JP2007126417A - Curable composition for dental use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental restoration material having good curability and transparency while keeping contradictive properties comprising flowability and shape retention. <P>SOLUTION: The curable composition for dental use contains (a) 50-90 mass% aromatic di(meth)acrylate mixture comprising two or more kinds of aromatic di(meth)acrylates expressed by general formula (1) and containing 5-70 mass% hydroxyl-containing compound, (b) 50-10 mass% aliphatic di(meth)acrylate (the components (a) and (b) constitutes 100 pts.mass of polymerizable monomer component), (c) 200-900 pts.mass of a filler component having a refractive index of 1.50-1.58 and (d) an effective amount of a polymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable composition suitable as a dental restorative material.

  Dental restoration material is a composite material mainly composed of a polymerizable monomer and filler, and can be imparted with the same color tone as natural tooth color and is easy to operate. In recent years, it has been widely used. The use site is wide, such as the restoration of the entire crown from the shallow cavity and the construction of an abutment that fills the gap of the root after extraction.

  Such dental restorative materials are required to have high mechanical strength that can withstand high occlusal pressure due to mastication and the like, and to have a certain degree of transparency in order to give the same color tone as natural teeth. And physical properties such as having radiopacity necessary for identifying the repair site are required.

  For the purpose of obtaining good mechanical strength as described above, a filler is blended in the dental restorative material. Generally, the larger the blending ratio of the filler, the better the performance. In order to develop radiopacity, it is generally performed to add a filler having radiopacity, and such a filler usually has a refractive index in the range of 1.50 to 1.58. Inorganic fillers are used. Furthermore, in order to obtain a dental restorative material having a color tone equivalent to that of a tooth, transparency must be ensured, and therefore the refractive index of the filler and the matrix needs to be approximately equal. Therefore, when an inorganic filler having a refractive index in the range of 1.50 to 1.58 is used, the refractive index of the matrix needs to be in the range of 1.50 to 1.58 after curing.

In order to obtain such a high-refractive index matrix, it is advantageous to have an aromatic ring in the molecule of the polymerizable monomer, and it is also advantageous to be bifunctional due to good mechanical strength. is there. And, since these requirements are satisfied, (a) the following general formula (1)
(Wherein, ^{R 1} and ^{R 2} is a hydrogen atom or a methyl group, ^{R 3} and ^{R 4} is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms,, p, q, r, and s is 0 And m and n are integers of 1 to 8, and the repeating units of m and n can take a plurality of repeating units different from each other.)
Aromatic di (meth) acrylates as shown in (1) to (3) are used. Among these aromatic di (meth) acrylates, a hydroxyl group-containing body in which R ³ and R ⁴ are hydroxyl groups, such as 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, It is suitable because it has excellent curability because of the entanglement between molecules due to the action of hydrogen bonding of the hydroxyl group.

JP-A-10-130116 JP 2001-139411 A Japanese Patent Laid-Open No. 2005-170813

  However, when a hydroxyl group-containing body of such aromatic di (meth) acrylate is used, the shapeability is extremely deteriorated when the fluidity of the curable composition is appropriately adjusted, such as a dental restorative material. In use, there is an inconvenience that the operability is greatly reduced. That is, when the shapeability of the curable composition is poor, it is molded into the desired shape in applications such as the case where the tooth neck and root are covered by hypersensitivity or root caries, or in the construction of an abutment. There was a problem that it was difficult and the shapeability was bad. It is surmised that the reason why the shapeability is poor is that the good affinity between the surface of the filler and the matrix is greatly influenced by the hydroxyl group of the hydroxyl group-containing body of the aromatic di (meth) acrylate.

  Therefore, in order to solve this problem, attempts have been made to mix low-viscosity aliphatic dimethacrylates, but the effect has not been improved, and a large amount of these aliphatic dimethacrylates have not been achieved. When added to the above, another problem arises in that the refractive index of the matrix is lowered and the transparency of the restoration material is lowered. Furthermore, as a filler to be used, it is possible to reduce the affinity with the filler by using a hydrophobized surface treatment agent with an extremely high hydrophobicity, but this method is satisfactory. The fact is that only the effect is not obtained.

