JPH11335220A - Curable composition for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject low-viscosity composition having a low plastic fluidity without sagging at the time of coating, further having a sufficient mechanical strength and useful as a restorative material for dental use, especially a material for covering a dental neck and a dental root parts by including a filler, a polymerizable monomer and a polymerization initiator. SOLUTION: This composition is obtained by including (A) a filler (e.g. a borosilicate glass), (B) a polymerizable monomer (e.g. methyl methacrylate or acrylic acid) and (C) a polymerization initiator (e.g. t-butyl hydroperoxide or N-methylaniline) and has 3-300 P viscosity and <=1 mm plastic flow distance. The composition preferably contains 100 pts.wt. of the ingredient A having 0.05-1 μm average particle diameter, 30-100 pts.wt. of the ingredient B and 0.003-5 pts.wt. of the ingredient C. The ingredient A is preferably a spherical inorganic filler and 0.1-10 pts.wt. of a particulate filler having <0.05 μm average particle diameter is preferably contained therein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dental restoration material,
Particularly, the present invention relates to a curable composition suitable as a material for covering a cervical or root part. More specifically, the present invention provides a dental curable composition which has a low viscosity and does not drip at the time of filling, so that the filling operation is easy.

[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 hyperesthesia or root caries, etc., the coating is usually performed without forming a cavity or for forming a very shallow cavity. It was difficult to make a thin coating using the composite resin. For this reason, in the clinical practice as described above, a low-viscosity composite restoration material that can be easily applied to the restoration surface using a small brush or a sponge has been desired.

On the other hand, as a low-viscosity composite restoration 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 brush or the like.
However, since the sealant has plastic fluidity,
When the coating is applied, sagging 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 the cured product to the root surface or the cervical region.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a dental hardening material which has a viscosity low enough to be applied with a small brush or the like, has low plastic fluidity, does not sag when coated, and has sufficient mechanical strength. It is intended to provide a neutral composition.

[0006]

Means for Solving the Problems The present inventors have made intensive 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 a polymerizable polymer. It has been found that the composition in which the particle diameter and the filling rate of the filler compounded in the monomer are adjusted to a specific range satisfies these properties can solve the above-mentioned problems of viscosity and sag simultaneously, and complete the present invention. Reached.

That is, the present invention is a dental curable composition comprising a filler, a polymerizable monomer, and a polymerization initiator, having a viscosity of 3 to 300 poise and a plastic flow distance. Is 1 mm or less.

[0008] The dental curable composition of the present invention can be suitably used as a curable composition for covering a tooth neck or a root.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The dental curable composition of the present invention comprises a filler, a polymerizable monomer (monomer), and a polymerization initiator.

The filler used in the present invention has a viscosity of 3 to 3 when mixed with a polymerizable monomer (monomer).
No particular limitation is imposed on the filler as long as it is a filler whose plastic flow distance can be adjusted to 1 mm or less, and organic and inorganic fillers are used without any limitation.

A specific example of such a filler is as follows:
Borosilicate glass, soda glass, and inorganic filler
Examples include glass containing heavy metals (for example, barium, strontium, and zirconium), aluminosilicate, glass ceramics, silica, and composite inorganic oxides such as silica-zirconia, silica-titania, and silica-alumina. Examples of the organic filler include acrylate or methacrylate homopolymers or copolymers, polyvinyl chloride, polystyrene, and polyester polyamide.

It is desirable that the above-mentioned inorganic filler be treated 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 for

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

In the present invention, among the various fillers described above, 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.

In the curable dental composition of the present invention,
By mixing the filler and the polymerizable monomer in a specific ratio, the viscosity of the dental curable composition becomes 3 to 3
At 00 poise, the plastic flow distance is controlled to 1 mm or less. At this time, since the shape, particle size, filling rate, and the like of the filler affect the above-mentioned physical properties, its control is important.

In general, when a filler having a large average particle size is used, plastic fluidity is generated, and there is a possibility that the filler will sag when coating the cured body composition. Although the plastic fluidity decreases, not only does the operability decrease due to the increase in viscosity, but also the filler filling rate decreases, and the mechanical strength of the cured product may decrease.

For this reason, in the present invention, among the above-mentioned fillers, fillers having an average particle size of 0.05 to 1 μm, in particular, an average particle size of 0.05 to 1 μm are preferable in that the physical properties of the dental curable composition can be easily obtained. An inorganic filler having a diameter of 0.05 to 1 μm is preferably used. Furthermore, among them, the use of a spherical inorganic filler increases the surface gloss of the cured product,
It is particularly preferable to use a spherical inorganic filler having an average particle diameter of 0.05 to 1 μm, preferably 0.05 to 1 μm.

In the dental curable composition of the present invention, by adding a small amount of fine particle filler in addition to the above-mentioned 0.5-1 μm filler, the plastic flow property is further reduced and the mechanical strength is reduced. Improvements can be made. The average particle size of the fine particle filler is 0.05μ
Organic and inorganic fine particle fillers less than m can be used without particular limitation.

Specific examples of the fine particle fillers that are generally preferably used include ultrafine silica, ultrafine alumina, ultrafine zirconia, and ultrafine silica.
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 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 oxide 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 is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the filler having an average particle diameter of 0.05 to 1 μm. If the amount of the fine particle filler is less than 0.1 part by weight, the plastic fluidity of the composition hardly changes, and 1
When the amount 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.
A typical polymerizable monomer (monomer) that can be suitably used is, for example, a polymerizable monomer having an acryloyl group and / or a methacryloyl group. These are concretely exemplified 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 anhydride, 6-methacryloyloxyhexamethylenemalonic acid, 10-methacryloyloxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyl Oxydecamethylene dihydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonate [bifunctional vinyl monomer] (1) 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-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; 2
Methacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates;
A diadduct obtained by addition of a vinyl monomer having an OH group and a diisocyanate compound having an 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,
Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or a vinyl monomer having an -OH group such as an acrylate corresponding to these methacrylates; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methyl cyclohexane, isophorone diisocyanate, 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 [trifunctional vinyl monomer] trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol tri Methacrylates such as methacrylate and trimethylolmethane trimethacrylate and acrylates corresponding to these methacrylates [tetrafunctional vinyl monomer] , Trimethylhexamethylene diisocyanate, Chirenbisu (4
-Cyclohexyl isocyanate), diadducts obtained from the addition of diisocyanate compounds such as 4,4-diphenylmethane diisocyanate, tolylene-2,4-diisocyanate and glycidol dimethacrylate.

These polymerizable monomers can be used alone or in combination of two or more. The amount of the polymerizable monomer to be added is not particularly limited as long as the viscosity of the dental curable composition falls within a range of 3 to 300 poise and the plastic flow distance thereof is 1 mm or less. The addition amount of a general polymerizable monomer in the curable composition for use, when a filler having an average particle diameter of 0.05 to 1 μm is used, 30 to 100 parts by weight, preferably 100 parts by weight of the filler, preferably Is 40 to 90 parts by weight. When the amount of the polymerizable monomer is less than 30 parts by weight, the viscosity of the dental curable composition increases. When the amount is more than 100 parts by weight, not only the plastic flow distance increases but also the dental curable composition becomes There is a possibility that the cured product may separate during storage or the strength of the cured product may be reduced.

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

Typical polymerization initiators include combinations of organic peroxides and amines, combinations of organic peroxides, amines and sulfinates, acidic compounds,
Combinations of arylborates and arylborates, chemical polymerization initiators such as barbituric acid and alkylborane; combinations of arylborates and photoacid generators; combinations of α-diketones and tertiary amines; acylphosphine oxides And tertiary amines, thioxanthones and tertiary amines, α-
Photopolymerization initiators such as a combination of aminoacetophenones and tertiary amines are exemplified.

Examples of compounds that can be preferably 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 tertiary amines, 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-xylysine, 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 in combination of two or more.

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 alkylborane, tributylborane, tributylborane 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, 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
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.

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

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-based 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 polymerization initiator such as a combination of diketones or acylosphin oxides and tertiary amines, most preferably a combination of camphorquinone and tertiary amines.

As for the amount of the polymerization initiator, a known addition range is employed without any particular limitation. When a filler having an average particle size of 0.05 to 1 μm is used, the amount of the general polymerization initiator in the dental curable composition of the present invention is 0.003 to 5 with respect to 100 parts by weight of the filler. Used in parts by weight. 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 5 parts by weight, the storage stability of the dental curable composition is reduced.

The dental curable composition of the present invention has a viscosity of 3 to 300 poise, preferably 5 to 100 poise, 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 poise, the composition easily flows and becomes difficult to apply, and if it is higher than 300 poise, it becomes difficult to take an appropriate amount with a small brush and it becomes difficult to perform a thinner coating.

The curable dental composition of the present invention must have a plastic flow distance of 1 mm or less in order to prevent sagging during coating. The plastic flow distance referred to in the present invention means that about 0.1 g of the hardenable dental composition is placed on a horizontal and smooth glass surface so that the diameter thereof is within 10 mm, and is naturally developed for 5 seconds. Means the distance that the lowermost position of the dental curable composition spread on the glass plane has moved in 3 minutes from immediately after the glass plane was vertical. At this time, when a photopolymerization initiator was used as the 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 conduct a test using a composition obtained by removing the polymerization catalyst from the dental curable composition.

The curable dental composition of the present invention may contain, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene, or a known ultraviolet absorber, pigment, or the like, as long as its performance 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 a filler, a polymerizable monomer, and a polymerization initiator, and if necessary, the above-mentioned various additives are appropriately added. It can be prepared by mixing. 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. In addition, some components may be mixed in advance, and the remaining components may be mixed with this immediately before use.

The curable dental composition of the present invention has a viscosity of 3 to 300 poise and a plastic flow distance of 1 mm or less, so that it can be applied thinly and uniformly, and has a substantially vertical tooth surface. Even when applied to, it is hard to cause dripping. For this reason, it can be particularly suitably used as a dental hardening composition used for covering a cervical part or a root part for the purpose of treating hyperesthesia or root caries.

When the dental curable composition of the present invention is used for such a purpose, for example, the curable composition is taken 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 appropriately cured according to the type of the polymerization initiator used.

[0049]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the mechanical strength of the cured product of the dental curable composition was evaluated by three-point bending strength. In addition, each embodiment,
The measurement of the filler particle diameter, the preparation of the paste of the dental curable composition and the measurement of the physical properties, and the curing of the dental curable composition in Comparative Examples and Comparative Examples were performed according to the following methods.

(1) Measurement of Filler Particle Diameter and Coefficient of Variation of Particle Size A photograph of the powder is taken with a scanning electron microscope (manufactured by JEOL Ltd., T-330A), and the particles observed in a unit field of view of the photograph are taken. And the average volume diameter of the raw material powder particles was determined by the following equation, and the average particle diameter was determined. Further, the coefficient of variation of the particle diameter was calculated.

[0051]

(Equation 1)

(2) Preparation of Dental Curable Composition A predetermined amount of a photopolymerization initiator was added to a polymerizable monomer to prepare a matrix 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.

(3) Measurement of Viscosity 0.05 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.

(4) Measurement of plastic flow distance About 0.1 g of the dental curable composition was placed on a glass plate so as to have a diameter of 10 mm or less, and was naturally developed for 5 seconds. When placed, the distance at which the lowermost position of the dental curable composition spread on the glass plane moved for 3 minutes immediately after the glass plane was vertical was measured and defined as the plastic flow distance.

(5) Evaluation of small brush applicability A small amount of the dental curable composition was collected with a small dental brush (manufactured by Tokuyama), and the extracted roots of the bovine teeth were coated so as to be thin and uniform. At this time, the operability was evaluated as × when the sample could not be collected with a small brush, Δ when the sample could be collected with a small brush but could not be coated uniformly, and ○ when the sample could be thinly and uniformly coated. Grading was performed.

(6) Three-point bending strength test The dental curable composition is filled in a Teflon mold having a 2 × 2 × 25 mm prismatic hole, and the upper portion is carefully covered with a polypropylene film so as to prevent air bubbles from entering. While pressing. Using a visible light irradiator (manufactured by Tokuyama, power light), 30 points at each of the two ends and the center of the mold
Light irradiation was performed for each second to prepare a test piece. The test piece was mounted on a tester (Autograph 5000D, manufactured by Shimadzu Corporation), and the three-point bending 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 was pressed with a polypropylene film while being careful not to allow air bubbles to enter. Light irradiation was performed with a visible light irradiator for 30 seconds to prepare a test piece. Next, after the surface of the test piece was roughened with # 800 emery paper, finish polishing was performed using a composite abrasive (manufactured by Matsukaze Co., Super Snap).

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. The maximum value of the glossiness is 45.0, and the higher the value, the better the surface glossiness.

The abbreviations and structures of the filler, polymerizable monomer, and polymerization initiator used in each of the 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 Variation coefficient: 0.13 0.2Si-Zr: main component; spherical silica-zirconia;
γ-methacryloyloxypropyltrimethoxysilane surface-treated material Average particle size: 0.21 μm Coefficient of variation: 0.04 0.2Si: Main component: spherical silica, γ-methacryloyloxypropyltrimethoxysilane surface-treated material 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 Coefficient of variation; 0.02 1.0 Cry: main component; amorphous quartz glass Average particle size; 0.98 μm Coefficient of variation; 0.22 [Average particle diameter Particles exceeding 1 μm (hereinafter, also simply referred to as “filler B”)] 6.2Cry: main component; amorphous quartz glass average particle size: 6.2 μm variation coefficient: 1.32 [average particle size 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 size: 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- (methacryloxyethoxy) phenyl) p Bread 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 Example 1 0.2 Si-Zr 100 parts by weight as filler, 47 parts by weight of D-2.6E as polymerizable monomer, 20 parts by weight of 3G, 0.17 parts by weight of CQ as polymerization initiator , DMBE
A dental curable composition was prepared using 0.17 parts by weight.

Each physical property was measured using the above-mentioned dental curable composition. The dental curable composition had a viscosity of 22 poises, no plastic flowability, and a plastic flow distance of 0. The dental curable composition had a pencil coatability of ○. The flexural strength was 129 MPa and the surface glossiness was 23.3, which was not different from the composite resin. For this reason, the dental curable composition of the present example can perform cervical or root coating with excellent operability.

Examples 2 to 12 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. Table 2 shows the results. In any of the compositions, the applicability of the pen brush is ○, and the dental curable composition of this example can coat the cervical portion or the root portion with excellent operability.

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[Table 1]

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[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 the physical properties were measured. Table 2 shows the results. The curable dental composition of Comparative Example 1 had a viscosity of more than 300 poise, and was inferior to the examples with small brush applicability. In addition, each of the dental curable compositions of Comparative Examples 2 and 3 has a viscosity in the range of 3 to 300 poise, but has a plastic dynamic property of 1 m.
m, and the applicability of a small brush is inferior to the examples. In addition, the flexural strength in Comparative Example 2 and the surface gloss in Comparative Example 3 were inferior to those in Examples. From this fact, it can be understood that the coating operation of the cervical part or the root part is difficult for any of the compositions.

Comparative Example 4 Each of the physical properties was measured using a dental composite resin parfic esterite (manufactured by Tokuyama) instead of the dental curable composition of the present invention. The viscosity was higher than the measurement limit because of high viscosity. Yes, plastic flow distance is 0, bending strength is 13
3 MPa and surface glossiness were 24.2. Further, the applicability of the small brush is poor, and it is difficult to cover the cervical part or the root part.

Comparative Example 5 Each of the physical properties was measured using a pit and fissure filling material Parfic light sealant (manufactured by Tokuyama) instead of the dental curable composition of the present invention. , 9mm, bending strength 96MPa, surface glossiness 2
2.6. Further, the applicability of the small brush was poor, and the coating operation of the cervical or root part was difficult, and the mechanical strength was low.

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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 does not sag during application due to low plastic fluidity. When the part is repaired, a thin and uniform coating can be applied to the tooth surface where no cavity is formed or a shallow cavity is formed.

Claims (5)

[Claims] 1. A dental curable composition comprising a filler, a polymerizable monomer and a polymerization initiator, having a viscosity of 3 to 300 poise and a plastic flow distance of 1
mm or less. 2. A composition comprising 100 parts by weight of a filler having an average particle size of 0.05 to 1 μm, 30 to 100 parts by weight of a polymerizable monomer, and 0.003 to 5 parts by weight of a photopolymerization initiator. The dental curable composition according to claim 1, wherein 3. 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. 4. The dental curable composition according to claim 2, further comprising 0.1 to 10 parts by weight of a fine particle filler having an average particle diameter of less than 0.05 μm. 5. The dental curable composition according to claim 1, wherein the dental curable composition is a curable composition for covering a cervical part or a root part.