JP5363843B2 - Dental filling and repair kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental filling/restoration kit that can harden a pretreatment material and a cavity restoration material by radiating light only once, improves adhesion between teeth and the cavity restoration material and gives the adhesion between teeth and the cavity restoration material almost independent on the thickness of the cavity restoration material and good appearance. <P>SOLUTION: The dental filling/restoration kit for dentistry is composed of the filling/restoration material (A) containing a radical-polymerizable monomer (a) not containing an acidic group, a tertiary amine compound (b), a photopolymerization initiator (c), a basic inorganic material (d) and a filler (e); and the pretreatment material (B) containing a radical-polymerizable monomer (f) containing an acidic group and water (g). The cavity restoration material (A) is directly filled in the cavity to which the pretreatment material (B) is applied and where the applied pretreatment material is not yet hardened. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a dental filling and repair kit comprising a photopolymerizable dental restorative material.

  Conventionally, small defects (cavities) caused by tooth tooth decay or the like are filled with a metal material. However, in recent years, a filling restoration material comprising an acrylic polymerizable monomer, an inorganic filler, and a photopolymerization initiator is preferred because it can impart a color tone equivalent to that of a natural tooth color and is easy to operate. It is used.

  However, since the resin-based filling / restoring material itself does not have adhesiveness to the teeth, if the cavity of the tooth is filled with only the resin-based filling / restoring material, a gap may be formed between the filling / restoring material and the tooth. is there. As a result, there is a high risk that bacteria may enter from the gap or the filling / restoring material may fall off from the teeth.

  In view of this, a proposal has been put into practical use in which a layer of a tooth surface treatment agent containing an acid group-containing monomer or the like as a main component is provided between a resin-based filling restoration material and a tooth. The tooth surface treatment agent acts as a surface treatment agent for tooth enamel and dentin, and acts to increase the adhesive force between the filling restorative material and the tooth. By interposing such a tooth surface treating agent between the tooth and the resin-based filling / restoring material, the filling / restoring material and the tooth can be bonded without a gap.

  The filling restorative material can be easily deformed when the tooth shape is applied, but is preferably cured as soon as filling is completed. For this reason, in recent years, filling restoration materials and tooth surface treatment agents contain a photopolymerization initiator as a polymerization initiator and are suitably cured using visible light that is harmless to a living body. In addition, an amine compound is generally added to the filling / restoring material as a polymerization accelerator. By using an amine compound in combination with a photopolymerization initiator, not only the curing rate is improved, but also a deeper curing depth can be secured, a site farther from the light irradiation surface of the filling restoration material filled in the tooth, That is, it is possible to sufficiently photocure even the filling restoration material closer to the tooth surface. As such an amine compound, an aromatic tertiary amine compound is widely used because of its particularly high activity.

  The operation of restoring a tooth is performed according to the following procedure. First, the tooth decay portion is cut to form a cavity. Next, a tooth surface treatment agent is applied to the cavity. Next, a tooth surface treating agent is hardened by irradiating visible light to the part which applied the tooth surface treating agent. Then, a filling restoration material is filled on the tooth surface treatment material layer. Finally, in order to cure the filling / restoring material, the filling / restoring material is irradiated with visible light.

  In the above-described repair method, it is necessary to irradiate visible light twice, but it is desirable to reduce the number of times of visible light irradiation from the viewpoint of reducing the burden on the patient and simplifying repair work. However, if the tooth surface treatment agent and the filling restorative material are simultaneously cured by only one irradiation of visible light, a large stress is generated at the adhesive interface due to the large amount of polymerization shrinkage of the filling restorative material. Moreover, the monomer containing the acidic group contained in the uncured pretreatment material and the amine compound in the filling restoration material cause a neutralization reaction, and the polymerization promoting effect of the amine compound is reduced. As a result, the adhesive strength between the tooth surface treating agent and the filling restorative material becomes very small, or the problem that the long-term adhesion durability is poor tends to occur.

  In order to solve such a problem, various dental filling / restoration kits have been developed. As an example, both a filling restorative material and a pretreatment material are provided with a monomer having an acidic group, an acidic group. A dental filling / restoration kit including a monomer not included and a polymerization initiator is known (for example, see Patent Document 1). In such a dental filling / restoration kit, since the filling / restoring material has a composition similar to that of the pretreatment material, the affinity of the interface between the pretreatment material and the filling / restoration material is increased. Peeling hardly occurs at the interface. Therefore, even when the pretreatment material and the filling / restoring material are simultaneously polymerized by only one light irradiation, the material has a relatively high adhesive strength.

  Similarly, a dental filling / restoration kit is known in which the amount of the polymerization inhibitor or the photopolymerization initiator contained in the filling / restoring material and the pretreatment material is adjusted to accelerate the photopolymerization start of the pretreatment material ( For example, see Patent Document 2). In such a dental filling / restoration kit, when the pretreatment material applied to the tooth surface and the filling / restoration material filled on the pretreatment material layer are simultaneously irradiated with light and cured, the photopolymerization of the pretreatment material layer starts quickly. Therefore, similarly, peeling hardly occurs at the interface between the pretreatment material and the filling restoration material. Accordingly, even when the pretreatment material and the filling / restoring material are polymerized simultaneously by only one light irradiation, the adhesive strength is relatively high.

JP 2006-131621 A (Claims) JP 2007-210944 A (Claims)

  However, the dental filling / restoration kit disclosed in Patent Document 1 has the following problems. When the pretreatment material and the filling / restoring material are simultaneously cured by only one light irradiation, the polymerization shrinkage amount of the filling / restoring material is increased. For this reason, a big stress arises in an adhesion interface. As a result, from the viewpoint of clinical practice, sufficient adhesive strength has not been obtained yet, and there is a problem that the long-term adhesion durability is poor. In particular, when the thickness of the filling / restoring material is increased, there is a problem in that it is difficult to complete the polymerization of the distal portion from the light irradiation surface. In particular, since amine compounds having a polymerization promoting effect are weakly basic, they are neutralized by the monomer having an acidic group contained in the filling restoration material, and the polymerization promoting effect is reduced. Since light is emitted from the occlusal surface of the tooth, polymerization on the pretreatment material side where light does not reach easily is difficult to complete, and the adhesive force and adhesion durability between the filling restoration material and the pretreatment material tend to be inferior There is.

  Moreover, since the filling restoration material used by the above-mentioned prior art contains the monomer which has an acidic group, it is easy to adsorb | suck the basic substance contained in food etc. For this reason, there exists a problem that the part of a filling restoration material is colored and lacks aesthetics.

  Similarly, even in the dental filling / restoration kit disclosed in Patent Document 2, when the thickness of the filling / restoring material increases, the polymerization start on the pretreatment material side where light does not easily reach tends to be delayed. Furthermore, in the vicinity of the interface where the pretreatment material and the filling / restoring material are in contact, the amine compound in the filling / restoration material is similarly neutralized by the monomer having an acidic group in the pretreatment material, thereby reducing the polymerization promoting effect. In addition to the pretreatment material layer, there is a problem that it is difficult to complete the polymerization of the filling / restoring material in contact with the pretreatment material. For this reason, similarly, the adhesive force between the filling restoration material and the pretreatment material is still not sufficient from the viewpoint of clinical practice, and the adhesion durability tends to be inferior.