  In the above background, the present invention is a dental curable composition containing a hydroxyl group-containing body of an aromatic di (meth) acrylate and a filler having a refractive index of 1.50 to 1.58. It aims at providing the composition which has moderate fluidity other than sclerosis | hardenability and shapeability, and also the transparency was maintained favorable.

  The present inventors have intensively studied to solve the above problems. As a result, in the aromatic di (meth) acrylate, the above problem can be solved by using a specific amount of a hydroxyl group-free product together with a hydroxyl group-containing product, and also using a specific amount of aliphatic dimethacrylate. The headline and the present invention were completed.

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

(Wherein, ^{R 1} and ^{R 2} is a hydrogen atom or a methyl group, ^{R 3} and ^{R 4} is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms,, p, q, r, and s is 0 And m and n are integers of 1 to 8, and the repeating units of m and n can take a plurality of repeating units different from each other.)
A mixture of two or more of the aromatic di (meth) acrylates represented by the formula, wherein each unit of m and n is a hydroxyl group-containing unit in which R ³ and R ⁴ are hydroxyl groups. An aromatic di (meth) acrylate mixture containing 30 to 95% by mass of a hydroxyl group-free product in which all of R ³ and R ⁴ are hydrogen atoms or hydrocarbon groups.
(B) Aliphatic di (meth) acrylate 50 to 10% by mass
100 parts by mass of a polymerizable monomer component comprising (c) 200 to 900 parts by mass of a filler component having a refractive index of 1.50 to 1.58, and (d) an effective amount of a polymerization initiator. It is a curable composition.

  The dental curable composition obtained by blending each component of the present invention has the conflicting properties of fluidity and shapeability, which has been difficult to achieve in the past, and has good curability, Also, it has excellent transparency.

  In the curable composition of the present invention, (a) an aromatic di (meth) acrylate compound represented by the following general formula (1) is used as the polymerizable monomer component.

(Wherein, ^{R 1} and ^{R 2} is a hydrogen atom or a methyl group, ^{R 3} and ^{R 4} is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms,, p, q, r, and s is 0 And m and n are integers of 1 to 8, and the repeating units of m and n can take a plurality of repeating units different from each other.)
In the present invention, R ¹ and R ² are a hydrogen atom or a methyl group.

R ³ and R ⁴ are a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and among these, a methyl group is preferable.

In the present invention, the aromatic di (meth) acrylate includes, as m and n units, a hydroxyl group-containing body in which R ³ and R ⁴ are each a hydroxyl group, and R ³ and R ⁴ are all hydrogen atoms. Or it mixes and uses the hydroxyl-non-containing body which is a C1-C3 alkyl group. In addition, in the hydroxyl group-containing body in which m and n are 2 or more, the repeating unit of m and n may be any unit in which at least one unit and R ³ and R ⁴ are hydroxyl groups, respectively, the R ³ and R ⁴ The more units that are hydroxyl groups, the better the curability and the more remarkable the effect of achieving both fluidity and shapeability effects. In all of the m and n repeating units, R ³ and R ⁴ are most preferably a hydroxyl group.

A hydroxyl group-free product in which all of R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms has a high refractive index due to the bisphenol structure at the center of the molecule as well as a hydroxyl group-containing product, but has a hydroxyl group. As a result, it does not hydrogen bond with other molecules like the hydroxyl group-containing substance. Therefore, when the non-hydroxyl group-containing material is mixed with the hydroxyl group-containing material as described above, the effect of diluting the entanglement of molecules by the hydroxyl group of the hydroxyl-containing material is exhibited, and the resulting curable composition has a high refractive index. While maintaining the properties of, the shapeability can be greatly improved.

  Here, in the said General formula (1), although p, q, r, and s are integers of 0-6, the integer of 0-2 is more preferable. m and n are integers of 1 to 8, but an integer of 1 to 2 is more preferable.

In the molecule, R ¹ and R ² , R ³ and R ⁴ , p, q, r, and s, m, and n may be different groups or integers from each other in the relationship. From the viewpoint of easiness, it is preferable that they are the same group or an integer.

