical (or cationic) polymerizable monomer, an oligomer or a polymer, and a colorant and an additive depending on the application. Colorants are roughly divided into pigments and dyes, and are blended to color the coating film, but they not only block light, but also have light absorption characteristics according to the color and part of the light to be irradiated. Since it is absorbed, the light may not reach the deep part of the applied coating film in the photosensitive composition containing the colorant. On the other hand, it has been proposed to use a specific photopolymerization initiator (see, for example, Patent Document 1).

Further, in the restoration of teeth damaged by caries, breakage, etc. in dental materials, a photocurable filling restoration material called a composite resin is widely used. This is because it has advantages such as simple operation and high aesthetics. Such composite resins usually consist of a photosensitive composition comprising a photopolymerizable monomer, particularly a (meth) acrylate-based monomer, a filler (inorganic filler or the like), a photopolymerization initiator and a sensitizer.

In this application, since the composition contains a large amount of a filler, it is difficult for ultraviolet rays (UV) to reach deep parts, and from the viewpoint of safety, a light source in the visible light region (for example, a halogen lamp) is used. A system in which a sensitizer, an iodonium salt, and an amine compound are used in combination as an initiator for exposing to ultraviolet light is known (Patent Document 2). However, conventionally known systems are not sufficiently satisfied with the deterioration of aesthetics due to coloring or discoloration of the cured product, and more recently, LED light sources (for example, 450 nm) have been used, and high sensitivity corresponding to these has been used. Development of initiators is required.

Japanese Unexamined Patent Publication No. 2009-19142 Japanese Patent No. 27444789

The problem to be solved by the present invention is a photosensitive composition that contains a high-concentration filler having a high light-shielding property such as a dental material and is excellent in curability with respect to a light source in the visible light region, and is a cured product. It is an object of the present invention to provide a photosensitive composition having an excellent hue.

As a result of diligent research to solve the above problems, the present inventors have found a photosensitive composition having excellent sensitivity to a light source in the visible light region.
That is, the present invention
(A) A photosensitive composition comprising a diallyl iodonium salt (B) sensitizer (C) radically polymerizable compound (D) filler represented by the general formula (1) as an essential component. be.
(Ar ¹ ) ₂ I ⁺ [(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ (1)
[In the formula, R ^{1 to} R ⁴ are alkyl groups or Ar having 1 to 18 carbon atoms independently of each other, except that at least one is Ar, and Ar has 6 to 14 carbon atoms (hereinafter). (Does not include the carbon number of the substituent), and some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, and alkyl groups having 1 to 8 carbon atoms substituted by halogen atoms. , an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or aryloxy group represented by -OR ^6, An acyl group represented by R ⁷ CO-, an acyloxy group represented by ^{R 8} COO-, an alkyl thio group or an aryl thio group represented by ^{-SR 9 , an amino group represented by -NR 10} R ¹¹ , or a halogen atom. R ^{6 to} R ⁹ may be an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ^{10 and R 11} may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. an aryl group having 6 to 14 carbon atoms; Ar ¹ has the same definition as Ar, 2 two Ar ¹ on iodonium cation may be the same or different. ]

Further, the present invention is a curing method comprising a step of irradiating the above-mentioned photosensitive composition with light in a visible light region having a wavelength of 400 nm to 600 nm.

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

The photosensitive composition of the present invention can be efficiently generated radicals and cured by being exposed to light in the visible light region having a wavelength of 400 nm to 600 nm. Further, even a composition containing an additive and a colorant that shields light can efficiently produce a cured product, and can suppress coloring of the cured product, for example, to improve aesthetics in a dental material. ..

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

The photosensitive composition of the present invention is characterized by containing a diaryliodonium salt (A) represented by the general formula (1).
(Ar ¹ ) ₂ I ⁺ [(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ (1)

In the formula, R ^{1 to} R ⁴ are alkyl groups or Ar having 1 to 18 carbon atoms independently of each other, except that at least one is Ar, and Ar has 6 to 14 carbon atoms (hereinafter, the following). It is an aryl group of (not including the carbon number of the substituent), and a part of the hydrogen atom in the aryl group is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted by a halogen atom, and the like. alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or aryloxy group represented by -OR ^6, R ⁷ An acyl group represented by CO-, an asyloxy group represented by ^{R 8} COO-, an alkyl thio group or an aryl thio group represented by ^{-SR 9 , an amino group represented by -NR 10} R ¹¹ , or a halogen atom. It may be substituted, R ^{6 to} R ⁹ are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 14 carbon atoms, R ¹⁰ and R ¹¹ are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or carbons. is a number 6 to 14 aryl group; Ar ¹ has the same definition as Ar, 2 two Ar ¹ on iodonium cation may be the same or different.