  The present invention has been made to solve the above-described problems, and its object is to provide a dental filling / restoration kit capable of curing the pretreatment material and the filling / restoring material by only one light irradiation. And, while improving the adhesive force between the tooth and the filling restorative material, the dental filling and restoration that makes it difficult for the adhesive force between the tooth and the filling restorative material to be influenced by the thickness of the filling restorative material and exhibits excellent aesthetics. To provide a kit.

  In order to achieve such an object, the present inventor has intensively studied, and as a result, after pretreatment using a pretreatment material containing a radical polymerizable monomer containing an acidic group and water, a tertiary amine compound and A filling restoration material containing a radically polymerizable monomer not containing an acidic group to which a basic inorganic material was added was filled in the cavity and cured by irradiation with visible light. The pretreatment material and the filling restoration material were once applied. Even when polymerized only by light irradiation, a stable high adhesive force is developed between the tooth and the filling restorative material, and further, the adhesive force between the tooth and the filling restorative material is not easily influenced by the thickness of the filling restorative material, And it discovered that a filling restoration material was hard to color, and came to complete this invention.

In particular, the present invention relates to (a) an acidic group-free radically polymerizable monomer, (b) an aromatic tertiary amine compound having a pKa value of 7.0 or less (hereinafter simply referred to as “aromatic tertiary amine ”). may be abbreviated as amine compound "), (c) a photopolymerization initiator, (d) the following formula (1) trivalent or more metal ion-eluting basic inorganic pH value difference value is 0.05 or more represented by A material (hereinafter, sometimes simply abbreviated as “trivalent or higher-valent metal ion-eluting basic inorganic material”) and (e) a filler restoration material (A), (f) an acidic group-containing radical polymerizable monomer (B) a pretreatment material containing water and (g) water, (A) a filling restoration material, (B) a pretreatment material is applied, and the applied pretreatment material is uncured It is made into the dental filling restoration kit which is directly filled into the cavity.
Formula (1) pH value difference value = S (pH) -R (pH)
[In the above formula (1), S (pH) is phosphoric acid in a solution in which distilled water and ethanol are mixed at a volume ratio of 1: 1 in a beaker having a bottom area of 706.5 mm ^{2 in} the inner space. Was added dropwise to 20 g of an acidic solution adjusted to pH 2.50 ± 0.03 at 23 ° C., and 1.0 g of the trivalent or higher metal ion-eluting basic inorganic compound was added, and the length was 8 mm in diameter. The pH value at 23 ° C. of the dispersion S immediately after stirring for 2 minutes at a rotation speed of 200 rpm at 23 ° C. using a 20 mm stirrer is shown.
R (pH) represents the pH value at 23 ° C. of Dispersion R prepared in Dispersion S that does not contain the trivalent or higher metal ion-eluting basic inorganic compound. ]

According to the present invention, the contact interface between the pretreatment material and the filling restorative material is obtained by filling the pretreatment material applied to the tooth with the filling restorative material containing the aromatic tertiary amine compound and the basic inorganic material. Then, a neutralization reaction occurs between the basic group of the trivalent or higher metal ion-eluting base inorganic material having a relatively high basicity and the acidic group of the acidic group-containing radical polymerizable monomer in the pretreatment material. The acid is weakened, and the reduction of the polymerization promoting effect of the aromatic tertiary amine compound can be avoided. As a result, the aromatic tertiary amine compound can sufficiently exhibit the polymerization promoting effect at the contact interface between the pretreatment material and the filling restoration material.

Furthermore, the radical polymerizable monomer contained in the filling / restoring material does not contain an acidic group, and the radical polymerizable monomer contained in the pretreatment material contains an acidic group. Therefore, since the pH of the former monomer is higher than the pH of the latter monomer, a pH gradient is generated between the filling / restoring material and the pretreatment material. As a result, the filling / restoring material and the pretreatment material are combined to form a mixed layer, and further, a neutralization reaction occurs between the trivalent or higher metal ion-eluting basic inorganic material and the acidic group. Therefore, even in this mixed layer, the photopolymerization promoting effect due to the inclusion of the aromatic tertiary amine compound is hardly lost.

Therefore, even when the thickness of the filling / restoring material is large and the light reaching the pretreatment material side is weak in the light irradiation at the time of curing, the polymerization on the pretreatment material side can sufficiently proceed, and as a result High adhesive strength can be realized between the tooth and the filling restorative material. Moreover, since the filling / restoring material does not contain an acidic group-containing radical polymerizable monomer, the filling / restoring material is hardly colored. For this reason, it becomes the dental filling restoration kit which can implement | achieve the filling excellent in aesthetics.
In addition, by using an aromatic tertiary amine compound having a relatively low basicity, the aromatic tertiary amine compound is mixed with the acidic group of the acidic group-containing radical polymerizable monomer in the pretreatment material. It is difficult to cause a sum reaction. For this reason, the high polymerization acceleration | stimulation effect of the photoinitiator of the contact interface of a pre-processing material and a filling restoration material and both inside can be improved more, and it can contribute greatly to acceleration | stimulation of photopolymerization.

Another aspect of the present invention is that (A) the filling / restoring material is (d) a trivalent or higher metal ion-eluting basic inorganic material with respect to 100 parts by mass of the radical polymerizable monomer not containing an acidic group. Is a dental filling and repair kit comprising at least 3 parts by mass.

  When a filling / restoring material having such a composition is used, a sufficient polymerization promoting effect during polymerization can be obtained. For this reason, the stable high adhesive force expresses between a tooth and a filling restoration material.

  In another aspect of the present invention, (a) 100 parts by mass of an acid group-free radical polymerizable monomer includes (a1) 3-30 parts by mass of an acid group-free and water-soluble radical polymerizable monomer. It is a dental filling and restoration kit.

  When the radically polymerizable monomer having no acidic group having such a composition is used, a more stable and high adhesive force is developed between the tooth and the filling restorative material.

Another invention of the present invention is (d) a dental filling / restoration kit in which the trivalent or higher valent metal ion-eluting basic inorganic material is fluoroaluminosilicate glass.

  When a dental filling / restoration kit using a photopolymerization initiator having such a composition is adopted, the polyvalent metal ions eluted from the fluoroaluminosilicate glass are polymerized with a polymer of a radical polymerizable monomer having an acidic group and ionic crosslinking. By doing so, the adhesiveness with a tooth substance and the physical property of a hardening body can be improved.

  Another aspect of the present invention is a dental filling / restoration kit in which (c) the photopolymerization initiator includes an acyl phosphine oxide-based polymerization initiator.

  When a dental filling / restoration kit using a photopolymerization initiator having such a composition is employed, the adhesive force between the tooth and the filling / restoring material can be further enhanced. Therefore, the filling restoration material is more difficult to peel off from the tooth.

  Another invention of the present invention is a dental filling / restoration kit (B) further comprising a vanadium compound in the pretreatment material and (A) a hydroperoxide in the filling restoration material.

  When the dental filling / restoration kit having such a composition is employed, the adhesive force between the tooth and the filling / restoring material can be further enhanced.

