JP6247549B2 - Dental pretreatment material and dental filling and repair kit - Google Patents

Description

  The present invention relates to a dental pretreatment material used for dental treatment and a dental filling / restoration kit having the dental pretreatment material.

In the treatment of dental caries and accompanying defects, restoration using a dental pretreatment material, a dental adhesive, and a dental filling restoration material is generally performed.
The following procedures are used for repair treatment. First, after carving the carious portion to form a cavity, a dental pretreatment material is applied to the cavity to decalcify the tooth surface, and then the dental pretreatment material is dried by blowing compressed air. Next, the dental adhesive is applied and cured by irradiation with visible light. Finally, the dental filling restorative material is filled into the cavity from the cured dental adhesive layer, and is cured by irradiation with visible light.
In the repair treatment, if the operation is inappropriate, the adhesive strength inherent to the material may not be obtained and the adhesive strength may decrease. When the adhesive strength is reduced, it causes secondary caries and filler loss, and it is necessary to prevent this. This bond strength is required for both tooth enamel and dentin.
Such a risk is reduced when the operation is simpler than when it is complicated. Therefore, a dental filling / restoration kit (see, for example, Patent Document 1) that does not require the dental adhesive and is easy to operate has been proposed.

However, the operational factors that reduce the adhesive strength of the ones that require or do not require the dental adhesive are not completely eliminated, and (I) the light irradiation intensity is low, (II) There is unevenness in the application of the dental pretreatment material, and the adhesion area of the dental adhesive on the decalcified tooth surface is insufficient. (III) The dental pretreatment material is insufficiently dried, and there remains a risk that water and solvent in the dental pretreatment material remain on the adherend surface.
Among these, the risk of (I) can be eliminated by methods such as measuring the irradiation intensity of the irradiator in advance or shortening the irradiation distance as much as possible, and the risk of (II) is the aforementioned dental pretreatment material It is solved by visually confirming whether the coating is uniformly applied.

On the other hand, the risk of (III) is only a careful operation and is difficult to eliminate. That is, since the dental pretreatment material volatilizes water and solvent due to drying, the fluidity gradually decreases, but the water and solvent content and fluidity differ depending on the type of the dental pretreatment material, It is very difficult to determine that it is sufficiently dry. In particular, since water is less volatile than a solvent, it tends to remain on the adherend surface.
In this respect, as a method of eliminating the risk of (III), that is, a method of reliably removing moisture in the dental pretreatment material, a method of drying for a very long time can be considered. According to this method, moisture can be removed with certainty, but there are problems that lead to a decrease in adhesive strength and an increase in treatment time due to unevenness of the dental pretreatment material that occurs during drying.
Accordingly, it has been desired to develop a new dental pretreatment material that can clearly and easily confirm the end point of the drying operation.

In connection with the method for confirming the presence or absence of moisture on the tooth surface, after moistening the tooth surface with a liquid containing an acid-sensitive dye and water, an acidic etching composition having a decalcifying action is applied, and There has been proposed a method for confirming whether or not the etching composition is properly applied by changing the color of the acid-sensitive dye (see Patent Document 2).
However, this method is a method for confirming the presence of moisture, and there is no method that can clearly and easily confirm the absence of moisture, that is, a method for clearly and easily confirming the dry state. There is no current situation.

JP 2009-167132 A Special table 2008-505924

  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 pretreatment material in which a dry state can be clearly and easily confirmed after application to a tooth and a dental filling / restoration material kit having the dental pretreatment material. .

Means for solving the problems are as follows. That is,
<1> At least selected from (a) an acidic group-containing polymerizable monomer, (b) water, (c) cobalt (II) chloride, iron (III) chloride, and nickel (II) sulfate. the color change material that allows check the dry state after application to the teeth by drying before and after the color change, (f) dental pretreatment material which comprises an alkali earth metal salt.
<2> The dental pretreatment material according to <1>, further comprising (d) a volatile organic solvent .
< 3 > The dental pretreatment material according to any one of <1> to < 2 >, further comprising (i) an acidic group-free polymerizable monomer and (j) a chemical polymerization initiator.
< 4 > (j) The dental pretreatment material according to < 3 >, wherein the chemical polymerization initiator is a fourth-period transition metal compound.
< 5 > The dental pretreatment material according to any one of <1> to < 2 >, (k) an acidic group-free polymerizable monomer containing a water-soluble polymerizable monomer, and (l) And a dental adhesive including a photopolymerization initiator.
< 6 > The dental pretreatment material according to any one of < 3 > to < 4 >, (m) a hardly water-soluble acidic group-free polymerizable monomer, (n) a filler, (o) And (p) a dental filling restorative material including (p) a chemical polymerization initiator that generates a polymerization initiating species by a chemical reaction with (j) the chemical polymerization initiator in the dental pretreatment material. A dental filling / restoration kit.
<7> The dental pretreatment material is a dental pretreatment material according to <4>, wherein the dental filling restorative material in the (p) Chemical polymerization initiator material is a peroxide according to <6> Dental filling and repair kit.

  ADVANTAGE OF THE INVENTION According to this invention, the said various problems in a prior art can be solved, and the dental pretreatment material which can confirm a dry state clearly after application | coating to a tooth, and the dental filling which has this dental pretreatment material A restorative kit can be provided.

(Dental pretreatment material)
The dental pretreatment material of the present invention contains at least (a) an acidic group-containing polymerizable monomer, (b) water, and (c) a color change material, and, if necessary, other materials. Including.

<(A) Acidic group-containing polymerizable monomer>
The (a) acidic group-containing polymerizable monomer is blended from the viewpoint of imparting a decalcifying action and a penetrating action on the tooth of the dental pretreatment material.
The (a) acidic group-containing polymerizable monomer means a compound having at least one acidic group and at least one polymerizable unsaturated group in one molecule. And can be appropriately selected from known compounds according to the purpose.
The acidic group means a functional group having a pKa of 6 or less. Such an acidic group is not particularly limited, but is preferably a phosphate group or a carboxy group that has a high demineralization effect on the tooth and a high adhesion to the tooth. Specific examples include the following groups: be able to. The acid anhydride group is also included in the acidic group as a hydrolyzed state.

  The polymerizable unsaturated group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. The acryloyl group, the methacryloyl group, the acrylamide group, and the methacrylamide group are preferable.

  Examples of the (a) acidic group-containing polymerizable monomer that can be suitably used include compounds represented by the following structural formula, vinylphosphonic acids in which a phosphate group is directly bonded to a vinyl group, acrylic acid, and methacrylic acid. An acid, vinyl sulfonic acid, etc. can be mentioned.