In the general formula (1), ^{the alkyl groups having 1 to 18 carbon atoms in R 1 to} R ⁴ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, etc. n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2- Ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and crosslinked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.) can be mentioned.

In the general formula ^(1), in R 1 to R ^4, Ar i.e., the aryl group having 6 to 14 carbon atoms (hereinafter the carbon number of the substituent is not included), a monocyclic aryl group (such as phenyl), Condensed polycyclic aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and aromatic heterocyclic hydrocarbon groups (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, etc.) Heterocycles; and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantrenyl, phenoxadinyl, phenoxatinyl, chromanyl, Isochromanyl, coumarinyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl and other fused polycyclic heterocycles) can be mentioned.
In addition to the above, the aryl group includes an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and a halogen atom. Substituted alkyl group with 1 to 8 carbon atoms, aryl group with 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, alkoxy group or aryloxy group represented by ^{−OR 6 , represented by R 7} CO−. It may be substituted with an acyl group, an acyloxy group represented by ^{R 8} COO −, an alkyl thio group represented by ^{−SR 9 or an aryl thio group, an amino group represented by −NR 10} R ¹¹ , or a halogen atom.

In the above substituent, the alkenyl group having 2 to 18 carbon atoms includes a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-octenyl, 1-. Decenyl, 1-octadecenyl, 1-1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2- Cyclohexenyl and 3-cyclohexenyl, etc.) and arylalkenyl groups (styryl, cinnamyl, etc.).

In the above substituent, the alkynyl group having 2 to 18 carbon atoms includes a linear or branched alkynyl group (ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-. 2-propynyl, 1,1-dimethyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 3-methyl-1-butynyl, 1-decynyl , 2-Decinyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl and 10-dodecynyl, etc.) and arylalkynyl groups (phenylethynyl, etc.).

In the above substituent, the alkyl group having 1 to 8 carbon atoms substituted with a halogen atom includes a linear alkyl group (trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trichloroethyl, 2,2). 2-Trifluoroethyl, 1,1-difluoroethyl, heptafluoro-n-propyl, 1,1-difluoro-n-propyl, 3,3,3-trifluoro-n-propyl, nonafluoro-n-butyl, 3 , 3,4,5,4-Pentafluoro-n-butyl, perfluoro-n-pentyl, perfluoro-n-octyl, etc.), branched alkyl groups (hexafluoroisopropyl, hexachloroisopropyl, hexafluoroisobutyl, nonafluoro- tert-butyl, etc.), cycloalkyl groups (pentafluorocyclopropyl, nonafluorocyclobutyl, perfluorocyclopentyl, perfluorocyclohexyl, etc.) and crosslinked cyclic alkyl groups (perfluoroadamantyl, etc.).

Among the above-mentioned substituents, an alkoxy group represented by ^{−OR 6;} an acyl group represented by ^{R 7} CO −, an acyloxy group represented by ^{R 8} COO −, an alkyl thio group represented by ^{−SR 9 , and −NR 10} the amino group represented by R ^11, include alkyl groups having 1 to 8 carbon atoms as R ⁶ to R ^11, include alkyl groups having 1 to 8 carbon atoms among the alkyl groups mentioned specifically ..

Among the above-mentioned substituents, an aryloxy group represented by ^{-OR 6} , an acyl group represented by ^{R 7} CO-, an acyloxy group represented by ^{R 8} COO-, an aryl thio group represented by ^{-SR 9, and -NR 10} of the amino group represented by R ^11, examples of R 6 ^{to R 11} include an aryl group having 6 to 14 carbon atoms, particularly an aryl group having 6 to 14 carbon atoms described above.