  According to the present invention, the pretreatment material and the filling restorative material can be cured by light irradiation only once, and the adhesive force between the tooth and the filling restorative material is further improved. It is possible to provide a dental filling / restoration kit that is less affected by the adhesive force and that can exhibit excellent aesthetics.

  Hereinafter, a preferred embodiment of a dental filling / restoration kit according to the present invention will be described. However, the present invention is not limited to the embodiments described below.

  The dental filling / restoration kit according to the embodiment of the present invention roughly includes a filling / restoring material (hereinafter referred to as a composite resin) and a pretreatment material (hereinafter referred to as a primer). The composite resin contains an acid group-free radical polymerizable monomer, a tertiary amine compound and a basic inorganic material, and the primer contains an acid group-containing radical polymerizable monomer.

(A) Acid group-free radical polymerizable monomer In the present embodiment, the composite resin contains a radical group-free monomer having no acid group. When an acidic group is present in the composite resin, the composite resin contains a tertiary amine compound and a basic inorganic material, which will be described later. A neutralization reaction occurs, and the polymerization promoting effect of the tertiary amine compound in the composite resin is reduced immediately after the production of the composite resin. On the other hand, when the composite resin does not contain an acidic group as in the present embodiment, before filling the dental cavity with the composite resin, the acidic group and the tertiary amine compound and basicity described below are used. Does not cause neutralization reaction with inorganic materials. Further, as in this embodiment, since the composite resin contains a basic inorganic material in addition to the tertiary amine having a high polymerization promoting effect, after the composite resin is filled, the primer and the composite resin are mixed. In the layer, the basic inorganic material is neutralized in competition with the tertiary amine, and the remaining tertiary amine that has not undergone the neutralization reaction enhances the polymerization promotion effect of the photopolymerization initiator in the mixed layer of both. be able to. In particular, this effect becomes remarkable when the basic inorganic material to be used is relatively basic, and is more preferable. In addition, since an acidic group-containing radically polymerizable monomer is not contained in the composite resin and a basic substance is not adsorbed, it is more difficult to be colored and excellent in aesthetics.

  In this Embodiment, as an acidic group non-containing radically polymerizable monomer, if it is a compound which does not have an acidic group in the molecule | numerator of this radically polymerizable monomer, it can be used without any limitation. Specifically, the acidic group refers to a functional group having a pKa of less than 5 and capable of dissociating active protons, such as a phosphinico group, a phosphono group, a sulfo group, or a carboxyl group.

  As such an acid group-free radical polymerizable monomer, a (meth) acrylate monomer is mainly used because of its good polymerizability. Specific examples of the (meth) acrylate monomer include the following (1) to (4).

(1) Monofunctional radical polymerizable monomer Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate cyclohexyl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, or glycidyl (meth) Alkyl ester of (meth) acrylic acid such as acrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1 Fluorine-containing (meth) acrylates such as H, 6H-decafluorohexyl methacrylate or 1H, 1H, 7H-dodecafluoroheptyl methacrylate, or the following formulas (g) to (k) and (p) to (q) ( And (meth) acrylate.

In the above formulas, R ¹ is a hydrogen atom or a methyl group. In addition, R ² or R ^{3 in} each of the above formulas is an independent alkylene group. R ^{4 in} each of the above formulas is an alkyl group. M in said each formula is 0 or an integer of 1-10, n is an integer of 1-10 (however, m + n is an integer of 2-10).

(2) Bifunctional radical polymerizable monomer Examples of the bifunctional radical polymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and butylene glycol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2-bis ((meth) acryloxyphenyl) propane, 2, 2-bis [4- (3- (meth) acrylic Loxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2, 2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydi) Propoxyphenylpropane, 2- (4-methacryloxyethoxyphenyl) -2- (4- (meth) acryloxydiethoxyphenyl) propane, 2- (4- (meth) acryloxydiethoxyphenyl) -2- (4 -(Meth) acryloxytriethoxyphenyl) propane, 2- (4- (meth) acryloxydipropoxypheny -2- (4- (meth) acryloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, or 2,2-bis (4- (meth) acryloxyiso) And propoxyphenylpropane.

(3) Trifunctional radical polymerizable monomer Examples of the trifunctional radical polymerizable monomer include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, or Examples include trimethylol methane tri (meth) acrylate.

(4) Tetrafunctional radical polymerizable monomer Examples of the tetrafunctional radical polymerizable monomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and pentaerythritol hexa (meth) acrylate. Is mentioned.

  Of the above-mentioned acidic group-free radical polymerizable monomers, bifunctional or higher radical polymerizable monomers are preferred from the viewpoint of mechanical strength.

  In the present invention, the radically polymerizable monomers as described above may be used alone, or two or more kinds of radically polymerizable monomers may be used in combination. Furthermore, you may combine the multiple types of radically polymerizable monomer from which a functional group number differs.

(A1) Acid group-free and water-soluble radical polymerizable monomer It is preferable that a part of the acid group-free radical polymerizable monomer contains a water-soluble radical polymerizable monomer. By including a water-soluble radical polymerizable monomer in a part of the acid group-free radical polymerizable monomer, a part of the radical polymerizable monomer contained in the composite resin is water-soluble. The affinity for the acidic group of the radical polymerizable monomer contained in the primer is high. Therefore, the affinity between the composite resin and the primer is high. Therefore, the radical polymerizable monomer is more likely to move to both due to the pH gradient between the composite resin and the primer, resulting in higher integration of both layers. In addition, when the radical polymerizable monomer contained in the composite resin advances to the primer side, the photopolymerization initiator is transferred simultaneously with the tertiary amine compound to be described later, and the primer shifts from the composite resin side to the primer side. Primer polymerization can be performed more efficiently.

  In this specification, water-soluble means that the solubility in water at 23 ° C. is 1 g / l or more. More preferably, the solubility is 100 g / l or more. Examples of such an acid group-free and water-soluble radical polymerizable monomer include any water-soluble (meth) acrylate monomers among the acid group-free (meth) acrylate monomers. Can be used without restriction. Specifically, a (meth) acrylate monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, methoxypolyethylene glycol methacrylate And methacrylate having an ethylene glycol chain in the molecule. These can be used alone or in admixture of two or more.

  Among the above-mentioned acidic group-free and water-soluble radical polymerizable monomers, it is preferable to use a polyfunctional radical polymerizable monomer. Specifically, polyfunctional radical polymerizable properties such as polyethylene glycol di (meth) acrylate rather than monofunctional radical polymerizable monomers such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate. It is preferable to use a monomer. By using a polyfunctional radically polymerizable monomer, the adhesive strength between the composite resin and the tooth, particularly the dentin can be improved via the primer.

  Examples of preferable water-soluble polyfunctional radical polymerizable monomers include polyethylene glycol dimethacrylate having a polymerization degree of 9-30, dimethacrylate of polyethoxylated bisphenols having a total polymerization degree of polyethylene glycol sites of 20-50, mono or Examples include methacrylic acid adducts of polyethylene glycol diglycidyl ether, among which polyethylene glycol dimethacrylate and polyethoxylated bisphenol A dimethacrylate are more preferable. Of these, polyethylene glycol dimethacrylate is most preferably used.

