JP2001151620A - Dental curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low viscosity dental curable composition not only suitable for the filling of a gum part, root part or very shallow cavity but also suitable for a deep cavity by imparting a polymerization shrinkage and marginal sealing property equivalent to those to a high viscosity dental restoring material to a low viscosity dental restoring material. SOLUTION: This dental curable composition is characterized by containing 100 pts.wt. polymerizable monomer containing >=30 wt.% polymerizable unsaturated bond-containing N-substituted amide compound having an amide bond, (meth)acryloy group or (meth)acrylamide group in its molecular structure, also having at least 1 kind of aromatic ring selected from a group consisting of benzene ring, naphthalene ring and anthracene ring and expressed by the following formula, 50-400 pt.wt. filler having 0.05-1 μm mean particle diameter and 0.03-20 pt.wt. polymerization initiator and showing 3-1,500 poise viscosity of it.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable dental composition suitable as a dental restorative material. More specifically, an object of the present invention is to provide a low-viscosity dental curable composition having a polymerization shrinkage smaller than that of a conventional low-viscosity dental restorative material and applicable to filling a relatively large cavity.

[0002]

2. Description of the Related Art A dental composite restoration material mainly composed of a filler component, a polymerizable monomer (monomer) component, and a polymerization initiator can provide a color tone equivalent to a natural tooth color and is easy to operate. In recent years, it has been frequently used as a restorative material in the dental field. The method of use is generally a method of directly filling a cavity of a tooth using a dental filling device or the like and restoring the tooth by polymerizing and curing by polymerization means such as light irradiation, and is generally called a composite resin. A composite material of viscosity is used.

[0003] However, when covering the cervical and root parts due to hypersensitivity or root caries, the coating is performed without forming a cavity or by forming a very shallow cavity. It was difficult to coat thinly with a composite resin. For this reason, clinically, there is a need for a composite restoration material that can be easily applied to the restoration surface using a small brush or a sponge, and that can be directly filled into the cavity from a syringe. Composite resins with low rates and low viscosities have attracted attention due to their good operability.

However, since the restoration material is made to have a low viscosity by lowering the filling rate of the filler,
Since the polymerization shrinkage ratio during curing is higher than that of the high-viscosity composite resin, when filling into cavities, especially deep cavities, the shrinkage at the periphery of the cavities increases,
There is a risk of secondary caries due to marginal coloration and bacterial invasion from the margins. Therefore, even if it is possible to improve the operability by lowering the viscosity, it is limited to filling the cervical region and root, or a very shallow cavity, or in the case of a deep cavity, filling and curing several times, It is necessary to perform so-called lamination filling, and there is a problem that it is difficult to shorten the chair time by improving operability.

[0005]

SUMMARY OF THE INVENTION The present invention provides a low-viscosity dental restorative material which has the same polymerization shrinkage and marginal sealing properties as a high-viscosity dental restorative material, and has a cervical part and a root part, or An object of the present invention is to provide a low-viscosity dental curable composition suitable not only for filling a very shallow cavity but also for directly filling a deep cavity.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned problems, and as a result, as a polymerizable monomer component of a dental curable composition, a specific polymerizable unsaturated bond containing The inventors have found that the above object can be achieved by using a polymerizable monomer containing 30% by weight or more of the N-substituted amide compound, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0008]

Embedded image

[In the formula, R ¹ is a C ¹ -C 3 -C 1 -C 6 -C 1 -C 3 -C 4 -C 3 -C 1 -C 3 -C 4 -C 1 -C 3 -C 1 -C 3 -C 1 -C 3 -C 4 -C 4 -C 4 -C 4 An organic group, and R ² has the following general formula:

[0010]

Embedded image

Wherein A ¹ and A ² are each independently an oxygen atom or —NH—; B ¹ and B ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, An alkoxy group having 1 to 5 carbon atoms or a phenyl group;
⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms, r ₁ ,
r ₂ and r ₃ are each independently an integer of 1 to 5,
In any group in the formula, the rightmost bond is -COCR
³ = bond and CH _2. Any group represented by｝,
R ³ is a hydrogen atom or a methyl group, and n is 1 to 3
Is an integer. ] The polymerizable unsaturated bond-containing N-
100 parts by weight of a polymerizable monomer containing 30% by weight or more of the substituted amide compound, 50 to 400 parts by weight of a filler having an average particle diameter of 0.05 to 1 μm, and 0.003 to 2 of a polymerization initiator.
A dental curable composition comprising 0 parts by weight, wherein the viscosity is 3 to 1500 poise.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The dental curable composition of the present invention comprises a polymerizable monomer (hereinafter, also referred to as a monomer), a filler,
And a polymerization initiator.

