JPH0662688B2 - Photocurable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in photocurability in a low temperature region near room temperature and under wet conditions, and has an adhesive performance such as a water resistant adhesive strength of a cured product.
The present invention relates to a photocurable composition excellent in color tone and the like. More specifically, tooth composite resin, tooth hard resin,
The present invention relates to a photocurable composition capable of exhibiting excellent performance as a photocurable composition for teeth such as a floor resin, and particularly excellent as an adhesive for these applications.

[Conventional technology]

BACKGROUND ART Conventionally, a curable composition for teeth such as an adhesive for teeth, a composite resin and a hard resin is a curable composition comprising a radical polymerizable monomer such as a (meth) acrylate vinyl monomer and a curing agent. Many things have been proposed.

The properties required for a tooth adhesive are that the curing rate is high in a low temperature region near room temperature, and that the cured product has excellent adhesive strength to teeth and metals and excellent water-resistant adhesive strength. Further, for the tooth composite resin and the hard tooth resin, it is required that the curing performance of the composition in the low temperature region near room temperature and the adhesive performance of the cured product to the teeth and the metal are excellent as described above. There is. With the recent remarkable progress in dental restorative treatment technology, the demand for the above-mentioned performance improvement of these tooth-curable compositions has been remarkably increased.

Among the curable compositions for teeth, which are composed of a radical polymerizable monomer such as a conventional (meth) acrylic acid vinyl monomer and a polymerization initiator, a photopolymerization initiator is used as a polymerization initiator and photocured. There are some proposals that attempt to achieve the above-mentioned performance improvement by adopting the method. For example, JP-B-54-10986 and JP-B-53-33687 propose a method of performing polymerization in the presence of a photopolymerization initiator composed of a carbonyl compound such as α-diketone and an amine. . However,
As a photopolymerization initiator, a photopolymerization initiator composed of a combination of a carbonyl compound and amines proposed in these prior art documents is used, and a (meth) acrylic acid ester-based radically polymerizable monomer is photocured. However, even if it is attempted to use the above photocurable composition for teeth, it has a drawback that the cured product is inferior in color tone and inferior in water-resistant adhesive strength, and it is not possible to exhibit sufficient performance. In addition, JP-A-56-120
Japanese Patent No. 610 proposes a photopolymerizable dental material composed of a vinyl monomer having an acidic group in the molecule, an α-diketone, and an aromatic sulfinate. However, although these photocurable compositions have excellent color tones, they all have the drawbacks of insufficient curing speed and low water-resistant adhesive strength, and are said to sufficiently satisfy the aforementioned performance. It was difficult.

[Problems to be solved by the invention]

The present inventors have considered that the conventional photocurable composition for teeth and the performance requirements for the composition are in the above-mentioned situations, and therefore, the photocurability of the composition, the adhesive performance of the cured product, and particularly the water resistance. As a result of diligent study of a photocurable composition having excellent adhesive strength, mechanical properties, water absorption resistance and color tone,
It was found that the above object can be achieved by irradiating a photocurable composition comprising a radically polymerizable unsaturated monomer and an α-ketocarbonyl compound, an amine and an aromatic sulfinic acid or a salt thereof with light to cure the composition, and The invention was reached.

〔The invention's effect〕

According to the present invention, the composition has a high photocuring rate in a low temperature region near room temperature, especially under wet condition, and has excellent adhesive strength, water-resistant adhesive strength, water-absorption resistance and color tone, and an adhesive for teeth and composites. Since the photocurable composition for teeth, such as a resin, a hard resin, and a floor resin, sufficiently satisfies the performances required for the tooth, it is suitable for use in these teeth. In particular, when it is used for an application such as an adhesive for adhering a tooth and a photo-curable composite resin, a metal or a tooth and a hard photo-curable resin, these cured products simultaneously cure the composite resin and the hard resin. It adheres strongly to metal and is suitable for these applications. It can also be used for applications such as adhesives for precision machining other than teeth, metal plastics, adhesives for glass, and various composite resins.

[Means for Solving Problems] and [Action] According to the present invention, (a) a radically polymerizable unsaturated monomer, (b) an α-ketocarbonyl compound, (c) an amine, and (d) ) A photocurable composition comprising an aromatic sulfinic acid or a salt thereof is provided.

The radical-polymerizable monomer (a) blended in the photocurable composition of the present invention is an unsaturated compound having radical-polymerizability. Specifically, alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate. , Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxycyclohexyl] propane, 2,2-bis [3- (meth) acryloyloxy-2 -Hydroxyp Pokishifueniru]
Propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane, γ -Methacryloxypropyl pentamethyldisiloxane, isopropyldimethacrylisostearoyl titanate, styrene, α-methylstyrene, vinyltoluene, divinyltoluene, divinylbenzene,
A vinyl compound (a ₁ ) such as vinyl acetate can be exemplified, and a mixed component of two or more kinds of these can also be used.

Further, in the photocurable composition of the present invention, other components that can be used as the radically polymerizable unsaturated monomer (a) include alkane polyols or polyamines having at least two hydroxyl groups in one molecule. One carboxyl of an aromatic polycarboxylic acid in which at least one hydroxyl group of an oxyalkane polyol forms an ester of (meth) acrylic acid and at least one hydroxyl group has at least three carboxyl groups Examples thereof include a (meth) acryloyloxyl group-containing aromatic polycarboxylic acid having a structure of forming an ester with a group or an acid anhydride (a ₂ ) thereof.

Examples of the alkane polyol having at least two hydroxyl groups in one molecule constituting the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride (a ₂ ) include ethylene glycol and 1,2-propylene. Examples thereof include glycol, 1,3-propylene glycol, butylene glycol, hexylene glycol, trimethylolpropane, glycerin and pentaerythritol. Further, as the polyoxyalkane polyol having at least two hydroxyl groups in one molecule, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol, ditrimethylol propane, diglycerin, triglycerin, diglycerin In addition to pentaerythritol And the like.

Further, the (meth) acrylic acid component constituting the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid is acrylic acid or methacrylic acid, and aromatic polycarboxylic acid having at least 3 or more carboxyl groups. The component is preferably an aromatic polycarboxylic acid in which at least two carboxyl groups are bonded to adjacent carbon atoms on the aromatic nucleus, and specifically, hemimellitic acid, trimellitic acid, prenitic acid, merophanic acid,
Pyromellitic acid and the like can be exemplified.

Examples of the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid or acid anhydride thereof include 4- (meth) acryloyloxymethoxycarbonylphthalic acid or acid anhydride thereof, 4- (meth) acryloyloxyethoxycarbonylphthalic acid or The acid anhydride, 4- [2-hydroxy-3- (meth) acryloyloxypropoxycarbonyl] phthalic acid or the acid anhydride, 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate Or an acid anhydride thereof, 2- (3,4-dicarboxybenzoyloxy) 1,3-dimethacryloyloxypropane or an acid anhydride thereof, [In the formula, R represents a hydrogen atom or a methyl group. ] Or these acid anhydride etc. can be illustrated. Among these, 4- (meth) acryloyloxyethoxycarbonylphthalic acid or its acid anhydride is preferable, and particularly 4
-Methacryloyloxyethoxycarbonyl phthalic anhydride is preferred. In addition to the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride (a ₂ ), it can be used as a radically polymerizable unsaturated monomer (a) in the photocurable composition of the present invention. As a component that can be used, a phosphoric acid group-containing unsaturated monomer (a ₃ ) can be used. Examples of such a monomer include 2- (meth) acryloyloxyethylphenyl acid phosphate,
Bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [3- (meth) acryloxypropyl] acid phosphate, 2- (meth) acryloyloxyethylphenylphosphonate, And the like.

In the photocurable composition of the present invention, the vinyl compound (a ₁ ) is used as the radically polymerizable unsaturated monomer (a) component.
Alternatively, the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride (a ₂ ) or the phosphoric acid group-containing unsaturated monomer (a ₃ ) may be used alone, or 2 It is also possible to use more than one component. Among these, when the vinyl compound (a ₁ ) and the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid and its acid anhydride (a ₂ ) are used in combination,
Photocurable composition with excellent adhesive performance such as adhesive strength and water resistant adhesive strength, edge sealing property, etc. is obtained, so it is suitable as a photocurable adhesive for teeth such as composite resin, hard resin and floor resin. Used for. When both are used in combination, the ratio of both monomers is such that the vinyl compound (a ₁ ) is usually in the range of 10 to 99.9 wt%, preferably 70 to 99 wt%, and the (meth) acryloyloxyl group-containing aroma is contained. Group polycarboxylic acid or its acid anhydride (a ₂ ) or phosphoric acid-containing monomer (a ₃ ) is usually 0.1 to 90 wt.
%, Preferably 1 to 30 wt%.

The photopolymerization initiator compounded in the curable composition of the present invention is α
A ketocarbonyl compound (b) and an amine (c) and an aromatic sulfinic acid or its salt (d).
Examples of the α-ketocarbonyl compound (b) include α-diketone, α-ketoaldehyde, α-ketocarboxylic acid, α-ketocarboxylic acid ester and the like. More specifically, diacetyl, 2,3-pentadione, 2,3
-Hexadione, benzyl, 4,4'-dimethoxybenzyl, 4,4'-diethoxybenzyl, 4,4'-oxybenzyl, 4,4'-dichlorobenzyl, 4-nitrobenzyl,
α-naphthyl, β-naphthyl, camphorquinone, 1,2
Α-diketones such as cyclohexanedione, methylglyoxal, α-ketoaldehydes such as phenylglyoxal, pyruvic acid, benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate,
Examples thereof include methyl phenylpyruvate and butyl phenylpyruvate. Among these α-ketocarbonyl compounds, α-diketones are preferably used in terms of stability and the like. Among the α-diketones, diacetyl, benzyl and camphorquinone are preferable.

Amines (c) blended in the photocurable composition of the present invention
May be any of an aliphatic amine, a cycloaliphatic amine, and an aromatic amine, and may be any of a primary amine, a secondary amine, and a tertiary amine. It is preferably an amine, and a tertiary amine is particularly preferably used. Specific examples of the amines (b) include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine,
Trioctylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, butylamine, hexylamine, octylamine, decylamine,
Aliphatic amines such as dodecylamine, tricyclohexylamine, dicyclohexylamine, cycloaliphatic amines such as cyclohexylamine, aniline, toluidine,
Xylidine, phenylenediamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-di (β-hydroxyethyl) aniline, N, N-dimethyltoluidine, N, N-
Diethyl toluidine, N, N-dimethylanisidine, N, N-
Diethylanisidine, N, N-dimethyl-t-butylaniline, N, N-diethyl-t-butylaniline, N, N-dimethyl-p-chloroaniline, diphenylamine, N, N-
Bis (β-hydroxyethyl) -p-toluidine, 4-
Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzoic acid, methyl 4-diethylaminobenzoate, N, N-dimethyl-p-cyanoaniline, N, N-dimethyl- Aromatic amino such as p-bromoaniline can be exemplified. Among these, aromatic tertiary amines are preferable, and particularly N, N-di (β-hydroxyethyl) aniline, N, N-dimethylaniline, N, N-di (β-hydroxyethyl) -p-toluidine, N , N-Dimethyl-p-toluidine, N, N-dimethylbenzoic acid and N, N-diethylbenzoic acid are preferably used.