  Moreover, in the case where 3 to 30 parts by mass of the above-mentioned acidic group-free and water-soluble radical polymerizable monomer is contained in 100 parts by mass of the acidic group-free radical polymerizable monomer contained in the composite resin. The adhesive strength of the composite resin to dentin is improved through the primer. Further, when the composite resin contains 3 parts by mass or more of a radical-polymerizable monomer that does not contain an acidic group, the polymerization initiator tends to move between the composite resin and the primer. Furthermore, when the radically polymerizable monomer is contained in an amount of 30 parts by mass or less, the water absorption can be lowered. Therefore, the tertiary amine compound and the basic inorganic material can be moved more easily, the photopolymerization initiator can be moved more easily, water absorption is suppressed, and the adhesive strength between the tooth and the composite resin is improved. In order to make it, it is preferable to use a composite resin containing 3 to 30 parts by mass of an acidic group-free and water-soluble radical polymerizable monomer out of 100 parts by mass of the acidic group-free radical polymerizable monomer. The amount of the acidic group-free and water-soluble radical polymerizable monomer is particularly preferably 5 to 25 parts by mass in 100 parts by mass of the radical polymerizable monomer.

(B) Tertiary amine compound In this Embodiment, (b) tertiary amine compound is mix | blended with a composite resin. By combining (b) a tertiary amine compound as a polymerization accelerator with respect to the photopolymerization initiator, the polymerization promotion effect of the photopolymerization initiator can be enhanced. In the present invention, any known tertiary amine compound may be used as long as it acts as such a polymerization accelerator.

Such tertiary amine compounds are generally roughly classified into aromatic tertiary amine compounds in which an aromatic group is bonded to a nitrogen atom and aliphatic tertiary amine compounds in which only an aliphatic group is bonded. The However, the tertiary amine compound used as an essential component in the dental filling / restoration kit of the present invention is an aromatic tertiary amine compound.

(B1) Aliphatic tertiary amine compound An aliphatic tertiary amine compound is preferably used for dentistry because it is relatively low in volatility and does not generate odor. In the present embodiment, specific examples of these aliphatic tertiary amine compounds include triethylamine, tributylamine, triallylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine. N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, dimethylethanolamine, diethylethanolamine, dipropylethanolamine, triethanolamine, tri (isopropanol) amine, tri (2- And aliphatic tertiary amine compounds such as hydroxybutyl) amine and tribenzylamine.

  Among the above-described aliphatic tertiary amine compounds, N, N—is easily available or synthesized, and has excellent chemical stability and solubility in polymerizable monomers. Dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, dimethylethanolamine, diethylethanolamine, triethylamine, Triethanolamine or tributylamine is preferably used. Among these, it is more preferable to use N, N-dimethylaminoethyl methacrylate, dimethylethanolamine or triethanolamine.

(B2) Aromatic tertiary amine compound In the present embodiment, a typical aromatic tertiary amine compound means at least one aromatic group at the nitrogen atom of the amino group, and at most two or less. An amine compound having an aliphatic group bonded thereto. In the present embodiment, as a typical aromatic tertiary amine compound, a known aromatic tertiary compound can be used without particular limitation, but is particularly preferably represented by the following general formula (3) from the viewpoint of easy availability. Is mentioned.

In formula (3), R ⁵ and R ⁶ are each independently an alkyl group, and R ⁷ is an alkyl group, aryl group, alkenyl group, alkoxy group, cyano group, carbonyl group, aminocarbonyl group, or alkyl group. An oxycarbonyl group and the like. Moreover, n represents the integer of 0-5. When n is 2 or more, the plurality of R ⁷ may be the same as or different from each other. Further, R ⁷ may be bonded to each other to form a ring.

The alkyl group in R ⁵ , R ⁶ and R ⁷ is preferably an alkyl group having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n- A hexyl group etc. can be mentioned. Further, the alkyl group may be a substituted alkyl group having a substituent as a matter of course. Examples of such a substituted alkyl group include halogen-substituted alkyl groups such as a fluoromethyl group and a 2-fluoroethyl group, Alternatively, a hydroxyl group-substituted alkyl group such as a 2-hydroxyethyl group can be exemplified.

In addition, any of the aryl group, alkenyl group, alkoxy group, cyano group, carbonyl group, aminocarbonyl group, alkyloxycarbonyl group, and the like in R ⁷ described above may have a substituent. Examples of the aryl group include those having 6 to 12 carbon atoms such as a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group, and a 4-biphenylyl group. Examples of the alkenyl group include those having 2 to 12 carbon atoms such as a vinyl group, a propenyl group, and a 2-phenylethenyl group. Examples of the alkoxy group include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group. Examples of the carbonyl group include a formyl group, an acetyl group, a propionyl group, and a benzoyl group. Examples thereof include aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group and the like, and alkyloxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, amyloxycarbonyl group, isoamyloxycarbonyl group, etc. Examples of the group having 1 to 10 carbon atoms are exemplified.

In the aromatic tertiary amine represented by the general formula (3), the R ⁵ and R ⁶ are preferably alkyl groups having 1 to 6 carbon atoms, and particularly unsubstituted C 1 to 3 carbon atoms. An alkyl group (for example, methyl group, ethyl group, n-propyl group) or 2-hydroxyethyl group is more preferable. Of these, a methyl group is more preferred.

In addition, when n = 1, the bonding position of R ⁷ is preferably para, and R ⁷ is preferably an alkyl group or an alkyloxycarbonyl group, and most preferably an alkyloxycarbonyl group. On the other hand, when 2 to 3 R ⁷ are bonded, the bonding position is preferably the ortho position and / or the para position. Among these, the case where n = 1 is more preferable.

When the aromatic tertiary amine compound represented by the general formula (3) is specifically exemplified, as a compound in which R ⁷ is an alkyloxycarbonyl group bonded to the para position, methyl p-dimethylaminobenzoate, p- Examples include ethyl dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate and the like. Specific examples of other aromatic amine compounds include N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine, N, N, 2,4,6-pentamethylaniline, N, N, 2,4-tetramethylaniline, N, N-diethyl-2, Examples include 4,6-trimethylaniline, N, N-dimethylacetophenone, N, N-dimethylcyanobenzene, p-dimethylaminobenzoic acid, and p-dimethylaminobenzoic acid amide. Of these, ethyl p-dimethylaminobenzoate or N, N-dimethyl-p-toluidine is particularly preferred, and ethyl p-dimethylaminobenzoate is most preferred.

  In addition, you may use these tertiary amine compounds by 1 type as needed, or in combination of 2 or more types.

  Among these, the neutralization reaction with the acidic group of the acidic group-containing radical polymerizable monomer contained in the primer described later is unlikely to occur, and from the viewpoint of relatively low basicity, the corresponding ammonium ion salt in 25 ° C. water An amine compound having a pKa value of 9 or less is preferably used, and an amine having a pKa value of 7.0 or less is particularly preferably used. Such a low basic amine is generally an aromatic tertiary amine, and by using at least one of the above-exemplified examples, the contact interface between the primer and the composite resin described below and the vicinity of the contact interface are used. The polymerization promoting effect of the photopolymerization initiator in both of these can be further enhanced.

