JP2661708B2 - Photocurable light-shielding composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a light-shielding composition excellent in curability by light, and furthermore, for example, high light hardness, adhesiveness, and water resistance used in dental treatment. And a photocurable light-shielding composition having

<Related Art> In dental treatment, when a crown portion of a tooth is lost due to dental caries or the like, an artificial crown (crown) combining a metal and a hard dental resin is prosthetic to a defective portion of the crown. In this case, a light-shielding curable composition (opaque material) containing a large amount of a light-shielding pigment such as titanium white is used between the metal and the hard resin to erase the color of the metal. Conventionally, a heat-curable light-shielding composition containing a radical polymerizable monomer, an inorganic filler and a peroxide as an opaque material (JP-A-61
-127717 and JP-A-61-152715) and a room-temperature-curable light-shielding composition containing a radical polymerizable monomer, tributylborane and a pigment encapsulated with a polymer (Dental Materials and Instruments, No. 7). Vol. 1, No. 27-32, 1988).

<Problems to be Solved by the Invention> Generally, the opaque material for dental treatment as described above is used. However, in the heat-curable light-shielding composition, an instrument for heating the composition to about 100 ° C. is required, and in the room-temperature-curable light-shielding composition,
About 5 minutes are required for the composition to cure, which limits the usable time.

In recent years, light-curable dental hard resins have appeared and have been widely used due to their good operability. Then, a photo-curable opaque material that combines the photo-curable hard resin with a metal and a light-shielding pigment and cures by light irradiation for a shorter time (about 1 minute) has been required.

However, simply using a mixture of a pigment, a radical polymerizable monomer, and a photopolymerization initiator, the pigment originally contains a light-shielding pigment, and the metal oxides and the like contained in the pigment undergo radical polymerization. Influences on speed, etc., causing problems such as the occurrence of many uncured portions even when light irradiation is performed, and the fact that the cured depth is not deep enough to be practical.

The present invention is intended to solve the above problems, removes the adverse effect of the pigment on the radical polymerization by coating the pigment with a polymer, a photocurable light-shielding composition having good curability by light, and It is an object of the present invention to provide a photocurable light-shielding adhesive composition having high adhesive strength and adhesion durability to an adherend such as a dental alloy.

<Means for Solving the Problems> The present invention provides a photocurable light-shielding composition comprising a pigment coated on the surface with a polymer, a radical polymerizable monomer, and a photopolymerization initiator. Things.

The present invention also includes a pigment whose surface is coated with a polymer, a radical polymerizable monomer, a photopolymerization initiator, and an acidic group-containing monomer containing at least one (meth) acryloyl group in one molecule. It is intended to provide a light-curable light-shielding adhesive composition characterized in that:

 Hereinafter, the present invention will be described in detail.

The photocurable light-shielding composition of the present invention contains a pigment whose surface is coated with a polymer, a radically polymerizable monomer, and a photopolymerization initiator.

The pigment coated on the surface with the polymer used in the present invention,
The pigment surface is coated almost uniformly with a polymer by a method such as a suspension polymerization method.
Vol. 1, No. 27-32, 1988.

(Production method of pigment coated on its surface with polymer) A pigment and an anionic surfactant are charged into a four-necked flask equipped with a stirrer, and the inside of the reactor is set to a nitrogen atmosphere, and then distilled water is injected and stirred. After a certain time, a polymerizable monomer is added,
The temperature is raised to 60 ° C., followed by addition of a polymerization initiator and stirring under nitrogen pressure. Polymerization is performed while adding a polymerizable monomer (twice). After a predetermined reaction time, the flask is cooled, a polymerization inhibitor is added, and the reaction is stopped. The reaction product is washed and dried.