The polymerizable monomer (monomer) used in the present invention contains at least 30% by weight of the polymerizable unsaturated bond-containing N-substituted amide compound represented by the general formula (1).

In the above general formula (1), R ¹ is a C 6-24 carbon atom having 1 to 3 at least one aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring and an anthracene ring. To a trivalent organic group.

R ¹ is not particularly limited as long as it is an organic group satisfying the above conditions.

[0016]

Embedded image Are represented.

In the above equation, R^Five, R⁶, R⁷Passing
And R⁸Are each independently a hydrogen atom, carbon number 1 to 10
Or an alkoxy group having 1 to 10 carbon atoms
You. R ^Five, R⁶, R⁷And R⁸Is an alkyl having 1 to 10 carbon atoms
In the case of a benzyl group, preferred examples of the alkyl group are exemplified.
If it is, a methyl group, an ethyl group, an n-propyl group, and is
o-propyl group and the like. Also, R^Five, R⁶, R⁷
And R⁸Is an alkoxy group having 1 to 10 carbon atoms
In the case, a preferred specific example of the alkoxy group is methoxy
Group, ethoxy group, n-propoxy group, and iso-pro
And a oxy group.

The alkyl group and the alkoxy group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from the group consisting of 1 to 10 carbon atoms. If the total number of carbon atoms in the group substituted on the aromatic ring exceeds 15, the refractive index and the strength of the cured product may be reduced, so that R ⁵ , R ⁶ , R ^7, and R ⁸ are It is preferable that the total number of carbon atoms be selected from a range not exceeding 15.

In the present invention, a particularly preferable structure of R ¹ has a large effect of improving strength.

[0020]

Embedded image The group shown by these is mentioned.

Further, R ¹ is represented by the following formula, because it is easily available and can form a crosslinked structure after curing.

[0022]

Embedded image Most preferably, it is a group represented by

In the general formula (1), R ² is a group represented by the following general formula.

[0024]

Embedded image

In the above formula, A¹And A^TwoAre independent of each other
An oxygen atom or -NH-, B ¹And B^TwoEach
A hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
1 to 5 alkoxy groups or phenyl groups. B¹Passing
And B^TwoIs an alkyl group having 1 to 5 carbon atoms,
Preferred specific examples of the kill group include a methyl group and an ethyl group.
Group, n-propyl group, iso-propyl group and the like.
Can be Also, B¹And B^TwoIs an alkoxy having 1 to 5 carbon atoms
When it is a group, preferred examples of the alkoxy group are exemplified.
A methoxy group, an ethoxy group, an n-propoxy group, and
iso-propoxy groups.

R ⁴ is a divalent hydrocarbon group such as an alkylene group or an alkenylene group having 1 to 12 carbon atoms. R
^If the number of carbon atoms of ⁴ exceeds 10, the refractive index may be reduced. Therefore, the number of carbon atoms is preferably selected from a range not exceeding 10.

Further, r₁, R_Two, And r_ThreeRespectively
It is an integer of 1 to 5 independently. r₁, R _Two, And r_ThreeIs above
The condition is not particularly limited as long as the condition is satisfied.
In each group, r₁, R_Two, And r_ThreeTotal number exceeds 10
May cause a decrease in the refractive index and the strength of the cured product.
Therefore, it is preferable to select from a range not exceeding 10.

When r ₁ and r ₃ are integers of 2 to 5, a plurality of-(B ¹ CB ² )-and-｛(C
^{_{H 2) r 2 A 2}}} - unit but is to be connected, this ^{time, B 1, B 2, r} 2, and the combination of A ² may be different in each unit.

In any of the groups in the formula, the bond at the right end is bonded to —COCR ³ ＣＨCH ₂ in the general formula (1).

As R ² , since the effect of improving the strength of the cured product is large, the following formula is used.

[0031]

Embedded image Preferably, the group is represented by

Among these groups, R ² is represented by the following formula because of ease of synthesis.

[0033]

Embedded image The group represented by is most preferred.