However, in the compound represented by the structural formula, R ₁ represents either a hydrogen atom or a methyl group.
Especially, the acidic group containing polymeric monomer shown by either of the following general formula (a-1) and (a-2) is preferable.

However, in the compounds represented by the general formulas (a-1) and (a-2), R ₁ represents either a hydrogen atom or a methyl group. R ₂ and R _{3 each} represents an alkyl chain, and the total number of carbon atoms of R ₂ and R ₃ is 4 or more and less than 20.

  Examples of the compound represented by the general formula (a-1) include 2- (meth) acryloyloxyethyl dihydrogen phosphate (“(meth) acryloyl” means acryloyl or methacryloyl, and the same applies to the following. 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) Acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihigh Rhogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyl Examples thereof include oxyhexadecyl dihydrogen phosphate and 20- (meth) acryloyloxyeicosyl dihydrogen phosphate.

  Examples of the compound represented by the general formula (a-2) include di [2- (meth) acryloyloxyethyl] hydrogen phosphate, di [4- (meth) acryloyloxybutyl] hydrogen phosphate, and di [6- (Meth) acryloyloxyhexyl] hydrogen phosphate, di [8- (meth) acryloyloxyoctyl] hydrogen phosphate, di [9- (meth) acryloyloxynonyl] hydrogen phosphate, di [10- (meta ) Acrylyloxydecyl] hydrogen phosphate and the like.

  In addition, as said (a) acidic group containing polymeric monomer, the above-mentioned compound may be used individually by 1 type, and may use 2 or more types together.

<(B) Water>
The (b) water is added from the viewpoint of enhancing the decalcification action of the tooth by the acidic group of the (a) acidic group-containing polymerizable monomer and promoting the penetration action into the tooth.
Although there is no restriction | limiting in particular as said (b) water, It is preferable that the impurity which reduces the storage stability, biocompatibility, etc. of the said dental pretreatment material is substantially not included, deionized water, distilled water, etc. Is preferably used.
The blending amount of the water (b) is not particularly limited, but 3 parts by mass to 200 parts by mass with respect to 100 parts by mass of the total polymerizable monomer including the acidic group-containing polymerizable monomer (a). Part is preferred.
The (b) water is dried and removed by spraying compressed air or the like after the dental pretreatment material is applied to teeth and before the (a) acidic group-containing polymerizable monomer is polymerized. Used.

<(C) Color change material>
The (c) color-changing material is a material that makes it possible to confirm a dry state after being applied to teeth by color change before and after drying, and the dental pretreatment material is applied to the teeth and then the dental Whether (b) water contained in the pretreatment material or water contained in the (d) volatile organic solvent described later is reliably removed, or (c) clearly and easily through the color change of the color changing material Confirming is the core of the technology.
Such (c) color changing material is not particularly limited as long as it changes color before and after drying, and can be appropriately selected according to the purpose. (E) Water-soluble metal salt, (g ) PH indicator, (h) redox indicator and the like. Of these, the water-soluble metal salt (e) is preferable because of its small influence on the adhesive strength.
In addition, as the (c) color change material, a material for confirming a color change by an apparatus such as a color sensor or a material for visually confirming a color change can be applied. It is preferable to select a material that has good visibility of color change because the item to be checked has less work load and the dried state can be more easily confirmed.

-(E) Water-soluble metal salt-
As the water-soluble metal salt (e), a material that changes color depending on the presence or absence of moisture can be applied, and examples thereof include nickel sulfide, nickel sulfate, and metal halide salts, but the visibility is good. Therefore, a metal halide salt is preferable.
Examples of the metal halide salt include iron (III) chloride, cobalt (II) chloride, copper (I) chloride, copper (II) chloride, nickel (II) chloride, silver (I) bromide, and manganese bromide. (II), manganese (I) iodide and the like can be mentioned, and among these, cobalt (II) chloride having good visibility is particularly preferable.
With regard to the color change of the water-soluble metal salt (e), the color change of the cobalt (II) chloride will be described as an example. (B) It turns blue when water is removed by drying. A dry state is confirmed using this color change. In addition, when the (d) volatile organic solvent is included, the cobalt (II) chloride is colored in blue, and when the (d) volatile organic solvent is volatilized, the (b) water is a nearly red color. When (b) water is removed by drying, the color is again blue.

Although there is no restriction | limiting in particular as a compounding quantity of said (e) water-soluble metal salt, 0.3 mass part-10 mass parts are preferable with respect to 100 mass parts of said all polymerizable monomers. If the blending amount exceeds 10 parts by mass, the adhesive strength of the adhesive component may decrease, and if it is less than 0.3 parts by mass, the visibility in the dry state may decrease. However, even if the blending amount is small and the visibility of the (e) water-soluble metal salt itself is low, the visibility can be improved by using it together with the (f) alkaline earth metal salt. It is possible to confirm the dry state clearly while maintaining the adhesive strength.
In addition, the water solubility in the (e) water-soluble metal salt means that the solubility in water at 20 ° C. is 0.005 g / 100 mL or more.

-(F) Alkaline earth metal salt--
As described above, the (f) alkaline earth metal salt is used in combination with the (e) water-soluble metal salt from the viewpoint of improving visibility.
Such (f) alkaline earth metal salt is not particularly limited and can be appropriately selected according to the type of the (e) water-soluble metal salt. For example, magnesium chloride, calcium chloride, magnesium chloride, Examples include strontium chloride, barium chloride, magnesium sulfate, calcium sulfate, and barium sulfate.
In addition, there is no restriction | limiting in particular as a compounding quantity of the said (f) alkaline-earth metal salt, It is about 0.1 mass part-1 mass part with respect to 100 mass parts of the said all polymerizable monomers.

-(G) pH indicator-
In the (g) pH indicator, the dry state is confirmed by utilizing the fact that the pH changes and changes color before and after the drying of moisture.
As the pH indicator (g), it is preferable to select a pH indicator having a color change range of pH 3.0 or less because it shows acidity in the dry state of the dental pretreatment material.
Such (g) pH indicator is not particularly limited, but thymol blue is particularly preferable because of good visibility.
Regarding (g) the color change of the pH indicator, the color change of the thymol blue will be described as an example. When water is present, the color changes to orange, and when the water is removed by drying, the color changes to reddish brown. . A dry state is confirmed using this color change.

  Although there is no restriction | limiting in particular as a compounding quantity of the said (g) pH indicator, 0.5 mass part-5 mass parts are preferable with respect to 100 mass parts of all the said polymerizable monomers. If the blending amount exceeds 5 parts by mass, the adhesive strength of the adhesive component may decrease, and if it is less than 0.5 parts by mass, the visibility in the dry state may decrease.