The pigment used for the pigment whose surface is coated with the polymer used in the present invention may be any of an inorganic pigment and an organic pigment,
Specific examples include titanium white, titanium yellow, titania, red iron oxide, ultramarine blue, iron oxide and the like, and preferably, titanium white, titanium yellow, red iron oxide and the like are used. In addition, the polymerizable monomer that is used as the polymer used for the pigment coated on the surface with the polymer is a liquid at normal temperature because the pigment surface is coated with the polymer by a suspension polymerization method or the like, and is insoluble or hardly soluble in water. Preferred are monofunctional and polyfunctional (meth) acrylates, vinyl compounds, alkenylbenzenes and the like.

More specifically, methyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, which is a monofunctional (meth) acrylate, Ethylene glycol di (meth) acrylate neopentyl glycol di (meth), which is a polyfunctional (meth) acrylate, such as trifluoroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and γ- (meth) acryloxypropyltrimethoxysilane ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (In the above formulas 1 to 5, R represents a hydrogen atom or a methyl group, m and n each represent a positive integer, and m + n = 2 to 10.), vinyl chloride which is a vinyl compound, vinyl halide of vinyl bromide , Vinyl acetates such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether, and alkenylbenenes such as styrene, vinyl toluene, α-methylstyrene, chloromethylsilene and styrene Ben and the like can be exemplified.

Among these, monofunctional (meth) acrylate, polyfunctional (meth) acrylate, styrene and vinyl acetate are preferred, and methyl (meth) acrylate is more preferred, from the viewpoint of ease of handling and high polymerizability.

In addition, the polymerizable monomer that becomes a polymer that coats the surface of the pigment, when used in an amount of 1 to 200% by weight based on the pigment,
The light-curable light-shielding composition has a good balance between the light-shielding properties and the polymerizability, and is therefore preferable.

The pigment coated on the surface with a polymer may be produced by a method other than the method of polymerizing the polymerizable monomer on the surface of the pigment, and as the polymer to be used, polyester,
A commonly used polymer such as polyurethane may be used.

Specific examples of the radical polymerizable monomer used in the present invention include monofunctional and polyfunctional (meth) acrylates.

More specifically, as the monofunctional (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate, dodecyl ( (Meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate and other hydrocarbon-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monooxide Ethylene glycol unit-containing (meth) acrylates such as silether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, and polyethylene glycol monoethyl ether (meth) acrylate; trifluoroethyl (meth) Silanes such as fluorine-substituted (meth) acrylates such as acrylate and perfluorooctyl (meth) acrylate, γ- (meth) acryloyloxypropyltrimethoxysilane, and γ- (meth) acryloyloxypropyltri (trimethylsiloxy) silane Examples thereof include (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
Poly (meth) acrylates of alkane polyols such as acrylate, hexylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) (Poly) such as acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate ) Poly (meth) acrylates of oxyalkane polyols, general formula [I] (Wherein, R represents a hydrogen atom or a methyl group, n represents 0 or a positive integer, R ¹ is CH _{2 2,} CH _{2 4,} Epoxy (meth) acrylate represented by the general formula [II] (Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is Is shown. An alicyclic or aromatic di (meth) acrylate compound represented by the general formula [III] (Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is Is shown. Alicyclic di (meth) acrylate compound represented by the formula (1), a polyfunctional (meth) acrylate compound having at least one urethane bond in one molecule, for example, 1 mol of a diisocyanate compound and 2-hydroxyethyl ( Examples thereof include adducts with 2 mol of a hydroxyl group-containing (meth) acrylate such as (meth) acrylate.

Incidentally, as the diisocyanate compound, aliphatic,
Both alicyclic and aromatic diisocyanates can be used. For example, hexamethylene diisocyanate, lysine diisocyanate, 2,2 (4), 4-trimethylhexamethylene diisocyanate, dicyclohexyldimethyl Methane-p, p'-diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and the like can be exemplified.

More specifically, (In the above formulas 6 to 14, R represents a hydrogen atom or a methyl group.).

As the polyfunctional (meth) acrylate, in addition to the above examples, a compound represented by the general formula [IV] (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent aromatic which has at least one aromatic ring and may have an oxygen atom or a sulfur atom in the molecule. Residues, m and n are positive integers.) There is a polyfunctional (meth) acrylate represented by (In the above formulas 15 to 20, R represents a hydrogen atom or a methyl group, m and n each represent a positive integer, and m + n = 2 to 20).