In the general formula (1), n is an integer of 1 to 3, and a particularly preferred number of n is 2 or 3 which can form a crosslinked structure after curing. Also, n
Is 2 or 3, there are a plurality of units enclosed in brackets ([]) bonded to R ¹ , but the combination of R ² and R ³ in each unit may be different.

The above-mentioned N-substituted amide compound having a polymerizable unsaturated bond may be any one represented by the general formula, but it is necessary to make the polymerization shrinkage smaller and the cured product to have excellent mechanical strength. In view of the high effect of the present invention and the ease of handling, the molecular weight is desirably 550 to 2,000.

Among the compounds represented by the general formula (1) used in the present invention, particularly preferred ones are as follows.

[0037]

Embedded image

In the curable dental composition of the present invention,
As the monomer component, only the polymerizable unsaturated bond-containing N-substituted amide compound represented by the general formula (1) can be used. However, in order to further improve the physical properties and adjust the viscosity, other polymerization is performed. The reactive monomer may be added up to 70% by weight of all monomer components.

The above-mentioned other polymerizable monomers are not particularly limited, and known polymerizable monomers which can be generally used in dental restorative materials can be used without any limitation. Examples of other polymerizable monomers that can be suitably used include a polymerizable monomer having a (meth) acryloyl group. Specific examples of such a polymerizable monomer include the following I) to IV) Each monomer shown in the above is mentioned.

(I) Monofunctional vinyl monomers Methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate and glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic acid, methacrylic acid , P-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid and its anhydride, 6-methacryloyloxyhexamethylenemalonic acid, 10- Methacryloyloxydecamethylene malonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyl Side Kamechi range hydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonate or the like.

(II) Bifunctional vinyl monomers (i) Aromatic compounds 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy)
-2-hydroxypropoxyphenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-
(Methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl)
Propane (hereinafter abbreviated as D-2.6E), 2,2-
Bis (4-methacryloyloxydiethoxyphenyl)
Propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4
-Methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 ( 4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane,
(4-methacryloyloxydipropoxyphenyl)-
2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-
Methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, and acrylates corresponding to these methacrylates. And diadducts obtained by addition of a vinyl monomer having a suitable -OH group and a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene and 4,4'-diphenylmethane diisocyanate.

(Ii) Aliphatic Compounds Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate , 1,3-butanediol dimethacrylate, 1,4
-Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
A vinyl monomer having an -OH group such as methacrylate such as 3-chloro-2-hydroxypropyl methacrylate or an acrylate corresponding to these methacrylates; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methyl cyclohexane, isophorone diisocyanate, and methylene bis. Diadduct obtained from addition with a diisocyanate compound such as (4-cyclohexyl isocyanate); acrylic acid anhydride, methacrylic anhydride;
1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) phosphate and the like.

(III) Trifunctional vinyl monomers Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethanetrimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.

(IV) tetrafunctional vinyl monomers pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanatemethylbenzene, diisocyanatemethylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 4,4-diphenylmethane diisocyanate,
Diadduct obtained from addition of a diisocyanate compound such as tolylene-2,4-diisocyanate and glycidol dimethacrylate.

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

The amount of the above-mentioned polymerizable monomer may be selected according to the purpose. The amount of the polymerizable unsaturated bond-containing N-substituted compound represented by the above general formula (1) in all the polymerizable monomers may be selected. Unless the amide compound is used so as to have a content of 30% by weight or more, the effect of reducing the polymerization shrinkage is not exhibited.

In the curable dental composition of the present invention,
The average particle size is 0.05 to 1 μm in order to obtain a moderate viscosity that gives good operability and a good mechanical strength of the cured product.
Is added to 50 parts by weight of 100 parts by weight of all monomer components.
４００400 parts by weight.

The filler is not particularly limited.
Known organic and inorganic fillers are used without any restrictions. Specific examples of fillers that can be used in the present invention include borosilicate glass, soda glass, glass containing heavy metals (eg, barium, strontium, zirconium), aluminosilicate, glass ceramics, silica, silica zirconia, silica Examples thereof include titania, composite inorganic oxides such as silica / alumina, and the like, and examples of the organic filler include homopolymers or copolymers of acrylic esters or methacrylic esters, polyvinyl chloride, polystyrene, and polyester polyamide.

It is desirable to treat the above-mentioned inorganic filler with a surface treating agent represented by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and improve the mechanical strength and water resistance. The surface treatment may be performed by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy)
Silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used.

An inorganic-organic composite filler obtained by pulverizing a composite of an inorganic oxide and a polymer obtained by polymerizing and curing a mixture of the above-mentioned inorganic filler dispersed and contained in a radical polymerizable monomer is also preferable. used.

The above fillers can be used alone or in combination of two or more.

In the present invention, among the above fillers,
It is preferable to use an inorganic filler from the viewpoint of improving the mechanical strength of the cured product and improving the weather resistance. It is particularly preferable to use a spherical or substantially spherical inorganic filler from the viewpoint of excellent surface lubricity of the cured product.

The filler is used in an amount of 50 to 400 parts by weight, preferably 120 to 300 parts by weight, based on 100 parts by weight of all the monomer components. If the amount of the filler is less than 50 parts by weight, the dental curable composition separates during storage or the cured body strength is reduced, and if it is more than 400 parts by weight, the dental curable composition has a high viscosity. Too much.

By appropriately adding a filler having an average particle size of 0.05 to 1 μm in a range of 50 to 400 parts by weight based on 100 parts by weight of all monomer components, the viscosity of the dental curable composition can be easily handled. 3 to 1500 poise can be controlled.

The optimum addition amount of the above-mentioned filler cannot be specified unconditionally because it varies depending on the composition of the monomer component to be used, the intended viscosity, and the mechanical strength of the cured product. When the amount of the added is large, the viscosity of the dental composition tends to increase, and
If the amount of the filler added is small or the proportion of the filler having a small particle size is large even with the same amount of the filler, the filler filling rate tends to decrease, and the mechanical strength of the cured product tends to decrease. Therefore, based on such a general tendency, it may be appropriately adjusted according to the particle size distribution of the filler used. .

If a small amount of a fine particle filler having an average particle size of less than 0.05 μm is further added in addition to the above-mentioned 0.5 to 1 μm filler, the viscosity can be easily adjusted while keeping the strength of the cured product high. Therefore, it is preferable to use such a fine particle filler in combination. By including such a fine particle filler, not only the viscosity of the dental curable composition can be easily adjusted, but also the thixotropy can be imparted, and the operability can be further improved.

As the fine particle filler, organic and inorganic fine particle fillers can be used without particular limitation as long as the average particle diameter is less than 0.05 μm.

Specific examples of the fine particle fillers that are generally preferably used include ultrafine silica powder, ultrafine alumina powder, ultrafine zirconia powder and inorganic fine particle filler.
Examples include inorganic oxides such as ultrafine powder titania, amorphous silica, silica-zirconia, silica-titania, silica-titania-barium oxide, quartz, and alumina. Further, a composite oxide in which a small amount of a metal oxide of Group I of the periodic table is present in an inorganic oxide can also be used. The composite oxide is characterized in that a dense one is easily obtained when fired at a high temperature. Examples of the organic fine particle filler include a homopolymer or a copolymer of an acrylate or a methacrylate, polyvinyl chloride polystyrene, and polyester polyamide.

The amount of the fine particle filler to be added is preferably 0.1 to 40 parts by weight, particularly preferably 1 to 15 parts by weight, based on 100 parts by weight of all the monomer components.

The polymerization initiator used in the dental curable composition of the present invention is not particularly limited, and a known radical polymerization initiator capable of polymerizing the above-mentioned radical polymerizable monomer by a radical mechanism is used without limitation. .

Representative polymerization initiators include combinations of organic peroxides and amines, combinations of organic peroxides, amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acid, A combination of a chemical polymerization initiator such as an alkylborane and an aryl borate and a photoacid generator, a combination of an α-diketone and a tertiary amine, a combination of an acylphosphine oxide and a tertiary amine, thioxanthones and Examples include photopolymerization initiators such as a combination of tertiary amines and a combination of α-aminoacetophenones and tertiary amines.

Examples of compounds that can be suitably used as the compounds used in the above-mentioned various chemical polymerization initiators are as follows.
Organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide,
Dicumyl peroxide, acetyl peroxide, lauroyl peroxide,
Benzoyl peroxide and the like. These can be used alone or in combination of two or more.

As the amines, secondary or tertiary amines are preferable, and specific examples thereof include N-methylaniline and N-methyl-p-toluidine. As the tertiary amine, N, N-dimethylaniline, N, N-diethylaniline, N, N-
Di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N , N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoate Acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N N-dimethyl-3,5-
Xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-
Naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine,
N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, and the like. These can be used alone or 2
More than one species can be used in combination.

Examples of the sulfinates include sodium benzenesulfinate, lithium benzenesulfinate,
sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate, p-
And sodium fluorobenzenesulfinate.

The aryl borates include tetraphenylboron, tetra (p-fluorophenyl) boron, tetra (p-chlorophenyl) boron, and trialkyl (p
-Fluorophenyl) boron, trialkyl (3,5-
Bistrifluoromethyl) phenylboron, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron, monoalkyltriphenylboron, monoalkyltriphenyl (P-chlorophenyl) boron,
Sodium salt of monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3,5-bistrifluoromethyl) phenylboron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), lithium Salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts and the like.

Examples of the barbituric acid include 5-butyl barbituric acid and 1-benzyl-5-phenyl barbituric acid.

As the alkyl borane, tributyl borane, tributyl borane partial oxide and the like are preferably used.

Further, when various compounds suitably used for the above-mentioned various photopolymerization initiators are exemplified, the same arylborates as those exemplified as the components of the chemical polymerization initiator can be mentioned.

Examples of the photoacid generator include 2,4,6-tris (trichloromethyl) -s-triazine and 2,4,6-triazine.
Tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl)
-S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (p-methylthiophenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-bromo Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (o-methoxystyryl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-butoxystyryl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3
Halomethyl-substituted-s-triazine derivatives such as 4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, Bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, p-
Examples include chlorides such as octyloxyphenylphenyliodonium, bromides, diphenyliodonium salt compounds such as tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and trifluoromethanesulfonate.

Examples of the α-diketones include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone and the like.

Examples of the tertiary amine include the same ones as those exemplified as the components of the chemical polymerization initiator.

As acylphosphine oxides, benzoyldiphenylphosphine oxide, 2,2
Examples thereof include 4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide.

The thioxanthones include 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like.

As α-aminoacetophenones, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,
2-benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1, 2-benzyl-dimethylamino-1- (4-
Morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1 and the like.

When a photoacid generator is used, it is preferable to add a coumarin dye capable of sensitizing and decomposing the photoacid generator. Specific examples of suitably used coumarin-based pigments include 3-thienoyl coumarin, 3- (4-methoxybenzoyl) coumarin, and 3- (3-methoxybenzoyl) coumarin.
Benzoylcoumarin, 3- (4-cyanobenzoyl) coumarin, 3-thienoyl-7-methoxycoumarin, 7-
Methoxy-3- (4-methoxybenzoyl) coumarin,
3-benzoyl-7-methoxycoumarin, 3- (4-cyanobenzoyl) -7-methoxycoumarin, 5,7-dimethoxy-3- (4-methoxybenzoyl) coumarin,
3-benzoyl-5,7-dimethoxycoumarin, 3-
(4-cyanobenzoyl) -5,7-dimethoxycoumarin, 3-acetyl-7-dimethylaminocoumarin, 7-
Diethylamino-3-thienoylcoumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin,
3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin, 3-cinnamoyl-7-diethylaminocoumarin, 3- ( p-Diethylaminocinnamoyl) -7-diethylaminocoumarin, 3-acetyl-7
-Diethylaminocoumarin, 3-carboxy-7-diethylaminocoumarin, 3- (4-carboxybenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (7-diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-10- (benzothiazoyl) -11-oxo-1H, 5H, 11H-
[1] benzopyrano [6,7,8-ij] quinolidine,
3,3'-carbonylbis (5,7-dimethoxy)-
3,3′-biscoumarin, 3- (2′-benzimidazoyl) -7-diethylaminocoumarin, 3- (2′-benzoxazoyl) -7-diethylaminocoumarin,
-(5'-phenylthiadiazoyl-2 ')-7-diethylaminocoumarin, 3- (2'-benzthiazoyl)
And -7-diethylaminocoumarin, 3,3′carbonylbis (4-cyano-7-diethylamino) coumarin and the like.

Among the above polymerization initiators, it is preferable to use a photopolymerization initiator which does not need to be separately packaged with the polymerizable monomer component. In particular, α which is less harmful to living organisms
It is preferred to use a visible light initiator such as a combination of diketones or acylphosphine oxides with tertiary amines, most preferably a combination of camphorquinone and tertiary amines.

The polymerization initiator is used in an amount of 0.003 to 20 parts by weight based on 100 parts by weight of all the monomer components. If the amount of the polymerization initiator is less than 0.003 parts by weight, the curing time is delayed, and if it is more than 20 parts by weight, the dental curable composition is colored.

Since the dental curable composition of the present invention can be applied to the tooth surface with a small brush or the like and can be directly filled from a syringe into a cavity, the viscosity of the dental curable composition is 3 to 1500.
It must be in poise, preferably in the range of 5 to 300 poise. When the viscosity of the dental curable composition is lower than 3 poise, the composition is easy to flow and it is difficult to apply the composition.
Above the poise, direct filling of the cavity from the syringe becomes difficult. As described above, the viscosity may be adjusted according to the monomer composition used or the type of the filler having an average particle diameter of 0.05 to 1 μm, or the amount of the filler added may be adjusted as needed. It can be easily realized by adjusting the amount of the filler having a diameter of less than 0.05 μm or the like.

The dental curable composition of the present invention may contain, if necessary, hydroquinone and / or hydroquinone as long as its performance is not reduced.
It is also possible to further add various additives such as polymerization inhibitors such as hydroquinone monomethyl ether and butylhydroxytoluene, and known UV absorbers and pigments.

The method for preparing the dental curable composition of the present invention is not particularly limited.
It can be prepared by appropriately mixing a filler, a polymerization initiator, and, if necessary, the above-mentioned various additives. All the components may be mixed immediately before use, or all the components may be mixed in advance under the condition that the polymerizable monomer is not polymerized. Alternatively, some components may be mixed in advance, and the remaining components may be mixed with this immediately before use.

Since the dental curable composition of the present invention has a viscosity of 3 to 1500 poise, it can be directly filled from a syringe and can be thinly and uniformly applied similarly to a conventional low-viscosity restoration material. Yes, it can be used to coat the cervical or root for therapeutic purposes such as hyperesthesia or root caries.
In addition, it has a smaller polymerization shrinkage than conventional low-viscosity dental restorative materials and has excellent marginal sealing properties. It can be used without it.

[0082]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Measurement of filler particle diameter in each of Examples and Comparative Examples, preparation of paste of dental curable composition and evaluation of its physical properties, evaluation of properties during curing of dental curable composition, and dental curable composition The physical properties of the cured product were evaluated according to the following methods.

(A) Measurement of Filler Particle Size A photograph of the powder was taken with a scanning electron microscope (manufactured by JEOL Ltd., T-330A), and the number and particle size of the particles observed in a unit field of view of the photograph were determined. Then, the average volume diameter of the raw material powder particles was determined by the following formula, and the average particle diameter was determined.

[0085]

(Equation 1)

(B) Preparation of Dental Curable Composition A matrix monomer was prepared by adding a predetermined ratio of a photopolymerization initiator to a polymerizable monomer. Next, the filler and the matrix monomer were put in an agate mortar and kneaded sufficiently in a dark place to obtain a uniform dental curable composition paste.

(C) Measurement of Viscosity 0.10 g of the dental curable composition was placed on a viscosity measuring device (manufactured by ITS, CS Rheometer), and the viscosity was measured while maintaining the composition at 23 ° C. The viscosity after seconds was defined as the viscosity of the dental curable composition.

(D) Evaluation of operability 2.5 ml equipped with a nozzle tip having an inner diameter of 0.05 mm
Of the dental curable composition in a syringe (manufactured by Terumo Corporation)
The operability was evaluated based on the possibility of ejection, resistance, and the presence or absence of dripping when g was filled and ejected.

The evaluation was performed in three stages. A sample having no strong resistance at the time of ejection and having no sagging after ejection was evaluated as ○. X.

(E) Measurement of Polymerization Shrinkage during Curing First, 10 ml of the dental curable composition was filled in a syringe, the weight was measured, and the specific gravity was calculated.

A dental curable composition was filled in a mold having a 25 × 40 × 4 mm prismatic hole, and pressed with a polypropylene film while being careful not to allow air bubbles to enter. Both sides were irradiated with light for 5 minutes using a visible light irradiator (manufactured by Tokuyama, α-light) to prepare a test piece. The specific gravity of the obtained cured product was measured with a hydrometer (manufactured by MiRAGE),
The polymerization shrinkage was calculated from the following equation.

[0092]

(Equation 2)

(F) Evaluation of marginal sealability at the time of hardening A cylindrical or dish-shaped cavity having a diameter of 4 mm and a depth of 2 mm was formed in the crown of the bovine tooth, and a dental adhesive (manufactured by Tokuyama, MacBond) II). The dental cavity was filled with the dental curable composition, light-cured with a visible light irradiator (manufactured by Tokuyama, power light) for 30 seconds, and then the sample was immersed in 37 ° C. water overnight. A flat surface was exposed using a waterproof abrasive paper No. 800 while dentin was not exposed, and a thermal cycle test at 60 ° C. and 4 ° C. was performed 2000 times. The sample was immersed in a 0.1% fuchsin aqueous solution at 37 ° C. for 24 hours, then cut, and the degree of penetration of the dye on the cross section was evaluated.

The evaluation was carried out on a five-point scale, with 5 having no dye penetration, 4 having penetrated half of the enamel, 4
Those that have penetrated to the boundary between enamel and dentin 3,
The one that penetrated into the dentin was designated as 2, and the one that entered the bottom of the cavity was designated as 1.

(G) Measurement of Three-Point Bending Strength of Cured Body The dental curable composition was filled in a mold having a 2 × 2 × 25 mm prismatic hole, and the upper portion was covered with a polypropylene film to prevent air bubbles from entering. Pressed with care. A test piece was prepared by irradiating each of the three locations at both ends and the center of the mold with a power light (manufactured by Tokuyama) for 30 seconds each.
The test piece was placed on a testing machine (Autograph 5000, manufactured by Shimadzu Corporation).
D), and the three-point bending strength was measured at a crosshead speed of 0.5 mm / min.

The abbreviations and structures of the filler, polymerizable monomer, polymerization initiator, and fine particle filler used in the examples and comparative examples are shown below.

(A) An N-substituted amide compound containing a polymerizable unsaturated bond represented by the general formula (1) (also simply referred to as an amide compound). Hereinafter, each compound is represented by a corresponding number, such as (2). ｝

[0098]

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[0099]

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[0100]

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(B) Other polymerizable monomers (also referred to as diluent monomers) 2,2-bis (4- (methacryloxopolyethoxy) phenyl) propane, D-5E (hereinafter abbreviated as KT-50) triethylene Glycol dimethacrylate (hereinafter abbreviated as 3G) 2,2-bis [(3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane (hereinafter bis)
-Abbreviated to GMA) 2,2-bis (4- (methacryloxoethoxy) phenyl) propane (hereinafter abbreviated as D-2.6E) 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethyl Hexane (hereinafter abbreviated as UDMA).

(C) Polymerization initiator camphorquinone (hereinafter abbreviated as CQ) dimethyl-p-toluidine (hereinafter abbreviated as DMPT).

(D) Filler having an average particle diameter of 0.05 to 1 μm Spherical silica-zirconia; average particle diameter: 0.52 μm (hereinafter abbreviated as F-1) Spherical silica-titania; average particle diameter: 0.08 μm F-2).

(E) Fine particle filler QS102 having an average particle diameter of less than 0.05 μm: main component; fine powder silica (hereinafter abbreviated as F-3); average particle diameter: 0.01 μm.

Example 1 50 parts by weight of the amide compound (2) and diluent monomer K
A monomer composition comprising 50 parts by weight of T50, F-1
And a polymerization initiator comprising 0.3 parts by weight of CQ and 0.5 parts by weight of DMPT were used to prepare a dental curable composition.

When the physical properties of the obtained dental curable composition were measured, the viscosity of the dental composition was 301 poise, the polymerization shrinkage was 1.9%, and the marginal sealing property was 5. Yes, operability is ○, bending strength of cured product is 12
It was 5 MPa. From this, the dental curable composition of this example has an excellent marginal sealing property, and is suitable not only for the cervical region and the root portion, or a very shallow cavity, but also for filling into a deep cavity. It can be seen that it is.

Examples 2 to 15 Dental curable compositions having the compositions shown in Table 1 were prepared in the same manner as in Example 1, and the physical properties were measured.

[0108]

[Table 1]

Table 2 shows the results.

[0110]

[Table 2]

The dental composition of each Example had a marginal sealing property of 5, and also had other good physical properties. Therefore, the dental composition is not limited to the cervical region and the root portion, or is filled not only in a very shallow cavity but also in a deep cavity. It turns out that it is also suitable for use.

Comparative Example 1 In Example 1, D- was used instead of the amide compound (2).
A curable dental composition was prepared using 2.6E and otherwise the same composition as in Example 1, and the physical properties were measured. The results are shown in Table 2.

The operability was ○ and the cured product had good strength, but the polymerization shrinkage was 3.1% and the marginal sealing property was 3, indicating that it was not suitable for filling deep cavities.

Comparative Example 2 In Example 2, bis was used instead of the amide compound (2).
Using -GMA, a dental composition was prepared in the same manner as in Example 2, except that the amounts of the fillers F-1 and F-2 were changed to 350 parts by weight and 150 parts by weight, respectively. The dental polymerizable composition in this example is almost the same as a commonly used high-viscosity dental restorative material.

Various physical properties of the obtained dental curable composition were measured. The results are shown in Table 2. It has a good cured product flexural strength, a polymerization shrinkage of 1.9%, and excellent edge sealing properties, but has an extremely high viscosity, resulting in poor operability.

Comparative Example 3 In Example 1, the amount of the amide compound (2) was changed to 20
A dental curable composition was prepared and the physical properties were measured in the same manner as in Example 1 except that the amount of the diluted monomer KT50 was changed to 80 parts by weight.

Table 2 shows the results. The operability is ○, but the polymerization shrinkage is 3.0%, the marginal sealing property is 3,
It can be seen that the effects of the present invention have not been obtained.

[0118]

EFFECT OF THE INVENTION The dental curable composition of the present invention has good operability and a suitable viscosity, so that it can be used for cervical and root parts,
Alternatively, it can be applied to filling a very shallow cavity. Moreover, the shrinkage during polymerization is smaller than that of the conventional low-viscosity composite resin, and the edge sealing property is excellent. The bending strength of the cured product is equivalent to that of a conventional high-viscosity composite resin. Therefore, it can be sufficiently applied to deep cavities.

As described above, the dental curable composition of the present invention has the excellent operability of the conventional low-viscosity composite resin and the excellent edge sealing property of the conventional high-viscosity composite resin. This is a new type of dental curable composition.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Junichiro Yamakawa 1-1-1, Mikage-cho, Tokuyama-shi, Yamaguchi F-term in Tokuyama Corporation (reference) 4C089 AA06 BC07 BC13 BD02 BD04 BD05 BE09 CA06 4J011 PA34 PA36 PA48 PA69 PB22 PC02 PC08 QA03 QA04 QA07 QA12 QA14 QA25 QA36 QA39 SA01 SA05 SA41 SA64 SA78 SA82 VA05 WA08 4J100 AJ02Q AL03Q AL62Q AL63Q AL66P BA02P BA05P BA15P BA34P BC43P BC44P BC45P BC49P CA01 CA04 DA09 FA03 JA52

Claims (3)

[Claims] [Claim 1] The following general formula (1) [In the formula, R ¹ is a C1-C24 1-3-valent organic group having 1-3 at least one aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, and an anthracene ring. R ² is represented by the following general formula: In the formula, A ¹ and A ² are each independently an oxygen atom or —NH—, and B ¹ and B ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, 5 is an alkoxy group or a phenyl group, and R ⁴ has 1 to 1 carbon atoms.
2 is a divalent hydrocarbon group, and r ₁ , r ₂ , and r ₃ are
They are each independently an integer of 1 to 5, and the bond at the right end of any group in the formula is bonded to —COCR ³ ＣＨCH ₂ . ｝, R ³ is a hydrogen atom or a methyl group, and n is an integer of 1 to 3. 100 to 100 parts by weight of a polymerizable monomer containing 30% by weight or more of the polymerizable unsaturated bond-containing N-substituted amide compound represented by the following formula, and a filler having an average particle diameter of 0.05 to 1 μm.
A dental curable composition comprising 00 parts by weight and 0.003 to 20 parts by weight of a polymerization initiator, the composition having a viscosity of 3
A dental curable composition having a viscosity of up to 1500 poise. 2. The filler having an average particle diameter of 0.05 to 1 μm is a spherical inorganic filler.
The curable dental composition as described in the above. 3. The dental curable composition according to claim 1, further comprising 0.1 to 40 parts by weight of a fine particle filler having an average particle diameter of less than 0.05 μm.