  Specific examples of the hydroxyl group-containing substance of aromatic di (meth) acrylate include 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis [4- ( 4-methacryloyloxy) -3-hydroxybutoxyphenyl] propane, 2,2-bis [4- (4-methacryloyloxy) -2-hydroxybutoxyphenyl] propane, 2,2-bis [4- (5-methacryloyloxy) ) -4-hydroxypentoxyphenyl] propane, 2,2-bis [4-di [(3-methacryloyloxy) -2-hydroxypropoxy] phenyl] propane, 2,2-bis [4-tri [(3- Methacryloyloxy) -2-hydroxypropoxy] phenyl] propane, 2- [4- (3-methacryloyloxy) -2- [ 4- (4-methacryloyloxy) -3-hydroxybutoxyphenyl] propane; and acrylates corresponding to these methacrylates. Among these, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane is easily available, and the effects of the present invention are most remarkably exhibited.

On the other hand, in the hydroxy group-free product, R ³ and R ⁴ are preferably a hydrogen atom or a methyl group, since the effects of the present invention are exhibited particularly well.

  Specific examples of such a hydroxyl group-free product include 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 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-methacryloyloxydi) Ethoxyphenyl) -2- (4-methacryloyloxyethoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2- (4-methacryloyloxydipropoxy) Feni ) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane; and their methacrylates And acrylates corresponding to the above. Among them, methacrylate is preferable from the point that it is used in dental materials and has high safety, and 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) is preferable. Most preferred are methacrylates wherein m and n are 1-2, such as -2- (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane).

  Each of these hydroxyl group-containing bodies and hydroxyl group-free bodies may be used in combination of two or more different types.

  The mixing ratio of the hydroxyl group-containing body and the hydroxyl group-free body is preferably 5 to 70% by mass, more preferably in the mixture, considering the balance between the curability, shapeability, transparency and fluidity. It is 30 to 60% by mass, and the latter needs to be 95 to 30% by mass, and more preferably 70 to 40% by mass. Here, when the mixing ratio of the hydroxyl group-containing material is smaller than 5% by mass, although the shapeability is excellent, the fluidity becomes insufficient, the refractive index is lowered, and the transparency is deteriorated. On the other hand, when the mixing ratio is more than 70% by mass, the shapeability is insufficient although the fluidity is excellent.

In the category of the aromatic di (meth) acrylate represented by the general formula (1), a compound having a hydroxyl group other than the above-defined hydroxyl group-containing compound, R ³ as a unit of only one of m and n, Alternatively, there may be a compound having a unit in which R ⁴ is a hydroxyl group. A compound having a hydroxyl group only in one of these chains is not easy to produce and is not a general-purpose compound. However, in the present invention, such a compound also maintains the mixing ratio of the hydroxyl group-containing substance and the hydroxyl group-free substance. However, it may be contained in a small amount as long as it does not affect the effect.

The method for synthesizing the aromatic di (meth) acrylate compound is not particularly limited, and any known method can be adopted without limitation. Generally, an alkylene oxide having a group of R ³ and R ⁴ and bisphenol A are used in an organic solvent. A method of reacting and further reacting (meth) acrylic acid or a derivative thereof is preferable. In addition, in the case of 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, which is the most preferred hydroxyl group-containing product, the bisphenol skeleton as a raw material is formed in an organic solvent. It can also be satisfactorily synthesized by a method of reacting an epoxy compound having (meth) acrylic acid or a derivative thereof.

  Furthermore, in this invention, in addition to the said aromatic di (meth) acrylate mixture, a specific amount of (b) aliphatic di (meth) acrylate is used together as a polymerizable monomer component. That is, in the aromatic di (meth) acrylate, the poor shapeability derived from the hydroxyl group-containing body is considerably improved by a specific amount of the hydroxyl group-free body, but that alone is not sufficient one step, In the present invention, aliphatic di (meth) acrylate is also used in combination.

  Here, the aliphatic di (meth) acrylate is not particularly limited, and a known aliphatic di (meth) acrylate can be used, but an aliphatic hydrocarbon group (polyethylene excluding the (meth) acryloyl group portion). Those having an oxygen atom such as an oxide group) having 2 to 60 carbon atoms, more preferably 2 to 40 carbon atoms are preferred.

  Preferably, the general formula (2)

(Wherein, ^{R 5} and ^{R 6} is a hydrogen atom or a methyl group, ^{R 7} is an alkylene group having 1 to 4 carbon atoms, t is an integer of 1 to 14.)
The compound shown by these is preferable.