Among these, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, or 2-hydroxyethyl (meth) acrylate, 2-hydroxy Hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate, poly (meth) acrylates of alkane polyols, (poly)
Poly (meth) acrylates, epoxy (meth) acrylates of oxyalkane polyols, aliphatic or alicyclic (meth) acrylates having at least one urethane bond in the molecule, and (poly) s having aromatic rings
Poly (meth) acrylate of oxyalkane polyol and the like are preferable, and methyl methacrylate, n-hexyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, ethylene glycol di (meth) acrylate, neopentyl glycol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, (Wherein, R represents a hydrogen atom or a methyl group), (Wherein, m and n are positive integers, and m + n = 2-10
It is. ) (Wherein, m and n are positive integers, and m + n = 2-10
It is. And the like.

These radically polymerizable monomers can be used alone or in combination of two or more.

The photopolymerization initiator used in the present invention is preferably one which is stable at room temperature for a long time, specifically, an α-ketocarbonyl compound alone, or an α-ketocarbonyl compound, and an amine or aromatic nitrogen-containing condensed ring. Used in combination with a compound.

As the α-ketocarbonyl compound, α-diketone,
Examples thereof include α-ketoaldehyde, α-ketocarboxylic acid, and α-kelcarboxylic acid ester.

More specifically, diacetyl, 2,3-pentadione, 2,3-hexadione, benzyl, 4,4'-dimethoxybenzyl, 4,4'-diethoxybenzyl, 4,4'-oxybenzyl, 4,4 Α-diketones such as' -dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, 1,2-cyclohexanedione, α-diketones such as methylglyoxal and phenylglyoxal
Examples thereof include carboxylic acids such as ketoaldehyde, pyruvic acid, benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate, and butyl phenylpyruvate, and esters thereof.

Among these α-ketocarbonyl compounds, α-diketones are preferable in terms of stability and the like, and diacetyl,
Benzyl and camphorquinone are more preferred.

As the amines used as the photopolymerization initiator, an aliphatic amine or an aromatic amine is preferable.

Particularly preferred aromatic amines are those of the general formula [V] (Wherein, R ¹ is a hydrogen atom, an alkyl group or a hydroxyalkyl group, R ² is a hydrogen atom, an alkyl group, a hydroxyalkyl group, or an aryl group, R ³ is an acyl group, a carboxy group, an alkoxycarbonyl group, a hydroxyacyl group , A carbamoyl group, a cyano group, a nitro group, or a halogen atom, which may have a substituent, wherein n is a positive integer of 5 or less.

As such a substituted aromatic amine, specifically, 4
-Dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4- (methylphenylamino) benzaldehyde, 4- (β-hydroxyethylmethylamino) benzaldehyde, 4-dimethylaminobenzoic acid, 4-diethylaminobenzoic acid, 4- (methylphenylamino ) Benzoic acid, 4- (β-hydroxyethylamino) benzoic acid, methyl 4-dimethylaminobenzoate,
Methyl-diethylaminobenzoate, methyl 4- (methylphenylamino) benzoate, propyl 4- (β-hydroxyethylmethylamino) benzoate, phenyl 4-dimethylaminobenzoate, 4-dimethylaminophthalic acid,
-Dimethylaminoisophthalate, N, N-dimethylanoaniline, N, N-dimethylnitroaniline, N, N-
Dimethylchloroaniline, N, N-dimethylbromoaniline, N, N-dimethyl-o-iodoaniline, N, N-diethylcyanoaniline, N, N-diethyl-p-chloroaniline, N, N-dipropyl-p- Cyanoaniline, N, N-methylphenyl-p-cyanoaniline, N, N-β-hydroxyethylmethyl-p-chloroaniline, N, N-dimethyl-2,4-dicyanoaniline, N, N-dimethyl-2 , 4-dinitroaniline, N, N-dimethyl-2,4-dichloroaniline and the like.