  In the present embodiment, the above-mentioned tertiary amine compound is generally added within a range of 0.1 to 10 times the weight of the photopolymerization initiator used. More preferably, relative to 100 parts by mass of the total amount of the acidic group-containing radical polymerizable monomer in the composite resin and the acidic group-containing radical polymerizable monomer in the primer, 0.01 to 10 parts by mass, particularly It is preferable to set it as the range of 0.02-5 mass parts.

(C) Photopolymerization initiator In the present embodiment, as the photopolymerization initiator contained in the composite resin, a compound that generates a radical capable of being polymerized by light irradiation is suitably used. Examples of such photopolymerization initiators include α-ketocarbonyl compounds and acyl phosphine oxide compounds.

  Examples of the α-ketocarbonyl compound include α-diketone, α-ketoaldehyde, and α-ketocarboxylic acid ester. Specifically, diacetyl, 2,3-pentadione, 2,3-hexadione, benzyl, 4,4′-dimethoxybenzyl, 4,4′-diethoxybenzyl, 4,4′-oxybenzyl, 4,4 ′ -Α-diketones such as dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, camphorquinonesulfonic acid ester, camphorquinonecarboxylic acid ester or 1,2-cyclohexanedione, methylglyoxal or phenylglyoxal Α-ketoaldehyde such as methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate or butyl phenylpyruvate, and the like.

  Among these α-ketocarbonyl compounds, α-diketones are preferably used from the viewpoint of stability and the like, and among the α-diketones, diacetyl, benzyl or camphorquinone is particularly preferable.

  Examples of the acylphosphine oxide compound include benzoyldimethoxyphosphine oxide, benzoylethoxyphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphineoxy or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  As these photopolymerization initiators, it is particularly preferable to use an acyl phosphine oxide compound which exhibits a polymerization promotion effect by a tertiary amine compound as a polymerization accelerator and has a sufficiently high polymerization initiation effect by itself. Moreover, it is preferable that the compounding quantity of a photoinitiator shall be the range of 0.01-5 weight part with respect to 100 mass parts of acidic group non-containing radical polymerizable monomers in a composite resin.

  Furthermore, if the dental filling / restoration kit according to the present embodiment is combined with a photopolymerization initiator and a photoacid generator, the polymerization activity can be further increased. As the photoacid generator, those that generate Bronsted acid or Lewis acid by light irradiation are preferably used.

  Examples of such photoacid generators include halomethyl group-substituted s-triazine derivatives, diaryliodonium salt compounds, sulfonium salt compounds, and pyridinium salt compounds. Among these photoacid generators, halomethyl group-substituted s-triazine derivatives or diaryliodonium salt compounds can be suitably used.

  Examples of the halomethyl group-substituted s-triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl- 4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s Triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloro Ethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (o-methoxystyryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -4,6-bis (tri (Loromethyl) -s-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Examples of the diaryliodonium salt compound include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) iodonium, p-tert- Chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexabutylphenylphenyliodonium, methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, 4-isopropylphenyl-4-methylphenyliodonium, etc. Examples include fluoroantimonate, tetrakis (pentafluorophenyl) borate, trifluoromethanesulfonate, etc. Tetrafluoroborate from the point, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethane sulfonate, tetrakis (pentafluorophenyl) borate salts are preferably used.

  You may use the above-mentioned photo-acid generator 1 type or in mixture of 2 or more types. The blending amount of these photoacid generators is not particularly limited as long as the effect is exhibited, but is 0.001 to 12 weights with respect to 100 parts by weight of the radical polymerizable monomer contained in the composite resin. Part is preferable, and the blending of 0.005 to 6 parts by weight is more preferable.

  In the present embodiment, the dental filling / restoration kit can obtain a high adhesive strength by one light irradiation without containing a photopolymerization initiator in the primer. By containing a photopolymerization initiator, a higher polymerization promoting effect can be obtained. Even when a photopolymerization initiator is contained in both the composite resin and the primer, the same compounds as described above can be used as the photopolymerization initiator. Moreover, the suitable compounding quantity is 0.01-5 weight part with respect to 100 mass parts of acidic group containing radically polymerizable monomers in a primer.

(D) Basic inorganic material In the present embodiment, the basic inorganic material contained in the composite resin improves the strength of the composite resin and also enhances the polymerization promoting effect of the tertiary amine compound during polymerization. Added. The basic inorganic material is usually contained in an amount of 3 parts by mass or more with respect to 100 parts by mass of the acidic group-free radical polymerizable monomer contained in the composite resin. The amount of the basic inorganic material is particularly preferably 5 to 80 parts by mass, and most preferably 8 to 30 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer contained in the composite resin. When the amount of the basic inorganic material is 3 parts by mass or more, a sufficient effect of promoting the polymerization of the tertiary amine compound at the time of polymerization can be obtained.

As the basic inorganic material in the present embodiment, those showing a high basicity when measured by the following method are usually used. That is, by adding phosphoric acid dropwise to a solution in which distilled water and ethanol are mixed at a volume ratio of 1: 1 in a beaker having a bottom area of 706.5 mm ^{2 in} the inner space, the pH is 2.50 ± 0.00 at 23 ° C. The dispersion immediately after adding 1.0 g of a basic inorganic compound to 20 g of the acidic solution adjusted to 03, and stirring at 23 ° C. for 2 minutes at a rotation speed of 200 rpm using a stirring bar having a diameter of 8 mm and a length of 20 mm The pH value at 23 [deg.] C. shows a pH value difference value higher by 0.05 or more than that containing no basic inorganic compound. The pH may be measured with a pH meter using a glass electrode using a potassium chloride solution.

  The basic inorganic material contained in the composite resin also has a function as a filler. Therefore, in the present embodiment, (A) the filling / restoring material includes “(a) an acid group-free radical polymerizable monomer, (b) a tertiary amine compound, (c) a photopolymerization initiator, ( d) Basic inorganic material and (e) containing filler ”, but specifically speaking, it is roughly divided into the following two types.

<First filling restoration material>
(A) acidic group-free radical polymerizable monomer, (b) tertiary amine compound, (c) photopolymerization initiator, and (d, e) basic inorganic material (the basic inorganic material is a filler) Also serves as a).
<Second filling restoration material>
(A) an acid group-free radical polymerizable monomer, (b) a tertiary amine compound, (c) a photopolymerization initiator, and (d, e) an inorganic filler excluding a basic inorganic material, an organic filler, and A mixed filler component comprising at least one filler selected from inorganic-organic composite fillers and a basic inorganic material is included.

  In the second filling / restoring material, the proportion of the basic inorganic material in the mixed filler component is preferably 0.5% by mass or more and 70% by mass or less, and more preferably 1.0% by mass or more and 50% by mass or less. By setting the ratio of the basic inorganic material in the mixed filler component to 0.5% by mass or more, the effect of promoting the polymerization of the tertiary amine compound during the polymerization can be reliably ensured.

The inorganic compound that can be used as the basic inorganic material is not particularly limited as long as the above-mentioned conditions are satisfied, but preferably, an oxide or hydroxide of Group I, II, or III, fluoride, carbonate, silicate or It can be selected from a mixture or complex salt thereof. The more preferable pH difference value is 0.10 to 4.50 from the viewpoint of storage stability, more preferably 0.10 to 2.00, and most preferably 0.15 to 1.00. Further, from the viewpoint of adhesive strength, an inorganic base material capable of eluting divalent or higher polyvalent metal ions is more preferable, and a basic inorganic material capable of eluting trivalent or higher polyvalent metal ions (trivalent or higher metal ion eluting properties). Basic inorganic materials) are most preferred. However, in the dental filling / restoration kit of the present invention, the basic inorganic material used as an essential component is a trivalent or higher metal ion-eluting basic inorganic material having a pH value difference value of 0.05 or more represented by formula (1). It is.

  Specific examples of typical basic inorganic materials include alumina, calcia, magnesia and the like as oxides. Examples of the hydroxide include hydroxides such as calcium hydroxide, magnesium hydroxide, and strontium hydroxide. Examples of the fluoride include sodium fluoride and calcium fluoride. Examples of the carbonate include Examples thereof include calcium carbonate, magnesium carbonate, and strontium carbonate. Examples of the silicate include calcium silicate, aluminum silicate, fluoroaluminosilicate glass, and other silicate glasses. Among these, metal ion-eluting basic inorganic materials such as calcium ions and aluminum ions can be preferably used. In particular, a trivalent or higher valent metal ion-eluting basic inorganic material is preferable, and it is most preferable to use fluoroaluminosilicate glass. This is because the polyvalent metal ions eluted from the fluoroaluminosilicate glass are ion-crosslinked with a polymer of a radical polymerizable monomer having an acidic group, thereby improving the adhesion to the tooth and the physical properties of the cured product. Because it can.

  As the fluoroaluminosilicate glass which can be suitably used, a known one used for dental cement, for example, glass ionomer cement can be used. The composition of commonly known fluoroaluminosilicate glasses is, in terms of ionic mass percent, silicon, 10-33; aluminum, 4-30; alkaline earth metal, 5-36; alkali metal, 0-10; 2-16; those of fluorine, 2-40 and residual oxygen are preferably used. More preferred compositional ranges include silicon, 15-25; aluminum, 7-20; alkaline earth metal, 8-28; alkali metal, 0-10; phosphorus, 0.5-8; fluorine, 4-40 and Remaining oxygen. What substituted some or all of the said calcium with magnesium, strontium, and barium is also preferable. The alkali metal is most commonly sodium, but it is also preferable to replace part or all of it with lithium, potassium or the like. If necessary, a part of the aluminum can be replaced with yttrium, zirconium, hafnium, tantalum, lanthanum, or the like.

  The shape of the basic inorganic compound that can be used in the present invention is not particularly limited, and may be pulverized particles or spherical particles obtained by normal pulverization. Can be mixed.

  In addition, the basic inorganic compound has an average particle size of 0.01 μm to 20 μm from the viewpoint of making the neutralization reaction with the acidic group-containing radical polymerizable monomer in the primer described later more rapid and not deteriorating operability. In particular, those in the range of 0.05 μm to 15 μm, more preferably 0.1 μm to 5 μm are most preferable.

  The above-mentioned basic inorganic material is treated with a surface treatment agent typified by a silane coupling agent, so that the affinity with the polymerizable monomer, the dispersibility in the polymerizable monomer, the mechanical properties of the cured product are increased. Strength and water resistance can be improved. The surface treatment agent and the surface treatment method are not particularly limited, and any known method can be employed without limitation. Silane coupling agents used for surface treatment of basic inorganic materials include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β -Methoxyethoxy) silane, [gamma] -methacryloyloxypropyltrimethoxysilane, [gamma] -chloropropyltrimethoxysilane, [gamma] -glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used. In addition to the silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a method using a zirco-aluminate coupling agent, or graft polymerization of the polymerizable monomer on the filler particle surface. Depending on the method, the surface treatment of the basic inorganic material can be performed.

(E) Filler In this Embodiment, the filler contained in a composite resin is added in order to improve the intensity | strength of a composite resin and to suppress the shrinkage | contraction at the time of superposition | polymerization. Further, the viscosity (operability) before the composite resin is cured can be adjusted by the addition amount of the filler. The filler is preferably contained in the range of 80 to 2000 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer contained in the composite resin. A particularly preferable amount of the filler is 90 to 500 parts by mass, and more preferably 100 to 230 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer contained in the composite resin. When the amount of the filler is 80 parts by mass or more, sufficient strength as a composite resin is obtained, and when it is 2000 parts by mass or less, the viscosity does not become too high, and the operability of the operation of filling the composite resin is improved. improves. Moreover, it is more preferable to add a filler to the primer because the adhesive strength becomes stronger. As the filler, one or more selected from inorganic fillers, organic fillers, and inorganic-organic composite fillers can be used as appropriate. Moreover, the inorganic filler can use suitably 1 or more types selected from basic inorganic material and inorganic fillers other than basic inorganic material.

  Specific examples of the organic filler used in the present invention include polymethyl (meth) acrylate, polyethyl (meth) acrylate, methyl (meth) acrylate / ethyl (meth) acrylate copolymer, methyl (meth) acrylate / butyl ( Non-crosslinkable polymer such as (meth) acrylate copolymer or methyl (meth) acrylate / styrene copolymer, methyl (meth) acrylate / ethylene glycol di (meth) acrylate copolymer, methyl (meth) acrylate / triethylene A (meth) acrylate polymer such as a glycol di (meth) acrylate copolymer or a copolymer of methyl (meth) acrylate and a butadiene monomer can be used. A mixture of two or more of these can also be used.

  As the kind of the inorganic filler used in the present invention, the above-mentioned basic inorganic material can be used. In addition, other known materials can be appropriately selected and used. Examples thereof include quartz, silica, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Two or more of these may be used in combination.

  In addition, some inorganic fillers other than the basic inorganic material have a strong acid point on the surface, and the above-mentioned tertiary amine may be adsorbed. Therefore, as an inorganic filler other than the basic inorganic material, an inorganic filler that does not exhibit a bluish purple color due to 4-phenylazodiphenylamine, which is an acid-base indicator, in anhydrous toluene is preferable.

  Here, the measurement of the acid point using 4-phenylazodiphenylamine may be performed according to a conventional method, but is usually performed by the following method. That is, first, after the filler was dried at 100 ° C. for 3 hours or longer, stored in a desiccator containing nitric pentoxide, 1 g of the filler was placed in a sample tube bottle, and then 3 g of anhydrous toluene was added and shaken vigorously. Disperse so that there is no aggregate. After dispersion, a drop (approximately 0.016 g) of an anhydrous toluene solution of 0.004 mol / l 4-phenylazodiphenylamine stored under shading is added to the sample tube bottle, and after shaking in the same manner, a blue-violet color is visually observed. Judgment should be made.

  Moreover, an inorganic-organic composite filler can also be used suitably. For example, a granular organic-inorganic composite filler can be obtained by adding a polymerizable monomer to an inorganic filler in advance, forming a paste, polymerizing, and pulverizing. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) can be used.