Here, as R ⁷ , examples of the alkylene group having 1 to ⁷ carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group, and among these, an ethylene group is particularly preferable.

  Specific examples of aliphatic di (meth) acrylates include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol di Methacrylates, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate; and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate And vinyl monomers having —OH groups such as methacrylates or acrylates corresponding to these methacrylates, Sa diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methyl cyclohexane, isophorone diisocyanate, methylenebis diadduct and the like obtained from the addition of a diisocyanate compound such as (4-cyclohexyl isocyanate) and the like.

  Among them, polyalkylene glycol di (meth) acrylate is preferable and triethylene glycol dimethacrylate is most preferable from the viewpoint of many achievements used in dental materials and high safety.

  In the polymerizable monomer component, the mixing ratio of the aromatic di (meth) acrylate mixture and the aliphatic di (meth) acrylate considers the balance between the curability, shapeability, transparency and fluidity. And the former is 50-90 mass%, More preferably, it is 55-80 mass%, The latter is 50-10 mass%, More preferably, it is 45-20 mass%. Here, when the mixing ratio of the aromatic di (meth) acrylate mixture is smaller than 10% by mass, the flowability is insufficient but the refractive index is lowered and the transparency is deteriorated although the shapeability is excellent. On the other hand, when the mixing ratio is more than 90% by mass, the shapeability is insufficient although the fluidity is excellent.

  In the present invention, the filler (c) having a refractive index of 1.50 or more and 1.58 or less can be used without particular limitation as long as the refractive index satisfies the above range, and among these, 1.51 To 1.56 is preferred.

  The material (component) of these inorganic fillers is not particularly limited as long as the refractive index falls within the range of 1.50 to 1.58, and is the same as the known inorganic filler as a compounding component of the dental curable composition. The thing of a material can be used. Specifically, aluminosilicate glass, fluoroaluminosilicate glass, glass containing heavy metals (for example, barium, strontium, zirconium); crystallized glass obtained by precipitating crystals on these glasses, crystals such as diopside, leucite, etc. Glass ceramics such as crystallized glass, etc. deposited with silica; composite inorganic oxides such as silica-zirconia, silica-titania, silica-alumina; or oxides obtained by adding group I metal oxides to these composite oxides; Can be used. Among these, composite oxides mainly composed of composite oxides of silicon and group IV metals are mainly used because the obtained cured product is easily imparted with transparency close to the tooth, and is less harmful to the living body. Is preferred. More preferably, the cured product obtained can be imparted with X-ray contrast properties, and further, a cured product with higher wear resistance can be obtained, and the refractive index is comparable to that of the polymerizable monomer. A composite oxide containing silica-zirconia as a main constituent component is particularly preferably used because high curable composition cannot be given high visible light transmittance.

  The particle size and shape of the filler of the present invention are not particularly limited, but from an amorphous filler having an average particle size of 1 μm to 6 μm and a spherical filler having an average particle size of 0.05 μm to 1 μm. And when the total amount of fillers is 100% by mass, these are 40 to 90% by mass of an amorphous filler having an average particle size of 1 μm or more and 6 μm or less, and an average particle size of 0.05 μm or more and 1 μm or less. It is preferable to mix | blend in the range of 10-60 mass% of spherical fillers. Here, the average particle diameter is a particle diameter in which particles having a particle diameter of 0.05 μm or more are calculated and the value of the integrated distribution is 50% in the particle diameter-volume integrated distribution.

  As the amorphous filler, those having an average particle diameter of 1 μm or more and 6 μm or less are preferable, but those having an average particle diameter of 3 μm or more and 5 μm or less are particularly preferable. Moreover, as said amorphous filler, since the stable mechanical and physical strength is acquired, it is preferable that a maximum particle size is 40 micrometers or less (it does not contain the particle | grains exceeding 40 micrometers in particle size). Furthermore, in order to achieve a high filler content, it is more preferable to employ an inorganic filler having an irregular filler with a coefficient of variation of 0.70 or more. The variation coefficient is a variation coefficient defined by JIS-Z8101-1 [standard deviation (σ) / average value]. The variation coefficient is an index representing the spread of the particle size distribution, and the larger the value, the wider the particle size distribution.