Examples ^{of the alkoxy group represented by −OR 6} include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and n−. Examples thereof include hexyloxy, n-octyloxy, n-decyloxy, n-dodecyloxy, n-octadecyloxy and 2-methylbutoxy.
Examples of the aryloxy group represented by −OR ^{6 include phenoxy and naphthoxy.}
Examples of the acyl group represented by R ⁷ CO- include acetyl, propanoyl, butanoyl, pivaloyl, benzoyl and the like.
Examples of the asyloxy group represented by R ⁸ COO- include acetoxy, butanoyloxy and benzoyloxy.
Examples ^{of the alkylthio group represented by −SR 9} include methylthio, ethylthio, butylthio, hexylthio, 2-ethylhexylthio, cyclohexylthio and the like.
Examples ^{of the arylthio group represented by −SR 9} include phenylthio, naphthylthio and the like.
Examples of the ^{amino group represented by −NR 10} R ¹¹ include methylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino, phenylmethylamino, diphenylamino and piperidino. Can be mentioned.
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 thermal stability, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, a halogen atom, a nitro group, or a cyano group is preferable, and an alkyl group having 1 to 8 carbon atoms substituted with a fluorine atom is preferable. And a fluorine atom are more preferred.

^{It is preferable that R 1} , R ² , R ³ , and R ⁴ , which are the anion moieties of the salt represented by the general formula (1), are a perfluoroalkyl group or a phenyl group substituted with a fluorine atom, and a pentafluorophenyl group. Alternatively, it is more preferably a bis (trifluoromethyl) phenyl group.
Particularly preferably, the onium gallate salt represented by the general formula (1) has a gallate anion represented by ^{[(R 1} ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ _{[Ga (C 6} F). _{5) 4]} ^- _{or, [Ga ((CF 3)} 2 C 6 H 3) 4] - is.

As the anion structure of the salt represented by the general formula (1), for example, those represented by the following chemical formulas (A-1) to (A-5) can be preferably exemplified.

^{Ar 1} in the formula (1) represents two substituents bonded to the iodonium cation, which may be the same or different, and is the same as Ar defined by ^{R 1 to} R ^{4 in the formula (1).} Is. That ^{is, examples of Ar 1} include an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms and an alkynyl group having 2 to 18 carbon atoms, and the aryl group is further carbon. the number 1 to 18 alkyl group, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, represented by -OR ⁶ An alkoxy group or an aryloxy group, an acyl group represented by ^{R 7} CO-, an acyloxy group represented by ^{R 8} COO-, an alkyl thio group or an aryl thio group represented by ^{-SR 9 , and -NR 10} R ^11. It may be substituted with an amino group or a halogen atom.

Examples of the aryl group having 6 to 14 carbon atoms, the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms and the alkynyl group having 2 to 18 carbon atoms in the organic group include R in the general formula (1). It may be the same as those described in ¹ to R ^4.

Specific examples of preferable iodonium cations include diphenyl iodonium, di-p-tril iodonium and 4-isopropylphenyl (p-tryl) iodonium, as well as di- (4-tert-butylphenyl) iodonium and di- (4-tert). -Pentylphenyl) Iodonium, 4-octyloxyphenylphenyliodonium, di-4-isopropylphenyliodonium, 4-isobutylphenyl (p-tolyl) iodonium, bis (2,4-diisopropylphenyl) iodonium, 4-hexylphenyl (p) -Trill) iodonium, 4-cyclohexylphenyl (p-tryl) iodonium, bis (4-dodecylphenyl) iodonium, 4-octyloxyphenyl (2,4,6-trimethoxyphenyl) iodonium, bis (4-octadecylphenyl) Examples thereof include iodonium, bis (4-methoxyphenyl) iodonium, bis (4-decyloxyphenyl) iodonium, and 4- (2-hydroxytetradecyloxyphenyl) phenyl iodonium.

Specific examples of the preferred diallyl iodonium salt (A) include the following.

These diallyl iodonium salts (A) may be used alone or in combination of two or more. The content of the diallyl iodonium salt (A) is usually 0.005 to 20% by weight, preferably 0.01 to 10% by weight, based on the weight of the radically polymerizable compound (C) described later.

The photosensitive composition of the present invention contains a sensitizer (B) that absorbs light having a wavelength in the visible light region (400 nm to 600 nm) and causes decomposition of the diaryliodonium salt (A) by energy or electron transfer. Known compounds are used.