  The above-mentioned inorganic filler or inorganic-organic composite filler is treated with a surface treatment agent typified by a silane coupling agent, so that it has affinity with a polymerizable monomer, dispersibility in the polymerizable monomer, and curing. The mechanical strength and water resistance of the body can be improved. The surface treatment agent and the surface treatment method are not particularly limited, and the same silane coupling agent used for the surface treatment of the above basic inorganic material may be employed.

  The refractive index of the filler described above is not particularly limited. Therefore, those having a refractive index in the range of 1.4 to 2.2 are preferably used for general dental applications. Moreover, there is no restriction | limiting in particular also about a shape or a particle diameter. The shape or particle size is appropriately selected and used, but the average particle size is usually 0.001 to 100 μm, and particularly preferably 0.001 to 10 μm. Among the fillers described above, it is particularly preferable to use a spherical inorganic filler since the surface smoothness of the obtained cured product is increased and an excellent repair material can be obtained.

(F) Acidic group-containing radical polymerizable monomer The acidic group-containing radical polymerizable monomer contained in the primer of the dental filling / restoration kit according to the present embodiment has at least one acidic group and 1 in one molecule. The compound is not particularly limited as long as it is a compound having one radical polymerizable unsaturated group, and a known compound can be used. Such acidic group-containing radical polymerizable monomer is preferably contained in an amount of 10 parts by mass or more in 100 parts by mass of the radical polymerizable monomer contained in the primer, and the radical polymerizable monomer 100 contained in the primer. It is more preferable that 30 parts by mass or more of the acidic group-containing radical polymerizable monomer is contained in the part by mass. Examples of the acidic group include a carboxyl group, a sulfo group, a phosphone group, a phosphoric acid monoester group, and a phosphoric acid diester group. Among them, a carboxyl group, a phosphoric acid monoester group, or a phosphoric acid diester group is more preferable as the acidic group having high adhesiveness to the tooth. Furthermore, for the purpose of activating the movement of the material between the composite resin and the primer, in order to make the pH gradient between the composite resin and the primer more steep, the acidic group-containing radical polymerizable monomer contained in the primer The acidic group of the body is most preferably strongly acidic. As such a strongly acidic acidic group, a phosphoric acid monoester group or a phosphoric acid diester group is most preferable.

  More specific examples of such acidic group-containing radical polymerizable monomers include 2- (meth) acryloyloxyethyl hydrogen maleate, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (Meth) acryloyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxyethyl-1,1-undecanedicarboxylic acid, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-( 3,4-dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid Carboxylic acid acidic radical polymerizable monomers such as 2- (meth) acryloyloxyethyl Phenyl hydrogen phosphate, bis ((meth) acryloyloxyethyl) hydrogen phosphate, (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxy Phosphoric acid group-containing radical polymerizable monomers such as hexyl dihydrogen phosphate; Phosphonic acid group-containing radical polymerizable monomers such as vinylphosphonic acid; Styrene sulfonic acid, 3-sulfopropane (meth) acrylate And sulfonic acid acidic group-containing radical polymerizable monomers such as 2- (meth) acrylamide-2-methylpropanesulfonic acid. Moreover, these acidic group-containing radically polymerizable monomers may be used in combination of two or more if necessary.

  In addition, the primer may contain a monomer not containing an acidic group. As the acid group-free polymerizable monomer, the above-mentioned acid group-free and water-soluble radical polymerizable monomer, or acid group-free and water-insoluble radical polymerizable monomer can be used. . In particular, when the primer contains a non-acidic group-free and water-soluble radical polymerizable monomer, the primer has penetrability with respect to the tooth, and the acid group-free and water-insoluble radical polymerizable monomer. It is preferable because the compatibility of the body with water is improved. On the other hand, when the primer contains an acid group-free and water-insoluble radical polymerizable monomer, the polymerizable monomer causes phase separation from water, and a polymerization initiator from the composite resin. There is a risk of hindering the entry. Therefore, the content of the acid group-free and water-insoluble radical polymerizable monomer in the primer is preferably 5 parts by mass or less in 100 parts by mass of the radical polymerizable monomer, and more than 5 parts by mass is blended. Is preferably used in combination with an acid group-free and water-soluble radical polymerizable monomer.

(G) Water Water contained in the primer of the dental filling / restoration kit according to the present embodiment has a function of assisting decalcification of the tooth by the acidic group-containing radical polymerizable monomer. Water is preferably contained in an amount of 5 to 300 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer contained in the primer, and in particular, 15 parts per 100 parts by mass of the radically polymerizable monomer contained in the primer. More preferably, ~ 200 parts by weight of water is included.

  In order to further improve the operability of the primer, the primer may contain a hydrophilic organic solvent having fluidity. For example, a solvent such as acetone, ethanol, isopropyl alcohol, or tertiary butanol may be contained. In particular, a solvent having high volatility and low toxicity such as acetone, ethanol, or isopropyl alcohol is preferably used because it can be easily dried later. The content of the hydrophilic organic solvent is preferably 20 to 400 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer contained in the primer, and the more preferable content of the hydrophilic organic solvent is contained in the primer. It is 50-300 mass parts with respect to 100 mass parts of radical polymerizable monomers.

  The primer may contain a filler in order to increase the strength of the cured primer layer. For example, the inorganic filler, organic filler, or inorganic-organic composite filler described above may be included. Among these, it is preferable to use an abasic inorganic filler. The blending amount of the filler is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer contained in the primer, and the more preferred blending amount of the filler is the radical polymerizable single amount contained in the primer. It is 1-30 mass parts with respect to 100 mass parts of bodies.

  In the embodiment, it is preferable that a vanadium compound is blended in the primer and a hydroperoxide which is an organic peroxide is blended in the composite resin.

  The vanadium compound used for the primer in the present embodiment is a + IV and / or + V vanadium compound. By blending a + IV and / or + V vanadium compound in the primer, an acidic radical-containing radical polymerizable monomer in the primer and an organic peroxide in the composite resin described later on the adhesive interface and inside the primer. A radical polymerization reaction is caused with a certain hydroperoxide, and the adhesiveness between the composite resin and the primer can be made extremely good.

  The vanadium compound has an oxidation number ranging from −I to + V. However, it is particularly preferable to use a + IV or + V valent vanadium compound because the vanadium compound used in the present invention has high stability and activity. Any known compound can be used as the + IV or + V vanadium compound without limitation. Specific examples include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) Examples of vanadium compounds such as vanadium (IV), oxovanadium (IV) bismaltolate, vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V), vanadium (V) oxytriisopropoxide, etc. It is done. Of these, vanadium oxide acetylacetonate (IV), oxovanadium (IV) bismaltolate, and vanadium (V) oxytriisopropoxide are preferable from the viewpoint of solubility in primers, and oxovanadium (IV) bismaltolate is most preferred. preferable.

  These + IV or + V valent vanadium compounds may be used in combination. In the following, for convenience, when referred to as a vanadium compound, a + IV or + V valent vanadium compound is indicated.

  The blending amount of the vanadium compound in the primer of the present embodiment is not particularly limited, but in order to obtain high adhesion, a larger blending amount is preferable, while a smaller blending amount is storage stability. Therefore, the amount is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total polymerizable monomer in the primer.