  The spherical filler preferably has an average particle size of 0.05 μm or more and 1 μm or less, and particularly preferably an average particle size of 0.1 μm or more and 0.5 μm or less. The term “spherical” as used herein means that the particles observed with a scanning electron microscope (hereinafter abbreviated as “SEM”) are rounded, and the average homogeneity obtained by dividing the particle diameter in the direction perpendicular to the maximum diameter by the maximum diameter. Is 0.6 or more.

  When the filler in the present invention is an inorganic filler, the surface of the filler should be hydrophobized for the purpose of improving the dispersibility in the polymerizable monomer and further improving the fluidity of the composition. Is preferred. Such a hydrophobizing treatment is not particularly limited, and a known method is employed without limitation.

  Illustrative examples of typical hydrophobizing treatment methods include silane coupling agents such as γ-methacryloyloxyalkyltrimethoxysilane, γ-methyltrimethoxysilane, γ-methacryloyloxyalkylmonomethyldimethoxysilane, hexamethyldithiophene as hydrophobizing agents. Treatment with an organosilicon compound such as silazane, monomethyltrichlorosilane, dimethyldichlorosilane, a titanate coupling agent, an aluminate coupling agent, a method using a zirco-aluminate coupling agent, There is a method of graft polymerization of a monomer. Such treatment may be performed after mixing various fillers, or may be performed in advance for each filler.

  The amount of the filler of the present invention is 200 to 900 parts by mass when the polymerizable monomer component is 100 parts by weight.

  The filler of the present invention may be used alone, but two or more kinds of fillers can be used in combination.

  In the dental curable composition of the present invention, in addition to the above-described components, an effective amount of (d) a polymerization initiator such as a photopolymerization initiator, a chemical polymerization initiator, or a thermal polymerization initiator is blended. Among these, the chemical polymerization initiator includes a combination of organic peroxides and amines, a combination of organic peroxides, amines and sulfinates, an acidic compound, and a combination of aryl borates, barbituric acid, Examples of the photopolymerization initiator include combinations of aryl borates and photo acid generators, combinations of α-diketones and tertiary amines, acylphosphine oxides and tertiary amines. Examples include combinations, combinations of thioxanthones and tertiary amines, combinations of α-aminoacetophenones and tertiary amines, and the like.

  Examples of compounds that can be suitably used as the compounds used in the various chemical polymerization initiators include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, peroxide, and the like. Examples include dicumyl oxide, acetyl peroxide, lauroyl peroxide, and benzoyl peroxide. 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, N-methyl-p-toluidine and the like as secondary 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-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylan Ranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-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-dimethyl Hexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethano And the like. These can be used individually or in mixture of 2 or more types.

  Examples of various compounds preferably used for the various photopolymerization initiators include α-diketones such as 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.

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

  Acylphosphine oxides include benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5 , 6-tetramethylbenzoyldiphenylphosphine oxide and the like.

  The blending ratio of the polymerization initiator is not particularly limited, but is 0.01 to 20 parts by weight, particularly preferably 0.1 to 8 parts by weight, when the polymerizable monomer component is 100 parts by weight. Is preferred.

  It is also possible to use a dual cure type in which a chemical polymerization initiator and a photopolymerization initiator are used in combination, and polymerization can be initiated by either chemical polymerization or photopolymerization.

  The dental curable composition of the present invention includes (a) an aromatic di (meth) acrylate mixture, (b) an aliphatic di (meth) acrylate, (c) a filler having a refractive index of 1.50 to 1.58, (D) In addition to the polymerization initiator, other known components may be blended as a blending component of the dental curable composition as long as the effects of the present invention are not impaired. Examples of such components include polymerization inhibitors such as hydrone, hydroquinone monomethyl ether and butylhydroxytoluene, polymerization retarders such as styrene derivatives described in JP-A-9-17621, etc., known UV absorbers, Examples thereof include pigments, antibacterial agents, metal salts, metal complexes, organic fillers, and organic-inorganic composite fillers.