Among these substituted aromatic amines, 4-dialkylaminobenzaldehyde, 4-dialkylaminobenzoic acid, 4-dialkylaminobenzoic acid ester, N, N-dialkyl-p-cyanoaniline are preferable, and 4-diethylaminobenzoic acid is preferable. More preferred.

The aromatic nitrogen-containing condensed ring compound used as a photopolymerization initiator includes a compound represented by the general formula [VI] [Wherein, X represents> NR ² , an oxygen atom or a sulfur atom, Y represents a hydrogen atom, —SR ³ or a monovalent metal, R ¹ represents an alkyl group, an aryl group, an aralkyl group, a halogen atom,
n is an integer of 0-4. When n is 2 or more, R ¹ may be the same or different groups. R ² is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ³ is an alkyl group, an aryl group or a general formula [VII] (Wherein, X, R ¹ and n are the same as those in the general formula [VI]). ] The aromatic nitrogen-containing fused ring compound represented by the formula:

As such an aromatic nitrogen-containing fused ring compound, specifically, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptomethylbenzimidazole,
2-mercaptomethylbenzoxazole, 2-mercaptomethylbenzothiazole, dibenzoxazyl disulfide, dibenzothiazyl disulfide, 2- (phenylthio) benzothiazole, and metal salts thereof,
For example, sodium salt, zinc (II) salt, copper (II) salt, nickel salt, 2-mercaptodimethylbenzimidazole,
Examples thereof include 2-mercaptodimethylbenzoxazole and 2-mercaptodimethylbenzothiazole.

Among these aromatic nitrogen-containing fused ring compounds, 2
-Mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2
-Mercaptomethylbenzothiazole, dibenzothiazyl sulfide, zinc (II) salt of 2-mercaptobenzimidazole, zinc 2-mercaptobenzothiazole (I
I) Salts and zinc (II) salts of 2-mercaptomethylbenzothiazole are preferred, and 2-mercaptobenzothiazole, 2-mercaptomethylbenzothiazole, zinc (II) salts of 2-mercaptobenzothiazole, 2-mercaptomethylbenzothiazole Are more preferred.

Further, the photocurable light-shielding adhesive composition of the present invention, a pigment coated on the surface with a polymer, a radical polymerizable monomer,
It contains a photopolymerization initiator and an acidic group-containing monomer containing at least one (meth) acryloyl group in one molecule.

Of the above components, a pigment whose surface is coated with a polymer,
For the radical polymerizable monomer and the photopolymerization initiator,
As described above.

The acidic group-containing monomer containing at least one (meth) acryloyl group in one molecule is specifically an aromatic polycarboxylic acid containing at least one (meth) acryloyloxyl group in one molecule. Acid or its acid anhydride, general formula [VIII] (Wherein, R represents a hydrogen atom or a methyl group) Phosphoric acid or sulfone containing at least one (meth) acryloyloxyl group per molecule represented by a monofunctional (meth) acrylamide monomer represented by the formula: Partial esters of acids (monoesters, diesters or mixtures of phosphoric acids, monoesters of sulfonic acids) and the like can be exemplified.

As the aromatic polycarboxylic acid containing at least one (meth) acryloyloxyl group in one molecule or the acid anhydride thereof, specifically, at least two (meth) acryloyloxyl groups are contained in one molecule.
Alkane polyols having at least one hydroxyl group and optionally containing an oxygen atom, wherein at least one hydroxyl group forms an ester of (meth) acrylic acid and at least one hydroxyl group Is a (meth) acryloyloxyl group-containing aromatic polycarboxylic acid having a structure in which an ester is formed with one carboxyl group of an aromatic polycarboxylic acid having at least three carboxyl groups, or an acid anhydride thereof. be able to.

Among the aromatic polycarboxylic acids having at least three carboxyl groups, aromatic polycarboxylic acids in which at least two carboxyl groups among at least three carboxyl groups are bonded to adjacent carbon atoms on an aromatic nucleus Acids are preferable, and specific examples thereof include hemi-mellitic acid, trimellitic acid, prenitic acid, melophanic acid, and pyromellitic acid.

Examples of the aromatic polycarboxylic acid having at least one (meth) acryloyloxyl group in one molecule or an acid anhydride thereof include 4- (meth) acryloyloxymethoxycarbonylphthalic acid or an acid anhydride thereof,
(Meth) acryloyloxyethoxycarbonylphthalic acid or its anhydride, 4- (meth) acryloyloxybutoxycarbonylphthalic acid or its anhydride, (In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 6 to 12.), (Wherein, R represents a hydrogen atom or a methyl group, and n represents an integer of 2 to 50). (Wherein R represents a hydrogen atom or a methyl group, n represents an integer of 1 to 50), 4- [2-hydroxy-3- (meth) acryloyloxypropoxycarbonyl] phthalic acid or an acid anhydride thereof, 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 can be exemplified.

Specific examples of the monofunctional (meth) acrylamide-based monomer represented by the general formula [VIII] include 3- (meth) acryloylaminosalicylic acid, 4- (meth) acryloylaminosalicylic acid, and 5- (meth) acryloyl Aminosalicylic acid, 3-hydroxy-2- (meth) acryloylaminobenzoic acid, 3-hydroxy-4- (meth) acryloylaminobenzoic acid, 3-hydroxy-5- (meth) acryloylaminobenzoic acid, 3-hydroxy-6
-(Meth) acryloylaminobenzoic acid, 4-hydroxy-2- (meth) acryloylaminobenzoic acid, 4-hydroxy-3- (meth) acryloylaminobenzoic acid and the like can be exemplified.

Specific examples of a partial ester of phosphoric acid or sulfonic acid containing at least one (meth) acryloyloxyl group in one molecule (monoester, diester or mixture of phosphoric acid, and monoester of sulfonic acid) include: Include 2- (meth) acryloyloxyethylphenylacid phosphate, bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [3-
(Meth) acryloyloxypropyl] acid phosphate, 2- (meth) acryloyloxyethylphenylphosphonate, (In the above formulas 21 to 25, R represents a hydrogen atom or a methyl group.).

Among these acidic group-containing monomers containing at least one (meth) acryloyl group in one molecule, aromatic polycarboxylic acids containing at least one (meth) acryloyloxyl group in one molecule Or an acid anhydride thereof, or a monofunctional (meth) acrylamide monomer represented by the general formula [VIII], and preferably 4- (meth) acryloyloxyethoxycarbonylphthalic acid or an acid anhydride thereof, or 4 -(Meth) acryloylaminosalicylic acid and 5- (meth) acryloylaminosalicylic acid are more preferable, and 4-methacryloyloxyethoxycarbonylphthalic anhydride is particularly preferable because the adhesion to teeth, water resistance and the like are improved.

The mixing ratio of the pigment and the radical polymerizable monomer whose surface is coated with the polymer used in the present invention is not particularly limited,
Usually, 1 to 99% of a pigment coated on the surface with a polymer and 99 to 1% of a radical polymerizable monomer, preferably 5 to 95% of a pigment coated on the surface with a polymer, 95 to 5% of a radical polymerizable monomer
%, More preferably a pigment whose surface is coated with a polymer
20 to 80%, and 80 to 20% of a radical polymerizable monomer. When it is in this range, the balance between the physical properties of the cured product and the light-shielding property is good, which is preferable.

The mixing ratio of the photopolymerization initiator used in the present invention is usually 30 to 0.001%, preferably 10 to 0.01%, and more preferably 5 to 0.1% based on the radical polymerizable monomer. Within this range, rapid and sufficient polymerization occurs.

The compounding ratio of the acidic group-containing monomer containing at least one (meth) acryloyl group in one molecule used in the present invention is usually 100% with respect to the radical polymerizable monomer.
~ 0.001%, preferably 30-0.01%, more preferably 1
It is 0-0.1%. Within this range, sufficient adhesive strength and adhesive durability can be obtained.

