JPH028203A - Photo-setting light-shielding composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a pigment surface-coated with a polymer, a radical polymerizable monomer and a photo-polymerization initiator, having high photo-setting property, adhesivity and water-resistance, exhibiting excellent adhesivity to metal, tooth, etc., and useful as a dental prosthetic material. CONSTITUTION:The objective composition contains (A) a pigment (preferably titanium white, titanium yellow, red iron oxide, etc.), surface-coated with a polymer such as polymethyl (meth)acrylate, (B) a radical polymerizable monomer [preferably methyl (meth)acrylate, etc.] and (C) a photo-polymerization initiator (e.g., alpha-diketone or 4-dimethylaminobenzaldehyde). The composition preferably further contains (D) a monomer containing acidic group and having at least one (meth)acryloyl group in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a light-shielding composition that has excellent photo-curability, and furthermore, has high photo-curability, adhesiveness, and water resistance for use in dental treatment, for example. The present invention relates to a photocurable light-shielding composition.

<Prior Art> In dental treatment, when the crown of a tooth is missing due to caries or the like, an artificial crown made of a combination of metal and hard dental resin is used to replace the missing part of the crown. In this case, a light-shielding curable composition (opaque material) containing a large amount of a groove-light pigment such as titanium white is used between the metal and the hard resin to erase the color of the metal. Conventionally, heat-curable light-shielding compositions containing radically polymerizable monomers, inorganic fillers, and peroxides (JP-A-61-127717 and JP-A-61-1527) have been used as opaque materials.
No. 15), a room-temperature-curable light-shielding composition containing a radically polymerizable monomer, tributylborane, and a pigment encapsulated with a polymer (Dental Materials and Instruments, No. 74J,
No. 1, 27-32, 1988), etc. have been used.

<Problems to be Solved by the Invention> Generally, the above-mentioned opaque materials for dental treatment are used. However, the heat-curable light-shielding composition described above requires a device to heat the composition to around 100°C, and the room-temperature-curable light-shielding composition requires a long time before the composition is cured. It takes about 5 minutes, which poses a problem in that the usable time is limited.

Recently, light-curable dental hard resins have appeared and are widely used because of their good operability. Then, there has been a demand for a photocurable opaque material that combines the above-mentioned photocurable hard resin, metal, and light-shielding pigment and is cured by light irradiation for a shorter period of time (about 1 minute).

However, even if a pigment, a radically polymerizable monomer, and a photopolymerization initiator are simply mixed and used, in addition to containing pigments that are originally light-blocking, the metal oxides contained in the pigments may prevent radical polymerization. This affected the speed, etc., and caused problems such as many uncured portions occurring even after light irradiation, and the curing depth not being deep enough for practical use.

The present invention aims to solve the above problems,
By coating the pigment with a polymer, we can eliminate the negative effects of the pigment on radical polymerization, and create a photopolymerizable light-shielding composition that has good light curability, and improves adhesive strength and adhesive durability to adherends such as dental alloys. The purpose of the present invention is to provide a highly photocurable light-shielding adhesive composition.

Means for Solving the Problems> The present invention provides a photocurable light-shielding composition characterized by containing a pigment whose surface is coated with a polymer, a radically polymerizable monomer, and a photopolymerization initiator. It is something.

The present invention also includes a pigment whose surface is coated with a polymer, a radically polymerizable monomer, a photopolymerization initiator, and an acidic group-containing carmer containing at least one (meth)acryloyl group in one molecule. The present invention provides a photocurable light-shielding adhesive composition characterized by the following.

The present invention will be explained in detail below.

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 whose surface is coated with a polymer used in the present invention is one whose surface is almost uniformly coated with a polymer by a method such as a suspension polymerization method. , 27-32. 1988.

(Method for producing a pigment whose surface is coated with a polymer) Pigment and anionic surfactant are placed in a four-bottle flask equipped with a stirrer, and after creating a nitrogen atmosphere in the reactor, distilled water is poured and stirred. After a certain period of time, a polymerizable monomer is added, the temperature is raised to 60 t, a polymerization initiator is subsequently added, and the mixture is stirred with a nitrogen pressure bar. Polymerization is carried out while adding the polymerizable monomer (twice).

After a predetermined reaction time has elapsed, the flask is cooled and a polymerization inhibitor is added to stop the reaction. Wash and dry the reaction product.

The pigment used in the pigment whose surface is coated with a polymer used in the present invention may be either an inorganic pigment or an organic pigment, and specific examples include titanium white, titanium yellow, titania, red iron oxide, ultramarine blue, and iron oxide. Preferably, titanium white, titanium yellow red iron, etc. are used. In addition, the polymerizable monomer that becomes the polymer used in the pigment whose surface is coated with a polymer is liquid at room temperature because the pigment surface is coated with the polymer by suspension polymerization, etc., and is insoluble or poorly soluble in water. Specifically, monofunctional and polyfunctional (
Examples include meth)acrylates, vinyl compounds, and alkenylbenzenes.

More specifically, monofunctional (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, Ethylene glycol di(meth)acrylate, neopentyl glycol di( meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Ni＞Cow( CHzCH*O)-<ΣOKΣ(OCHzC
lk). ocobe (4), (In the above formulas 1 to 5, R is a hydrogen atom or a methyl group, m and n are positive integers, and m + n = 2 to 10.), vinyl chloride which is a vinyl compound, odor Vinyl halides such as vinyl oxide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether; and styrene, which is an alkenylbenzene.
Examples include vinyltoluene, α-methylstyrene, chloromethylstyrene, and stilbene.

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

In addition, when the polymerizable monomer that becomes the polymer that coats the surface of the pigment is 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 light-shielding properties and polymerizability, and is therefore preferable.

Incidentally, the pigment whose surface is coated with a polymer may be produced by a method other than the above-mentioned method of polymerizing the polymerizable monomer on the pigment surface, and the polymer used may include commonly used polymers such as polyester and polyurethane. It may be a polymer.

Specifically, the radically polymerizable monomer used in the present invention is:
Examples include monofunctional and polyfunctional (meth)acrylates.

More specifically, monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethyl-hexyl (meth)acrylate, dodecyl ( Hydrocarbon group-containing (meth)acrylates such as meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2
- Hydroxyl group-containing (meth)acrylates such as hydroxypropyl (meth)acrylate, ethylene glycol 1,000 methyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monododecyl ether (meth)acrylate, diethylene glycol 1,000 methyl ether (Meth)acrylate, (meth)acrylate containing ethylene glycol units such as polyethylene glycol methyl ether (meth)acrylate, polyethylene glycol monoethyl ether (meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctyl (meth)acrylate (meth)acrylates containing fluorine substituents, silane-based (meth)acrylates such as γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltri(trimethylsiloxy)silane, tetrahydrofurfuryl ( Examples include meth)acrylate and the like.

Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and butylene glycol di(meth)acrylate.
Polymers of alkane polyols such as acrylate, neobentyl glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. (meth)acrylate, diethylene glycol di(meth)acrylate, dibrobylene glycol di(meth)acrylate, triethylene glycol di(
Poly(meth)acrylate of (poly)oxyalkane polyol such as meth)acrylate, tetraethylene glycol di(meth)acrylate, dibutylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, general formula (1) % formula % (wherein R is a hydrogen atom or a methyl group, n is 0 or a positive integer, R1 is +C) 12+7, (-CH2+4, epoxy (meth)acrylate represented by the general formula (
II) (In the formula, R1 is a hydrogen atom or a methyl group, R2 is t, N5 -0-'”・-0-゛CB.

BeE-’“・(Σ・ CM.

shi113 Yaku=〉OC820Yo or Shii3 is shown. ) Alicyclic or aromatic di(meth)acrylate compounds represented by general formula (III) (wherein represents a hydrogen atom or a methyl group, or Bekobe=); Di(meth)acrylate compounds, polyfunctional (meth)acrylate compounds having at least one urethane bond in one molecule, such as 1 mol of diisocyanate compound and hydroxyl group-containing compounds such as 2-hydroxyethyl (meth)acrylate ( Examples include adducts with 2 moles of meth)acrylate.

Note that as the diisocyanate compound, any of aliphatic, alicyclic, and aromatic diisocyanates can be used, such as hexamethylene diisocyanate,
Lysine diisocyanate, 2.2 (4), 4-trimethylhexamethylene diisocyanate, dicyclohexyldimethylmethane-p,p-diisocyanate, isophorone diisocyanate, tolylene diisocyanate,
Examples include xylylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate.

More specifically, (in the above formulas 6 to 14, R represents a hydrogen atom or a methyl group), etc. can be exemplified.

In addition to the above-mentioned examples, the polyfunctional (meth)acrylate includes the general formula (IVI (wherein, R1 is a hydrogen atom or a methyl group, R2 has at least one aromatic ring, and There is a polyfunctional (meth)acrylate represented by (having an oxygen atom or a sulfur atom and showing the number), (In the above formulas 15 to 20, R is a hydrogen atom or a methyl group, and m and n are positive integers. , m+nx2~20
It is. ) etc. can be exemplified.

Among these, alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, hexyl (meth)acrylate, dodecyl (meth)acrylate, etc.
Acrylate or 2-hydroxyethyl (meth)
Acrylate, hydroxyl group-containing (meth)acrylate such as 2-hydroxypropyl (meth)acrylate, poly(meth)acrylate of alkane polyol, poly(meth)acrylate of (poly)oxyalkane polyol, epoxy (meth)acrylate, per molecule at least 1 in
Preferred are aliphatic or alicyclic (meth)acrylates having two urethane bonds, and poly(meth)acrylates of (poly)oxyalkane polyols having an aromatic ring, such as methyl methacrylate, n-hexyl methacrylate, 2-hydroxy Ethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol di(meth)acrylate, neopentyl glycol (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1':l+.

(In the formula, m and n represent positive integers, m+nw2~1
It is 0. ) (where m and n represent positive integers, m
+n=2-10. ) etc. are more preferable.

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

(In the formula, R represents a hydrogen atom or a methyl group.) The photopolymerization initiator used in the present invention is preferably one that is stable for a long time at room temperature, and specifically, an α-ketocarbonyl compound alone or an α-ketocarbonyl compound alone or - A ketocarbonyl compound and an amine or an aromatic nitrogen-containing clamp ring compound are used in combination.

α-ketocarbonyl compounds include α-diketone, α
Examples include -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'-jethoxybenzyl, 4.4'-oxybenzyl, 4.4' -dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone,
1. α-diketones such as 2-cyclohexanedione, α-ketaldehydes such as methylglyoxal and phenylglyoxal, pyruvic acid, benzoylformic acid, phenylpyruvic acid, methylpyruvate, ethyl benzoylformate, methyl phenylpyruvate, phenylpyruvic acid Examples include carboxylic acids such as butyl and esters thereof.

Among these α-ketocarbonyl compounds, α-diketones are preferred from the viewpoint of stability, and diacetyl, benzyl, and camphorquinone are more preferred.

The amines used as photopolymerization initiators are preferably aliphatic amines or aromatic amines.

Particularly suitable aromatic amines have the general formula [V] (wherein R1 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, R2 is a hydrogen atom, an alkyl group, a hydroxyalkyl group, or an aryl group, and R' is an acyl group. , a carboxy group, an alkoxycarbonyl group, a hydroxyacyl group, a carbamoyl group which may have a substituent, a cyano group, a nitro group, a halogen atom, n is a positive integer of 5 or less). It is a substituted aromatic amine.