  The method for producing the dental curable composition of the present invention is not particularly limited, and may be performed in accordance with a known method for producing a dental curable composition. For example, a predetermined amount of (a) hydroxyl group is used. -Containing aromatic di (meth) acrylate compound, (b) hydroxyl-free aromatic di (meth) acrylate, and (c) aliphatic di (meth) acrylate, (d) filler having a refractive index of 1.50 to 1.58 In addition, it can be prepared by mixing the above-described various optional components blended as necessary and kneading until a uniform paste is obtained.

  The use of the dental curable composition of the present invention is not particularly limited as long as it is dental, but it is more strongly required to have excellent fluidity and shapeability and good polymerizability. Therefore, it is preferably used as a dental restoration material (composite resin). When used as a dental restoration material, it can be used for restoration of the entire crown from a shallow cavity, especially for the construction of an abutment in place of the removed tooth or pulp in a deep cavity. It is preferred to use.

  The use method for constructing such an abutment is described as follows. The dental curable composition of the present invention is prepared by treating the cavity of the tooth to be repaired in the oral cavity with the dental direct restoration adhesive. A method in which a product is filled and formed into a tooth shape and then polymerized and cured (direct method), and a water-soluble or water-insoluble separation material is applied to the cavity of the tooth to be restored, and the dental of the present invention is applied thereto. The curable composition is filled, and the polymerized and cured product is taken out once, and further polymerized by chemical polymerization, photopolymerization, thermal polymerization, etc., and then adhered using an adhesive for indirect dental restoration Method (direct indirect method), method of forming a tooth shape with a cavity model outside the oral cavity, polymerizing and curing, and then using the adhesive for indirect dental restoration to repair the tooth (indirect Law).

EXAMPLES Hereinafter, although the content of this invention is demonstrated in detail by an Example, this invention is not limited to these Examples. In addition, the definitions of various quantities relating to the properties of the materials shown in the text and the examples and the measuring methods thereof are as follows.
(1) Preparation of paste A matrix was prepared by adding a predetermined proportion of tertiary amine or organic peroxide to the polymerizable monomer. Next, the filler and the matrix were put in an agate mortar and sufficiently kneaded to obtain a uniform paste to prepare a paste.

The raw materials used in the examples and comparative examples are as follows.
(2) Curing time 0.13 g of the paste to be measured was collected and kneaded for 30 seconds. It was filled in a sheet wax of 3 mm thickness having a 6 mmφ hole, placed in a 37 ° C. constant temperature bath 1 minute after the start of kneading, and the time when the value of the thermoelectromotive force peaked was defined as the curing time. As shown in ISO 4049, in order to obtain good curability, the curing time needs to be within 10 minutes.
(3) Fluidity 0.1 g of the paste to be measured was weighed on a polyester film and pressed using a 120 g weight for 30 seconds. The diameters in the vertical and horizontal directions were measured, the average of each was determined, and the value was defined as fluidity. In the dental curable composition of the present invention, when the fluidity value is in the range of 10 mm or more, the object can be achieved. When the fluidity value is 10 mm or less, it is difficult to fill the details, and thus the object of the present invention cannot be achieved.
(4) Shapeability 0.1 g of the paste to be measured was weighed on a glass plate and held in a 37 ° C. incubator for 2 minutes. The diameters in the vertical and horizontal directions were measured, the average of each was determined, and the value was defined as the shapeability. In the dental curable composition of the present invention, the object can be achieved when the shapeability value is in the range of 10 mm or less.

When the shapeability value is 10 mm or more, the shape cannot be maintained when the paste is built up, and thus the object of the present invention cannot be achieved.
(5) Refractive index The refractive index of the filler was measured by the method shown below. Add 0.1 g of filler to 5 ml of ethanol, add 1-bromonaphthalene with a dropper, and observe the transparency of the dispersion with the naked eye. When the dispersion between the filler and the liquid disappears and the dispersion becomes transparent, the refractive index of the dispersion is measured with an Abbe refractometer. This value was taken as the refractive index of the filler.

  The refractive index of the monomer and polymer was measured with an Abbe refractometer.

The raw materials used in the examples and comparative examples are as follows.
(A) Aromatic di (meth) acrylate / hydroxyl group-containing aromatic di (meth) acrylate 2,2-bis [4 (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (hereinafter abbreviated as bis-GMA). )
-Hydroxyl-free aromatic di (meth) acrylate 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane) mixture (m + n having an average of 2.6) (hereinafter abbreviated as D-26E)
(B) Aliphatic di (meth) acrylate / triethylene glycol dimethacrylate (hereinafter abbreviated as 3G)
Polyethylene glycol dimethacrylate [mixture in which R ⁷ is an ethylene group and the average value of t is 9 in the general formula (2)] (hereinafter abbreviated as 9G)
(C) Filler Amorphous silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 4.2 μm, refractive index 1.54 (hereinafter abbreviated as LGFH)
Spherical silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 0.1 μm, refractive index 1.52 (hereinafter abbreviated as FXCPH)
(D) Polymerization initiator N, N-dimethyl-p-toluidine (hereinafter abbreviated as DEPT)
Benzoyl peroxide (hereinafter abbreviated as BPO)
Example 1
CR-1A: A matrix was prepared by adding bis-GMA 30% by mass as a polymerizable monomer, D26E 40% by mass and 3G 30% by mass, and DEPT 2 parts by mass as a tertiary amine. A paste was prepared according to the above preparation method using 200 parts by mass of LGFH and 120 parts by mass of FXCPH as fillers with respect to 100 parts by mass of the matrix.

  CR-1B: A matrix was prepared in which bis-GMA 30% by mass as a polymerizable monomer, D26E 40% by mass and 3G 30% by mass, and BPO 2 parts by mass as a tertiary amine were added. A paste was prepared according to the above preparation method using 200 parts by mass of LGFH and 120 parts by mass of FXCPH as fillers with respect to 100 parts by mass of the matrix.

  When the obtained two pastes were kneaded and each item was evaluated, the curability was good at a curing time of 4 minutes and 00 seconds, the fluidity was 16 mm, and the shapeability was 6 mm. .

Examples 2-6
Dental curable compositions having the compositions shown in Table 1 were prepared. When the two pastes obtained in the same manner as in Example 1 were kneaded and evaluated for each item, they were all excellent in curability, fluidity, and shapeability.

Comparative Example 1
Dental curable compositions having the compositions shown in Table 1 were prepared. Although it does not contain a hydroxyl group-free aromatic di (meth) acrylate, it is excellent in fluidity and curability, but the shapeability is 12 mm, which is insufficient.

Comparative Example 2
Dental curable compositions having the compositions shown in Table 1 were prepared. Although it did not contain a hydroxyl group-containing aromatic di (meth) acrylate, it was excellent in formability, but was inadequate with a curability of 12 minutes 10 seconds and a fluidity of 9 mm.

Claims (3)

(A) The following general formula (1)

(Wherein, ^{R 1} and ^{R 2} is a hydrogen atom or a methyl group, ^{R 3} and ^{R 4} is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms,, p, q, r, and s is 0 And m and n are integers of 1 to 8, and the repeating units of m and n can take a plurality of repeating units different from each other.)
A mixture of two or more of the aromatic di (meth) acrylates represented by the formula, wherein each unit of m and n is a hydroxyl group-containing unit in which R ³ and R ⁴ are hydroxyl groups. An aromatic di (meth) acrylate mixture containing 95 to 30% by mass of a hydroxyl group-free product in which all of R ³ and R ⁴ are hydrogen atoms or hydrocarbon groups.
(B) Aliphatic di (meth) acrylate 50 to 10% by mass
100 parts by mass of a polymerizable monomer component comprising (c) 200 to 900 parts by mass of a filler component having a refractive index of 1.50 to 1.58, and (d) an effective amount of a polymerization initiator. Curable composition. (A) In the aromatic di (meth) acrylate mixture, the hydroxyl group-containing body is 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, and the hydroxyl group-free body is 2 , 2-bis (4-methacryloyloxyethoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxy) The dental curable composition according to claim 1, which is phenyl) propane) or a mixture thereof. (B) The aliphatic di (meth) acrylate has the general formula (2)

(Wherein, ^{R 5} and ^{R 6} is a hydrogen atom or a methyl group, ^{R 7} is an alkylene group having 1 to 4 carbon atoms, t is an integer of 1 to 14.)
The dental curable composition according to claim 1, which is a compound represented by the formula: