JP6112887B2 - Dental curable composition - Google Patents

Description

  The present invention relates to a chemically polymerizable dental curable composition.

  In the dental field, a polymerizable composition containing a polymerizable monomer and a polymerization initiator is used as a dental resin cement, a dental adhesive, a dental coating material, a pit and fissure filling material, a composite resin, and a dental room temperature polymerization. It is widely used as a resin, a dental pretreatment material, a denture base material, and the like. The polymerization initiator used in the polymerizable composition is roughly classified into a photopolymerization initiator and a chemical polymerization initiator. Photopolymerization of the polymerizable composition by photopolymerization is started by performing light irradiation using a dental light irradiator. On the other hand, the polymerizable composition by chemical polymerization is stored by dividing the components of the polymerizable composition into at least two packages, and chemical polymerization is started by mixing and kneading each package at the time of use. .

In general, the chemical polymerization initiator tends to have a lower polymerization activity than the photopolymerization initiator. In particular, when used as a dental cement or adhesive, moisture and the like are present at the tooth interface, and therefore high polymerization activity for imparting strong adhesiveness is required.
As the chemical polymerization initiator having a high polymerization activity, a redox polymerization initiator in which an organic peroxide and an amine compound that is a reducing substance are combined is known and widely used in the dental field (for example, patents) References 1-2).
As the organic peroxide, diacyl peroxides such as benzoyl peroxide impart a high polymerization activity and are very useful because curing proceeds smoothly even at room temperature. However, due to its high polymerization activity, when it is stored at room temperature for a long period of time, it decomposes and radicals are generated and deactivated. There is a problem going on.
In addition, as the amine compound combined with the organic peroxide, an aromatic tertiary amine compound has an excellent polymerization promoting action and is preferably used. However, the aromatic tertiary amine compound is liable to be changed into a colored substance, and there is a problem that aesthetics are impaired in the cured product.

By the way, in order to adhere the tooth and the restoration with high strength in the harsh environment of the oral cavity, the dental cement or adhesive contains an acidic group such as phosphate group or carboxylic acid as an adhesive component. It has become common to blend polymerizable monomers.
However, when an acidic group-containing polymerizable monomer is blended as the polymerizable monomer, when the redox polymerization initiator is applied as the chemical polymerization initiator, the amine compound as a reducing substance is converted into the acidic group. There is a problem that it is neutralized by the acidic group of the containing polymerizable monomer and its polymerization activity is greatly reduced.

Here, a combination of a hydroperoxide and a thiourea compound has been proposed as the chemical polymerization initiator when an acidic group-containing polymerizable monomer is used (see Patent Documents 3 and 4). Since the hydroperoxide has higher thermal stability than benzoyl peroxide and the like, it can be stored for a long period of time at room temperature, and the thiourea compound is colored like the amine compound. Since it is not easy, there are few use restrictions, Therefore It can use suitably for the said chemical polymerization initiator.
However, the combination of the hydroperoxide and the thiourea compound improves the activity under acidic conditions than the combination of the benzoyl peroxide and the amine compound, but still has low activity and insufficient adhesive strength. There is a problem.

Therefore, when the combination of the hydroperoxide and the thiourea compound is applied, the chemical polymerization initiator that improves the curability by using a copper compound as a curing accelerator has been proposed (for example, , See Patent Document 5).
However, even when the copper compound is used, there is a problem that sufficient adhesive strength cannot be achieved although the curing activity is improved.
Therefore, the combination of the hydroperoxide and the thiourea compound is excellent in color tone stability and storage stability, but the present situation is that the bond strength is not satisfactory.

JP 2009-114221 A Japanese Patent Publication No. 6-2651 JP 2005-8622 A JP 2009-144054 A JP 2007-56020 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a dental curable composition having excellent adhesive strength.

In order to achieve the above object, the present inventors have intensively studied, and as the chemical polymerization initiator for the polymerizable monomer containing the acidic group-containing polymerizable monomer, the hydroperoxide, the thiourea When applying the combination of a compound and the said copper compound, when the water-soluble copper compound was used as said copper compound, the knowledge that adhesive strength could be improved was acquired.
The reason why such adhesive strength can be improved is not necessarily clear, but when the water-soluble copper compound is used as the copper compound, the polymerization activity at the hydrophilic tooth surface interface is improved. Inferred. That is, in the dentin, particularly dentin, the collagen fibers contain water, so the interface is hydrophilic. In order to increase the adhesive strength, a resin-impregnated layer in which the polymerizable monomer of the dental adhesive composition has penetrated is formed at the hydrophilic tooth interface, and the polymerization rate is increased to obtain a strong adhesive layer. There is a need. Since the polymerization initiator used in a normal dental composition has low hydrophilicity, the activity at such an interface tends to decrease. On the other hand, the water-soluble copper compound used in the present invention is considered to have high adhesive strength because it does not cause a decrease in activity.
Furthermore, when a water-soluble copper compound with low solubility in the polymerizable monomer is used, the initiator dissolves only at the hydrophilic interface, so the curing time before the treatment becomes longer, Since the operation time until the dental therapist mixes and operates each package in the chemical polymerization initiator is increased, the burden on the therapist is reduced.

The present invention is based on the above knowledge, and means for solving the above problems are as follows. That is,
<1> (A) a polymerizable monomer containing an acidic group-containing polymerizable monomer, (B) a thiourea derivative, (C) a hydroperoxide organic peroxide, and (D) water-soluble copper and compounds, only including, wherein the amount of said (D) water-soluble copper compound, the polymerizable monomer (a) 100 parts by weight per 0.04 parts by weight to 0.3 parts by weight A dental curable composition.
<2> (D) The dental curable composition according to <1>, wherein the water-soluble copper compound is a copper compound having a water solubility at 20 ° C. of 10 g / 100 mL or more.
<3> (D) The water-soluble copper compound according to any one of <1> to <2>, wherein the solubility in the polymerizable monomer (A) at 20 ° C. is less than 0.1 g / 100 g at most. The dental curable composition as described.
<4> The dental curable composition according to any one of <2> to <3>, wherein (D) the water-soluble copper compound is any one of copper sulfate, chlorophyllin copper sodium, copper gluconate, and a mixture thereof. .
<5> The dental curable composition according to any one of <1> to <4>, further comprising (E) an aryl borate compound.
<6> The dental curable composition according to any one of <1> to <5>, further comprising a fluoroaluminosilicate glass.
<7> Dental curing according to any one of <1> to <6>, wherein the dental hardening is divided and stored in at least two packages, and (D) the water-soluble copper compound is contained in one package in an undissolved state. Sex composition.
<8> Among (A) polymerizable monomers, at least an acidic group-containing polymerizable monomer and (B) a thiourea derivative are encapsulated in one package, and (C) a hydroperoxide-based organic peroxide (D) The dental curable composition according to <7>, wherein the water-soluble copper compound is contained in another package.

  ADVANTAGE OF THE INVENTION According to this invention, the said various problems in a prior art can be solved, and the dental curable composition excellent in adhesive strength can be provided.

(Dental curable composition)
The dental curable composition of the present invention includes (A) a polymerizable monomer containing an acidic group-containing polymerizable monomer, (B) a thiourea derivative, and (C) a hydroperoxide-based organic peroxide. And (D) a water-soluble copper compound, and if necessary, other components.

<(A) Polymerizable monomer>
The (A) polymerizable monomer means a compound having at least one radical polymerizable unsaturated group in one molecule.
The radical polymerizable unsaturated group is not particularly limited, and specific examples thereof include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, (meth) acryloylthio group and the like ( Examples thereof include a derivative group of a (meth) acryloyl group, a vinyl group, an allyl group, a styryl group, and the like, and the (meth) acryloyl group is preferable in consideration of harm to a living body as a dental use.

The (A) polymerizable monomer includes an acidic group-containing polymerizable monomer as at least a part. Here, the acidic group is a group in which an aqueous solution or a suspension of a polymerizable monomer having the group exhibits an acidity, and is not only an acidic group but also an acid anhydride obtained by dehydration condensation of two of the acidic groups. The structure may be an acid halide group in which an acidic group is halogenated. Specifically, a phosphinico group {= P (═O) OH}, a phosphono group {—P (═O) (OH) ₂ }, a carboxyl group {—C (═O) OH}, a dihydrogen phosphate monoester Group {—O—P (═O) (OH) ₂ }, hydrogen phosphate diester group {(—O—) ₂ P (═O) OH}, sulfo group (—SO ₃ H), and acid anhydride skeleton {-C (= O) -OC (= O)-} and the like, and is highly stable against water, so that dissolution of the smear layer of the tooth surface and tooth decalcification can be carried out gently, so that the carboxyl group The dihydrogen phosphate monoester group and the hydrogen phosphate diester group are preferable, and the dihydrogen phosphate monoester group and the hydrogen phosphate diester group are more preferable.

  Examples of the polymerizable monomer having the dihydrogen phosphate monoester group or the hydrogen phosphate diester group include 2- (meth) acryloyloxyethyl dihydrogen phosphate and bis [2- (meth) acryloyloxy. Ethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 6- (meth) acryloyloxyhexylphenyl hydrogen phosphate, 10- (meth) Acryloyloxydecyl dihydrogen phosphate, 1,3-di (meth) acryloylpropane-2-dihydrogen phosphate, 1,3-di (meth) acryloylpropane-2-phenylhydrogenphos Eto, bis [5- {2- (meth) acryloyloxy} heptyl] hydrogen phosphate, and the like.

  Examples of the polymerizable monomer having a carboxyl group include 4- (meth) acryloxyethyl trimellitic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di ( Examples include (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and the like.

  Examples of the polymerizable monomer having a sulfo group include 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, vinylsulfonic acid, and the like. Is mentioned.

Such an acidic group-containing polymerizable monomer is not particularly limited and may be used as the total amount of the polymerizable monomer (A). However, the penetrability of the adhesive composition to the tooth can be adjusted, From the viewpoint of improving the strength of the cured product, it is preferable to use it together with an acidic group-free polymerizable monomer.
The content of the acidic group-containing polymerizable monomer when used in combination is not particularly limited, but from the viewpoint of improving the adhesive strength to both enamel and dentin, the (A) polymerizable monomer 5 mass% or more is preferable in the whole quantity of a body, 5 mass%-60 mass% are more preferable, and 10 mass%-50 mass% are especially preferable.