-(H) Redox indicator-
In the (h) redox indicator, the dry state is confirmed by utilizing the fact that the redox potential changes before and after the moisture drying and changes color.
As the (h) redox indicator, it is preferable to select a redox indicator having a color change range of 1.0 V or less because the dental pretreatment material exhibits a low redox potential in the dry state.
The (h) redox indicator is not particularly limited, but methylene blue is particularly preferable because of good visibility.
Regarding the color change of the (h) redox indicator, the color change of the methylene blue will be described as an example. When the water is present, the color is colorless when the water is present, and when the water is removed by drying, the color is green. A dry state is confirmed using this color change.

  Although there is no restriction | limiting in particular as a compounding quantity of said (h) oxidation-reduction indicator, 0.5 mass part-5 mass parts are preferable with respect to 100 mass parts of said all polymerizable monomers. If the blending amount exceeds 5 parts by mass, the adhesive strength of the adhesive component may decrease, and if it is less than 0.5 parts by mass, the visibility in the dry state may decrease.

<Other materials>
The other materials are not particularly limited as long as the effects of the present invention are not hindered, and can be appropriately selected according to the purpose. For example, (d) volatile organic solvent, (i) acid group-free polymerizable Monomers, (j) chemical polymerization initiators, silica fillers, and the like.

-(D) Volatile organic solvent-
The (d) volatile organic solvent is blended from the viewpoint of the storage stability of the dental pretreatment material while allowing a component effective for adhesion to penetrate into the tooth structure.
Here, the (d) volatile organic solvent is an organic solvent that is volatile at room temperature and exhibits water solubility, and the volatile property has a boiling point at 760 mmHg of 100 ° C. or less and 20 It means that the vapor pressure at ° C. is 1.0 KPa or more. The term “water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 mL or more, and it is preferably compatible with water at 20 ° C. in an arbitrary ratio.
The (d) volatile organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. Can do. Of these, ethanol, isopropyl alcohol, and acetone are preferable in view of toxicity to the living body.
In addition, these may be used individually by 1 type and may use 2 or more types together.

Although there is no restriction | limiting in particular as a compounding quantity in the case of mix | blending the said (d) volatile organic solvent, 30 mass parts-500 mass parts are preferable with respect to 100 mass parts of all the said polymerizable monomers.
In addition, the (d) volatile organic solvent is applied by blowing compressed air or the like after the dental pretreatment material is applied to teeth and before the (a) acidic group-containing polymerizable monomer is polymerized. Used after dry removal.

-(I) Non-acidic group-containing polymerizable monomer-
The (i) acidic group-free polymerizable monomer is an adhesive component in the case of directly filling a dental filling restorative material without applying a dental adhesive described later after applying the dental pretreatment material. Is formulated as
The (i) acidic group-free polymerizable monomer refers to a compound having at least one polymerizable unsaturated group and not having the acidic group, and is appropriately selected from known compounds for use. Can do. Among these, the polyfunctional polymerizable monomer having a plurality of the polymerizable unsaturated groups is preferably used from the viewpoint of improving the curing speed, the mechanical properties of the cured body, the water resistance, the color resistance, and the like. A (meth) acrylate polymerizable monomer is preferably used. Representative examples of the polyfunctional (meth) acrylate polymerizable monomer include bifunctional polymerizable monomers, trifunctional polymerizable monomers, and four compounds shown in the following (1) to (3). A functional polymerizable monomer is mentioned.

(1) Bifunctional polymerizable monomer Examples of the bifunctional polymerizable monomer include aromatic compound-based polymerizable monomers and aliphatic compound-based polymerizable monomers.
Examples of the aromatic compound-based polymerizable monomer include 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 2,2′-bis [ 4- (meth) acryloyloxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxydiethoxyphenyl] propane 2,2′-bis [4- (meth) acryloyloxytetraethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxypentaethoxyphenyl] propane, 2,2′-bis [4- (Meth) acryloyloxydipropoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxypheny ] Propane, 2- [4- (meth) acryloyloxydiethoxyphenyl] -2- [4- (meth) acryloyloxytriethoxyphenyl] propane, 2- [4- (meth) acryloyloxydipropoxyphenyl]- Addition of 2- [4- (meth) acryloyloxytriethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxypropoxyphenyl] propane; and an OH group-containing vinyl monomer and an aliphatic diisocyanate compound And diaducts obtained from the above.
Examples of the OH group-containing vinyl monomer include methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate, and acrylates corresponding to these methacrylates. Examples of the diisocyanate include diisocyanate methylbenzene and 4,4′-diphenylmethane diisocyanate.

Examples of the aliphatic compound-based polymerizable monomer include 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetra Ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates, 1,8- Methacrylates such as octanediol dimethacrylate, 1,10-decanediol dimethacrylate, ethylene glycol diglycidyl ether dimethacrylate, etc. Corresponding acrylate or the like; diadduct and the like obtained from the addition of the well OH group-containing vinyl monomer and aliphatic diisocyanate compounds.
Examples of the OH group-containing vinyl monomer include those exemplified above, and examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, Examples include forone diisocyanate and methylenebis (4-cyclohexylisocyanate).

(2) Trifunctional polymerizable monomer Examples of the trifunctional polymerizable monomer include, for example, methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate; Examples thereof include acrylates corresponding to these methacrylates.

(3) Tetrafunctional polymerizable monomer Examples of the tetrafunctional polymerizable monomer include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate; and a diadduct obtained from an adduct of a diisocyanate compound and glycidol dimethacrylate. Can be mentioned.
Examples of the diisocyanate compound include diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 4,4-diphenylmethane diisocyanate, and tolylene-2. 4-diisocyanate etc. can be mentioned.
In addition, these polyfunctional (meth) acrylate type | system | group polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

Furthermore, you may use a monofunctional (meth) acrylate type | system | group polymerizable monomer as needed.
Examples of the monofunctional (meth) acrylate polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth). Examples include acrylate and glycidyl (meth) acrylate.

Moreover, you may use polymerizable monomers other than the said (meth) acrylate type | system | group polymerizable monomer.
Examples of such polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; styrenes such as styrene, divinylbenzene, α-methylstyrene, and α-methylstyrene dimer. Compounds; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate;

When the polymerizable monomer contains a large amount of hydrophobic polymerizable monomer, an amphiphilic polymerizable monomer is used in combination as the (i) acidic group-free polymerizable monomer. It is preferable.
Examples of the amphiphilic polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate (polyethylene glycol polymerization degree 9 to 50), 1 2,3,4-butanetetraol-1,4-di (meth) acrylate and the like. By blending such an amphiphilic polymerizable monomer, the uniformity of the composition can be ensured and the permeability to dentin is further improved. As a result, high adhesive strength can be obtained stably.

  In addition, although there is no restriction | limiting in particular as said (i) acidic group non-containing polymerizable monomer, 10 mass parts-90 mass parts are preferable in 100 mass parts of said all polymeric monomers.

-(J) Chemical polymerization initiator-
The dental pretreatment material may include the chemical polymerization initiator (j) according to the purpose. As one of the purposes, the dental filling material described later is formulated when the dental pretreatment material is applied and then the dental filling restorative material is directly filled without using the dental adhesive. The (p) chemical polymerization initiator in the inside may be chemically reacted to initiate polymerization and curing of the adhesive component.
Here, the chemical polymerization initiator includes a plurality of components, and when these components come into contact with each other, a material that generates a polymerization initiating species (radical) is applicable.
The (j) chemical polymerization initiator is not particularly limited and may be appropriately selected depending on the purpose as long as it generates the polymerization initiation species by chemically reacting with the other chemical polymerization initiator. However, in the dental pretreatment material containing (a) the acidic group-containing polymerizable monomer and (b) water, a fourth-period transition metal compound can be suitably used.

The fourth period transition metal compound is a metal compound of Group 3-12 of the fourth period of the periodic table, specifically scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), It is a metal compound of manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). By compounding these metal compounds in the pretreatment material, the (p) chemical polymerization initiator and radical polymerization initiator contained in the dental filling / restoration material are formed at the adhesive interface, The adhesiveness of the dental filling restorative material can be made extremely good.
As the transition metal element in the fourth-period transition metal compound, each may take a plurality of valences, but any valence that can exist stably, for example, Sc (III), Ti (IV), V (III to V), Cr (II, III, VI), Mn (II to VII), Fe (II, III), Co (II, III), Ni (II), Cu (I, II), Zn (II) is applicable.
Specific examples of such compounds include scandium (III) iodide as a + III valent scandium compound, and titanium (IV) chloride, titanium (IV) tetraisopropoxide, etc. as + VI valent titanium compounds. As the + IV valent vanadium compound, divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1, 3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV) and the like, and + V-valent vanadium compounds include vanadium pentoxide (V), sodium metavanadate and the like, Chromium chloride (I + III-valent chromium compound can include chromium (III) chloride, etc. + VI-valent chromium compound can include chromic acid, chromate, etc., + II-valent manganese compound As examples, manganese acetate (II), manganese naphthenate (II) and the like can be cited. As the + II valent iron compound, iron acetate (II), iron (II) chloride and the like can be cited. Examples include iron (III) acetate and iron (III) chloride. Examples of the + II-valent cobalt compound include cobalt (II) acetate and cobalt (II) naphthenate. Examples of the + II-valent nickel compound include chloride. Nickel (II) etc. can be mentioned, and copper chloride (I), copper bromide (I) etc. can be mentioned as a + I value copper compound. + II valent copper chloride as the copper compound (II), copper (II) acetate and the like can be exemplified, zinc (II) chloride as + II valent zinc compounds include zinc acetate (II) and the like. Among these, V (IV, V), Mn (II), Fe (II, III), and Co (II) are preferable, and among them, higher adhesive strength can be obtained, so + IV and / or + V valent vanadium. Compounds are preferred.

  In addition, although there is no restriction | limiting in particular as a compounding quantity of said (j) chemical polymerization initiator, 0.05 mass part-3 mass parts are preferable with respect to 100 mass parts of said all polymerizable monomer components.

-Silica filler-
The said silica type filler is mix | blended from a viewpoint which suppresses gelatinization at the time of the preservation | save of the said dental pretreatment material.
There is no restriction | limiting in particular as said silica type filler, According to the objective, it can select suitably, In addition to crystalline silica, such as quartz, amorphous silica, silica, such as silica titania and silica zirconia, is the main component. Examples thereof include composite metal oxides with other metal oxides.
Among these, the amorphous silica is preferable. Examples of the amorphous silica include those synthesized by a production method different from a wet method and a dry method, but those synthesized by a dry method are preferable, and fumed silica is particularly preferable.

The specific surface area of the silica filler is not particularly limited, preferably at least ^{50m 2 / g, 100m 2 /} g~300m 2 / g is more preferable. In addition, the specific surface area of a silica type filler can be measured by BET method.
Further, the particle diameter of the silica filler is not particularly limited, but those having a primary particle diameter of 1 nm to 100 nm and a secondary particle diameter of 0.1 μm to 10 μm are preferable. The particle diameter can be measured with an electron microscope.

As the silica-based filler, by making it hydrophobic with a surface treatment material typified by a silane coupling material, the compatibility with various polymerizable monomers can be improved, and the mechanical strength and water resistance can be improved. .
The hydrophobization method is not particularly limited and may be a known method. For example, as the run coupling material, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) ) Silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysila And hydrophobization using β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane and the like.

  Although there is no restriction | limiting in particular as a compounding quantity of the said silica type filler, 5 mass parts-35 mass parts are preferable with respect to 100 mass parts of the said all polymerizable monomers.

  Furthermore, as the dental pretreatment material, various components contained in known dental pretreatment materials can be used in addition to the above materials, as long as the effects of the present invention are not hindered. Organic thickeners such as polymer compounds such as polyvinyl pyrrolidone, carboxymethyl cellulose, and polyvinyl alcohol can be added. Various additives such as ultraviolet absorbers, dyes, antistatic materials, pigments, and fragrances can be selected and used as necessary. Further, a filler (n) described later can be added.

  In addition, there is no restriction | limiting in particular as a preparation method of the said dental pretreatment material, The method of mixing each said material until it becomes uniform by a well-known method is mentioned.

(Dental filling restoration kit)
The dental filling and repair kit of the present invention includes the dental pretreatment material of the present invention, and after application and drying of the dental pretreatment material, the dental adhesive is applied and polymerized and cured, and then The type using a dental filling restorative material and the type using the dental filling restorative material without applying the dental adhesive after applying and drying the dental pretreatment material can be configured. .
That is, the former is configured to include the dental pretreatment material and the dental adhesive, and the latter is configured to include the dental pretreatment material and the dental filling / restoration material. The
In addition, about the former, you may comprise further having the said dental filling restoration material.