In the photocurable composition of the present invention, the aromatic sulfinic acid or its salt (d) may be a usual alkali metal salt, alkaline earth metal salt, amine salt or ammonium salt of aromatic sulfinic acid or aromatic sulfinic acid. Although a compound is used, it is preferable to use an aromatic sulfinate salt because the cured product has an excellent color tone. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like, and examples of the alkaline earth metal salt include magnesium salt, calcium salt, strontium salt, barium salt and the like, and amine salt. Is a salt of a primary amine such as methylamine, ethylamine, propylamine, butylamine, aniline, toluidine, phenylenediamine, xylylenediamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, N-methylaniline, N. -Salts of secondary amines such as ethylaniline, diphenylamine, N-methyltoluidine, trimethylamine, triethylamine, pyridine, N, N-dimethylaniline, N, N-di (β-hydroxyethyl) aniline, N, N-diethylamine, N, N-dimethy Toluidine, N, N-bis (beta-hydroxyethyl) can be exemplified salts of tertiary amines such as toluidine,
Examples of salts of ammonium compounds include ammonium salts, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, trimethylbenzylammonium salts and the like.

Specific examples of the aromatic sulfinic acid include benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, and chlorobenzenesulfinic acid. Phynoic acid, naphthalene sulfinic acid and the like can be exemplified.

Specific examples of the aromatic sulfinate include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate,
Strontium benzenesulfinate, barium benzenesulfinate, butylamine benzenesulfinate, aniline benzenesulfinate, toluidine benzenesulfinate, phenylenediamine benzenesulfinate, diethylamine benzenesulfinate,
Benzenesulfinic acid diphenylamine salt, benzenesulfinic acid triethylamine salt, ammonium benzenesulfinate, tetramethylammonium benzenesulfinate, trimethylbenzylammonium benzenesulfinate, lithium o-toluenesulfinate, o-
Sodium toluenesulfinate, calcium o-toluenesulfinate, aniline o-toluenesulfinate, ammonium o-toluenesulfinate, tetraethylammonium o-toluenesulfinate, lithium p-toluenesulfinate, p- Sodium toluenesulfinate, p-toluenesulfinate potassium, p-
Toluenesulfinate barium, p-toluenesulfinate ethylamine salt, p-toluenesulfinate toluidine salt, p-toluenesulfinate N-methylaniline salt, p-toluenesulfinate pyridine salt, p-toluenesulfin Ammonium acid, tetrabutylammonium p-toluenesulfinate, sodium β-naphthalenesulfinate, strontium β-naphthalenesulfinate, triethylamine β-naphthalenesulfinate, N-methyltoluidine β-naphthalenesulfinate, β- Examples include ammonium naphthalene sulfinate, trimethylbenzyl ammonium β-naphthalene sulfinate, and the like. Among these, lithium salt and sodium salt of benzelsulfinic acid and lithium salt and sodium salt of p-toluenesulfinic acid are preferable.

In the photocurable composition of the present invention, the blending ratio of the α-ketocarbonyl compound (b) is usually 0.01 to 15 parts by weight, preferably 0.05 to 0.05 parts by weight based on 100 parts by weight of the radically polymerizable monomer (a). The content of the amine (c) is usually 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the radical-polymerizable monomer. The amount of the aromatic sulfinic acid or its salt (d) is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the radical-polymerizable monomer.

Further, the α-ketocarbonyl compound, amines, aromatic sulfinic acid or a salt thereof in the photocurable composition of the present invention can be used as one liquid together with the radically polymerizable monomer, or can be divided. It can also be stored and mixed immediately before use for use as a curable composition.

The photocurable composition of the present invention further contains other components, such as a powdered inorganic filler, an organic polymer, a tackifier, a photosensitizer, a radical polymerization initiator, a polymerization regulator, if necessary. A polymerization inhibitor or the like can also be added. Specific examples of the powdery inorganic filler include kaolin, talc, clay, calcium carbonate, silica, silica-alumina, alumina, titanium oxide, calcium phosphate, glass powder and quartz powder. Examples of the organic polymer include wax, ethylene / vinyl acetate copolymer, polymethyl acrylate, polymethyl methacrylate and copolymers thereof. Examples of radical polymerization initiators include peroxides such as benzoyl peroxide and cumene hydroperoxide. The mixing ratio of these components is appropriate.

By irradiating the photocurable composition of the present invention with light, polymerization occurs and the composition is cured. The light beam may be a natural light beam or an artificial light beam, and a light beam from the ultraviolet region to the visible region can be adopted. As the artificial light ray, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a halogen lamp, a tungsten lamp or the like can be used. The temperature at the time of photocuring is usually 0 to 80 ° C, preferably 5 to 50 ° C, and the time of light irradiation is usually 1
Seconds to 5 minutes.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

The method for evaluating the photocurable composition of the present invention and the production examples of the photocurable composites resin used in Examples and Comparative Examples are shown below. Further, the following abbreviations used in the following examples and comparative examples respectively represent the following compounds.

MMA …… Methyl methacrylate NPG …… Neopentyl glycol dimethacrylate 2G …… Diethylene glycol dimethacrylate HEMA …… β-hydroxyethyl methacrylate BISGMA …… 4-META ...... 4-MET ... PMMA ... Polymethylmethacrylate VR-60 ... Methacrylic acid modified epoxy resin (manufactured by Showa K.K.) BPO ... Benzoyl peroxide DMPT ... Dimethyl-p-toluidine DEPT ... di (β- Hydroxyethyl) -p-toluidine DEAB …… Diethylaminobenzoic acid PTSS …… Sodium p-toluenesulfinate BSS …… Sodium benzenesulfinate PTSL …… Lithium p-toluenesulfinate (I) Adhesion evaluation method Beef The enamel surface or dentin surface of the anterior labial surface of NO.6 /
After thoroughly polishing with 0 emery paper to make the surface smooth, the enamel was subjected to etching treatment with 65% phosphoric acid aqueous solution and dentin with 10% citric acid and 3% ferric chloride aqueous solution for 45 seconds each. After thoroughly washing with water, the etching surface was dried with air, and cellophane tape (about 13 mm × 13 mm) with a hole having a diameter of 5.4 mm was attached. The photocurable composition described in Examples or Comparative Examples was applied to the circular holes and lightly blown with air. After that, a Teflon mold (a cylinder having a diameter of 5.4 mm and a depth of 5 mm) fitted to the circular hole was filled with the photopolymerizable composites resin described below, and after covering the surface with cellophane paper, visible light was irradiated from above. Device (Kulzer, Transl
ux) for 30 hours of visible light (wavelength 350-700nm)
It was irradiated for seconds to prepare an adhesion test piece. After left at room temperature for 30 minutes, the adhesion test piece of bovine tooth enamel was immersed in 37 ° C water for 24 hours and then alternately placed in cold water at 4 ° C and hot water at 60 ° C for 1 minute each.
It was immersed 0 times for a total of 2 hours. After that, the adhesive force between bovine teeth and composites resin was measured at a temperature of 23 ° C. for 10 minutes in the air and at a temperature of 23 ° C. and a pulling rate of 2 mm / min. The adhesion test piece of bovine dentin was immersed in 37 ° C. water for 24 hours, left at 23 ° C. in the air for 10 minutes, and then 23
A tensile test was performed at a temperature of ℃ under the same conditions as for bovine tooth enamel, and the adhesive strength was measured.

(II) Evaluation method of marginal sealing property A cavity is opened on the labial surface of the anterior surface of a cow with a diameter of 3 mm and a depth of 3 mm over both enamel and dentin (silicone point finish), and this cavity is treated with a 65% phosphoric acid aqueous solution. Etching processing was performed for 45 seconds. After sufficiently washing with water, the etching surface was dried with air, and the photocurable composition described in Examples or Comparative Examples was applied to the circular holes and lightly blown with air. After that, the photocurable composition was applied or the cavity was filled with the photopolymerizable composites resin described below, and a visible light (wavelength 350 to 700 was used using a visible light irradiator (Kulzer, Translux)).
(nm) for 30 seconds. The surface is finished with white points and then with silicone points, and then stained with fuchsin at 4 ° C.
Alternating cold water of 60 ℃ and hot water of 60 ℃ for 1 minute 60 times in total 2
Soak for hours. After that, the cylindrical sinus filled with composite resin was cut in the depth direction, and the edge sealing property was judged by the degree of fuchsin progress of the cut surface.

(III) Evaluation Method of Color Tone The photocurable composition was applied on a glass plate, lightly air-blown, and then exposed to visible light (Translux, manufactured by Kulzer) for 2 minutes to cure. After that, the color tones were compared after being left for 1 day under the sun.

(IV) Preparation of photocurable composite resin: Triethylene glycol dimethacrylate 7.5 g, 1,3-
7.5 g of dimethacryloxyethoxybenzene, 15 g of an adduct of 1 mol of 2,2,4-trimethylhexamethylenediamine diisocyanate and 2 mol of 2-hydroxyethyl methacrylate, 40 g of a composite filler synthesized by the method described below.
And fine powder silica RM-50 (fine powder silica manufactured by Nippon Aerozin Co., Ltd.) 30 g Hydroquinone monomethyl ether 4 mg was kneaded with two rolls at 35 ° C. to prepare a composition. 10 g of this composition was thoroughly mixed with 45 mg of camphorquinone and 45 mg of 4-diethylaminobenzoic acid with a spatula to prepare a photocurable composites resin.

(V) Production Example of Composite Filler A solution of 0.1 g of benzoyl peroxide dissolved in 10 g of trimethacrylate of methylol propane was placed in a mortar and pestle, and further, hydrophobic fine powder silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd., average particle size). 16mμ)
Was added little by little and mixed. The mixture was hung on a small rubber roll at a time when the viscosity gradually increased and became dull, and fine silica powder was intermittently added to give a final addition amount of fine silica powder of 9.5 g. Remove the obtained paste from the roll and press it at a mold temperature of 110 ° C for 150
It was heat-cured at a pressure of kg / cm ² to 200 kg / cm ² for 10 minutes. The cured product was crushed with a ball mill to obtain 18.0 g of a composite filler that passed through a 230 mesh sieve. The average particle size of this composite filler was 11μ.

Example 1 6 g of methyl methacrylate, 2.5 g of neopentyl glycol dimethacrylate, 1.5 g of 4-methacryloyloxyethoxycarbonyl phthalic anhydride (4-META),
Camphorquinone 0.02 g, polymethylmethacrylate 0.
Solution (A) consisting of 4 g and hydroquinone monomethyl ether 0.02 g and dimethyl-p-toluidine 0.05 g,
A solution (B) composed of 0.35 g of sodium p-toluenesulfinate, 8 g of ethanol and 30 g of methyl methacrylate was prepared. These solutions were mixed in equal weight before use to prepare a photo-curable composition, which was used for evaluation tests of adhesive strength, edge sealing property and color tone. The results are shown in Table 1.

Examples 2 to 8 and Comparative Examples 1 to 3 In Example 1, except for the solution A other than hydroquinone monomethyl ether, those described in Example 1 were used in the proportions described in Example 1, and solutions A and B were used. The solution was prepared and mixed with equal weight of A and B before use to prepare a photocurable composition, which was used for a test such as adhesive strength. The results are shown in Table 1.

Claims (1)

[Claims] 1. A photocurable composition comprising (a) a radically polymerizable unsaturated monomer, (b) an α-ketocarbonyl compound, (c) an amine, and (d) an aromatic sulfinic acid or a salt thereof. object