Specifically, such substituted aromatic amines include 4-
Dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-(methylphenylamino)induldehyde, 4-(β-hydroxyethylmethylamino)benzaldehyde, 4-dimethylaminobenzoic acid,
4-diethylaminobenzoic acid, 4-(methylphenylamino)benzoic acid, 4-(β-hydroxyethylamino)
Benzoic acid, methyl 4-dimethylaminobenzoate, methyl 4-diethylaminobenzoate, methyl 4-(methylphenylamino)benzoate, propyl 4-(β-hydroxyethylmethylamino)benzoate, phenyl 4-dimethylaminobenzoate , 4-dimethylaminophthalic acid, dimethyl 4-dimethylaminoisophthalate, N,N-dimethylcyanoaniline, N,N-dimethylnitroaniline, N
, N-dimethylchloroaniline, N,N-dimethylbromoaniline, N,N-dimethyl-0-iodoaniline,
N,N-diethylcyanoaniline, N,N-diethyl-
p-Chloraniline, 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 preferred, and 4-diethylaminobenzoic acid is preferred. More preferred.

In addition, the aromatic nitrogen-containing linear gold ring compound used as a photopolymerization initiator has the general formula [Vl] [where X is >NR', an oxygen atom or a sulfur atom, Y is a hydrogen atom, -3R'' or 1 ~Trivalent metal, R1 represents an alkyl group, an aryl group, an aralkyl group, or a halogen atom, and n is an integer of 0 to 4. When n is 2 or more, R1 may be the same or different groups. R2 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R3 is an alkyl group, an aryl group, or a general formula [■] (wherein, X, R', and n are the above general formula [VI]
It is an aromatic nitrogen-containing linear metal ring compound represented by ].

Specific examples of such aromatic nitrogen-containing linear metal ring compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptomethylbenzimidazole, and 2-mercaptobenzimidazole.
-Mercaptomethylbenzoxazole, 2-mercaptomethylbenzothiazole, dibenzoxazyl disulfide, dibenzothiazyl disulfide, 2-(phenylthio)benzothiazole, and metal salts thereof, such as sodium salt, zinc(11) salt, copper(11) ) salt, nickel salt, 2-mercaptodimethylbenzimidazole, 2-mercaptodimethylbenzoxazole, 2-mercaptodimethylbenzothiazole, and the like.

Among these aromatic nitrogen-containing linear gold ring compounds, 2-
Mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-
Preferred are mercaptomethylbenzothiazole, dibenzothiazyl disulfide, zinc (II) salt of 2-mercaptobenzimidazole, zinc (II) salt of 2-mercaptobenzothiazole, and zinc (II) salt of 2-mercaptomethylbenzothiazole. Mercaptobenzothiazole, 2-mercaptomethylbenzothiazole, 2
- Zinc salt of mercaptobenzothiazole and zinc (II) salt of 2-mercaptomethylbenzothiazole are more preferred.

The photocurable light-shielding adhesive composition of the present invention also includes a pigment whose surface is coated with a polymer, a radically polymerizable monomer, a photopolymerization initiator, and at least one (meth) in each molecule.
Contains an acidic group-containing monomer containing an acryloyl group.

Among the above components, the pigment whose surface is coated with a polymer, the radically polymerizable monomer, and the photopolymerization initiator are as described above.

Specifically, the acidic group-containing monomer containing at least one (meth)acryloyl group in one molecule is an aromatic polycarbonate containing at least one (meth)acryloyloxyl group in one molecule. An acid or its acid anhydride, a monofunctional (meth)acrylamide monomer represented by the general formula [■] (wherein R represents a hydrogen atom or a methyl group), at least one ( Examples include partial esters of phosphoric acid or sulfonic acid (monoesters of phosphoric acid, diesters or mixtures thereof, monoesters of sulfonic acid) containing a meth)acryloyloxyl group.

Specifically, the aromatic polycarboxylic acid containing at least one (meth)acryloyloxyl group in one molecule or its acid anhydride has at least two hydroxyl groups in one molecule, and , at least one hydroxyl group forms an ester of (meth)acrylic acid among the alkane polyols which may contain an oxygen atom, and at least one hydroxyl group forms at least three carboxyl groups. Examples include (meth)acryloyloxyl group-containing aromatic polycarboxylic acids having a structure in which an ester is formed with one carboxyl group of an aromatic polycarboxylic acid, or an acid anhydride thereof.