<Dental adhesive>
The dental adhesive includes (k) an acidic group-free polymerizable monomer and (l) a photopolymerization initiator, and may include other materials as necessary.

-(K) Non-acidic group-containing polymerizable monomer-
The (k) non-acidic group-containing polymerizable monomer blended in the dental adhesive contains a water-soluble polymerizable monomer.
The water-soluble polymerizable monomer means a water-soluble compound having no acidic group and having at least one hydroxyl group and at least one polymerizable unsaturated group in one molecule. For example, there is no restriction | limiting in particular, According to the objective, it can select from a well-known compound suitably and can use. Here, the acidic group and the polymerizable unsaturated group are the same as those described in the above (a) acidic group-containing polymerizable monomer. The term “water-soluble” means that the solubility in water at 20 ° C. is 70 or more, and it is preferably compatible with water at 20 ° C. in an arbitrary ratio.

  Specific examples of the water-soluble polymerizable monomer include 2-hydroxyethyl (meth) acrylate (“(meth) acrylate” means acrylate or methacrylate, and the same shall apply hereinafter), 3 -Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meta ) Acrylamide, 2,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 2,4-dihydroxybutyl (meth) acrylate, 2-hydroxymethyl-3-hydroxypropyl (meth) acrylate, 2,3,4-trihydroxybutyl (medium ) Acrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono ( Examples include meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, and N-methylol (meth) acrylamide. Of these, 2-hydroxyethyl (meth) acrylate is preferred.

The (k) acidic group-free polymerizable monomer may include other polymerizable monomers not containing the acidic group in addition to the water-soluble polymerizable monomer.
The other polymerizable monomer is not particularly limited and may be appropriately selected depending on the purpose. However, the bifunctional polymerizable monomer described as the (i) acidic group-free polymerizable monomer is used. A monomer, the trifunctional polymerizable monomer, and the tetrafunctional polymerizable monomer can be preferably used.
In addition, when mix | blending the said other polymerizable monomer, it is preferable that the said water-soluble polymerizable monomer in the said (k) acidic group non-containing polymerizable monomer is 20 mass% or more.

-(L) Photopolymerization initiator-
The photopolymerization initiator is not particularly limited. For example, camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and the like. Α-diketones, thioxanthones such as 2,4-diethylthioxanthone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morphol Linophenyl) -butanone-1,2-benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2 -Benzyl-dimethylamino-1- (4-morpholinophenyl) -pen Α-aminoacetophenones such as Tanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide and other acyl phosphine oxide derivatives.

The polymerization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 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 -Dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxy Tyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N -Dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, Tertiary amines such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, 5-butylbarbituric acid, 1-benzyl-5 Such as phenyl barbituric acid Examples include mercapto compounds such as rubituric acids, dodecyl mercaptan, pentaerythritol tetrakis (thioglycolate) and the like.
Furthermore, in addition to the polymerization initiator and the polymerization accelerator, an electron acceptor such as an iodonium salt, a trihalomethyl-substituted S-triazine, or a phenanthylsulfonium salt compound may be added.

-Other materials-
The other materials are not particularly limited as long as the effects of the present invention are not hindered, can be selected according to the purpose, and various components included in known dental adhesives can be applied.

<Dental restoration material>
The dental filling restorative material includes (m) an acid group-free polymerizable monomer, (n) a filler, (o) a photopolymerization initiator, and (j) a chemical polymerization initiator.

-(M) Non-acidic group-containing polymerizable monomer-
The (m) non-acidic group-containing polymerizable monomer is hardly water-soluble and is composed of a hardly water-soluble polymerizable monomer.
The poorly water-soluble polymerizable monomer means a water-soluble compound having no acidic group and having at least one polymerizable unsaturated group in one molecule. However, it can be appropriately selected from known compounds according to the purpose. Here, the acidic group and the polymerizable unsaturated group are the same as those described in the above (a) acidic group-containing polymerizable monomer. The poorly water-soluble means that the solubility in water at 20 ° C. is 5% by weight or less.
The poorly water-soluble polymerizable monomer is not particularly limited as long as it has the characteristics described above, and can be appropriately selected according to the purpose. However, (i) the acidic group-free polymerizable monomer The bifunctional polymerizable monomer, the trifunctional polymerizable monomer, and the tetrafunctional polymerizable monomer described as the body can be suitably used.

-(N) Filler-
There is no restriction | limiting in particular as said (n) filler, It can select from a well-known compound suitably and can be used, An inorganic filler, an organic-inorganic filler, and an organic filler are mentioned.
Examples of the inorganic filler include silica, zirconia, titania, silica-zirconia, silica-titania, barium glass, strontium glass, lanthanum glass, fluoroaluminosilicate glass, ytterbium fluoride, and the like.

The inorganic filler is made hydrophobic with a surface treatment material typified by a silane coupling material, so that it can be used well with a polymerizable monomer, and mechanical strength and water resistance can be improved.
There is no restriction | limiting in particular as the method of the said hydrophobization, A well-known method is mentioned. That is, as the silane coupling material, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, 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) ethyltrimethoxysila , N- phenyl--γ- aminopropyltrimethoxysilane, hydrophobic and the like with hexamethyldisilazane.
Further, as the organic-inorganic composite filler, a granular material obtained by preliminarily adding a polymerizable monomer to the inorganic filler, forming a paste, polymerizing and pulverizing, or the inorganic filler A granular material obtained by impregnating aggregated particles with the polymerizable monomer is used.
Moreover, as the organic filler, a granular material obtained by polymerizing the polymerizable monomer is used.
There is no restriction | limiting in particular as an average particle diameter of these fillers, Although 0.01 micrometer-100 micrometers of the magnitude | size normally used as a dental material may be sufficient, 0.01 micrometer-5 micrometers are preferable. Further, the refractive index of the filler is not particularly limited, and may be 1.4 to 1.7 which a general dental filler has. The filler may be used alone or in combination with a plurality of fillers having different particle size ranges, average particle sizes, refractive indices, and materials.
There is no restriction | limiting in particular as a shape of these fillers, Although any of an indeterminate form, spherical shape, and substantially spherical shape may be sufficient, a spherical inorganic filler is preferable especially.

  Although there is no restriction | limiting in particular as a compounding quantity of the said filler, 70 mass parts-700 mass parts are preferable with respect to 100 mass parts of said (m) acidic group non-containing polymerizable monomers.