In the present invention, in addition to the essential components, other components such as a thermal radical polymerization initiator, a room temperature radical polymerization initiator, an organic polymer, a powdered inorganic filler, and a polymerization inhibitor may be added as necessary. Can be.

As the thermal radical polymerization initiator, for example, dibenzoyl peroxide, dilauroyl peroxide, di-
t-butyl peroxide and the like.

Examples of the room temperature radical polymerization initiator include, for example, trialkylboron and its analogs such as tributylboron, tripropylboron and their partially oxidized analogs, dibenzoyl peroxide, dilauroyl peroxide, di-t Organic peroxide such as -butyl peroxide and N, N-dimethylaniline, N, N-dimethyl-p-
Examples include a mixed system with an amine such as toluidine and N, N-diethanol-p-toluidine, and a mixed system with an aromatic sulfinic acid such as p-toluenesulfinic acid and benzenesulfinic acid and an acidic compound.

Examples of the organic polymer include wax, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyethyl methacrylate, and copolymers thereof.

As the powdered inorganic filler, for example, kaolin, talc, clay, silica, silica-alumina, glass powder,
Quartz powder and the like can be mentioned.

Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether.

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

In the following examples and comparative examples, the following abbreviations are used.

(Reference Example I) Method for producing a pigment coated on the surface with a polymer A stirring blade was attached to a 500 ml four-necked flask.
After putting 0 g of rutile-type titanium dioxide (manufactured by Wako Pure Chemical Industries) and 0.087 g (0.3 mmol) of sodium dodecyl sulfate into a nitrogen atmosphere in the reactor, 300 ml of distilled water was injected, and the stirring blade was rotated at 300 rpm. To stir the contents. After one hour, the rotation speed is set to 600 rpm, 3 g of methyl methacrylate (MMA, manufactured by Wako Pure Chemical Industries, Ltd.) is added, and the mixture is further stirred for 10 minutes. Then, the temperature in the reactor is raised to 60 ° C. To this, a solution prepared by dissolving 0.082 g of potassium sulfate as a radical polymerization initiator in 10 ml of water is added. 60 minutes and 120 minutes after the addition of the polymerization initiator, 3 g of MMA is further added in increments of 3 g, and the mixture is further stirred at 60 ° C. for 60 minutes to polymerize the MMA. After completion of the polymerization, the temperature in the reactor is lowered to room temperature, and 0.5 g of hydroquinone is added to stop the polymerization. The reaction product is washed with water and methanol and dried in a nitrogen stream under reduced pressure (100 mmHg) at 60 ° C. to constant weight.

Polymethyl methacrylate (PMMA) in the obtained composite
Is the weight loss when the temperature is raised to 500 ° C with a thermal analyzer.
Calculate from residual amount. In addition, the produced PMMA is injected from the complex using acetone, and the number average molecular weight is determined using gel permeation chromatography (GPC).
Calculated as polystyrene equivalent molecular weight.

Hereinafter, titanium dioxide whose surface is coated with this polymer and polymer-coated titanium dioxide are called.

(Reference Example II) Photocurable light-shielding adhesive composition for metal
Evaluation method of 10mm x 10mm x 3mm dental cobalt-chromium alloy
Metacast, Metacast ) The surface has a particle size of 10
Sandblast using μm alumina. This service
The sample is ultrasonically washed in acetone for 10 minutes and then dried.
Cellophane with a hole of 5mm diameter on the surface and 200μm thickness
Glue the tape and determine the adhesive surface area and composition thickness.
Set. Into this, light-curing light-shielding adhesive composition is charged,
Stick a cellophane tape to the surface, glass with a flat surface
Press down on plate to make composition thickness constant (200 μm).
This is supplied with a dental visible light irradiator (Kentzer, Dentac
olor Xs ) And cure by irradiating with light for 90 seconds.

 After removing the cellophane tape, an additional 5 mm diameter hole
Attach a 1mm thick Teflon mold
Dental hard resin (made by Sun Medical Co.,
ー , Shade DB-2) and the above dental visible light illumination
Light cures for 90 seconds in a projectile to cure.

 This includes a dental adhesive (Super, manufactured by Sun Medical Co., Ltd.)
ー Bond ) To connect an acrylic rod with a diameter of 6mm.
To wear.

The sample is subjected to a tensile test as it is, or is placed in a heat cycle tester, and 4 to 60 ° C. is repeated 2000 times, and then a tensile test is performed to measure the force (adhesive strength and adhesive durability) at the time of sample peeling. In addition, the test condition was a temperature of 23.
° C and a pulling speed of 2 mm / min.

[Examples 1 to 11, Comparative Examples 1 to 10] Mixing the components shown in Table 1 in the amounts shown in Table 1.
Put the thing in a Teflon mold with a depth of 1 mm and a diameter of 10 mm,
Dental visible light irradiator (Dentacolor Xs ) Within 90 seconds light
Irradiated.

Immediately after irradiation, remove from the irradiator, remove the sample from the Teflon mold, remove the uncured part,
The cured thickness was measured using a micrometer.

 The results are shown in Table 1.

[Examples 12 to 23] Using the photocurable light-shielding adhesive composition in which the components shown in Table 2 were blended in the amounts shown in Table 2, the force at the time of sample peeling was measured by the method shown in Reference Example II. did.

 The results are shown in Table 2.

[Example 24] A dental cobalt-chrome alloy of 10 mm x 10 mm x 3 mm (sa
Metacast, Metacast ) The surface has a particle size of 10
Sandblast using μm alumina. This service
The sample is ultrasonically washed in acetone for 10 minutes and then dried.
Cellophane with a hole of 5mm diameter on the surface and 200μm thickness
Glue the tape and determine the adhesive surface area and composition thickness.
Specified. Write a composition of MMA / 4-META = 95/5 on the surface.
Spread lightly and air blow lightly to spread evenly
Was. On top of that, polymer-coated titanium dioxide / UDMA / CPQ /
Fill the composition with DEBA / HQME = 100/200/2/1 / 0.024 and add
Glue cellophane tape to the surface
To a constant thickness (200μm)
Was. This is a dental visible light irradiator (Kulzer, De
ntacolor Xs ) And cure by irradiating with light for 90 seconds
Was. After removing the cellophane tape, an additional 5 mm diameter
Attach a 1mm thick Teflon mold with holes
Dental hard resin (made by Sun Medical Co.,
Ra , Shade DB-2) and the above visible dental light
It was cured by irradiating it with light for 90 seconds in an irradiator.

 This includes a dental adhesive (Super, manufactured by Sun Medical Co., Ltd.)
ー Bond ) With a 6mm diameter acrylic acid rod
I wore it.

Put this sample in a heat cycle tester, 4 ℃ ～ 60 ℃
Was repeated 2000 times, a tensile test was performed at a temperature of 23 ° C. and a speed of 2 mm / min, and the force at the time of peeling the sample was measured.

As a result, the adhesive corrosion resistance was 132 kg / cm ² .

Example 25 Instead of the composition of MMA / 4-META = 95/5, MMA / 5-MASA =
Except for using the composition of 98/2, treated in the same manner as in Example 17,
The force at the time of sample peeling was measured.

The adhesion durability was 118 kg / cm ² .

From the above results, it can be seen that all of the examples are excellent in photocurability, adhesive strength, adhesive durability and water resistance.

<Effect of the Invention> According to the present invention, a photocurable light-shielding composition having excellent photocurability can be obtained.

In addition, a photocurable light-shielding adhesive composition having excellent photocurability and excellent adhesion and durability to metals, teeth, and the like can be obtained.

The above composition can be effectively used especially as a dental prosthesis and the like.

Claims (2)

(57) [Claims] 1. A photocurable light-shielding composition comprising a pigment whose surface is coated with a polymer, a radically polymerizable monomer, and a photopolymerization initiator. 2. A pigment coated on its surface with a polymer, a radical polymerizable monomer, a photopolymerization initiator and an acidic group-containing monomer containing at least one (meth) acryloyl group in one molecule. A light-curable light-shielding adhesive composition, comprising: