JP3526742B2 - Dental curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dental restorative material,
Particularly, the present invention relates to a curable composition suitable as a material for coating a tooth neck or a tooth root. More specifically, the present invention provides a dental curable composition that has a low viscosity and does not drip during filling, so that the filling operation is easy.

[0002]

2. Description of the Related Art A dental composite restorative material mainly composed of a filler component, a polymerizable monomer (monomer) component, and a polymerization initiator can give a color tone equivalent to a natural tooth color and is easy to operate. Recently, it has been widely used as a restorative material in the dental field. The method of use is to directly fill the cavity of the tooth with a dental filling machine or the like, and to cure the tooth by polymerizing and curing it by a polymerization means such as light irradiation, which is generally called a composite resin. A viscosity composite material is used.

However, when coating the cervical part and the root part due to hypersensitivity or caries of the root surface, the cavity is not formed or the very shallow cavity is formed. It was difficult to coat thinly with this composite resin. Therefore, in the above clinical practice, there is a demand for a low-viscosity composite restorative material that can be easily applied and coated on the restorative surface using a small brush or sponge.

On the other hand, as a low viscosity composite restorative material,
There is a composite material called a sealant used for filling the pit and fissure, and this material can be applied with a small pen or the like.
However, since the sealant has plastic flowability,
When the coating is applied, dripping occurs and it is difficult to perform uniform coating. Further, the strength of the cured product itself is not so high, and it is difficult to apply it to the root surface or tooth neck.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a dental curing material that has a viscosity that is low enough to be applied with a small brush, has a low plastic flowability, does not drip during coating, and has sufficient mechanical strength. The present invention aims to provide a sex composition.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to overcome the above-mentioned problems and found that a composition having a specific viscosity range and a specific plastic fluidity distance is specifically polymerizable. By finding that the composition in which the particle size and the filling rate of the filler to be blended in the monomer are adjusted to a specific range satisfies these physical properties, it is possible to simultaneously solve the above-mentioned viscosity and sagging problems, and complete the present invention. Came to.

That is, in the present invention, the average particle size is 0.05 to
100 parts by weight of 1 μm filler, average particle size is 0.05
0.1 to 10 parts by weight of fine particle filler less than μm , 30 to 100 parts by weight of polymerizable monomer, and 0.003 of polymerization initiator
Comprising a 5 parts by weight, the viscosity of 3 to 300 poise, and its plastic flow distance is 1mm or less, the teeth
A dental curable composition for coating the neck or root .

[0008] The dental curable composition of the present invention is used as the cervical portion or root portion for coating the curable composition.

The dental curable composition of the present invention has an average particle size of
100 parts by weight of filler having a diameter of 0.05 to 1 μm, average particles
Fine particle filler having a diameter of less than 0.05 μm 0.1 to 10
Parts by weight , 30 to 100 parts by weight of a polymerizable monomer, and 0.003 to 5 parts by weight of a polymerization initiator.

The filler used in the present invention has a viscosity of 3 to 3 when mixed with a polymerizable monomer (monomer).
00 poise, which can adjust the plastic flow distance 1mm or less, need use organic and inorganic fillers of a particular average particle size.

A specific example of such a filler is as follows.
Borosilicate glass as an inorganic filler, soda glass,
Examples thereof include glasses containing heavy metals (for example, barium, strontium, zirconium), aluminosilicates, glass ceramics, silica, and composite inorganic oxides such as silica / zirconia, silica / titania, silica / alumina and the like. Examples of the organic filler include homopolymers or copolymers of acrylic acid ester or methacrylic acid ester, polyvinyl chloride, polystyrene, polyester polyamide and the like.

It is desirable that the above-mentioned inorganic filler is treated with a surface treatment agent typified by a silane coupling agent in order to improve compatibility with the polymerizable monomer and improve mechanical strength and water resistance. The surface treatment may be carried out by a known method, and 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.

Further, an inorganic-organic composite filler obtained by pulverizing a composite of an inorganic oxide and a polymer obtained by polymerizing and curing a mixture obtained by dispersing and containing the above-mentioned inorganic filler in a radical-polymerizable monomer is also suitable. Used for.

The above-mentioned various fillers can be used alone or in admixture of two or more.

In the present invention, among the above-mentioned various fillers, it is preferable to use an inorganic filler from the viewpoint of improving the mechanical strength and weather resistance of the cured product.

In the dental curable composition of the present invention,
By mixing the above-mentioned filler and the polymerizable monomer in a specific ratio, the dental curable composition has a viscosity of 3 to 3
At 100 poise, the plastic flow distance is controlled to 1 mm or less. At this time, the shape, particle size, filling rate, etc. of the filler influence the above-mentioned physical properties, so that control thereof is important.

Generally, when a filler having a large average particle diameter is used, plastic flowability is generated, and there is a risk of sagging when coating the hardened composition, and when a filler having a small average particle diameter is used, a dental curable composition is obtained. Although the plastic fluidity is reduced, not only the operability is lowered because the viscosity is increased, but also the filler filling rate is lowered, which may lower the mechanical strength of the cured product.

Therefore, in the present invention, among the above-mentioned fillers, a filler having an average particle diameter of 0.05 to 1 μm is used in that the physical properties of the dental curable composition can be easily obtained . Especially the average particle size is 0.05-1μ
m inorganic filler is preferably used. Furthermore, among this, due to the increased surface gloss of the cured product using a spherical inorganic filler, that flat Hitoshitsubu diameter used spherical inorganic filler 0.05~1μm is particularly preferred.

Further, in the dental curable composition of the present invention, a small amount of a fine particle filler is contained in addition to the above-mentioned filler having a particle size of 0.5 to 1 μm, whereby the plastic fluidity is further reduced and the mechanical strength is reduced. It intends line improvement. As the fine particle filler, organic and inorganic fine particle fillers having an average particle size of less than 0.05 μm can be used without particular limitation.

Specific examples of fine particle fillers that are generally suitably used include, as inorganic fine particle fillers, ultrafine powder silica, ultrafine powder alumina, ultrafine powder zirconia,
Inorganic oxides such as ultrafine powder titania, amorphous silica, silica-zirconia, silica-titania, silica-titania-barium oxide, quartz and alumina can be mentioned. 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 complex oxide is characterized in that it is easy to obtain a dense one when it is fired at a high temperature. Examples of the organic fine particle filler include homopolymers or copolymers of acrylic acid ester or methacrylic acid ester, polyvinyl chloride polystyrene, polyester polyamide and the like.

The amount of the fine particle filler added is in the range of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the filler having an average particle size of 0.05 to 1 μm. When the amount of the fine particle filler added is less than 0.1 part by weight, the plastic flowability of the composition hardly changes, and
If it exceeds 0 parts by weight, the viscosity of the composition increases.

The polymerizable monomer (monomer) used in the present invention is not particularly limited, and a known radical polymerizable monomer generally used as a dental monomer can be used.
If the typical polymerizable monomer (monomer) which can be used conveniently is illustrated, the polymerizable monomer which has an acryloyl group and / or a methacryloyl group will be mentioned. Specific examples of these are as follows.

[Monofunctional Vinyl Monomer] Methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 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 anhydrides, 6-methacryloyloxyhexamethylenemalonic acid, 10-methacryloyloxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyl Oxydecamethylene dihydrogen phosphate, 2-hydroxyethyl hydrogenphenyl phosphonate [difunctional vinyl monomer] (1) Aromatic compound-based 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-26E), 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, 2 (4
-Methacryloyloxydipropoxyphenyl) -2-
(4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; Two
-Methacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or acrylates corresponding to these methacrylates-
Diadduct obtained from addition of vinyl monomer having OH group and diisocyanate compound having aromatic group such as diisocyanate methylbenzene and 4,4′-diphenylmethane diisocyanate (2) Aliphatic compound-based 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 a methacrylate such as 3-chloro-2-hydroxypropyl methacrylate or an acrylate corresponding to these methacrylates, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis Diadducts obtained from addition with diisocyanate compounds such as (4-cyclohexyl isocyanate); acrylic anhydride, methacrylic anhydride,
1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) phosphate [trifunctional vinyl monomer] trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol tri Methacrylate, methacrylates such as trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates (tetrafunctional vinyl monomers) pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate , Trimethylhexamethylene diisocyanate, Renbisu (4
-Cyclohexyl isocyanate), 4,4-diphenylmethane diisocyanate, diadducts obtained from the addition of diisocyanate compounds such as tolylene-2,4-diisocyanate and glycidol dimethacrylate.

These polymerizable monomers may be used alone or in a mixture of two or more kinds. The addition amount of the polymerizable monomer viscosity of the dental curable composition is in the range of 3 to 300 poise, Ru amount der its plastic flow distance is 1mm or less. The addition amount of the heavy polymerizable monomer that put the dental curable composition of the present invention has an average particle size relative to filler -1 00 parts by weight of 0.05 to 1 [mu] m 3
It is 0 to 100 parts by weight, preferably 40 to 90 parts by weight. When the addition amount of the polymerizable monomer is less than 30 parts by weight, the viscosity of the dental curable composition increases, and when it is more than 100 parts by weight, not only the plastic flow distance increases but also the dental curable composition is It may separate during storage or the strength of the cured product may decrease.

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

As typical polymerization initiators, a combination of organic peroxides and amines, a combination of organic peroxides, amines and sulfinates, acidic compounds,
And a combination of aryl borates, a chemical polymerization initiator such as barbituric acid and alkyl borane; and a combination of aryl borates and a photoacid generator, a combination of α-diketones and tertiary amines, acylphosphine oxide And a combination of tertiary amines, a combination of thioxanthones and a tertiary amine, α-
Examples thereof include photopolymerization initiators such as a combination of aminoacetophenones and tertiary amines.

Examples of compounds that can be preferably used as the compounds used in the above-mentioned various chemical polymerization initiators are shown below.
Examples of organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide,
Dicumyl peroxide, acetyl peroxide, lauroyl peroxide,
Examples thereof include benzoyl peroxide. These can be used alone or in combination of two or more.

The amines are preferably secondary or tertiary amines, 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-dimethyl Aniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone,
p-Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxy Ethyl-p-toluidine, p
-Dimethylaminophenethyl alcohol, p-dimethylaminostilbene, 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-dimethylaminoethylmethacrylate, N, N-diethylaminoethylmethacrylate, 2,2 '-( Examples include n-butylimino) diethanol. These may be used alone or in combination of two or more.

The sulfinates include sodium benzenesulfinate, lithium benzenesulfinate,
Sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate, p-
Examples include sodium fluorobenzenesulfinate and the like.

The aryl borates include tetraphenylboron, tetra (p-fluorophenyl) boron, tetra (p-chlorophenyl) boron and trialkyl (p).
-Fluorophenyl) boron, trialkyl (3,5-
Bistrifluoromethyl) phenyl boron, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron, monoalkyltriphenylboron, monoalkyltri (P-chlorophenyl) boron,
Sodium salt of monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3,5-bistrifluoromethyl) phenylboron (wherein the alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), lithium Examples thereof include 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 alkylborane, tributylborane, tributylborane partial oxide and the like are preferably used.

As examples of various compounds that are preferably used for the various photopolymerization initiators, the same aryl borate compounds as those exemplified as the components of the chemical polymerization initiator can be mentioned.

As the photoacid generator, 2,4,6-tris (trichloromethyl) -s-triazine and 2,4,6-
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- (3,3
Halomethyl group-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 thereof include chlorides such as octyloxyphenylphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and diphenyliodonium salt compounds such as trifluoromethanesulfonate.

As the α-diketones, camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1, 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone and the like can be mentioned.

As the tertiary amine, the same ones as exemplified as the component of the chemical polymerization initiator can be mentioned.

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

Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1, as α-aminoacetophenones
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 photo-acid generator is used, it is also preferable to add a coumarin-based dye which can sensitize and decompose the photo-acid generator. Specific examples of coumarin dyes that are preferably used include 3-thienoyl coumarin, 3- (4-methoxybenzoyl) coumarin and 3-
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, 3
-(5'-phenylthiadiazoyl-2 ')-7-diethylaminocoumarin, 3- (2'-benzthiazoyl)
Examples thereof include -7-diethylaminocoumarin and 3,3'carbonylbis (4-cyano-7-diethylamino) coumarin.

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 visible light polymerization initiators such as a combination of diketones or acylosphine oxides and tertiary amines, most preferably a combination of camphorquinone and tertiary amines.

The compounding amount of the above-mentioned polymerization initiator may be selected from known addition ranges without particular limitation. The amount of heavy initiator that put the dental curable composition of the present invention has an average particle diameter of 0.
0.00 against the Philadelphia-1 00 parts by weight of 05~1μm
It is used in a proportion of 3 to 5 parts by weight. If the compounding amount of the polymerization initiator is less than 0.003 parts by weight, the curing time will be delayed, and if it is more than 5 parts by weight, the storage stability of the dental curable composition will be deteriorated.

The dental curable composition of the present invention has a viscosity of 3 to 300 poises, preferably 5 to 100 poises, so that the dental curable composition can be applied to the tooth surface with a small brush or the like. Must. If the viscosity of the dental curable composition is lower than 3 poises, the composition tends to flow and it is difficult to apply, and if it is higher than 300 poises, it becomes difficult to take an appropriate amount with a small brush, and it becomes difficult to apply a thinner coating.

The dental curable composition of the present invention must have a plastic flow distance of 1 mm or less in order to prevent sagging during application. In the present invention, the plastic flow distance means that about 0.1 g of the dental curable composition is placed on a horizontal and smooth glass flat surface so that the diameter is within 10 mm, and the glass flat surface is vertically spread after being naturally expanded for 5 seconds. When left still, the position of the lowermost end of the dental curable composition spread on the glass plane means the distance moved within 3 minutes immediately after the glass plane was made vertical. At this time, when a photopolymerization initiator was used as a polymerization initiator of the dental curable composition, the test was performed under light shielding or in a system excluding the photopolymerization initiator, and when a chemical polymerization initiator was used, the test was performed. It is necessary to carry out the test using a composition obtained by removing the polymerization catalyst from the dental curable composition.

The dental curable composition of the present invention may contain a polymerization inhibitor such as hydridoquinone, hydroquinone monomethyl ether, butylhydroxytoluene or the like, a known ultraviolet absorber, a pigment, etc., as long as the performance thereof is not deteriorated. It is also possible to add.

The method for preparing the dental curable composition of the present invention is not particularly limited, and a predetermined amount of filler, a polymerizable monomer, a polymerization initiator and, if necessary, the above various additives are appropriately added. It can be prepared by mixing. Immediately before use, all the components may be mixed, or under the condition that the polymerizable monomer does not polymerize, all the components may be mixed in advance. Alternatively, some components may be mixed in advance, and the remaining components may be mixed therewith just before use.

Since the dental curable composition of the present invention has a viscosity of 3 to 300 poise and a plastic flow distance of 1 mm or less, it can be applied thinly and uniformly, and the tooth surface is almost vertical. Even if it is applied to, no dripping is likely to occur. Therefore, it can be particularly suitably used as a dental curable composition used for coating the cervical part or the root part for the purpose of treating hypersensitivity, root caries and the like.

When the dental curable composition of the present invention is used for such a purpose, for example, the curable composition is taken by using a dental writing brush or a filling device and thinly applied to the restoration surface of the tooth. It may be applied so as to form a uniform film, and may be appropriately cured depending on the type of the polymerization initiator used.

[0049]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The mechanical strength of the hardened dental curable composition was evaluated by the three-point bending strength. In addition, each example,
The measurement of the filler particle size, the preparation of the dental curable composition paste and the measurement of the physical properties thereof, and the curing of the dental curable composition in the Reference Examples and Comparative Examples were carried out according to the following methods.

(1) Measurement of Filler Particle Diameter and Coefficient of Variation of Particle Diameter Particles of a powder taken by a scanning electron microscope (T-330A, manufactured by JEOL Ltd.) and observed in a unit visual field of the photograph. The number and particle diameter of the powder were calculated, and the average volume diameter of the raw material powder particles was calculated by the following formula, and the average particle diameter was determined. Also, the coefficient of variation of particle diameter was calculated.

[0051]

[Equation 1]

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

(3) Viscosity measurement 0.05 g of the dental curable composition was placed on a viscosity measuring device (CS rheometer manufactured by ITS), and the viscosity was measured while maintaining it at 23 ° C. The viscosity after the second was defined as the viscosity of the dental curable composition.

(4) Measurement of plastic flow distance About 0.1 g of a dental curable composition was placed on a glass plate so that the diameter was within 10 mm and allowed to spontaneously develop for 5 seconds, and then the glass plane was made vertical and allowed to stand still. When placed, the distance at which the position of the lowermost end of the dental curable composition spread on the glass plane was moved within 3 minutes immediately after the glass plane was made vertical was measured and defined as the plastic flow distance.

(5) Evaluation of applicability with small brush A small amount of the dental curable composition was taken with a small dental brush (manufactured by Tokuyama), and the extracted root of the bovine tooth was thinly and uniformly coated. The operability at this time was x for those that could not be sampled with a small pen, Δ for those that could be sampled with a small pen but for which a thin and uniform coating could not be obtained, and ○ for those with a thin and uniform coating. A graded evaluation was performed.

(6) Three-point bending strength test The dental curable composition was filled in a Teflon mold having 2 × 2 × 25 mm prismatic holes, and the polypropylene film was used to prevent air bubbles from entering the upper part. While pressing. Use a visible light irradiator (Power Light, made by Tokuyama) to place 30 at each of the three ends of the mold and in the center.
Light irradiation was performed for each second to prepare a test piece. The sample piece was mounted on a tester (manufactured by Shimadzu Corporation, Autograph 5000D), and the three-point bending fracture strength was measured at a crosshead speed of 0.5 mm / min.

(7) Surface gloss test The dental curable composition was filled in a Teflon mold having a hole of 6 mmφ × 3 mm, and the upper portion thereof was pressed with a polypropylene film while being careful so that no air bubbles would enter. Light was irradiated for 30 seconds with a visible light irradiator to prepare a test piece. Next, after roughening the surface of the test piece with # 800 emery paper, finish polishing was performed with a composite abrasive (Super Snap, manufactured by Shofu Co., Ltd.).

The surface reflectance of the cured product was measured using a gloss meter (TC-108D, manufactured by Tokyo Denshoku Co., Ltd.), and this was defined as the gloss level. The maximum value of the glossiness is 45.0, and the higher the value, the better the surface gloss.

The abbreviations and structures of the fillers, polymerizable monomers and polymerization initiators used in each of the examples , reference examples and comparative examples are shown below.

(A) Filler [particles having an average particle diameter of 0.05 to 1 μm (hereinafter, also simply referred to as “filler A”)] 0.5Si-Zr: main component; spherical silica-zirconia,
γ-methacryloyloxypropyltrimethoxysilane surface-treated product average particle size; 0.52 μm coefficient of variation; 0.13 0.2 Si-Zr: main component; spherical silica-zirconia,
γ-methacryloyloxypropyltrimethoxysilane surface-treated product average particle size; 0.21 μm coefficient of variation; 0.04 0.2Si: main component; spherical silica, γ-methacryloyloxypropyltrimethoxysilane surface-treated product average particle size; 0 .22 μm coefficient of variation; 0.06 0.06 Si: main component; spherical silica-zirconia, γ-
Methacryloyloxypropyltrimethoxysilane surface-treated product average particle size; 0.06 μm variation coefficient; 0.02 1.0 Cry: main component; amorphous quartz glass average particle size; 0.98 μm variation coefficient; 0.22 [average particle size Particles exceeding 1 μm (hereinafter, also simply referred to as “filler B”)] 6.2 Cry: main component; amorphous silica glass average particle diameter; 6.2 μm coefficient of variation; 1.32 [average particle diameter less than 0.05 μm Particles (fine particle filler, hereinafter also simply referred to as “filler C”)] QS102: main component; fine powder silica average particle diameter; 0.01 μm (b) polymerizable monomer: bis-GMA: 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane D-2.6E: 2,2-bis (4- (methacryloxoethoxy) phenyl) propa 3G: triethylene glycol dimethacrylate UDMA: 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethylhexane (c) polymerization initiator CQ: camphorquinone BDPP: benzoyldiphenylphosphine oxide DMBE: 4- Ethyl dimethylaminobenzoate DMBA: Dimethylaminobenzaldehyde Reference Example 1 0.2 Si-Zr 100 parts by weight as a filler, D-2.6E47 parts by weight as a polymerizable monomer, 3G 20 parts by weight, CQ 0.17 parts by weight as a polymerization initiator. , DMBE
A dental curable composition was prepared using 0.17 part by weight.

Each physical property was measured using the above-mentioned dental curable composition. The dental curable composition had a viscosity of 22 poise, had no plastic flowability, and had a plastic flow distance of 0, and the dental curable composition had a writing brush coatability of O. The flexural strength was 129 MPa and the surface glossiness was 23.3, which was not different from the composite resin. From this, the dental curable composition of the present example can be coated with excellent operability on the neck or root.

Reference Examples 2 to 9 and Examples 1 to 3 In the same manner as in Reference Example 1, a dental curable composition having the composition shown in Table 1 was prepared and its physical properties were measured. The results are shown in Table 2. In any of the compositions, the coatability with a writing brush is ◯, and the dental curable composition of this example is capable of covering the cervical portion or the root portion with excellent operability.

[0063]

[Table 1]

[0064]

[Table 2]

Comparative Examples 1 to 3 Dental curable compositions having the compositions shown in Table 1 were prepared in the same manner as in Example 1 and their physical properties were measured. The results are shown in Table 2. The dental curable composition of Comparative Example 1 had a viscosity of more than 300 poise, and was inferior to the Examples in applicability with a small brush. Further, the dental curable compositions of Comparative Examples 2 and 3 both have viscosities in the range of 3 to 300 poise, but have a set plasticity of 1 m.
m, and the applicability of a small brush is inferior to that of the example. The bending strength of Comparative Example 2 and the surface gloss of Comparative Example 3 are inferior to those of the Examples. From this, it is understood that it is difficult to cover the tooth neck or the tooth root with any of the compositions.

Comparative Example 4 The physical properties of the dental composite resin Palfique Esterite (manufactured by Tokuyama Corp.) were measured in place of the dental curable composition of the present invention. Yes, plastic flow distance is 0, bending strength is 13
The surface glossiness was 3 MPa and the surface glossiness was 24.2. The applicability with a small brush is x, which makes it difficult to cover the tooth neck or tooth root.

Comparative Example 5 The physical properties of the dental curable composition of the present invention were measured by using a pit fissure sealant, Palfikhlite sealant (manufactured by Tokuyama), and the viscosity was 15 poise and the composition flow distance was measured. , 9 mm, bending strength 96 MPa, surface gloss 2
It was 2.6. In addition, the applicability with a small brush was Δ, the covering operation of the tooth neck or tooth root was difficult, and the mechanical strength was low.

[0068]

EFFECTS OF THE INVENTION The dental curable composition of the present invention has such a low viscosity that it can be applied with a small brush or the like, and since it has a low plastic flowability, it does not drip during application, and therefore it has a tooth neck and a root. When repairing a part, it is possible to apply a thin and uniform coating to the tooth surface on which a cavity is not formed or a shallow cavity is formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-76702 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 6/00-6/10

Claims (3)

(57) [Claims] 1. A filler having an average particle diameter of 0.05 to 1 μm.
-100 parts by weight, fine particles with an average particle size of less than 0.05 μm
Child filler 0.1 to 10 parts by weight , polymerizable monomer 30 to 1
00 parts by weight, and comprising a polymerization initiator 0.003 parts by weight, the viscosity of 3 to 300 poise, and its plastic flow distance is 1mm or less, cervical or root portion
Dental curable composition for coating . Wherein the polymerization initiator is a photopolymerization initiator der Ru claim 1 dental curable composition. 3. The filler having an average particle diameter of 0.05 to 1 μm is a spherical inorganic filler.
Or the dental curable composition according to 2.