-(O) Photopolymerization initiator-
The (o) photopolymerization initiator is blended from the viewpoint of polymerizing and curing a region of the dental restorative material filled in the cavity that does not come into contact with the dental pretreatment material.
There is no restriction | limiting in particular as said (o) photoinitiator, It can select suitably according to the objective, Apply the same thing as said (l) photoinitiator in the said dental adhesive material. Can do.
Although there is no restriction | limiting in particular as a compounding quantity of the said (o) photoinitiator, 0.01 mass part-20 mass parts are with respect to 100 mass parts of said (m) acidic group non-containing polymerizable monomers. preferable.

-(P) Chemical polymerization initiator-
The (p) chemical polymerization initiating material is in contact with the dental pretreatment material among the dental restorative materials filled in the cavity, and the (j) chemical polymerization initiation in the dental pretreatment material It mix | blends from a viewpoint which produces | generates a polymerization start seed | species by chemical reaction with material, and starts the superposition | polymerization of an adhesive component.
The (p) chemical polymerization initiator is not particularly limited and may be appropriately selected depending on the purpose. (J) When the fourth period transition metal compound is selected as the chemical polymerization initiator, An oxide can be suitably used.

There is no restriction | limiting in particular as said peroxide, According to the objective, it can select suitably, An organic peroxide and an inorganic peroxide can be applied.
The organic peroxide is not particularly limited, and known hydroperoxides, peroxyketals, ketone peroxides, alkylsilyl peroxides, diacyl peroxides, peroxyesters and the like are applied. Can do.

  Examples of the hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide. Examples thereof include oxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

  Examples of the peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis. (T-butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis ( t-Butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like.

  Examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.

  Examples of the alkylsilyl peroxides include t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyltrimethylsilyl peroxide, t-hexyltrimethylsilyl peroxide, and the like.

  Examples of the diacyl peroxides include benzoyl peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, and the like.

  Examples of the peroxyesters include t-butyl peroxyneodecanoate and cumyl peroxyneodecanoate.

  Among these, the hydroperoxide, the peroxyketal, the ketone peroxide, and the alkylsilyl peroxide are preferable because the reaction with the fourth period transition metal compound is fast, and the hydroperoxide is particularly preferable.

  The inorganic peroxide is not particularly limited, and known inorganic peroxides such as peroxodisulfate, alkali metal peroxide, alkaline earth metal peroxide, and transition metal peroxide are applied. can do. Examples of the peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate. Examples of the alkali metal peroxide include lithium peroxide, sodium peroxide, and potassium peroxide. Examples of the alkaline earth metal peroxide include magnesium peroxide, calcium peroxide, and barium peroxide. Examples of the transition metal peroxide include zinc peroxide, cadmium peroxide, and mercury peroxide.

  In addition, there is no restriction | limiting in particular as a compounding quantity of the said (p) chemical polymerization initiator, However, 0.1 mass part-10 mass with respect to 100 mass parts of said (m) acidic group non-containing polymerizable monomers. Part is preferred.

-Other materials-
The other materials are not particularly limited as long as the effects of the present invention are not hindered, can be selected according to the purpose, and various components included in known dental filling and restorative materials can be applied.

  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 an Example and a comparative example, its abbreviation and abbreviation, it is as follows.

(Each component and its abbreviations and abbreviations)
[(A) Acidic group-containing polymerizable monomer]
PM: Mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate MHP: 8-methacryloxyhexyl dihydrogen phosphate MDP: 10-methacryloxydecyl dihydrogen phosphate MAC- 10: 11-methacryloyloxy-1,1-undecanedicarboxylic acid [(b) water]
Water: Distilled water IPA: Isopropyl alcohol Ethanol [(c) Color change material]
-(E) Water-soluble metal salt-
CoCl ₂ : Cobalt (II) chloride
FeCl ₃ : Iron (III) chloride
NiSO ₄ : Nickel (II) sulfate
-(F) Alkali metal earth salt-
MgCl ₂ : Magnesium chloride CaCl ₂ : Calcium chloride-(g) pH indicator-
TB: Thymol blue (color change range: pH 1.2 to pH 2.8)
-(H) Redox indicator-
MB: Methylene blue (color change range: 0.53V)
[(D) Volatile organic solvent]
Acetone [acidic group-free polymerizable monomer]
BisGMA: 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate BisGMA and 3G are sparingly water-soluble acids It is a group-free polymerizable monomer, and HEMA is a water-soluble acidic group-free polymerizable monomer.
[Fourth-period transition metal compound]
BMOV: oxovanadium (IV) bis (maltrate)
V ₂ O ₅ : Vanadium pentoxide (V)
[Photopolymerization initiator]
CQ: camphorquinone DMBE: ethyl 4-dimethylaminobenzoate BTPO: bis (2,6-dimethylbenzoyl) phenylphosphine oxide [peroxide]
TMBPO: 1,1,3,3-tetramethylbutyl hydroperoxide CHPO: cumene hydroperoxide KPS: potassium peroxodisulfate [polymerization inhibitor]
BHT: Dibutylhydroxytoluene [filler]
F: Silica-zirconia filler hydrophobized with γ-methacryloyloxypropyltrimethoxysilane and silica-titania filler hydrophobized with γ-methacryloyloxypropyltrimethoxysilane at a mass ratio of 70:30 Mixed mixture [Dental restoration material]
EFQ: Estelite Flow Quick made by Tokuyama Dental Co., Ltd.

(Dental pretreatment material)
<Example 1>
According to the following composition, after mixing each component, it stirred until these became uniform, and the dental pretreatment material which concerns on Example 1 was manufactured. The dental pretreatment material according to Example 1 is a dental pretreatment material of the type used for dental restoration together with a dental adhesive.

-Composition-
・ (A) Acidic group-containing polymerizable monomer PM 100 g
・ (B) 100g of water
(D) Volatile organic solvent Acetone 100g
(E) Water-soluble metal salt CoCl ₂ 1.0 g
・ Polymerization prohibited material BHT 0.1g

<Examples 2 to 24 / Comparative Examples 1 to 6>
Moreover, except that it manufactured based on the composition of following Table 1, it carried out similarly to Example 1, and manufactured each dental pretreatment material which concerns on Examples 2-24 and Comparative Examples 1-6.

(Dental adhesive)
According to the following composition, after mixing each component, it stirred until these became uniform, and manufactured dental adhesive material B-1.

-Composition-
(K) Non-acidic group-containing polymerizable monomer HEMA 40 g
BisGMA 36g
3G 24g
・ (L) Photopolymerization initiator CQ 1.4g
DMBE 1.4g
・ Polymerization prohibited material BHT 1.0g

  Moreover, except having manufactured based on the composition of following Table 2, dental adhesive B-2 was manufactured like dental adhesive B-1.

(Dental filling restoration kit)
<Examples 25-49 / Comparative Examples 7-13>
Each dental pretreatment material according to Examples 1 to 24 and Comparative Examples 1 to 6 and dental adhesives B-1 and B-2 were combined in combinations shown in Table 3 below, and these were combined in Example 25. -49 and Comparative Examples 7 to 13 were used as dental filling and repair kits and used for adhesion tests. Hereinafter, the content of the adhesion test will be described.

<Adhesion test>
First, the anterior teeth of the mandibular jaw extracted within 24 hours after slaughter are polished with # 600 emery paper (water-resistant abrasive paper) under water injection, and the enamel and dentin planes are cut out to be parallel to the labial surface. did.
Next, after compressed air was blown onto these planes and dried, double-sided tapes with a 3 mm diameter circular hole were fixed to these planes to define the bonding area.
Next, a paraffin wax having a diameter of 8 mm with a hole having a diameter of 8 mm was pasted on the double-sided tape at a position where the hole was at the same center as the circular hole of the double-sided tape to form a simulated cavity. .
Each dental pretreatment material according to Examples 1 to 24 and Comparative Examples 1 to 6 was applied to the simulated cavity and allowed to stand for 20 seconds, and then dried by blowing compressed air. Here, the dry state was confirmed according to the criteria defined in Table 4 below. Moreover, when visually confirming the dry state of each dental pretreatment material according to Examples 1 to 24 including the color changing material (c), the visibility was evaluated according to the following criteria.
-Visibility in dry condition-
(Double-circle): It can confirm easily.
○: Can be confirmed.
×: Cannot be confirmed.

After the dental adhesive B-1 or B-2 was applied to the simulated cavity after drying, it was irradiated with light for 10 seconds using a dental light irradiator (manufactured by Tokuyama Dental Co., Ltd.).
Then, the dental filling restoration material EFQ was filled in the simulated cavity and covered with a polyester film, and then irradiated with light for 20 seconds using a dental light irradiator (manufactured by Tokuyama Dental Co., Ltd.). The polyester film and the paraffin wax were carefully removed to obtain an adhesion test piece I.
After immersing the adhesion test piece I in water at 37 ° C. for 24 hours, a metal jig was attached, and a tensile tester (Shimadzu Autograph AG5000) was used and the crosshead speed was 2 mm / min. A tensile test was conducted to measure the adhesion strength to the enamel plane and the dentin plane. In addition, the measurement result of this adhesive strength was calculated as an average value of each measurement value repeatedly measured under the same conditions 20 times, and the standard deviation when repeatedly measured under the same conditions was also calculated.
The measurement results of the adhesive strength, the standard deviation, and the visibility in the dry state are shown in Table 3 below.

As shown in Table 3 above, in each dental filling / restoration kit according to Examples 25 to 49 using each dental pretreatment material according to Examples 1 to 24, before each dental according to Comparative Examples 1 to 6 Compared with each dental filling / restoration kit according to Comparative Examples 7 to 13 using the treatment material, adhesion strength and visibility are good. In each of the dental filling / restoration kits according to Comparative Examples 7 to 13, since the determination of the dry state varies, it is confirmed that the standard deviation becomes large and the adhesive strength becomes unstable.
In addition, in each dental filling / restoration kit according to Examples 27, 44, and 47 using each dental pretreatment material according to Examples 2, 19, and 22, each dental according to Examples 1, 3, 20, and 23 is used. Compared with each dental filling / restoration kit according to Examples 25, 28, 45, and 48 using the pretreatment material for use, the amount of the color changing material (c) added is small, so that a decrease in visibility is confirmed.
In the dental filling / restoration kits according to Examples 29 to 31, 46, and 49 using the dental pretreatment materials according to Examples 4 to 6, 21, and 24, Examples 1, 3, 20, and 23 are used. Compared with each dental filling / restoration kit according to Examples 25, 28, 45, and 48 using each dental pretreatment material according to (c), since the amount of the color change material added is large, the adhesive strength is reduced. Is confirmed.
Moreover, in each dental filling / restoration kit according to Examples 28 and 41 using each dental pretreatment material according to Examples 3 and 16, Example 43 using the dental pretreatment material according to Example 18 was used. Compared with such a dental filling / restoration kit, since the metal halide is used as the water-soluble metal salt (e), the visibility is good. Among them, the visibility of the dental filling / restoration kit according to Example 28 using the dental pretreatment material according to Example 3 using cobalt (II) chloride was the best.
Further, in each of the dental filling and repair kits according to Examples 36 and 37 using the dental pretreatment materials according to Examples 11 and 12, Example 27 using the dental pretreatment material according to Example 2 was used. Compared with such a dental filling / restoration kit, the visibility can be improved because the (f) alkaline earth metal salt is added. In the dental filling / restoration kit according to Example 42 using the dental pretreatment material according to Example 17 to which the (f) alkaline earth metal salt was added, good visibility was obtained.

(Dental pretreatment material)
<Example 50>
According to the following composition, after mixing each component, it stirred until it became uniform, and the dental pretreatment material which concerns on Example 50 was manufactured. In addition, the dental pretreatment material according to Example 50 serves as the dental adhesive, and is a type of dental pretreatment used for the restoration of teeth using a dental filling restorative material without the dental adhesive. It is a material. That is, in the following composition, the fourth period transition metal compound reacts with a peroxide contained in a dental filling restorative material described later, and chemical polymerization is started. In the cavity, the photopolymerization is started by the photopolymerization initiator contained in the dental filling / restoration material at a position where the dental pretreatment material and the dental filling / restoration material do not contact each other.

-Composition-
・ (A) Acidic group-containing polymerizable monomer PM 30 g
・ (B) 100g of water
(D) Volatile organic solvent Acetone 100g
(E) Water-soluble metal salt CoCl ₂ 1.0 g
・ (I) Acidic group-free polymerizable monomer HEMA 30 g
BisGMA 24g
3G 16g
・ Polymerization prohibited material BHT 1.0g
・ Fourth period transition metal compound BMOV 1.0g

<Examples 51-76 / Comparative Examples 14-22>
Moreover, except for having manufactured based on the composition of following Table 5, it carried out similarly to Example 50, and manufactured each dental pretreatment material which concerns on Examples 51-76 and Comparative Examples 14-22.

(Dental restoration material)
According to the following composition, after mixing each component, it stirred until they became uniform, and dental filling restoration material CR-1 was manufactured.

-Composition-
(M) Acidic group-free polymerizable monomer BisGMA 60 g
3G 40g
・ (N) Filler F 230g
・ (O) Photopolymerization initiator CQ 1.0g
DMBE 1.0g
・ Peroxide TMBPO 2.0g
・ Polymerization prohibited material BHT 0.1g

  Further, dental filling / restoration materials CR-2 to CR-4 were produced in the same manner as the dental filling / restoration material CR-1 except that the dental filling / restoration material CR-1 was produced based on the composition described in Table 6 below.

(Dental filling restoration kit)
<Examples 77 to 106 / Comparative Examples 23 to 34>
Each of the dental pretreatment materials according to Examples 50 to 76 and Comparative Examples 14 to 22 and dental filling / restoration materials CR-1 to CR-4 were combined in combinations shown in Table 7 below, and these were used as examples. It was set as each dental filling restoration kit concerning 77-106 and Comparative Examples 23-34, and was used for the adhesion test. Hereinafter, the content of the adhesion test will be described.

<Adhesion test>
First, the anterior teeth of the mandibular jaw extracted within 24 hours after slaughter are polished with # 600 emery paper (water-resistant abrasive paper) under water injection, and the enamel and dentin planes are cut out to be parallel to the labial surface. did.
Next, after compressed air was blown onto these planes and dried, double-sided tapes with a 3 mm diameter circular hole were fixed to these planes to define the bonding area.
Next, a paraffin wax having a diameter of 8 mm with a hole having a diameter of 8 mm was pasted on the double-sided tape at a position where the hole was at the same center as the circular hole of the double-sided tape to form a simulated cavity. .
Each dental pretreatment material according to Examples 50 to 76 and Comparative Examples 14 to 22 was applied to the simulated cavity and left for 20 seconds, and then dried by blowing compressed air. Here, the dry state was confirmed according to the criteria defined in Table 4 above. Moreover, when visually confirming the dry state of each dental pretreatment material according to Examples 50 to 76 including the (c) color change material, evaluation of visibility based on the visibility standard of the dry state. Went.

After filling the simulation cavity after drying, any one of dental filling restorative materials CR-1 to CR-4 is covered with a polyester film, and then a dental light irradiator (manufactured by Tokuyama Dental Co., Ltd.) is used. Then, the polyester film and the paraffin wax were carefully removed to obtain an adhesion test piece II.
After the adhesion test piece II was immersed in water at 37 ° C. for 24 hours, a metal jig was attached, and a tensile tester (Autograph AG5000 manufactured by Shimadzu Corp.) was used and the crosshead speed was 2 mm / min. A tensile test was conducted to measure the adhesion strength to the enamel plane and the dentin plane. In addition, the measurement result of this adhesive strength was calculated as an average value of each measurement value repeatedly measured under the same conditions 20 times, and the standard deviation when repeatedly measured under the same conditions was also calculated.
Table 7 below shows the measurement results of the adhesive strength, the standard deviation, and the visibility in the dry state.

As shown in Table 7 above, each dental filling / restoration kit according to Examples 77 to 106 using each dental pretreatment material according to Examples 50 to 76 is used before each dental according to Comparative Examples 14 to 22. Compared with each dental filling / restoration kit according to Comparative Examples 23 to 34 using the treatment material, adhesion strength and visibility are good. In each of the dental filling / restoration kits according to Comparative Examples 23 to 34, the determination of the dry state varies, so that it is confirmed that the standard deviation increases and the adhesive strength becomes unstable.
Moreover, in each dental filling / restoration kit according to Examples 83, 101, and 104 using each dental pretreatment material according to Examples 53, 71, and 74, each dental according to Examples 50, 54, 72, and 75 is used. Compared with each dental filling / restoration kit according to Examples 77, 84, 102, and 105 using pretreatment materials for use, the amount of the color changing material (c) added is small, and thus a decrease in visibility is confirmed.
Moreover, in each dental filling / restoration kit according to Examples 85-87, 103, 106 using the dental pretreatment materials according to Examples 55-57, 73, 76, Examples 50, 54, 72, 75 are used. Compared with each dental filling / restoration kit according to Examples 77, 84, 102, and 105 using each dental pretreatment material according to (c), since the amount of the color change material added is large, the adhesive strength is reduced. Is confirmed.
In addition, in each of the dental filling and repair kits according to Examples 84 and 98 using the dental pretreatment materials according to Examples 54 and 68, Example 100 using the dental pretreatment material according to Example 70 is used. Compared with such a dental filling / restoration kit, since the metal halide is used as the water-soluble metal salt (e), the visibility is good. Among these, the visibility of the dental filling / restoration kit according to Example 84 using the dental pretreatment material according to Example 54 using cobalt (II) chloride was the best.
Further, in each dental filling and repair kit according to Examples 92 and 93 using the dental pretreatment materials according to Examples 62 and 63, Example 83 using the dental pretreatment material according to Example 53 was used. Compared with such a dental filling / restoration kit, the visibility can be improved because the (f) alkaline earth metal salt is added. In the dental filling / restoration kit according to Example 99 using the dental pretreatment material according to Example 69 to which the (f) alkaline earth metal salt was added, good visibility was obtained.

Claims (7)

At least before and after drying , selected from (a) an acidic group-containing polymerizable monomer, (b) water, (c) cobalt (II) chloride, iron (III) chloride and nickel (II) sulfate A dental pretreatment material comprising: a color changing material capable of confirming a dry state after being applied to teeth by color change of (f); and (f) an alkaline earth metal salt .   The dental pretreatment material according to claim 1, further comprising (d) a volatile organic solvent. The dental pretreatment material according to any one of claims 1 to 2, further comprising (i) an acidic group-free polymerizable monomer and (j) a chemical polymerization initiator. (J) The dental pretreatment material according to claim 3, wherein the chemical polymerization initiator is a fourth-period transition metal compound. The dental pretreatment material according to any one of claims 1 to 2,
  (K) an acidic group-free polymerizable monomer containing a water-soluble polymerizable monomer, and (l) a dental adhesive containing a photopolymerization initiator,
  A dental filling / restoration kit comprising: The dental pretreatment material according to any one of claims 3 to 4,
  (M) a hardly water-soluble acidic group-free polymerizable monomer, (n) a filler, (o) a photopolymerization initiator, and (p) (j) a chemical polymerization initiator in the dental pretreatment material A dental filling restorative material including a chemical polymerization initiator that generates a polymerization initiating species by a chemical reaction with
  A dental filling / restoration kit comprising: The dental pretreatment material according to claim 4, wherein the dental pretreatment material is a dental pretreatment material, and the (p) chemical polymerization initiator in the dental filling and restoration material is a peroxide. kit.