  The acidic group-free polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, 2 -Cyanomethyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) Mono (meth) acrylate monomers such as acrylate and 2- (meth) acryloxyethyl acetyl acetate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Nonaethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, dipropylene glycol di (meth) acrylate, 2,2′-bis [4- (meth) acryloxyethoxyphenyl] propane, 2,2 '-Bis [4- (meth) acryloxyethoxyethoxyphenyl] propane, 2,2'-bis {4- [3- (meth) acryloxy-2-hydroxypropoxy] phenyl} propane, 1,4-butanediol Polyfunctional (meth) acrylate monomers such as di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, etc. Can be mentioned.

<(B) Thiourea derivative>
The (B) thiourea derivative is blended as a reducing agent for redox reaction.
As the (B) thiourea derivative, a compound having a thiourea skeleton can be used without any particular limitation, and includes a thiourea compound and a mercaptobenzimidazole compound described later, and can be appropriately selected according to the purpose. For example, as the thiourea compound, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-di-n-propylthiourea, dicyclohexylthiourea, trimethylthiourea, triethylthiourea, trin -Propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra n-propylthiourea, tetracyclohexylthiourea, ethylenethiourea, trimethylenethiourea, tetramethylenethiourea, pentamethylenethiourea, tetrahydro-4H- 1,3,5-oxadiazine-4-thione, tetrahydro-4H-1,3,5-thiadiazine-4-thione, tetrahydro-1,3,5-triazine-2 (1H) -thione, 1- (2- Pyridyl) -2-thiourea, 1- (2-tetrahydro) Rufuryl) -2-thiourea, 1-acetyl-2-thiourea, 1-phenyl-2-thiourea, N-methylthiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, phenol Examples thereof include thiourea, 1-allyl-2-thiourea, benzoylthiourea and the like. From the viewpoint of polymerization activity, ethylenethiourea, N, N′-dimethylthiourea, 1- (2-pyridyl) -2- Thiourea, 1- (2-tetrahydrofurfuryl) -2-thiourea is preferred. Examples of the mercaptobenzimidazole compound include 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzimidazole, 2-mercapto-5-ethoxybenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5- Examples thereof include ethyl benzimidazole, 2-mercapto-5-benzimidazole carboxylic acid, 5-chloro-2-mercaptobenzimidazole, 5-bromo-2-mercaptobenzimidazole and the like. From the viewpoint of polymerization activity, 2- Mercaptobenzimidazole, 2-mercapto-5-methoxybenzimidazole, 2-mercapto-5-ethoxybenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-ethylbenzoi Imidazole is preferred. The mercaptobenzimidazole compound is particularly preferable when used in a dual-curing dental composition because it has higher activity than the thiourea compound and functions as a reducing agent for the photopolymerization initiator. .
As said thiourea derivative, you may use individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a compounding quantity of the said (B) thiourea derivative, Although it can select suitably according to the objective, 0.1 mass parts-100 mass parts of said (A) polymerizable monomers- 10 mass parts is preferable and 0.5 mass part-5 mass parts are more preferable. When the blending amount is less than 0.1 parts by mass, the polymerization activity may be lowered and the adhesive strength may be insufficient. When it exceeds 10 parts by mass, the strength of the polymerized cured product may be decreased.

<(C) Hydroperoxide-based organic peroxide>
The (C) hydroperoxide-based organic peroxide is a compound containing at least one hydroperoxide group and is blended as an oxidizing agent for redox reaction.
The (C) hydroperoxide-based organic peroxide is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of storage stability when used as a polymerizable composition, it is reduced by half for 10 hours. Compounds having an initial temperature of 100 ° C. or higher are preferred. Here, the 10-hour half-life temperature is a glass container in which the (C) hydroperoxide-based organic peroxide is dissolved in a solvent relatively inert to radicals, for example, benzene, and substituted with nitrogen. When it is thermally decomposed in the medium, it is a temperature at which the concentration becomes half of the initial value in 10 hours.

Examples of such hydroperoxide-based organic peroxides include p-menthane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and t-hexyl hydro Peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, pinane hydroperoxide and the like can be mentioned. Among these, 1,1,3,3-tetramethylbutyl hydroperoxide and p-menthane hydroperoxide are preferable because high polymerization activity can be obtained.
In addition, as said (C) hydroperoxide type organic peroxide, it may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a compounding quantity of the said (C) hydroperoxide type | system | group organic peroxide, Although it can select suitably according to the objective, It is 0 per 100 mass parts of said (A) polymeric monomers. 0.1 to 10 parts by mass is preferable, and 0.5 to 2 parts by mass is more preferable. When the blending amount is less than 0.1 parts by mass, the polymerization may be insufficient, and when it exceeds 10 parts by mass, the strength of the polymerized cured product may be reduced.

<(D) Water-soluble copper compound>
The (D) water-soluble copper compound is blended to promote the redox reaction initiated by the (B) thiourea derivative and the (C) hydroperoxide organic peroxide. In the present invention, the use of the (D) water-soluble copper compound as a copper compound is the core of the technology, and by using such a water-soluble copper compound (D), the adhesive strength of the dental curable composition can be increased. An improvement in height can be achieved.

Here, “water-soluble” means that the solubility in water at 20 ° C. is 1 g / 100 mL or more, and the (D) water-soluble copper compound has a solubility of at least 1 g / 100 mL. The copper compound which is 10 g / 100 mL or more is preferable.
Examples of the water-soluble copper compound include copper sulfate, chlorophyllin copper sodium, copper acetate, copper chloride, copper bromide, copper gluconate, copper nitrate, copper formate, potassium tetrachlorocuprate, tetraammine copper sulfate and these. A mixture is mentioned.
The water-soluble copper compound preferably has a solubility in the polymerizable monomer (A) at 20 ° C. of less than 0.1 g / 100 g at most from the viewpoint of extending the operation time. Specifically, it is 0. In addition, although the solubility to the said (A) polymeric monomer of the said water-soluble copper compound changes with kinds of said (A) polymeric monomer mix | blended, said (A) polymeric monomer In particular, it can be measured by taking the point of complete dissolution when the refined water-soluble copper compound is stirred for 2 hours as the solubility.

  There is no restriction | limiting in particular as a compounding quantity of said (D) water-soluble copper compound, Although it can select suitably according to the objective, 0.001-3 per 100 mass parts of said (A) polymeric monomers. A mass part is preferable and 0.01 mass part-0.3 mass part are more preferable. If the blending amount is less than 0.001 part by mass, the effect of improving adhesiveness may be insufficient. If the amount exceeds 3 parts by mass, the operation time may be extremely shortened, or the water absorption and solubility may be reduced. It may get worse.

<Other ingredients>
The said other component can be mix | blended according to the objective as an arbitrary component, unless the effect of this invention is prevented.
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, (E) aryl borate compound, (F) filler, photoinitiator, other chemical polymerization initiator, other Examples thereof include a polymerization accelerator, water, an organic solvent, a thickener, a polymerization inhibitor, and an ultraviolet absorber.

-(E) Aryl borate compound-
The (E) aryl borate compound means a compound having at least one boron-aryl bond in one molecule. The (E) aryl borate compound is blended as a curing accelerator for the purpose of accelerating the curing of the dental curable composition and improving the adhesive strength.

The (E) aryl borate compound is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of high storage stability, ease of handling, and availability, four boron atoms per molecule. -Aryl borates having an aryl bond are preferred.
Examples of the aryl borate having four boron-aryl bonds in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl). ) Phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis ( m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyl) Oxyphenyl) boron, tetraki (M-octyloxyphenyl) salt of a boron compound such as boron can be cited.
Examples of the cation that forms a salt with the boron compound include metal ions, tertiary or quaternary ammonium ions, quaternary pyridinium ions, quaternary quinolinium ions, and quaternary phosphonium ions.
Although there is no restriction | limiting in particular as a salt of the said boron compound, Tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetrakis (p-fluorophenyl) boron sodium, butyl tri (p -Fluorophenyl) sodium boron and the like are preferable.

  As a compounding quantity of the said (E) aryl borate compound, 10 mass parts-1,000 mass parts are preferable with respect to 100 mass parts of said (C) hydroperoxide type organic peroxide, 50 mass parts-500 mass parts. Part is more preferred. When the blending amount is less than 10 parts by mass, sufficient polymerization activity may not be exhibited, and when it exceeds 1,000 parts by mass, the curing time may be too short.

-(F) Filler-
The filler (F) is blended in order to improve mechanical strength and operability in the cured body of the dental curable composition.
There is no restriction | limiting in particular as said (F) filler, A well-known inorganic filler, an organic filler, and an inorganic-organic composite filler can be used.

  Examples of the organic filler include polymethyl (meth) acrylate, polyethyl (meth) acrylate, methyl (meth) acrylate / ethyl (meth) acrylate copolymer, and methyl (meth) acrylate / butyl (meth) acrylate copolymer. , Non-crosslinkable polymers such as methyl (meth) acrylate / styrene copolymer, or methyl (meth) acrylate / ethylene glycol di (meth) acrylate copolymer, methyl (meth) acrylate / triethylene glycol di (meth) Examples thereof include acrylate copolymers and (meth) acrylate polymers such as a copolymer of methyl (meth) acrylate and a butadiene monomer.

Examples of the inorganic filler include periodic groups I, II, III, IV, transition metals, or oxides thereof, hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, or A silicate etc. can be mentioned. In addition, these may be a mixture or a complex salt.
Preferred examples include quartz, silica, alumina, zirconia, silica-titania, silica-zirconia, lanthanum glass, barium glass, strontium glass, fumed silica, calcium hydroxide, strontium hydroxide, zinc oxide, and silicate glass. It is done.
In addition, as the inorganic filler, a cation-eluting filler such as fluoroaluminosilicate glass can also be expected because the effect of improving the strength of the cured product and the adhesive strength can be expected by ionic crosslinking with the acidic group-containing polymerizable monomer. It can be used suitably.
Among these inorganic fillers, the silica, the alumina, the zirconia, the silica-titania, the silica-zirconia, and the fluoroaluminosilicate glass are more preferable, and the fluoroaluminosilicate glass is particularly preferable.

Although there is no restriction | limiting in particular as said inorganic-organic composite filler, The polymeric monomer was previously added to the inorganic filler, and after making it paste-form, it superposed | polymerized and grind | pulverized to the granular material is preferable.
In the case of using the inorganic filler or the inorganic-organic composite filler as the filler (F), the affinity for the polymerizable monomer and the dispersibility are improved, and the cured product of the dental curable composition is used. In order to improve mechanical strength and water resistance, it is preferable to use after surface treatment with a silane coupling agent or the like.
Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ -Methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane or hexamethyldisilazane can be preferably used.
In addition to the silane coupling agent, surface treatment may be performed with a titanate coupling agent, an aluminate coupling agent, a zirco-aluminate coupling agent, or the like.
Further, the polymerizable monomer may be graft polymerized on the surface of the filler particles.
In addition, these fillers may be used individually by 1 type, and may use 2 or more types together.
Yes.

The refractive index of the filler (F) is not particularly limited, but is preferably 1.4 to 2.2.
Moreover, since the unevenness | corrugation may arise on the surface of the said dental curable composition when the average particle diameter of the said filler particle is too large, 0.001 micrometer-100 micrometers are preferable, and 0.001 micrometer-10 micrometers are more. preferable. The average particle diameter is calculated from the average of the measured values by taking a photograph of the filler particles with a scanning electron microscope, measuring the number of particles observed in the unit field of view of the photograph, and the particle diameter. be able to.

  The blending amount of the filler (F) is not particularly limited, but in consideration of the viscosity (operability) and mechanical properties of the resulting cured product, per 100 parts by weight of the polymerizable monomer (A). 10 mass parts-1,000 mass parts are preferable, and 100 mass parts-700 mass parts are more preferable.

-Photopolymerization initiator-
As the dental curable composition, a dual cure curable composition can be obtained by further blending the photopolymerization initiator.
There is no restriction | limiting in particular as said photoinitiator, According to the objective, it can select suitably, A well-known photoinitiator can be used.
Representative photopolymerization initiators include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9, Α-diketones such as 10-phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether, 2,4-diethoxythioxanthone, 2-chlorothioxanthone and methylthioxanthone Thioxanthone derivatives such as benzophenone, p, p′-dimethylaminobenzophenone, benzophenone derivatives such as p, p′-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-di) Toxibenzoyl) -2,4,4-trimethylpentylphosphine oxide, acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and aryl borate compound / dye / photoacid generator Is mentioned. Among these, an α-diketone photopolymerization initiator having an absorption wavelength range suitable for a dental light irradiator is particularly preferable.
The α-diketone is not particularly limited, but camphorquinone and benzyl are preferable, and camphorquinone exhibiting particularly high activity is most preferable.
In addition, as said photoinitiator, 1 type may be used individually and 2 or more types may be used together.

  Although there is no restriction | limiting in particular as a compounding quantity of the said photoinitiator, 0.1 mass part-10 mass parts are preferable per 100 mass parts of said (A) polymeric monomers, 0.2 mass part-2 Part by mass is more preferable. With such a blending amount, the polymerizable monomer (A) can be cured with higher polymerization activity.

-Other chemical polymerization initiators and polymerization accelerators-
The dental curable composition may be used in combination with other chemical polymerization initiators and polymerization accelerators as long as the effects of the present invention are not impaired.
Examples of the other chemical polymerization initiator include organic compounds such as diacyl peroxides such as benzoyl peroxide, acetyl peroxide and lauroyl peroxide, di-t-butyl peroxide and dicumyl peroxide. A peroxide is mentioned.

Examples of the other polymerization accelerator include barbituric acid, alkylborane, and metal complex.
Examples of the barbituric acid include 5-butyl barbituric acid and 1-benzyl-5-phenylbarbituric acid.
Examples of the alkyl borane include tributyl borane, tributyl borane partial oxide, and triphenyl borane.
Examples of the metal complex include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedio) Nate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), vanadium compound such as ammonium metavanadate (V), acetylacetone copper (II), olein Insoluble copper compounds such as acid copper (II), copper octylate (II), copper naphthenate (II), and benzoylacetone copper (II) are listed. However, many of the metal complexes have a deep color tone, and even when the blending amount is small, the color tone may be affected. Therefore, when using the metal complex which affects a color tone, the compounding quantity is 0.1 mass part or less with respect to 100 mass parts of said (A) polymerizable monomers, and it is preferable to set it as a small quantity of compounding.

As the water, distilled water or ion-exchanged water is preferably used so that there are no impurities that adversely affect the adhesion.
Examples of the organic solvent include hexane, heptane, octane, toluene, dichloromethane, methanol, ethanol, acetone, and ethyl acetate.
Examples of the thickener include polymer compounds such as polyvinyl pyrrolidone, carboxymethyl cellulose, and polyvinyl alcohol, and highly dispersible silica.
Examples of the polymerization inhibitor include 2,6-di-t-butylhydroxytoluene.
In order to match the color tone of the teeth, pigments, fluorescent pigments, dyes, and ultraviolet absorbers for preventing discoloration with respect to ultraviolet rays may be further blended.

<Storage form of dental curable composition>
In the dental curable composition, if each component is allowed to coexist in the same package, chemical polymerization will start. Therefore, at the time of storage, it is divided into at least two packages so that all these components do not coexist in one package. It is necessary to divide into
In addition, when the (D) water-soluble copper compound coexists with a component that dissolves it, the effect of extending the operation time may be lost or the storage stability may be lowered. The compound is preferably stored in an undissolved state in one package.
In addition, when the (D) water-soluble copper compound is packaged in the same packaging as the (B) thiourea derivative, the operation time may be shortened. Therefore, the (B) thiourea derivative is preferably packaged separately. .
The (B) thiourea derivative can be polymerized when mixed with the (C) hydroperoxide organic peroxide. Therefore, the (B) thiourea derivative is packaged separately from the (C) hydroperoxide organic peroxide. It is preferable to do.
In addition, among the (A) polymerizable monomers, the acidic group-containing polymerizable monomer may be deteriorated in storage stability when the (C) hydroperoxide-based organic peroxide is mixed. Therefore, it is preferable to use separate packaging.
Accordingly, when the dental curable composition is divided into at least two packages for storage, at least the acidic group-containing polymerizable monomer and the (B) thiol among the (A) polymerizable monomers. The urea derivative is included in one package, and the (C) hydroperoxide organic peroxide and the (D) water-soluble copper compound are stored in another package. preferable.
In addition, among the fillers (F), the fluoroaluminosilicate glass is gelled by ionic cross-linking when the acidic group-containing polymerizable monomer is mixed among the polymerizable monomers (A) and is stable in storage. Since the properties may be reduced, it is preferable to use separate packaging.

<Application>
Since the dental curable composition contains the acidic group-containing polymerizable monomer, a dental resin cement, a dental pretreatment material, a dental adhesive, a dental coating material, a foveal fissure filling material, It can be used as a material for forming a layer by adhering to the surface of a tooth such as a filler or an abutment construction material. In particular, a tooth damaged by caries or an accident, and a material for restoring the tooth (for example, a crown restoration material such as a composite resin, metal, ceramics, etc.) are bonded between the two. It can be suitably used as a dental resin cement, a dental pretreatment material, a dental adhesive, or a self-adhesive composite resin.

  Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the technical idea of the present invention is not limited by these. In addition, about each component used for manufacture of the said Example and the said comparative example, its abbreviation and abbreviation, it is as follows.

(Each component and its abbreviations and abbreviations)
<(A) Polymerizable monomer>
-Acidic group-containing polymerizable monomer-
PM: Mixture of 2-methacryloxyethyl dihydrogen phosphate and bis (2-methacryloxyethyl) dihydrogen phosphate MAC-10: 11-methacryloyloxy-1,1-undecanedicarboxylic acid MDP: 10-methacryloxydecyl di Hydrogen phosphate

-Non-acidic group-containing polymerizable monomer-
BisGMA: 2,2-bis (4- (2-hydroxy-3-methacryloxypropoxy) phenyl) propane 3G: triethylene glycol dimethacrylate D2.6E: 2,2-bis (4- (methacryloyloxyethoxy) phenyl) Propane UDMA: 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethylhexane

<(B) Thiourea derivative>
ETU: ethylene thiourea DTU: dimethyl thiourea MBI: 2-mercaptobenzimidazole

<(C) Hydroperoxide-based organic peroxide>
Permenta H: p-menthane hydroperoxide Perocta H: 1,1,3,3-tetramethylbutyl hydroperoxide

<(D) Water-soluble copper compound>
Copper sulfate: Copper sulfate (II) ... The copper sulfate (II) has a solubility in water at 20 ° C of 30 g / 100 mL.
CuChNa: chlorophyllin copper sodium: The chlorophyllin copper sodium has a solubility in water at 20 ° C. of 10 g / 100 mL or more, but has a deep color tone when dissolved in water and is soluble at a higher concentration. Cannot be determined.
Copper acetate: Copper acetate (II) monohydrate ... Copper acetate (II) monohydrate has a solubility in water at 20 ° C of 7.2 g / 100 mL.
Among the copper compounds, copper (II) sulfate and chlorophyllin copper sodium have a solubility in the polymerizable monomer used in the examples of less than 0.1 g / 100 mL, and copper (II) acetate monohydrate The product has a solubility in the polymerizable monomer of 0.1 g / 100 mL or more.

<Other copper compounds>
CuAcAc: Acetylacetone copper ... The acetylacetone copper has a solubility in water at 20 ° C of 0.02 g / 100 mL.

<Other ingredients>
-(E) Aryl borate compound-
PhBTEOA: Tetraphenyl boron triethanolamine salt

-(F) Filler-
F1: Spherical silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product, average particle diameter 0.2 μm, particle diameter range 0.08 μm to 0.60 μm
F2: regular silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product, average particle size 3.5 μm, particle size range 0.8 μm to 7.0 μm
F3: Fumed silica, methyltrichlorosilane surface-treated product, average particle size 0.01 μm, particle size range 0.005 μm to 0.04 μm
F4: Fluoroaluminosilicate glass, average particle size 1.0 μm, particle size range 0.001 μm to 5 μm

-Polymerization inhibitor-
BHT: 2,6-di-t-butylhydroxytoluene

-Photopolymerization initiator-
CQ: camphorquinone

(Manufacture of dental curable composition)
<Example 1>
According to the following composition, each component was stirred and mixed until uniform to prepare a paste-like composition (I).

-Composition-
・ (A) Polymerizable monomer Acid group-containing polymerizable monomer MDP 15 g
Acid group-free polymerizable monomer D2.6E 15 g
3G 20g
・ (B) Thiourea derivative ETU 1.0g
・ Other ingredients (F) Filler F1 45g
F2 75g
Polymerization inhibitor BHT 0.05g

  Moreover, according to the following composition, each component was stirred and mixed until it became uniform, and paste-form composition (II) was prepared. By the above, the dental polymerizable composition which concerns on Example 1 comprised with the said paste-form composition (I) and the said paste-form composition (II) was manufactured. In addition, what packaged the said paste-form composition (I) is set as the package 1, and what packaged the said paste-form composition (II) is set as the package 2.

-Composition-
・ (A) Polymerizable monomer Acid group-free polymerizable monomer BisGMA 12.5 g
UDMA 12.5g
3G 25g
・ (C) Hydroperoxide organic peroxide
Perocta H 1.0g
・ (D) Water-soluble copper compound Copper sulfate 0.1g
・ Other ingredients (F) Filler F1 43g
F2 75g
F3 2g
Polymerization inhibitor BHT 0.05g

<Examples 2 to 15 and Comparative Examples 1 to 4>
In the same manner as in Example 1 except that the preparation of the paste-like composition (I) and the paste-like composition (II) was carried out based on the composition described in Table 1 below, Example 2 15 and each of the dental polymerizable compositions according to Comparative Examples 1 to 4 were produced.

(Measurement and evaluation of physical properties)
<Operation time>
Using the dental curable compositions according to Examples 1 to 15 and Comparative Examples 1 to 4, the operation time from the start of polymerization to curing was measured. The measurement of the operation time is performed according to JIST6611: 2009, and specifically, the paste composition (I) and the paste composition (in a mass ratio of 1: 1 from the package 1 to the package 2). II) was weighed and stirred and mixed for 20 seconds to obtain a uniform mixed paste. The mixed paste was allowed to stand for a predetermined time and then placed on a glass plate and immediately sandwiched between the second glass plates to form a thin layer. Here, from the end of the stirring and mixing process to when the uniformity of the thin layer changes (for example, when cracks or cavities are observed in the thin layer, or when the thin layer cannot be formed due to increased viscosity) The time was defined as the operation time, and the measurement of the operation time was performed under a constant temperature condition of 23 ° C.
As the evaluation of the operation time, a case where the operation time is 2 minutes or more, preferably 2.5 minutes or more can be judged as good.

<Adhesive strength>
The bovine anterior teeth removed within 24 hours after slaughter were polished with # 600 emery paper under running water to reveal the dentin plane so that the labial side was parallel and flat in the occlusal direction. Next, after compressed air was blown onto the exposed dentin plane for about 10 seconds and dried, a double-sided tape having a 3 mm diameter hole was attached to the dentin plane to form a simulated cavity.
Then, using each dental curable composition which concerns on Examples 1-15 and Comparative Examples 1-4, the said paste-form composition (I) and the said packaging 1 and the said packaging 2 with a mass ratio of 1: 1. The pasty composition (II) was weighed and stirred and mixed for 20 seconds to obtain a uniform mixed paste. This mixed paste was placed on a stainless steel attachment, pressed against the simulated cavity, and the excess paste was removed to obtain an adhesion test piece.
Subsequently, the said adhesive test piece was left still for 1 hour in a 37 degreeC * humidity 100% constant temperature high humidity box, and each dental curable composition which concerns on Examples 1-15 and Comparative Examples 1-4 was chemically polymerized. I let you.
After this polymerized adhesion test piece was immersed in water at 37 ° C. for 24 hours, the stainless steel attachment was pulled using a tensile tester (manufactured by Shimadzu Corporation, Autograph AG5000D), and the polymerized adhesion test piece was The tensile bond strength with the dentin plane was measured. The tensile tester was pulled at a crosshead speed of 1 mm / min.
In the measurement of the tensile adhesive strength, four adhesive test pieces were prepared for each dental curable composition, and the average value was taken as the value of the corresponding tensile adhesive strength.
As the evaluation of the tensile adhesive strength, it can be determined that the adhesive strength is good when the value of the tensile adhesive strength is 10 MPa or more.

The composition of the paste-like composition (I) and the paste-like composition (II) in each dental curable composition according to Examples 1 to 15 and Comparative Examples 1 to 4, the operation time, and the adhesive strength Shown in Table 1 below.
In the column of “Composition” in Table 1 below, the packaging 1 is represented as (I) and the packaging 2 is represented as (II).

As shown in Table 1, the operating times of the dental curable compositions according to Examples 1 to 15 all show good results, and at the same time, the adhesive strength also shows all good results. ing.
On the other hand, each of the dental curable compositions according to Comparative Examples 1 to 4 has insufficient adhesive strength, and is inferior to the dental curable compositions according to Examples. It has become.
That is, the dental curable composition according to Comparative Example 2 in which (D) the water-soluble copper compound is not added has a higher adhesive strength than that in Example 1 in which the (D) water-soluble copper compound is added. It is weak.
Moreover, it replaced with said (D) water-soluble copper compound, and the comparative examples 3 and 4 which added the water-insoluble copper compound are the cases where this copper compound is added to either the packaging 1 or the packaging 2, However, compared with Example 1 to which the (D) water-soluble copper compound was added, the operation time was short and the adhesive strength was weak.

Moreover, in the comparison between each dental curable composition which concerns on Example 3, 9, the direction of the dental curable composition which concerns on Example 3 rather than the dental curable composition which concerns on Example 9 The operation time can be maintained longer. This is because, in the dental curable composition according to Example 9, the (B) thiourea derivative and the (D) water-soluble copper compound are in the same packaging, This is probably because part of the salt formation with the (B) thiourea derivative speeds up the polymerization and shortens the operation time.
Moreover, in the comparison between each dental curable composition which concerns on Example 3, 11, the direction of the said dental curable composition which concerns on Example 11 which added the said (E) aryl borate compound was said (E). The adhesive strength is superior to the dental curable composition according to Example 3 to which no aryl borate compound is added, and the adhesive strength can be improved by the addition of the (E) aryl borate compound. .
Moreover, in the comparison between each dental curable composition which concerns on Example 1, 13, each dental curable composition which concerns on Example 13 which added fluoroaluminosilicate glass as a part of said (F) filler. The product is superior to each dental curable composition according to Example 1 in which the fluoroaluminosilicate glass is not added, and the adhesive strength is increased by the addition of the fluoroaluminosilicate glass. Can be improved.

(Measurement and evaluation of physical properties for dual-curing dental curable composition)
<Hardness of cured body (Vickers hardness)>
Using each dental curable composition (dual cure type dental curable composition) according to Example 12 and Example 14, the paste composition at a mass ratio of 1: 1 from the package 1 to the package 2 The product (I) and the paste-like composition (II) were weighed and stirred and mixed for 20 seconds to obtain a uniform mixed paste.
Immediately after mixing, the mixed paste was poured into a mold made of polytetrafluoroethylene having a hole of 6 mmφ × 1.0 mm, and then pressed with a polypropylene film from the outer surface side of the mixed paste. (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 600 mW / cm ² ) was brought into close contact with the film, irradiated with light for 10 seconds, and the resulting cured product was used as a test sample.
The hardness of the test sample was measured using a micro hardness meter (MHT-1 type manufactured by Matsuzawa Seiki Co., Ltd.). The hardness was evaluated by Vickers hardness, and was determined by using a Vickers indenter and the diagonal length of a recess formed in the cured body with a load of 100 gf and a load holding time of 30 seconds.
As the evaluation of the hardness, it was judged that the hardness of the test sample was good when the Vickers hardness was 30 or more.
From the evaluation results, the Vickers hardness of the dental curable composition according to Example 12 was 12, and the Vickers hardness of the dental curable composition according to Example 14 was 43. Addition of the mercaptobenzimidazole compound as a photopolymerization reducing agent can improve the curability in photopolymerization.

Claims (8)

(A) a polymerizable monomer containing an acidic group-containing polymerizable monomer;
(B) a thiourea derivative;
(C) a hydroperoxide-based organic peroxide;
(D) a water-soluble copper compound;
Only including,
The dental curable composition characterized in that the amount of the water-soluble copper compound (D) is 0.04 to 0.3 parts by mass per 100 parts by mass of the polymerizable monomer (A). object.   The dental curable composition according to claim 1, wherein the water-soluble copper compound is a copper compound having a water solubility at 20 ° C of at least 10 g / 100 mL or more.   (D) The water-soluble copper compound has a solubility in the polymerizable monomer (A) at 20 ° C. of at most 0.1 g / 100 g or less, and the dental curability according to claim 1. Composition.   The dental curable composition according to any one of claims 2 to 3, wherein (D) the water-soluble copper compound is any one of copper sulfate, chlorophyllin copper sodium, copper gluconate, and a mixture thereof.   The dental curable composition according to any one of claims 1 to 4, further comprising (E) an aryl borate compound.   Furthermore, the dental curable composition in any one of Claim 1 to 5 containing fluoroaluminosilicate glass.   The dental curable composition according to any one of claims 1 to 6, wherein the dental curable composition is divided into at least two packages and stored, and (D) the water-soluble copper compound is encapsulated in one package in an undissolved state.   (A) Among the polymerizable monomers, at least an acidic group-containing polymerizable monomer and (B) a thiourea derivative are included in one package, and (C) a hydroperoxide-based organic oxide and (D) The dental curable composition according to claim 7, wherein the water-soluble copper compound is contained in another package.