Specific examples of the sensitizer (B) include ketone compounds {2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4- Bencoyl-4'-methyldiphenylsulfide, 3,3'-carbonylbis (7-diethylaminocoumarin), bis (4,4'-dimethylamino) benzophenone and bis (4,4'-diethylamino) benzophenone, etc.}; Diketone compounds {Camferquinone, 9,10-phenanthracenequinone, 4,4'-dimethoxybenzyl, 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone, 2-methylanthracene, 2- Ethylanthracene, acenaphthenequinone, etc.}; Thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; , N-ethylphenothiazine, N-phenylphenothiazine, etc.}; Xantone; anthracene {7- (diethylamino) 4- (trifluoromethyl) anthracene, 3- (2-benzothiazolyl) -7- (diethylamino) cmarin, etc.}; carbazole { N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; Anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, etc. , 2-Ethryl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.} and the like.
In particular, from the viewpoint of electron acceptability, it is preferable to use a sensitizer of a ketone compound or a diketone compound because a high sensitizing effect can be obtained.

These sensitizers (B) may be used alone or in combination of two or more. The content of the sensitizer (B) is usually 0.005 to 20 weight based on the total weight of the sensitizer (B), the diallyl iodonium salt (A) and the radically polymerizable compound (C) described later. %, Preferably 0.01 to 10% by weight.

As the radically polymerizable compound (C) contained in the photosensitive composition of the present invention, any known radical-polymerizable compound can be used without particular limitation.
For example, (meth) acrylate compound (C11), acrylamide compound (C12), and other radically polymerizable compounds (C13) can be mentioned.
In the above and below, when referring to both or either of "acrylate" and "methacrylate", "(meth) acrylate" and when referring to both or either of "acrylic" and "methacryl", "(meth) acrylic". ", Each may be described.

Examples of the (meth) acrylate compound (C11) include the following monofunctional to hexafunctional (meth) acrylates.
Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate. ) Acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (Meta) acrylate, alkoxymethyl (meth) acrylate, alkoxyethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, phenoxymethyl (Meta) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, diethylene glycol monovinyl ether monoacrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, Polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinate Acid, 2-methacrylooxyhexahydrophthalic acid, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified -2-ethylhexyl (meth) acrylate, etc. Can be mentioned.

Examples of the bifunctional (meth) acrylate include 1,4-butanedi (meth) acrylate, 1,6-hexanediacrylate, polypropylene diacrylate, 1,6-hexanediol di (meth) acrylate, and 1,10-decanediol di. (Meta) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethyl propanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, bisphenol A diglycidyl di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate of hydroxypivalate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4 -Butandiol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, urethane (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate and tricyclodecandi (meth) Examples include acrylate.

Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, and diethylolpropane. Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meth) ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin triacrylate and the like.

The tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and pentaerythritol tetraacrylate ethoxylated. Examples include (meth) acrylate.

Examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Be done.

Examples of the (meth) acrylamide compound (C12) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylic ad, N-propyl (meth) acrylamide, and N-n-butyl (meth). ) Acrylamide, N-tert-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, Examples include N-diethyl (meth) acrylamide and (meth) acryloylmorpholin.

Other radically polymerizable compounds (C13) include aromatic vinyl compounds (styrene, methylstyrene, etc.), vinyl ether compounds (butyl vinyl ether, phenoxyvinyl ether, etc.), acryloylnitrile, vinyl ester compounds (vinyl acetate, vinyl propionate, and versatic acid). Vinyl, etc.), maleimide compounds (1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylene bismaleimide, etc.), allyl ester compounds (allyl acetate, etc.), halogen-containing monomers (vinylidene chloride and Radical polymerizable compounds with phosphoric acid (2-) such as vinyl chloride), radically polymerizable compounds with carboxylic acids ((meth) acryloyl, N- (meth) acryloyl glycine, N- (meth) acryloyl aspartic acid). (Meta) Acryloyl Oxyethyl Dihydrogen Phosphate, Bis (2- (Meta) Acryloyl Oxyethyl) Hydrogen Phosphate, 2- (Meta) Acryloyl Oxyethylphenyl Hydrogen Phosphate, 10- (Meta) Acryloyl Oxydecyl In addition to dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate) and the like, and olefin compounds (ethylene, propylene, etc.), oligomers having a plurality of (meth) acrylate groups are also included. Examples of the polyfunctional (meth) acrylate oligomer include oligomers such as epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polysiloxane (meth) acrylate oligomer, and polyester (meth) acrylate oligomer. Can be mentioned.

Of these, (meth) acrylate compound (C11) and acrylamide compound (C12) are preferable from the viewpoint of curing rate. These radically polymerizable compounds (C) may be used alone or in combination of two or more.

As the filler (D) contained in the photosensitive composition of the present invention, a known filler that can be used for a general dental composite resin is used without particular limitation. Such fillers are usually roughly classified into organic fillers and inorganic fillers.

Specific examples of typical organic fillers that can be suitably used for the photosensitive composition of the present invention include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, crosslinked polymethylmethacrylate, and crosslinked type. Examples thereof include polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, etc., and these are used as one or a mixture of two or more kinds. be able to.

Specific examples of typical inorganic fillers that can be suitably used for the photosensitive composition of the present invention include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass, and various cations. Elution filler and the like can be mentioned. Examples of this cation-eluting filler include hydroxides such as calcium hydroxide and strontium hydroxide, and oxides such as zinc oxide, silicate glass, and fluoroaluminosilicate glass. These inorganic fillers may also be used alone or in admixture of two or more.

Further, a granular organic-inorganic composite filler obtained by mixing these inorganic fillers and a polymerizable monomer in advance to form a paste, polymerizing the mixture, and pulverizing the mixture may be used. Further, the above-mentioned organic filler, inorganic filler and organic-inorganic composite filler can be appropriately combined and used.

The particle size and shape of these fillers are not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm, which are generally used as dental materials, can be appropriately used depending on the purpose. Further, the refractive index of the filler is not particularly limited, and those in the range of 1.4 to 1.7 of general dental fillers can be used without limitation.

The blending ratio of these fillers may be appropriately determined depending on the purpose of use, taking into consideration the viscosity (operability) when mixed with the polymerizable monomer, the mechanical properties of the cured product, and the like, but in general, Is used in the range of 50 to 1500 parts by weight, preferably 70 to 1000 parts by weight with respect to 100 parts by weight of the radically polymerizable compound (C).

The photosensitive composition of the present invention may further contain the tertiary amine compound (E) for the purpose of promoting the polymerization reaction. It is known that this tertiary amine compound (E) acts as an electron donor and efficiently promotes the reaction by interacting with a sensitizer (B) or the like (Patent Document 2).

Examples of the tertiary amine compound (E) that can be suitably used in the present invention include ethyl 4-dimethylaminobenzoate, propyl 4-dimethylbenzoate, amyl 4-diethylbenzoate, N, N-dimethylaniline, N, N. Examples thereof include -diethylaniline, 3,5,N, N-tetramethylaniline, N-phenylglycine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylaminoethyl (meth) acrylate and the like.

These tertiary amine compounds (E) may be used alone or in combination of two or more. The content of the tertiary amine compound (E) is usually 0.005 to 10% by weight, preferably 0.01 to 5% by weight, based on the weight of the radically polymerizable compound (C).

The photosensitive composition of the present invention may contain a cationically polymerizable compound depending on the intended use in order to control the appearance and physical properties of the cured product. In this case, the acid generated by decomposing the diallyl iodonium salt (A) contained in the present invention by light irradiation causes cationic polymerization.

As the cationically polymerizable compound, known compounds can be used, and examples thereof include vinyl ether compounds, epoxy compounds, oxetane compounds, aziridine compounds, episulfide compounds, cyclic acetal compounds, cyclic carbonate compounds, and spirothoester compounds. In particular, when a dental material is taken into consideration, an epoxy compound and an oxetane compound are preferably used in that the volume shrinkage is small and the polymerization reaction is fast. Specific compounds are described, for example, in Japanese Patent No. 4344026.

