JPH03109307A - Light-shielding composition - Google Patents

Abstract

PURPOSE:To provide the subject composition giving the cured product having excellent mechanical properties, durability, operability, adhesivity, etc., by containing a pigment surface-treated with a titanate coupling agent, a radically polymerizable monomer and a radical polymerization initiator. CONSTITUTION:A light-shielding composition contains (A) a pigment such as TiO2 or WO3 surface-treated with a titanate coupling agent (e.g. isopropyldimethalisostearoyl titanate), (B) a radical polymerizable monomer such as methyl (meth)acrylate ester or an alkanepolyol (meth)acrylate and (C) a radical polymerization initiator such as an organic peroxide or azo compound. The addition of an acidic group-containing monomer containing at least one (meth)acryloyl group, such as an aromatic polycarboxylic acid containing (meth)acryloyl groups, to the composition permits to improve especially the adhesivity of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a light-shielding composition that has excellent mechanical properties, operability, extubation properties, and the like. More specifically, the present invention relates to a light-shielding composition that exhibits high mechanical properties, durability, operability, neck attachment, etc., and is used, for example, in dental treatment.

Technical Background of the Invention In dental treatment, when the crown of a tooth is damaged due to caries, etc., a person who combines metal and dental hard resin]
- A method has been adopted in which a crown is used to replace the missing part of the tooth. In this case, a light-shielding curable composition (opaque) containing a large amount of light-shielding pigment such as titanium white is used between the metal and the hard resin in order to erase the color of the metal.

Conventionally, as such opaque) heat-curable light-shielding cured products containing radically polymerizable monomers, inorganic fillers, and peroxides (JP-A-61-12771 and JP-A-61-15271) 5), and dental base materials containing polymerizable (meth)acrylic acid esters, photopolymerization catalysts, and pigments such as zirconium dioxide, tungsten trioxide, and titanium dioxide (see JP-A-59-110806). ) etc. are used.

However, in opaque materials for dental treatment, it is often difficult to properly mix pigments and radically polymerizable monomers due to their poor compatibility (wettability). There was an operational problem in that the particles could separate over time. Furthermore, in the cured product formed using such a composition, defects are likely to occur near the interface between the pigment and the polymerized cured product of the radically polymerizable monomer for the same reason. If this occurs, the mechanical properties (compressive strength, bending strength, etc.) of the cured product of the composition deteriorate, resulting in problems such as destruction of the opaque material portion during use.

Invention 1-1 The present invention attempts to solve the problems associated with the prior art as described above, and by using pigments that have been subjected to a specific surface treatment, mechanical properties, durability, Our goal is to provide a light-shielding composition with excellent properties such as ease of use.

Furthermore, it is an object of the present invention to provide a light-shielding adhesive composition having excellent properties such as mechanical properties, durability, and operability.

Summary of the Invention The light-shielding composition according to the present invention comprises: a pigment (B) whose surface has been treated with a titanate coupling agent (A), a radically polymerizable illumer (C), and a radical polymerization initiator (D). It is characterized by containing.

Furthermore, the light-shielding composition according to the present invention includes a pigment (B) surface-treated with a titanate coupling agent (A), a radically polymerizable +11 ffi body (C), a radical polymerization initiator, and It is characterized by containing an acidic group-containing monomer (E) containing at least one (meth)acryloyl group.

Since the surface of the pigment used in the light-shielding composition and light-shielding adhesive composition of the present invention is treated with a titanate coupling agent, it has a high resistance to other components such as radically polymerizable monomers. Due to its good wettability, this pigment can be well mixed with other components such as radically polymerizable monomers, and in a polymerized and cured product containing such a pigment, the pigment and radically polymerizable monomer can be mixed well. Defects are less likely to occur at the junction between the polymer and the cured polymer. Therefore, by using the composition and the extubable composition of the present invention, a cured product with excellent mechanical properties is formed.

Detailed Description of the Invention The light-shielding composition and light-shielding adhesive composition of the present invention will be described in detail below.

The light-shielding composition of the present invention contains a pigment surface-treated with a titanate coupling agent, a radically polymerizable monomer, and a radical polymerization initiator.

The surface of the pigment (B) used in the present invention is treated with a titanate coupling agent (A).

In the present invention, as the titanate coupling agent (A) used for treating the surface of the pigment, commonly used titanate coupling agents can be used. Examples include: isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl)
Titanate, Tetraoctylbis(ditridecylphosphite) titanate, Tetra(2,2-diallyloxymethyl-1-butylhubis(ditridecyl)phosphite titanate, Bis(
Dioctyl pyrophosphate) oxyacetate titanate, Bis(dioctyl pyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, Isoprolyl dimethacrylylisostearoyl titanate, Isopropyl tridodecyl benzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, Isopropyl tri( Mention may be made of dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

Such titanate coupling agents can be used alone or in combination. Among such titanate coupling agents, isopropyl dimethacrylylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, or isopropyl tri(dioctyl phosphate) is particularly suitable.
h) Preference is given to using titanates.

In the present invention, as the pigment (B) that is surface-treated with the titanate coupling agent as described above, both hexagonal pigments and inorganic pigments can be used. Specific examples of pigments that can be used in the present invention include titanium dioxide, zirconium dioxide, tungsten trioxide, titanium yellow, titania, red iron oxide, ultramarine blue, and iron oxide.

These pigments can be used alone or in combination.

Among such pigments, it is particularly preferable to use titanium dioxide, zirconium dioxide, tungsten dioxide or titanium yellow.

In the present invention, a monofunctional monomer (C1) and/or a polyfunctional monomer (C2) can also be used as the radically polymerizable monomer (C).

Specifically, it is preferable to use a monofunctional (meth)acryloyl compound as the polyfunctional monomer (C1).

Such li-functional monomers (cl) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (
Hydrocarbon esters of (meth)acrylic acid, such as meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, and Hydroxyalkyl esters of (meth)acrylic acid such as 2-hydroxypropyl (meth)acrylate; ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monododecyl ether (meth)acrylate, diethylene glycol (Poly)alkylene glycol monoether (meth)acrylates such as monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, and polyethylene glycol monoethyl ether (meth)acrylate; trifluoroethyl (meth)acrylate;
acrylates, and fluoroalkyl esters of (meth)acrylic acids such as perfluorooctyl (meth)acrylate; γ-(meth)acryloxypropyltrimethquinone, γ-(meth)acryloxypropyltri(trimethylsiloxy)silane Examples include silane compounds having a (meth)acryloxyalkyl group such as, and tetrahydrofurfuryl (meth)acrylate.