Among the aromatic polycarboxylic acids having at least three carboxyl groups, at least two carboxyl groups among the at least three carboxyl groups are bonded to adjacent carbon atoms on the aromatic nucleus. Acids are preferred, and specific examples include hemimellitic acid, trimellitic acid, blendic acid, merophanic acid, pyromellitic acid, and tonic acid.

The aromatic polycarboxylic acid containing at least one (meth)acryloyloxyl group in one molecule or its acid anhydride includes 4-(meth)acryloyloxymethoxycarbonylphthalic acid or its acid anhydride; (
meth)acryloyloxyethoxycarbonylphthalic acid or its acid anhydride, 4-(meth)acryloyloxybutoxycarbonylphthalic acid or its acid anhydride, (wherein R is a hydrogen atom or a methyl group, and n is an integer of 6 to 12) (In the formula, R is a hydrogen atom or a methyl group, n is an integer of 2 to 50.), (In the formula, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 50. ), 4-[2-hydroxy-3-(meth)acryloyloxyethoxycarbonylphthalic acid or its acid anhydride, 2
．． 3-bis(3,4-dicarboxybenzoyloxy)
Propyl (meth)acrylate or its acid anhydride, 2
-(3,4-dicarboxybenzoyloxy)1.3-
Examples include dimethacryloyloxypropane or its acid anhydride.

Specifically, the monofunctional (meth)acrylamide monomer represented by the general formula [■] includes 3-(meth)acryloylaminosalicylic acid, 4-(meth)acryloylaminosalicylic acid, 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
Examples include -(meth)acryloylaminobenzoic acid, 4-hydroxy-3-(meth)acryloylaminobenzoic acid, and the like.

In addition, as partial esters of phosphoric acid or sulfonic acid containing at least one (meth)acryloyloxyl group in one molecule (monoesters of phosphoric acid, diesters or mixtures thereof, monoesters of sulfonic acid), specific include 2-(meth)acryloyloxyethyl phenyl azide phosphate, bis(2-(meth)acryloyloxyethyl)acidophosphate, bis(3-(meth)acryloyloxypropyl)acidophosphate, 2-(meth)acryloyloxy Examples include ethyl phenylphosphonate, (in formulas 21 to 25 above, 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 its acid anhydride;
Alternatively, a monofunctional (meth)acrylamide monomer represented by the general formula [■] is preferable, and 4-(meth)acryloyloxyethoxycarbonylphthalic acid or its acid anhydride, or 4-(meth)acryloylamino Salicylic acid and 5-(meth)acryloylaminosalicylic acid are more preferred, and 4-methacryloyloxyethoxycarbonylphthalic anhydride is particularly preferred because it improves adhesive strength to teeth, water resistance, and durability.

The blending ratio of the pigment whose surface is coated with a polymer used in the present invention and the radically polymerizable monomer is not particularly restricted, but usually, the pigment whose surface is coated with a polymer is 1 to 99%, and the amount of the radically polymerizable monomer is 99 to 99%. 1%, preferably 5-95% of pigment surface coated with polymer, 9% of radically polymerizable monomer
5 to 5%, more preferably 20 to 80% pigment whose surface is coated with polymer, and 80 to 20% radically polymerizable monomer.
%. When it is within this range, the physical properties of the cured product and the light-shielding property are well balanced, which is preferable.

Further, the blending ratio of the photopolymerization initiator used in the present invention is usually 30 to 0, ooi%, to the radically polymerizable monomer.
Preferably 10-0.01%, more preferably 5-0
．． It is 1%. Within this range, rapid and sufficient polymerization occurs.

Further, the blending ratio of the acidic group-containing polymer containing at least one (meth)acryloyl group in one molecule used in the present invention is usually 100 to
It is 0.001%, preferably 30-0.01%, more preferably 10-0.1%. In this range,
Sufficient adhesive strength and adhesive durability can be obtained.

In the present invention, other components such as a thermal radical polymerization initiator, a room temperature radical polymerization initiator, an organic polymer, a powdery inorganic filler, a polymerization inhibitor, etc. may be blended as necessary in addition to the above-mentioned essential components. I can do it.

Examples of the thermal radical polymerization initiator include dibenzoyl peroxide, dilauroyl peroxide, di-t
-Butyl peroxide, etc. can be mentioned.

Examples of room-temperature radical polymerization initiators include trialkylboron and its analogs such as tributylboron, tripropylboron, and partially oxidized analogs thereof, dibenzoyl peroxide, dilauroyl peroxide, di-t -Organic peroxide such as butyl peroxide and N,N-dimethylaniline, N,N-dimethyl-
Examples include mixtures with amines such as p-toluidine, N,N-jetanol-p-toluidine, and mixtures of aromatic sulfinic acids and acidic compounds such as p-toluenesulfinic acid and benzenesulfinic acid. can.

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

Examples of the powdered inorganic filler include kaolin, talc, clay silica, silica-alumina, glass powder, and quartz powder.

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

2.6E (In the formula, m+nx2.6 (average)) DMA <Example> Next, the present invention will be specifically explained using examples.

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

Abbreviation Official name or chemical formula MMA... Methyl methacrylate MA n-hexyl methacrylate G Triethylene glycol dimethacrylate PEMA DMA Bis-GMA -META (CHI) (H) -MET -MASA -MASA EBA MBA PQ QME IH N, N-diethylaminobenzoic acid N, N-dimethylaminobenzaldehyde camphor 1-quinone hydroquinone monomethyl ether (Reference Example I) Manufacturing method of pigment whose surface is coated with polymer Attach a stirring blade to a four-bottle flask with a capacity of 500 mJi , 30 g of rutile titanium dioxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.087 g of sodium dodecyl sulfate (0.3 mmo
fL) and create a nitrogen atmosphere inside the reactor, then distilled water 300mJ! was injected, and the contents were stirred by rotating the stirring blade at 30 rpm. After 1 hour, increase the rotation speed to 60O
rpm, and after adding 3 g of methyl methacrylate (MMA, manufactured by Wako Pure Chemical Industries, Ltd.) and stirring for an additional 10 minutes, the temperature inside the reactor was raised to 60°C. To this, add 0.082 g of potassium sulfate as a radical polymerization initiator to 10 mJ of water.
Add the solution dissolved in l. 60 minutes and 120 minutes after the addition of the polymerization initiator, 3 g of MMA was further added, and stirring was continued at 60° C. for an additional 60 minutes to polymerize the MMA.

After the polymerization is completed, the temperature inside 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 at 60° C. under reduced pressure (100 mmHg) in a nitrogen stream until a constant weight is reached.

Polymethyl methacrylate (PMMA) in the resulting composite
) is determined from the weight loss/residual amount when the temperature is raised to 500°C using a thermal analyzer.

Further, the generated PMMA is injected from the complex using acetone, and its number average molecular weight is calculated as a polystyrene equivalent molecular weight using gel permeation chromatography (GPC).

Afterwards, titanium dioxide whose surface was coated with this polymer was
It is called polymer-coated titanium dioxide.

(Reference Example If) Method for evaluating the adhesion strength and adhesion durability of a photocurable light-shielding adhesive composition to metal. Sandblast using alumina with a diameter of 10 μm. This sample is ultrasonically cleaned in acetone for 10 minutes, dried, and a cellophane tape with a thickness of 200 μm with holes of 5 mm in diameter is attached to the surface to define the adhesion surface area and the thickness of the composition. A photocurable light-shielding adhesive composition is placed in a bottle, a cellophane tape is attached to the surface, and the composition is pressed against a flat glass plate to maintain a constant thickness (20011 m). This was applied using a dental visible light irradiator (manufactured by Kultur, Dentacolor X).
S■) and irradiated with light for 90 seconds to cure.

After removing the cellophane tape, a Teflon mold with a thickness of 1 mm with a hole of 5 mm in diameter was attached, and a bottle of dental hard resin (manufactured by Sun Medical Co., Ltd., Metacolor ■ EN-AED DB-2) was placed in the hole, and the above-mentioned 9 in a dental visible light irradiator
Cure by irradiating light for 0 seconds.

An acrylic rondo with a diameter of 6 mm is adhered to this using a dental adhesive (Super Bond ■, manufactured by Sun Medical Co., Ltd.).

This sample is subjected to a tensile test as it is, or it is placed in a heat cycle tester and the temperature is repeated 2000 times at 4 to 60°C, and then a tensile test is conducted to measure the force (adhesion strength, adhesion durability) when the sample is peeled off. Note that the test conditions were a temperature of 23° C. and a tensile speed of 2 mm/min.

[Examples 1 to 11, Comparative Examples 1 to 10] A mixture containing the components listed in Table 1 in the amounts listed in Table 1 was placed in a Teflon mold with a depth of 1 mm and a diameter of 10 mm, and a dental visible light irradiator was placed. (Dentacolor XS
(2) Light was irradiated for 90 seconds.

Immediately after irradiation, the sample was removed from the irradiator, removed from the Teflon solder, the uncured portion was removed, and the cured thickness was measured using a micrometer.

The results are shown in Table 1.

[Examples 12 to 23] Using a photocurable light-shielding adhesive composition containing the components listed in Table 2 in the amounts listed in Table 2, the force during sample peeling was measured by the method shown in Reference Example II. did.

The results are shown in Table 2.

(Example 24) The surface of a dental cobalt-chromium alloy (Metacast ■, manufactured by Sun Medical Co., Ltd.) measuring 10 mm x 1 O mm x 3 mm was sandblasted using alumina with a particle size of 10 μm. This sample was ultrasonically cleaned in acetone for 10 minutes, dried, and a thickness of 2 mm with holes of 5 mm diameter formed on the surface.
A cellophane tape of 1 m at 00°C was attached to determine the adhesion surface area and the thickness of the composition. On the surface, MMA/
Applying a composition of 4-META=9515 using a brush,
Blow air lightly to spread it evenly. in addition,
Polymer coated titanium dioxide/UDMA/CPQ/DE
BA/HQME=1 00/200/2/110.02
The composition of No. 4 was placed in a bottle, cellophane tape was attached to the surface, and the bottle was pressed against a glass plate with a flat surface to make the composition thickness constant (200 μm). This was applied using a dental visible light irradiator (manufactured by Kultur, Dentacolor X).
S■) and was cured by irradiating light for 90 seconds.
After removing the cellophane tape, a Teflon mold with a thickness of 1 mm with a hole of 5 mm in diameter was attached, and a bottle of dental hard resin (manufactured by Sun Medical Co., Ltd., Metacolor ■ Shade DB-2) was placed in the hole. It was cured by irradiating it with light for 90 seconds in a visible light irradiator.

An acrylic rod with a diameter of 6 mm was adhered to this using a dental adhesive (Superpond ■, manufactured by Sun Medical Co., Ltd.).

Place this sample in a heat cycle tester and test it at 4°C to 60°C.
After repeating 2000 times, the temperature was 23℃ and the speed was 2mm.
A tensile test was conducted under the condition of /min, and the force when the sample was peeled off was measured.

As a result, the adhesive corrosion resistance was 132 kg/ca2.

(Example 25) Instead of the composition of MMA/4-META=9515, M
The process was carried out in the same manner as in Example 17 except that the composition MA15-MASA-98/2 was used, and the force at the time of sample peeling was measured.

Adhesion durability was 118 kg/cm''.

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

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

Furthermore, a photocurable light-shielding adhesive composition having excellent photocurability and excellent adhesive strength and adhesive durability to metals, teeth, etc. can be obtained.

The above composition can be effectively used, particularly as a dental prosthetic agent.

Claims (2)

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