In order to control the appearance and physical properties of the cured product, the photosensitive composition of the present invention contains colorants (pigments and dyes such as inorganic pigments and organic pigments used in paints and inks) according to the purpose of use. Metal oxide particles, metal powder, solvent, adhesion imparting agent, dispersant, defoaming agent, leveling agent, thixotropy imparting agent, slip agent, flame retardant, antistatic agent, antioxidant, ultraviolet absorber and polymerization prohibited It can contain agents and the like.

The method for producing the photosensitive composition of the present invention is not particularly limited, and a known method as a method for producing a photopolymerizable curable composition may be appropriately adopted. Specifically, the components constituting the photosensitive composition of the present invention may be weighed and mixed in a predetermined amount. At this time, it is preferable to carry out the composition under light-shielding conditions so that the composition does not cure.

The photosensitive composition of the present invention is a light source capable of irradiating an energy ray in the visible light region using an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, a xenon lamp or an LED light source. Can be used. Further, depending on the application, in addition to the generally used high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, and the like can also be used because energy rays are generated at 400 nm or more.

The photosensitive composition of the present invention can generate a radical by irradiating it with light to accelerate the curing reaction and obtain a cured product. Therefore, as a method for producing such a cured product, is it possible to select a sensitizer (B) according to the wavelength of light as a light source and irradiate the light with the one contained in the photosensitive composition? It is preferable to include a step of irradiating light with a light source corresponding to the absorption wavelength of the sensitizer (B) used. In the curing reaction, it is preferable to adjust the blending ratio so that the irradiation time is about 5 to 60 seconds, although it depends on the usage conditions.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not intended to be limited thereto. Unless otherwise specified,% means% by weight.

Production Example 1 Synthesis of Lithium Tetrakis (3,4,5-Trifluorophenyl) Galate (A-1) 360 parts of super-dehydrated diethyl ether and 3,4,5 in a 125 mL four-necked flask sufficiently dried under a nitrogen atmosphere. Twenty-six parts of −trifluoro-1-bromobenzene was charged and cooled to −78 ° C. using a dry ice / acetone bath. 70 parts of a 2.5 mol / L n-butyllithium hexane solution was added dropwise over 10 minutes, and then the mixture was stirred at −78 ° C. for 30 minutes. To this, 68 parts of a diethyl ether solution in which 5 parts of gallium (III) chloride was dissolved was added dropwise over 10 minutes, and the mixture was stirred at −78 ° C. for 3 hours. The reaction mixture was stirred while gradually returning to room temperature, and after returning to room temperature, the mixture was further stirred for 5 hours. The precipitated solid was filtered, the reaction solution was transferred to an evaporator, and the solvent was distilled off to obtain a grayish white product. The product was washed 4 times with 50 parts of ultra-dehydrated hexane and then vacuum dried overnight to give lithium tetrakis (3,4,5-trifluorophenyl) gallate (A-1). The product was ^{identified by 19} F-NMR.

Production Example 2 Lithium tetrakis (2,4-bis (trifluoromethyl) phenyl) gallate (A-2)
In Production Example 1, the same operation as in Production Example 1 was performed except that 26 parts of 3,4,5-trifluoro-1-bromobenzene was changed to 36 parts of 2,4-bis (trifluoromethyl) -1-bromobenzene. This was carried out to obtain lithium tetrakis (2,4-bis (trifluoromethyl) phenyl) gallate (A-2).

Production Example 3 Synthesis of Lithium Tetrakis (Pentafluorophenyl) Galate (A-3) In Production Example 1, 26 parts of to 3,4,5-trifluoro-1-bromobenzene is used as 30 parts of pentafluorobromobenzene. The same operation as in Production Example 1 was carried out to obtain lithium tetrakis (pentafluorophenyl) gallate (A-3).

Production Example 4 Synthesis of iodonium salt (IS-1) 5.4 parts of di (tert-butylphenyl) iodonium hexafluorophosphate (manufactured by Tokyo Kasei) and 30 parts of dichloromethane were added to the reaction vessel. While stirring, 9.3 parts of the lithium salt (A-2) synthesized in Production Example 2 and 50 parts of water were added, and the mixture was stirred at room temperature for 18 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was further washed with 50 parts of water 5 times. The organic solvent was distilled off under reduced pressure to obtain 12.5 parts of a white solid. The ^{1 H, 19 F,} this compound was confirmed to be the iodonium salt (IS-1).

Production Example 5 Synthesis of Iodonium Salt (IS-2) Described in Production Example 4 except that in Production Example 4, 6.0 g of lithium salt (A-1) is used instead of 9.3 g of lithium salt (A-2). According to the method, 8.0 g of the target product was obtained. ^{1 H, 19} F from the white solid was confirmed to be the iodonium salt (IS-2).

Production Example 6 Synthesis of Iodonium Salt (IS-3) In Production Example 4, the description is described in Production Example 4 except that 7.5 g of lithium salt (A-3) is used instead of 9.3 g of lithium salt (A-2). According to the method, 10.3 g of the target product was obtained. ^{1 H, 19} F from the white solid was confirmed to be the iodonium salt (IS-3).

Production Example 7 Synthesis of iodonium salt (IS-4) 2 parts of 4-methyliodobenzene is added to a reaction vessel, and 5 mL of acetic acid and 1 mL of sulfuric acid are further added to dissolve the mixture. 1 g of potassium was added little by little. The reaction was carried out at 20 ° C. for 4 hours, and 2.4 parts of cumene was added dropwise thereto so as not to exceed 20 ° C. Then, it was reacted at room temperature for 20 hours. The reaction mixture was added to a solution prepared by dissolving 7.5 g of lithium salt (A-3) in 50 mL of water, and the mixture was further stirred for 3 hours. 50 mL of dichloromethane was added thereto. After standing, the aqueous layer was removed by liquid separation, and the organic layer was washed 5 times with 50 mL of water. Dichloromethane was concentrated and recrystallized from cyclohexane to obtain 7.8 parts of a white solid. The ^{1 H,} 19 ^F-NMR, this product was confirmed to be an iodonium salt (IS-4).

Production Example 8 Synthesis of Iodonium Salt (IS-5) In Production Example 7, 7.5 parts of lithium salt (A-3) is replaced with 9.3 parts of lithium salt (A-2). The desired product was obtained according to the method described. The ^{1 H,} 19 ^F-NMR, it was confirmed that the iodonium salt (IS-5).

Production Example 9 Synthesis of iodonium salt (IS-6) In Production Example 7, except that 2 parts of 4-methyliodobenzene is 1.9 parts of iodobenzene and 2.4 parts of cumene is 4.2 parts of n-octyloxybenzene. Obtained the desired product according to the method described in Production Example 7. The ^{1 H,} 19 ^F-NMR, it was confirmed that the iodonium salt (IS-6).

<Examples 1 to 14 and Comparative Examples 1 to 10>
[Preparation of photosensitive composition]
100 g of radically polymerizable compound (C) (blending ratio and amount are shown in Table 1), 1 g of diallyl iodonium salt (A), 0.2 g of sensitizer (B) and, if necessary, tertiary amine compound (E). 0.2 g was uniformly mixed to prepare a photosensitive composition of the present invention and a comparative photosensitive resin composition. The types of raw materials used are shown in Table 1. This photosensitive composition was poured into a mold made of polytetrafluoroethylene having an inner diameter of 10 mm, a wall thickness of 5 mm, and a height of 10 mm with a glass plate pressed against it, and an irradiation device LIGHTNINGCURE spot light source LC8 ( Exposure was performed using Hamamatsu Photonics Co., Ltd.). The exposure was performed through a sharp cut filter (manufactured by HOYA) Y44 (cut of 430 nm or less). The curability and appearance of the cured product were confirmed by the following evaluation methods. The results are shown in Table 1.
[Raw materials used]
IS-1 to IS-6 (iodonium salt described above)
IS'-1: Diphenyliodonium hexafluorophosphate IS'-2: 4-isopropylphenyl (p-tolyl) Iodonium tetrakis (pentafluorophenyl) borate B-1: camphorquinone B-2: 3,3'-carbonylbis ( 7-diethylaminocoumarin)
C-1: Dipentaerythritol Pentaacrylate C-2: Triethylene glycol dimethacrylate C-3: Bisphenol A diglycidyl ether Dimethacrylate E-1: 4-Dimethylaminoethyl benzoate
[Curability evaluation]
Curability: The cured product was taken out from the mold, the degree of surface hardening of the cured product was confirmed by touch, and the thickness of the sufficiently cured product was measured.
◎ There is no tack on the surface, it will not be scratched even if it is scratched with a nail, and the thickness of the cured product is 5 mm or more.
〇 There is no tack on the surface, it will not be scratched even if it is scratched with a nail, and the thickness of the cured product is less than 5 mm.
△ Tack remains on the surface.
× It does not cure in liquid form.
Appearance of cured product: The transparent appearance of the cured product was evaluated as ◯, the yellowish one was evaluated as Δ, and the yellow to brown one was evaluated as ×.

From the results in Table 1, the photosensitive composition of the present invention can be efficiently cured by irradiation with light in the visible light region, and the yellowing of the cured product is suppressed as compared with the comparative photosensitive composition. I understand.

<Example 15 and Comparative Example 11>
A filler-containing photosensitive composition further containing 7 parts of the filler (D) was prepared with respect to 3 parts of the photosensitive composition blended in Example 13 and Comparative Example 9, and the same curability test as described above was performed. As a result, good cured products were obtained in both cases, but white cured products were obtained in the examples, whereas slightly yellow cured products were obtained in the comparative examples. From this, since the photosensitive composition of the present invention can suppress the coloring of the cured product, it can be suitably used for dental materials whose aesthetics are an issue.

The photosensitive composition of the present invention utilizes light (particularly in the visible region to the infrared region) to provide dental materials (dental formulations, dental composites), paints, coating agents, and various coating materials (hard coats, etc.). Anti-staining coating material, anti-fog coating material, anti-contact coating material, optical fiber, etc.), back treatment agent for adhesive tape, release coating material for adhesive label release sheet (release paper, release plastic film, release metal foil, etc.), printing Plates, inks, inkjet inks, positive resists (connection terminals for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, wiring pattern formation, etc.), resist films, liquid resists, negative resists (transparent electrodes for semiconductor elements and FPDs) Surface protective films such as (ITO, IZO, GZO), interlayer insulating films, permanent film materials such as flattening films, etc.), resists for MEMS, positive photosensitive materials, negative photosensitive materials, various adhesives (various electrons) Temporary fixing agent for parts, adhesive for HDD, adhesive for pickup lens, adhesive for functional film (deflector, antireflection film, etc.) for FPD, insulating film for circuit formation and semiconductor encapsulation, heteroconductive Adhesive (ACA), film (ACF), paste (ACP), etc.), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, rib, alignment film for liquid crystal, sealant for FPD, etc.) , Optical members, molding materials (for building materials, optical parts, lenses), casting materials, putties, glass fiber impregnants, sealants, sealants, flip chips, chip encapsulants such as COF, CSP or BGA, etc. It is suitably used for packaging encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, optical molding materials, micro optical molding materials and the like.

Claims (5)

(A) A photosensitive composition comprising a diallyl iodonium salt (B) sensitizer (C) radically polymerizable compound (D) filler represented by the general formula (1) as an essential component.
(Ar ¹ ) ₂ I ⁺ [(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ (1)
[In the formula, R ^{1 to} R ⁴ are alkyl groups or Ar having 1 to 18 carbon atoms independently of each other, except that at least one is Ar, and Ar has 6 to 14 carbon atoms (hereinafter). (Does not include the carbon number of the substituent), and some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, and alkyl groups having 1 to 8 carbon atoms substituted by halogen atoms. , an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or aryloxy group represented by -OR ^6, An acyl group represented by R ⁷ CO-, an acyloxy group represented by ^{R 8} COO-, an alkyl thio group or an aryl thio group represented by ^{-SR 9 , an amino group represented by -NR 10} R ¹¹ , or a halogen atom. R ^{6 to} R ⁹ may be an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ^{10 and R 11} may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. an aryl group having 6 to 14 carbon atoms; Ar ¹ has the same definition as Ar, 2 two Ar ¹ on iodonium cation may be the same or different. ] The photosensitive composition according to claim 1, further comprising (E) a tertiary amine compound. A method for curing a photosensitive composition, which comprises a step of irradiating the photosensitive composition according to claim 1 or 2 with light in a visible light region of 400 to 600 nm. A cured product obtained by curing the photosensitive composition by the method according to claim 3. A dental material obtained by curing a photosensitive composition by the method according to claim 3.