In addition, as the polyfunctional qt m-form (C2), for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene gelicoldi(meth)acrylate, neobentyl glycol di(meth)acrylate, Alkane polyol (meth)acrylates such as hexylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; and diethylene glycol di(meth)acrylate acrylate, dibropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dibutylene glycol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate ( Examples include poly)oxyalkane polyol poly(meth)acrylate and the like.

Furthermore, as the polyfunctional lit m-form (C2), in addition to the above, for example, epoxy (meth)acrylate represented by the formula shown below: (wherein, R represents a hydrogen atom or a methyl group, and n represents ,0
or a positive integer, R is -(C112> 2- -(CIl□)T-
(In the formula, R represents hydrogen or a methyl group, and R1 represents.

) Represents an alicyclic di(meth)acrylate represented by the following formula. ) Alicyclic or aromatic di(meth)acrylates represented by the following formula; (wherein, R represents hydrogen or a methyl group, and represents R1 or).

Furthermore, polyfunctional (meth)acrylates having at least one urethane bond in the molecule, such as adducts of 1 mole of a diisocyanate compound and 2 moles of a hydroxyl group-containing (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, etc. can also be exemplified. As the diisocyanate compound used in this case, either an aliphatic alicyclic diisocyanate or an aromatic diisocyanate can be used. Thus, for example, hexamethylene diisocyanate, lysine diisocyanate, 2.2.4- or 2.4.4-trimethylhexamethylene diisocyanate-1, dicyclohexyldimethylmethane-f), f)-diisocyanate, isophorone. Examples include diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate.

Therefore, as the polyfunctional (meth)acrylate having at least one urethane bond in the molecule, for example, (wherein R represents a hydrogen atom or a methyl group), (wherein, R represents a hydrogen atom or a methyl group), ) (in the formula, R represents a hydrogen atom or a methyl group) (in the formula, R represents a hydrogen atom or a methyl group), (in the formula, R represents a hydrogen atom or a methyl group), (in the formula, R represents a hydrogen atom or a methyl group), (in the formula, R represents a hydrogen atom or a methyl group), and the like.

As a polyfunctional (meth)acrylate type Illm,
In addition to the above-mentioned examples, it is further represented by the following formula -0 However, in the above formula, R represents a hydrogen atom or a methyl group, R1 has at least one aromatic ring, and
It represents a divalent aromatic residue which may have an oxygen atom or a sulfur atom in the molecule, and n and m each represent a positive integer.

Such polyfunctional (meth)acrylate +1t H-
O (wherein R represents a hydrogen atom or a methyl group, m+nm
It is 2-20. ), (wherein R represents hydrogen or a methyl group.

(In the formula, R represents a hydrogen atom or a methyl group, m+n-
It is 2-20. ), (wherein R represents a hydrogen atom or a methyl group, m+n-
It is 2-20. ), (wherein R represents a hydrogen atom or a methyl group, m+n-
It is 2-20. ), (wherein R represents a hydrogen atom or a methyl group, m+n-
It is 2-20. ), (wherein R represents a hydrogen atom or a methyl group, m+n=
It is 2-20. ) etc.

Among the above-mentioned examples, examples of the monofunctional 11-mer (CI) include alkyl (meth)acrylate, ethyl (meth)acrylate, hexyl (meth)acrylate, dodecyl (meth)acrylate, etc. Acrylates or hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are preferably used.

In addition, the polyfunctional monomer (C2) includes poly(meth)acrylate of alkane polyol, poly(meth)acrylate of (poly)oxyalkane polyol, epoxy(meth)acrylate, and at least one urethane bond in the molecule. aliphatic or alicyclic (meth)acrylates having a, and poly(meth)acrylates of (poly)oxyalkane polyols having an aromatic ring,
In particular, ethylene glycol di(meth)acrylate, neopentyl glycol (meth)acrylate, triethylene glycol di(meth)acrylate (wherein R represents a hydrogen atom or a methyl group, and m+n-2 to 20). (In the formula, R represents a hydrogen atom or a methyl group), (In the formula, R represents a hydrogen atom or a methyl group), (In the formula, R represents a hydrogen atom or a methyl group), (In the formula, R represents a hydrogen atom or a methyl group, and is m+n-2 to 20.

) etc. are preferred.

These can be used alone or as a mixture of two or more.

In the present invention, as the radical polymerization initiator (D), any compound capable of polymerizing and curing the above monomers can be used without particular limitation. As such a radical polymerization initiator, organic peroxides, azo compounds, trialkylborons and their analogs, mixtures of organic peroxides and amines, etc. are used.

As the organic peroxide, any organic peroxide can be used without particular limitation as long as it is normally used as a polymerization initiator. For example, dibenzoyl peroxide, dilauroyl peroxide, di[-butyl peroxide, 2,5-dimethyl-2,5 di(t-
butylperoxy)hexane, t-butylperoxide, and [-butyl I\hydroberoxybenzoate, etc.].

Any azo compound can be used without particular limitation as long as it is normally used as a polymerization initiator. For example, 2.2°-azobis(4-methoxy-2,4-dimethylvaleronitrile)
, 2.2-azobis(2,4-dimethylvaleronitrile), 2.2-azobisisobutylnitrile, dimethyl-2,2-azobisisobutyrate, 1,l-azobis(1-cyclohexanecarbonitrile), Mention may be made of 2-(carbamoylazo)isobutyronitrile and 2,2-azobis(2-methylbutyronitrile)'8.

Examples of trialkylboron include triethylboron, tri-n-propylboron, triisopropylboron, trilobylboron, triisobutylboron,
Tri-S-amyl boron, tri-S-amyl boron, and the like can be mentioned. Moreover, trialkylboron analogs in which a portion of these is oxidized can also be used.

Furthermore, as the mixture of organic peroxide and amine, a mixture of organic peroxide and aromatic amine as described above is preferably used. Examples of aromatic amines include:
Although any of primary, secondary and tertiary amines can be used, tertiary amines are particularly preferably used. Examples of such aromatic amines include aniline, toluidine, xylidine, phenylenediamine,
N,N-diethylaniline, N,N-di(β-hydroxyethyl)aniline, N,N-dimethyl I.Luidine%
N+N-diethyltoluidine, N,N-dimethylanisidine, N,N-diethylanisidine, N,N-dimethyl-[-butylaniline, N,N-diethyl-butylaniline, N,N-dimethyl-p -chloroaniline,
Examples include diphenylamine and N,N-(β-hydroxyethyl)-p-toluidine. Among these, N,N-dimethyl-p-toluidine, N,N-dimethyl-p-t-butylaniline, N,N
-dimethylanisidine, N,N-dimethyl-p-chloroaniline, N,N-di(β-hydroxyethyl)-〇-
A tertiary aromatic amine having an electron-donating substituent at the p-position of the benzene ring, such as toluidine, is preferably used.

Further, the composition of the present invention can be cured by light irradiation,
It can also be made to exhibit an adhesive function. In such a case, the adhesive composition contains a photopolymerization initiator as a radical ff1 initiator.

The photopolymerization initiator used here is usually α-
Ketocarbonyl compounds are used. Furthermore, this β-ketocarbonyl compound can be used alone or in combination with amines or aromatic nitrogen-containing integrated ring compounds.

As the α-ketocarbonyl compound, for example, α-
Diketones, α-ketoaldehydes, α-ketocarboxylic acids, α-ketocarboxylic acid esters, and the like are preferably used.

More specifically, for example, 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 and 1.
α-diketones such as 2-cyclohexanedione, methylglyoxal; α-ketoaldehydes such as phenylglyoxal; pyruvic acid, benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate and butyl phenylpyruvate, etc. Mention may be made of α-ketocarboxylic acids or esters thereof.

Among these α-ketocarbonyl compounds, α-diketones are particularly preferred from the viewpoint of stability, and for example, diacetyl, benzyl, and camphorquinone are particularly preferably used.

Further, as the amines used in combination with the α-ketocarbonyl compound, aliphatic amines or aromatic amines are preferable. Particularly suitable aromatic amines are substituted aromatic amines represented by the following formula.

However, in the above formula, R1 represents hydrogen, an alkyl group or a hydroxyalkyl group, R2 represents hydrogen, an alkyl group, a hydroxyalkyl group or an aryl group, and R
3 represents an acyl group, a carboxyl group, an alkoxycarbonyl group, a hydroxyacyl group, a carbamoyl group (which may have a substituent), a cyano group, a nitro group, or a nitrogen atom.

Specific examples of such substituted aromatic amines include 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-(methylphenylamino)
Aldehydes such as benzaldehyde, 4-(β-hydroxyethylamino)benzaldehyde; 4-dimethylaminobenzoic acid, 4-diethylaminobenzoic acid, 4-(methylphenylamino)benzoic acid, 4-(
β-hydroxyethylmethylamino)benzoic acid, methyl 4-dimethylaminobenzoate, methyl 4-diethylaminobenzoate, methyl 4-(methylphenylamino)benzoate, propyl 4-(β-hydroxyethylmethylamino)benzoate and benzoic acid derivatives such as phenyl 4-dimethylaminobenzoate, phthalic acid derivatives such as 4-dimethylaminophthalic acid and dimethyl 4-dimethylaminoisophthalate, N,N-dimethylcyanoaniline, N,N-dimethylnitro Aniline, N, N-dimethylchloroaniline, N,
N-dimethylbromoaniline, N,N-dimethyl-〇-
iodoaniline, N, N-diethylcyanoaniline, N
, N-diethyl-p-chloroaniline, N,N-dipropyl-ρ-cyanoaniline, N,N-methylphenyl-
p-cyanoaniline, N,N-β-hydroxyethylmethyl-p-chloroaniline, N,N-dimethyl-2,4
-dicyanoaniline, N,N-dimethyl-2,4-dinitroaniline and N,N-dimethyl-2,4-dichloroaniline.

Among these substituted aromatic amines, 4-dialkylaminobenzaldehyde, 4-dialkylaminobenzoic acid, 4-dialkylaminobenzoic acid ester, N,N-
Dialkyl-p-cyanoaniline and the like are preferred, particularly,
4-diethylaminobenzoic acid is preferably used.

Further, as the aromatic nitrogen-containing condensed ring compound used in combination with the α-ketocarbonyl compound, a sulfur compound represented by the following formula is preferably used.

However, in the above formula, X is >Nl? 2,'-represents a hydrogen atom or a sulfur atom, Y is hydrogen, -3t? It represents a trivalent or mono- to trivalent metal, and R1 represents an alkyl group, an aryl group, an aralkyl group, or a halogen atom. In addition, n represents an integer from 0 to 4, and when n is 2 or more, R1 is the phase r7
．． may be different groups. Furthermore, R2 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Furthermore, R3 is an alkyl group, an aryl group, or a group represented by the following formula.

In the formula, X, R' and n have the same meanings as above.

Examples of such aromatic nitrogen-containing condensation compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
2-mercaptomethylbenzimidazole, 2-mercaptomethylbenzothiazole, dibenzoxazyl sulfide, dibenzothiazyl disulfide, 2-(phenylthio)benzothiazole, and metal salts thereof (e.g., sodium salt, zinc (n) salt, fn (■) salt, nickel salt): 2-mercaptodimethylbenzimidazole,
Examples include 2-mercaptodimethylbenzoxazole and 2-mercaptodimethylbenzothiazole.

Among these sulfur compounds, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole,
-Mercaptobenzothiazole, 2-mercaptomethylbenzothiazole, dibenzothiazyl disulfide, 2
-Mercaptobenzimidazole zinc (If) salt, 2-
Mercaptobenzothiazole zinc (■) salt and 2-mercaptomethylbenzothiazole zinc (n) salt are preferred;
In particular, 2-mercaptobenzothiazole, 2-mercaptomethylbenzothiazole zinc (II) salt, and 2-mercaptomethylbenzothiazole zinc (b) salt are preferably used.

At least i fl,' in one molecule used in the present invention
The acidic group-containing monomer (E) containing a (meth)acryloyl group of il is an aromatic polycarboxylic acid having at least one (meth)acryloxy group in the molecule or its acid anhydride (El).
or, alternatively, partial esters of phosphoric or sulfonic acids having at least one (meth)acryloxy group in the molecule (e.g.
monoesters, diesters or mixtures thereof of phosphoric acid;
monoester of sulfonic acid, etc.) (R2), and the like.

Aromatic polycarboxylic acid having at least one (meth)acryloxy group in the molecule or its acid anhydride (El)
For example, at least one hydroxyl group of an alkane polyol having two or more hydroxy groups (this polyol may contain an oxygen atom in addition to the hydroxyl groups) is (meth)
It forms an ester bond with acrylic acid,
It has a structure in which at least one hydroxyl group forms an ester bond with one carboxyl group of an aromatic polycarboxylic acid having three or more carboxyl groups (
Examples include aromatic polycarboxylic acids containing meth)acryloxy groups or acid anhydrides thereof.

Among the above-mentioned aromatic polycarboxylic acids having three or more carboxyl groups, the aromatic polycarboxylic acids in which at least two carboxyl groups among the three or more carboxyl groups are bonded to adjacent carbon atoms on the aromatic ring are further used. Preferably, it is a carboxylic acid, and specific examples of such aromatic polycarboxylic acids include hemimellitic acid, trimellitic acid, brenidic acid, merofanic acid, pyromellitic acid, and the like.

Examples of the (meth)acryloxy group-containing aromatic polycarboxylic acid or its acid anhydride include 4-(meth)acryloxymethoxycarbonylphthalic acid or its anhydride, 4-(meth)acryloxyethoxycarbonylphthalic acid, or its anhydride, 4-(meth)acryloxybutoxycarbonylphthalic acid or its anhydride, (wherein R represents a hydrogen atom or a methyl group, and n is 6 to
Indicates 12 integers. ), (wherein R represents a hydrogen atom or a methyl group, and n is 2-
Indicates an integer of 50. ), (wherein R represents a hydrogen atom or a methyl group, and n is 1 to
Indicates an integer of 50. ), 4-[2-hydroxycarbonyl]phthalic acid or its acid anhydride, 2,3-bis(3,4-dicarboxybenzoyloxy)propyl (meth)acrylate or its anhydride, 2-(3,4- Examples include dicarboxybenzoyloxy)-1,3-dimethacryloxybroban or its anhydride.

In addition, the partial ester of phosphoric acid or sulfonic acid (monoester of phosphoric acid, diester or mixture thereof, monoester of sulfonic acid) having at least one (meth)acryloxy group in the molecule (E2) specifically includes is, for example, 2-(meth)acryloxyethyl phenyl acid phosphate, bis[2-(meth)acryloxyethyl] acid phosphate, bis[3-(meth)acryloxypropyl] acid phosphate, 2-(meth)
acryloxyethylphenyl phosphate, (wherein R
represents a hydrogen atom or a methyl group), (in the formula, R represents a hydrogen atom or a methyl group) (in the formula, R represents a hydrogen atom or a methyl group), tart-butylacrylamide sulfonic acid (in the formula, R represents a hydrogen atom or a methyl group), represents a hydrogen atom or a methyl group).

Among the acidic group-containing monomers (El) containing at least one (meth)acryloxy group in the molecule, aromatic polycarboxylic acids or acid anhydrides containing at least one (meth)acryloxy group in the molecule is preferably used.

These 111m bodies! 11 can be used alone or as a mixture of two or more.

A composition with excellent adhesiveness can be obtained by blending this component (E) with the other components (A) to (C). When producing the pigment (B), it can also be blended together with the titanate coupling agent (A). In this way, by blending the titanate coupling agent (A) and the acidic group-containing Qiffi body (E) containing at least one (meth)acryloyl group in one molecule and surface-treating the titanate-based coupling agent (A), titanate-based A pigment (B) whose surface is coated with the coupling agent (A) and the acidic L&-containing monomer (E) or its cured product is obtained.

In addition to the components described above, the composition of the present invention may optionally contain other components such as other polymerizable monomers,
It can contain appropriate amounts of organic solvents, powdered inorganic fillers, organic polymers, polymerization inhibitors, and the like.

Examples of polymerizable qt totalers having the above functions include vinyl halides such as vinyl chloride and vinyl bromide, vinyl esters such as vinyl acetate and vinyl propionate, methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether tonovinyl ether. , styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, and alkenylbenzenes such as stilbene.

Examples of organic solvents include ethanol, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, N
, N-dimethylacetamide, N-methylpyrrolidone,
Dimethyl sulfoxide and the like can be mentioned.

Examples of the powdered inorganic filler include kaolin, talc, clay, calcium carbonate, silica, silica Φ alumina, calcium phosphate, glass powder, and quartz powder.

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

The composition according to the present invention comprises: (1) a pigment (B) surface-treated with a titanate coupling agent (A), a radically polymerizable Ill 3 substance (C), and a polymerization initiator (
D), or (2) a pigment (B) surface-treated with a titanate coupling agent (A), a radically polymerizable monomer (C), a polymerization initiator (D), and at least one ( The compositions (1) and (2) above may further contain the above-mentioned other additives as required.

Here, the above (A), (B), (C), (D) and (
The amount of each component (E) can be varied over a wide range depending on the application.

In the composition of the present invention, the titanate coupling agent (A) is usually used in an amount of 0.1 to 100% by weight based on the pigment (B) to be surface treated. In particular, it is preferable to use the titanate coupling agent (A) in an amount within the range of 1 to 20 ffl1%.

Further, the radically polymerizable monomer (C) is usually used in an amount of 5 to 500 fffffi% with respect to the pigment (B) that has been surface-treated with the titanate coupling agent (A). In particular, it is preferable to use the radically polymerizable monomer (C) in an amount within the range of 20 to 200% by weight.

Furthermore, the polymerization initiator (D) is a radically polymerizable monomer (
It is usually contained in an amount of 0.01 to 100% by weight based on C). In particular, the polymerization initiator (D) is 0.1 to 30ffi11
It is preferred to use amounts within the range of %.

The light-shielding composition of the present invention can be obtained by blending the components (A) to (D) in the amounts described above.

By further blending component (E) with such a light-shielding composition, adhesiveness can be particularly improved.

In this case, the acidic group-containing monomer (E) containing at least one (meth)acryloyl group in one molecule is a pigment (
It is usually used in an amount of up to 50% by weight relative to B). In particular, by using component (E) in an amount within the range of 0.1 to 20% by weight, a composition with particularly excellent adhesive properties can be obtained.

The composition according to the present invention comprises (A) to (D) as described above.
It can be prepared by mixing the components or components (A) to (E), but some of the components, for example, except for the polymerization initiator (D), are dissolved in a solvent in advance, and the remaining components are dissolved at the time of use. It is preferable to use it in combination with a component such as a polymerization initiator (D). Alternatively, each component can be applied separately to the surface to which it is adhered, and then mixed and cured on the surface of the tube. By employing the above method, it is possible to effectively suppress the hardening of the composition during storage.

In addition, among the radical polymerization initiators (D), the above-described trial-alkali boron and its analogs are the above-mentioned (A) and (B).
When mixed with monomers such as component The monomer is usually stored separately from the monomers such as components (A), (B), (C) and component (E), and mixed immediately before use.

In addition, when using a mixture of organic peroxide and amines, if the 9-organic peroxide and amines are mixed, a redox reaction will proceed between them, and the polymerization initiation activity will be activated in a relatively short time. In order to prevent the loss of oxidation, it is preferable to store the 9-unit peroxide and the amines separately and mix them immediately before use.

Such a composition of the present invention can be used in the same manner as, for example, commonly used dental adhesive compositions.

Effects of the Invention The light-shielding composition of the present invention has higher operability and strength than conventional dental light-shielding compositions because it contains a pigment whose surface has been treated with a titanate coupling agent. Furthermore, by adding an acidic l&gold-containing it m form containing at least one (meth)acryloyl group in each molecule, it has an excellent balance of light-shielding properties, initial adhesion, adhesion durability, water resistance, etc. It can be suitably used as a light-shielding adhesive composition.

Furthermore, the light-shielding composition according to the present invention can be suitably used as a coating composition for paints and other coatings, for example.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition,
In the following, abbreviations have the following meanings.

MMA: Methyl methacrylate 1G = Ethylene glycol dimethacrylate 3G Nitriethylene glycol dimethacrylate NPG: Neopentyl glycol dimethacrylate-1. GMA: 2.8 E: UDMA: (e113> (I+)) PMMA: Polymethyl methacrylate 1. BPO: dibenzoyl peroxide 4-META: substance DEPT: N,N-jetanol-p-)luidine CQ: camphorquinone DEABA: N,N-diethylaminobenzoic acid Examples include titanium oxide (rutile type, Wako Tsumugi) Isopropyl tri(dioctyl phosphate) titanate (KR-12, manufactured by Ajinomoto ■) in 100 parts by weight of Yakuhin Co., Ltd.) and 50 parts by weight of acetone.
A solution of 2 parts by weight was added and mixed well to form a homogeneous mixture. The acetone was evaporated and removed at room temperature using an evaporator to prepare a pigment whose surface was treated with a titanate coupling agent.

Example 2 Titanium dioxide (rutile type, manufactured by Wako Tsumugiku) 100ffN
For the EL part, 50 fflf parts of acetone and 2 ff of isopropyl dimethacrylylisostearoyl titanate (manufactured by K-Door, Ajinomoto ■)! The dissolved melon part was added and mixed well to form a homogeneous mixture. The acetone was evaporated and removed at room temperature using an evaporator to prepare a pigment whose surface was treated with a titanate coupling agent.

Example 3 The dispersibility of the pigment surface-treated with the titanate coupling agent prepared in Example 1 into a radically polymerizable lit ffi substance was investigated.

50 parts by weight of UDMA (Art Resin 311-5 (1013, manufactured by Negami Tamagyo ■) and 50 parts of 3G (NK Ester 3G, manufactured by Shin Nakamura Chemical Industry ■) were mixed to form a homogeneous mixture. Example 1 Equal amounts of the pigments prepared in 2 and 2 that were surface-treated with a titanate coupling agent or unsurface-treated (titanium dioxide: rutile type, manufactured by Wako Tsumugi Co., Ltd.) were mixed, and their dispersibility was investigated. As a result, the wetting of radically polymerizable monomers with pigments that have not been surface-treated is poor, resulting in uneven areas and poor dispersibility, whereas pigments that have been surface-treated with a titanate coupling agent are It was found that when used, a cream-like homogeneous composition was formed immediately after mixing, and the dispersibility was greatly improved.

Example 4 3G (N ester 3G, manufactured by Shin-Nakamura Chemical Industry ■) 100
Parts by weight, 100 parts by weight of the pigment surface-treated with a titanate coupling agent prepared in Example 2, and 1 part by weight of BPO (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) were mixed and sufficiently kneaded to obtain a uniform composition. Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. Thereafter, polymerization was carried out for 30 minutes at 100° C. and 5 kgf'/c in a dental heat-pressure polymerization pot (manufactured by Shofusha).

After polymerization, it is removed from the mold and the compression test piece is 3 dragons x 3 mm x
3mm, bending test piece is 2 +u x 2 +n x 2
It was ground with #600 emery paper to a thickness of 50 m+*.

Measurement of Compressive Strength A sample was placed on a universal tester, Autograph DO3-500 (manufactured by Yasutsu Seisakusho), and a compressive load was applied at a crosshead speed of 2 ms/+In. The value obtained by dividing the load at which the sample broke by the area to be compressed was defined as the compressive strength.

Autograph I) CS-5 of 11-1 constant sample of bending strength with distance between supporting points of 20 degrees
00, and a load was applied to the center at a crosshead speed of 1/a+in until it broke. Note that the bending strength was calculated using the following formula.

Bending strength (δ) −3Pl, / (2bd) (
kgr/mm2) P: Load at break ffI (kg (') L: Pressure between fulcrums 1f!i (++) b: Thickness of sample (-m) d: Width of sample (in order) Compression and bending samples In both cases, the number of samples was 5, and the average value was calculated and converted to MPa.

The results are shown in Table 1.

(Left below) Comparative Example 1 3G (NK Ester 3G, manufactured by Shin-Nakamura Chemical Industry ■) 100
Parts by weight, titanium dioxide (rutile type, manufactured by Wako Tsumugi Yakimi) 10
0 parts by weight and 1 part by weight of BPO (manufactured by Wako Tsumugi Pharmaceutical ■) were mixed,
The mixture was sufficiently kneaded to form a uniform composition. Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. After this, use a dental heating and pressure polymerization pot (manufactured by Shofusha).
Polymerization was carried out for 30 minutes at 100°C and 5 kgr/c-.

After polymerization, it was removed from the mold and the compression test piece was 311■×3
am x 3 mm, bending test piece is 2IIm x 2II1
After grinding with #600 emery paper to a size of 1 x 2501 mm, the compressive strength and bending strength were measured in the same manner as in Example 4.

The results are shown in Table 1.

Table] - Compressive strength (MPa) Bending strength (MPa) Example 4
41G, 7 114.9 Comparative Example 1
350.8 105.9 Example 5 Titanium dioxide (rutile type, manufactured by Wako Tsumugi Pharmaceutical ■) 100ff1
To 1 part, 2 parts by weight of isopropyltri(dioctylphosphate) titanate (KI?-12, manufactured by Ajinomoto) and 2 parts by weight of 4-methacryloxyethyl trimellitic anhydride were dissolved in 50 parts by weight of acetone, Mix well to obtain a homogeneous mixture. Acetone was evaporated and removed at room temperature using an evaporator to prepare a pigment whose surface was treated with a titanate coupling agent and 4-methacryloxyethyl trimellitic anhydride.

Example 6 100 parts by weight of titanium dioxide (rutile type, manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), 2 parts by weight of isopropyl dimethacrylylisostearoyl titanate (KR-7, manufactured by Ajinomoto Co., Ltd.) and 4-methacrylate trimellitic anhydride were added to 50 parts by weight of acetone. A solution of roxyethyl was added and mixed well to form a homogeneous mixture. Acetone was evaporated and removed at room temperature using an evaporator to prepare a pigment whose surface was treated with a titanate coupling agent and 4-methacryloxyethyl trimellitic anhydride.

Example 7 The dispersibility of the pigment surface-treated with the titanate coupling agent prepared in Example 1 and 4-methacryloxyethyl trimellitate anhydride in a radically polymerizable monomer was investigated.

50 parts by weight of UDMA (Art Resin 511-500B, manufactured by Negami Tamagyo ■) and 50 parts by weight of 3G (NK Ester 3G, manufactured by Shin-Nakamura Chemical Industries) were mixed to form a homogeneous mixture.

Equivalent amounts of pigments that had been surface-treated with a titanate coupling agent or those that had not been surface-treated were mixed with this, and their dispersibility was examined. As a result, the wetting of the radically polymerizable monomer with unsurface-treated pigments is poor, resulting in uneven areas and poor dispersibility, whereas titanate coupling agents and trimellitic anhydride 4- It was found that when a pigment surface-treated with methacryloxyethyl was used, a cream-like homogeneous composition was formed immediately after mixing, and the dispersibility was greatly improved.

Example 8 100 parts by weight of 3G (Light Ester 3G, manufactured by Shin Nakamura Chemical), 100 parts by weight of the pigment surface-treated with the titanate coupling agent prepared in Example 2, BPO (manufactured by Wako Tsumugi Pharmaceutical)
1 part by weight was mixed and sufficiently kneaded to obtain a uniform composition.

Then, place it in a Teflon mold fixed on a glass plate,
The top surface was also fixed with a glass plate. Thereafter, polymerization was carried out for 30 minutes at 100°C and 5 kgf'/c- in a dental heat-pressure polymerization pot (manufactured by Shofu Co., Ltd.).

After polymerization, it was removed from the mold and the compression test piece was 31wIM x 3.
After grinding with emery paper so that the bending test pieces were in the order of 2 x 2 mm x 250, the compressive strength and bending strength were measured in the same manner as in Example 4.

The results are shown in Table 2.

Example 9 50 parts by weight of 3G (Light Ester 3G, manufactured by Shin Nakamura Kagaku ■), UDMA (Art Resin SI+-50013,
50 parts by weight of the titanate coupling agent prepared in Example 2 and 100 parts by weight of the pigment surface-treated with 4-methacryloxyethyl trimellitate anhydride.
1 part by weight of BPO (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was mixed and thoroughly kneaded to obtain a uniform composition.

Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. After this, it was heated to 5 kg f'/c at 100°C in a dental heat-pressure polymerization pot (manufactured by Shofusha).
Polymerization was carried out for 30 minutes under the conditions of d.

After polymerization, it was removed from the mold and the compression test piece was 3IllIX3.
The bending test piece is 2I! I11×2×250■
After grinding with emery paper so that it becomes 1, the compressive strength and bending strength were determined as δP1 in the same manner as in Example 4.

The results are shown in Table 2.

Example 10 UDMA (Art Resin S II-500I3,
100 parts by weight of the titanate coupling agent prepared in Example 2 and trimellitic anhydride 4-
100 parts by weight of a pigment surface-treated with methacryloxyethyl and 1 LIf part of BPO (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) were mixed and sufficiently kneaded to obtain a uniform composition. Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. Thereafter, polymerization was carried out for 30 minutes at 100° C. and 5 kg [′/cd] in a dental heat-pressure polymerization pot (manufactured by Shofu T1.).

After polymerization, it was removed from the mold and compression test 11 was carried out using 3 squares x 311
+1X31111% bending test piece is 2 mm x 2 w
After grinding with emery paper so that the strength was 250 am, the compressive strength and bending strength were determined to be 1 11 J in the same manner as in Example 4.

The results are shown in Table 2.

Comparative Example 2 100 parts by weight of 3G (Light Ester 3G, manufactured by Shin Nakamura Chemical ■), 100 parts by weight of titanium dioxide (rutile type, manufactured by Wako Tsumugi Chemical ■)
Parts by weight and 1 part by weight of BPO (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) were mixed and sufficiently kneaded to obtain a uniform composition. Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. Thereafter, polymerization was carried out for 30 minutes at 100''C and 5kg g'/c in a dental heat-pressure polymerization pot (manufactured by Shofusha).

After polymerization, it is removed from the mold and the compression test piece is 3■■×311
1+1X31111% bending test piece is 2 am X 2
After grinding with emery paper to give mw x 250 +n, the compressive strength and bending strength were measured in the same manner as in Example 4.

The results are shown in Table 2.

Comparative Example 3 50 parts by weight of 3G (Light Ester 8G, manufactured by Shin Nakamura Kagaku ■), UDMA (Art Resin 811-500B).

50 parts by weight, titanium dioxide (rutile type,
100 parts by weight (manufactured by Wako Tsumugi Pharmaceutical ■), BPO (manufactured by Wako Tsumugi Pharmaceutical ■)
1 part by weight was mixed and sufficiently kneaded to obtain a uniform composition.

Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. After this, it was heated to 100°C and 5 kgf'/cd (D
Polymerization was carried out under these conditions for 30 minutes.

After polymerization, it is removed from the mold and the compression test piece is 3mm x 3mm.
3mms bending test piece is 2 wm x 2 mm x 2
After grinding with emery paper so that the strength was 50 +*+e, the compressive strength and bending strength were determined to be ΔP1 in the same manner as in Example 4.

The results are shown in Table 2.

Comparative Example 4 100 parts by weight of UDMA (Art Resin 811-5008. Nedo manufactured by Yugyo), 100 parts by weight of titanium dioxide (rutile type, manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), BPO (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) lf
fi parts were mixed and sufficiently kneaded to obtain a uniform composition.

Thereafter, it was placed on a Teflon mold fixed on a glass plate, and the top surface was also fixed with pressure on the glass plate. Thereafter, polymerization was carried out for 30 minutes at 100° C. and 5 kgr/c− in a dental heating and pressurizing ff1 kettle (manufactured by Shofusha Co., Ltd.).

After polymerization, it was removed from the mold and the compression test piece was 3 mm x 3.
m@X 3 ms, bending test piece is 2 mm X 2
After grinding with emery paper to give +u+ x 250 mm, the compressive strength and bending strength were measured in the same manner as in Example 4.

The results are shown in Table 2.

Table 2 Compressive strength (MPa) Bending strength (MPa) Example 8 Comparative example 2 440.0 350.8 118.9 105.9 Example 9 Comparative example 3 491.9 490.2 147.1 180.5 Example 10 483.2 141.5 Comparative Example 4 452.1 104.8 Example 1
1 To 100 parts by weight of a mixture of 50 parts by weight of GMA (NK Ester D-GMA, manufactured by Shin Nakamura Chemical Industry ■), 50 parts by weight of NPC (NK Ester NPC, manufactured by Shin Nakamura Chemical Industry ■), and DMPT (manufactured by Wako Tsumugi Yakumi) , 80 parts by weight of the pigment surface-treated with the titanate coupling agent prepared in Example 2, and 1 part by weight of BPO (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) were mixed and gently kneaded for about 30 seconds to form a uniform composition. did.

At this time, the blending of the two was very good, and a uniform paste was formed within a few seconds after the start of kneading. Immediately after kneading, the mixture was placed in a Teflon mold fixed on a glass plate, and the top surface was also pressed and fixed with a glass plate. After this, the composition was allowed to fff and harden when left at room temperature for 30 minutes.

After polymerization, it was removed from the mold and the compression test piece was 3 mm x 3.
ms x 3 vgvb, bending test piece is 2 m+s
After grinding with emery paper to give X 2 + m + s X 250 m + *, the compressive strength and bending strength were measured in the same manner as in Example 4.

The results are shown in Table 3.

Comparative Example 5 GMA (NK Ester D-GMA, Shin Nakamura Chemical) Second Industry■
(manufactured by) 50ff! Quantity parts, NPC (NK ester Nr'G,
(Manufactured by Shin Nakamura Chemical Industry ■) 5 [] parts by weight and DMPT (
Titanium dioxide (
80 parts by weight of rutile type (manufactured by Wako Tsumugi Pharmaceutical ■) and lfffffi parts of BPO (manufactured by Wako Tsumugi Pharmaceutical ■) were mixed and gently kneaded for about 30 seconds to obtain a uniform composition.

At this time, the compatibility between the two was clearly worse than in Example 5, and it was likely to become non-uniform. Immediately after kneading, the mixture was placed in a Teflon mold fixed on a glass plate, and the top surface was also pressed and fixed with a glass plate. Thereafter, the composition was allowed to stand at room temperature for 30 minutes to polymerize and harden.

After ff1 /y, remove from the mold, and the compression test piece is 3mm.
×3II■X3111 bending test piece is 2m■X2 ww
After grinding with emery paper to a size of 250 ml, compressive strength and bending strength were measured in the same manner as in Example 4.

The results are shown in Table 3.

Table 3 Compressive strength (MPa) Bending strength (MPa) Example 11
305.8 97.5 Comparative example 5
270.2 91.3 Example 12 100 parts by weight of titanium dioxide (rutile type, manufactured by Wako Tsumugi Yami), 200 parts by weight of acetone, 1 part of isopropyl isostearoyl diacryl titanate (KR-It, manufactured by Ajinomoto Co., Ltd.)
A solution of 0 parts by weight was added and mixed well to form a homogeneous mixture. After evaporating and removing acetone at room temperature using an evaporator, the mixture was further heated under reduced pressure (approximately 1010 mm/1 liter at 80° C. for 1 hour in vacuum drying 4) to prepare a pigment surface-treated with a titanate coupling agent.

Example 13 30 parts by weight of the pigment surface-treated with the titanate coupling agent prepared in Example 6 was mixed with 70 ffl parts of PMMA powder (Superbond powder, manufactured by Sun Medical Co., Ltd.) and mixed well to form a uniform powder. . Separately, a solution was prepared by dissolving 5 parts by weight of 4-META (manufactured by Sun Medical Co., Ltd.) in 95 fiQ parts of MMA (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.).

After polishing the surface of a 1.0 mm x 10 m x 3 plate of dental cobalt-chromium alloy (Metacast, manufactured by Sunmedical 11.) with #600 emery paper, it was thoroughly washed first with water and then with acetone. After that, it was left at room temperature to dry. Cellophane tape with a hole of 5 cm in diameter was pasted on this board to define the adhesion area.

80 parts by weight of the above powder, 100 parts by weight of solution and TBB
-0 (manufactured by Sun Medical Co., Ltd.) 25 ffl quantity (
Immediately after mixing to form a syrup, it was used to bond the cobalt-chromium alloy plate to a PMMAM% tip with a diameter of 6 mm.

After 1 hour, the sample was subjected to 2000 heat cycles of immersion in water at 60°C and 4°C, respectively. after that,
P at a tensile speed of 2 mm/sin at a temperature of 23°C.
Adhesive strength was measured between the MMA rod and the cobalt-chromium alloy plate. The test was conducted on five samples, and the average value was taken as the adhesive strength.

The results are shown in Table 4.

Comparative Example 6 70 parts by weight of PMMA powder (Superbond powder) was mixed with 30 parts by weight of titanium dioxide (rutile type, manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) and stirred well to form a uniform powder. Apart from that, MMA
A solution was prepared by dissolving 5 parts of 4-META (manufactured by Sanmedical 1) in 95 parts by weight (manufactured by Wako Tsumugi Yakumi).

10mm x 10m+s x 3m+s of dental cobalt-chromium alloy (Metacast, Sun Medical L Earthen)
After polishing the surface of the plate with #600 emery paper, it was thoroughly washed first with water and then with acetone, and then left to dry at room temperature. Cellophane tape with a hole of 5 mm in diameter was attached to this plate to define the adhesion area.

80 ffl parts of the above powder, 1 part of 1100 ff solution, and 25 parts by weight of TBB-0 (manufactured by Sun Medical 11.) were quickly mixed to form a syrup, and immediately used to form a syrup with the cobalt-chromium alloy plate having a diameter of 6 mm. +ww was attached to the tip of the PMMA rod.

After 1 hour, the sample was subjected to 2000 heat cycles of immersion in water at 60°C and 4°C, respectively. after that,
P at a temperature of 23°C and a pulling speed of 2n+n/min.
The adhesive strength between the MMA rod and the cobalt-chromium alloy plate was determined to be 71-1. The test was conducted on five samples, and the average value was taken as the contact strength.

The results are shown in Table 4.

Table 4 Contact strength (MPa) Example 13 12.6 Comparative example 6 6.8 Example 14 Titanate cup prepared in Example 6 was added to 50 parts by weight of PMMA powder (Superbond powder, manufactured by Sun Medical). Mix 50 parts by weight of pigment surface-treated with a ring agent,
Stir well to make a uniform powder. Separately, 25 parts by weight of IG (NK Ester IG, manufactured by Shin-Nakamura Chemical Industry), 2.6E
(NK ester 1)-2,617, manufactured by Shin Nakamura Kagaku Tamagoi) 50 parts by weight, UDMA (Art Resin 5IN-50)
08, 25 parts by weight of CQ (manufactured by Wako Tsumugi ■), 2 fff parts of CQ (manufactured by Wako Tsumugi ■) and Yoshibi DEABA (manufactured by Wako Tsumugi ■)
2 parts by weight of the polymerizable monomers were mixed and stirred to form a homogeneous polymerizable monomer mixture.

After polishing the surface of a 10 mw x 10 w x 3 mm plate of dental cobalt-chromium alloy (Metacast, Sunmedical Dosei) with #600 emery paper, first wash thoroughly with water and then with acetone, then let it cool to room temperature. abandoned,
Dry. A cellophane tape with a hole of 50 μm in thickness and 5 mm in diameter was pasted on this plate to define the adhesion area, and then 4-META (manufactured by Sun Medical Co., Ltd.) 5! I! J1
and 95 parts by weight of MMA (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was applied thinly and uniformly using a brush, left at room temperature for 5 minutes, and air-dried.

100 parts by weight of the above powder and 100 parts by weight of the polymerizable monomer mixture
Mix the weight parts quickly, make a homogeneous syrup, put a small amount on the cellophane tape hole on the surface of the cobalt-chromium alloy, cover with thin cellophane, and then press with a glass plate to make this syrup. The thickness was defined as 5 [] μm.

This sample was treated with a dental visible light irradiator (Dentaka-XS).
(manufactured by Kultzer) and exposed to light for 180 seconds to polymerize and cure the composition.

The glass plate and cellophane were removed from this sample, and a PM with a diameter of 60 mm was applied to the polymerized and hardened composition using a dental adhesive (Super Bond, manufactured by Sun Medical Co., Ltd.).
The tip of the MA rod was glued.

After 1 hour, the sample was subjected to 2000 heat cycles of immersion in water at 60°C and 4°C, respectively. after that,
P at a tensile speed of 2 mm/s+in at a temperature of 23°C.
The contact strength between the MMA rod and the cobalt-chromium alloy plate was determined to be 1llll. The test was conducted on five samples, and the average value was taken as the adhesive strength.

The results are shown in Table 5.

Comparative Example 7 131 parts of 50ff of PMMA powder (Superbond powder, manufactured by Sun Medical Co., Ltd.) were mixed with 50fflffi parts of titanium dioxide (rutile type, manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) and stirred well to form a uniform powder. Separately, rG (NK ester IG
, Shin Nakamura Chemical Industry ■) 2Sfii part, 2.6E (NK
Ester D-2,61, manufactured by Shin Nakamura Chemical Industry B1) 5
0 parts by weight, UDMA (7-L, Gin 311-500
25 parts by weight (manufactured by Negami Kogyo ■), 2 parts by weight CQ (manufactured by Wako Tsumugi ■) and 2 parts by weight DEABA (manufactured by Wako Tsumugi ■) were mixed and stirred well to form a homogeneous polymerizable monomer mixture. .

10m+*X 10mm section 3mi of dental cobalt-chromium alloy (Metacast, manufactured by Sun Medical Co., Ltd. L)
After polishing the surface of the board with #600 emery paper and thoroughly cleaning it first with water and then with acetone,
It was left at room temperature to dry. After pasting cellophane tape with a hole of 17 x 5 μm and a diameter of 5111 on this plate to define the area of the horizontal tube, a 5 mm section of 4-META (manufactured by Sun Medical Co., Ltd.) and a 95 mm piece of MMA (manufactured by Wako Tsumugi Co., Ltd.) were attached. A mixture of parts by weight was applied thinly and uniformly using a brush, left at room temperature for 5 minutes, and air-dried.

1. Quickly mix 100 parts by weight of the above powder and 1 m part of m-combinable +1t two-body mixture 10Dff. The thickness of this syrup was defined as 50 μm by making it into a homogeneous syrup and pouring a small amount onto the hole in the cellophane tape on the surface of the cobalt-chromium alloy, covering it with a thin layer of cellophane, and then pressing it with a glass plate.

This sample was heated using a dental visible light irradiator (Dentacolor x81).
(manufactured by Kultur) and irradiated with light for 180 seconds to polymerize and cure the composition.

The glass plate and cellophane were removed from this sample, and a dental adhesive (Super Bond, manufactured by Sun Medical Co., Ltd.) was applied to the polymerized and hardened composition to form a 60 mm diameter P.
The tip of the MMA rod was touched.

After 1 hour, the sample was subjected to 2000 heat cycles of immersion in water at 60°C and 4°C, respectively. after that,
P at a tensile speed of 2 mm/s+In at a temperature of 23°C.
The contact strength between the MMA rod and the cobalt-chromium alloy plate was measured. The test was conducted on five samples, and the average value was taken as the adhesive strength.

The results are shown in Table 5.

table Contact strength (MPsa) Example 14 Comparative example 7 10, 2 7, 8 representative person

Claims (2)

[Claims] (1) A light-shielding composition characterized by containing a pigment (B) surface-treated with a titanate coupling agent (A), a radically polymerizable monomer (C), and a radical polymerization initiator (D) thing. (2) A pigment (B) surface-treated with a titanate coupling agent (A), a radically polymerizable monomer (C), a radical polymerization initiator (D), and at least one (meth) in each molecule. ) A light-shielding composition characterized by containing an acidic group-containing monomer (E) containing an acryloyl group.