  The hydroperoxide used for the composite resin in the present embodiment is not particularly limited, and any known one can be used without any limitation. Representative hydroperoxides include parameter hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl. A hydroperoxide etc. are mentioned.

  Hydroperoxide may be appropriately selected and used depending on the structure and blending amount of the acid group-free radical polymerizable monomer in the composite resin, the acid group-containing radical polymerizable monomer in the primer, or the vanadium compound. From the viewpoint of permeability to the primer, paraffin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide are preferred, and 1,1,3 , 3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide are preferred. Of these, 1,1,3,3-tetramethylbutyl hydroperoxide is most preferred because of its relatively low volatility.

  In addition, you may use these hydroperoxides individually or in combination of 2 or more types as needed.

  The blending amount of hydroperoxide is not particularly limited, and may be appropriately determined depending on the type, blending amount, and blending ratio of other components of the non-acidic group-containing radical polymerizable monomer in the composite resin. Is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the acid group-free radical polymerizable monomer constituting the composite resin. It mix | blends in 5 mass parts.

  Furthermore, in the dental filling / restoration kit according to the present embodiment, a coloring material such as a pigment or a fluorescent pigment can be blended to match the color tone of the tooth or gum. Further, an ultraviolet absorber may be added to prevent discoloration with respect to ultraviolet rays. Furthermore, it is also preferable to add a polymerization inhibitor in order to improve storage stability. Moreover, you may add a stabilizer or a disinfectant.

  The usage method of the primer of the dental filling / restoration kit according to the present embodiment is not particularly limited. In general, since the primer has good fluidity, a method of applying to the cavity or spraying to the cavity with a brush, a spatula, a brush, a roller or the like can be employed. The primer may be applied a plurality of times. Moreover, when it is necessary to use an etching agent separately, you may use before apply | coating a primer.

  After the primer is applied or sprayed onto the cavity, it is preferably dried to evaporate excess moisture and solvent. As a drying method, for example, there are natural drying, heat drying, air drying, vacuum drying, or a combination of these drying methods. In consideration of drying in the oral cavity, an air gun that emits dry air is used. It is preferable to air dry.

  Next, a composite resin is placed on the dried primer to fill the cavity. At this time, the usage of the composite resin is not particularly limited. Generally, it is arranged with a spatula or the like and arranged in the same shape as an actual tooth. Finally, the primer and the composite resin in the filling and repairing part can be cured by irradiating the filling and repairing part with visible light using a dental light irradiation machine.

  In addition, the packaging form of the dental filling / restoration kit according to the present embodiment is not particularly limited. However, since the operation is simpler, each is packaged in the same container and is a single paste composite resin. And more preferably packaged as a one-part primer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples. The compositions of the prepared composite resins are shown in Tables 2 and 3, and the compositions of the prepared primers are shown in Tables 4 and 5, respectively. In addition, Table 6, Table 7 and Table 8 show the composition of the dental filling / restoration kit, the initial adhesion test result, and the adhesion durability test result of the filled portion in each Example and each Comparative Example, respectively.

  First, the compounds and their abbreviations used in Examples and Comparative Examples, the measurement method of the initial adhesion test between the tooth and the composite resin, the preparation method of the composite resin, and the preparation method of the primer will be described.

(1) Compounds used and their abbreviations [acidic group-containing radical polymerizable monomer]
“PM”: Mixture “MDP” in which 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate are mixed at a mass ratio of 2: 1 “MDP”: 10-methacryloxydecyl dihydro Genphosphate “MAC-10”: 11-methacryloyloxy-1,1-undecanedicarboxylic acid

[Radical polymerizable monomer containing no acidic group]
“D-2.6E”: 2,2′-bis (4- (methacryloxyethoxy) phenyl) propane “BisGMA”: 2,2′-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl ] Propane "3G": Triethylene glycol dimethacrylate

[Acid-group-free and water-soluble radical polymerizable monomer]
“HEMA”: 2-hydroxyethyl methacrylate “14G”: polyethylene glycol (degree of polymerization 14) dimethacrylate (structural formula of Chemical Formula 4)
“BPE-1300”: ethoxylated bisphenol A dimethacrylate (the structural formula of Chemical Formula 5)

[Volatile water-soluble organic solvent]
“IPA”: isopropyl alcohol acetone

[Tertiary amine]
“DMBE”: ethyl p-N, N-dimethylaminobenzoate “TMPT”: N, N-dimethyl-p-toluidine “DMEM”: N, N-dimethylaminoethyl methacrylate

[Photopolymerization initiator]
“CQ”: camphorquinone “BN”: benzyl “TPO”: 2,4,6-trimethylbenzoyldiphenylphosphine oxide “BTPO”: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Polymerization inhibitor]
“HQME”: Hydroquinone monomethyl ether “BHT”: 2,6-di-t-butyl-p-cresol

[Basic inorganic compounds]
“AO”: Alumina powder (average particle size 0.02 μm)
“ FNa ”: sodium fluoride (average particle size: 4.0 μm)
“CS”: calcium silicate (average particle size 5.0 μm)
“MF”: fluoroaluminosilicate glass powder (Tokuso Ionomer, manufactured by Tokuyama Corporation) was pulverized to a mean particle size of 0.5 μm using a wet continuous ball mill (New My Mill, manufactured by Mitsui Mining Co., Ltd.) Then, the filler surface was modified for 20 minutes with 20 g of 5.0 N hydrochloric acid per 1 g of pulverized powder.
(Average particle size: 0.5 μm, amount of ions eluted for 24 hours: 27 meq / g filler)

[Hydroperoxide]
“Perocta H”: 1,1,3,3-tetramethylbutyl hydroperoxide (compound of formula 6)
“Permenta H”: Paramentane hydroperoxide (compound of formula 7)
“Perbutyl H”: t-butyl hydroperoxide (compound of formula 8)

[Vanadium compounds]
“BMOV”: oxovanadium (IV) bismaltoate “VO (OPr) 3”: vanadium (V) oxytriisopropoxide

[Photoacid generator]
“IMDPI”: (compound of formula 9)
“TAZ”: (compound of formula 10)

[Other ingredients]
“F1”: spherical silica-zirconia (average particle size 0.4 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane, and spherical silica-titania (average particle size 0.08 μm) γ-methacryloyloxypropyl Mixture “F2” obtained by mixing with hydrophobized trimethoxysilane at a mass ratio of 70:30: fumed silica (average particle size 0.02 μm) surface-treated with methyltrichlorosilane

(2) Method for measuring adhesion strength of 0.5 mm-thick composite resin Cattle were slaughtered, and the bovine front teeth were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm is affixed to this plane, and a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm is placed at the center of the hole of the double-sided tape previously attached, A simulated cavity was formed by fixing the center of the paraffin wax hole together. A primer was applied to the simulated cavity and left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Furthermore, a composite resin is filled on the surface, and visible light is irradiated for 30 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Co., Ltd.) to obtain an adhesive test piece having a composite resin thickness of 0.5 mm. Produced.

  After the above-mentioned adhesion test piece was immersed in water at 37 ° C. for 24 hours, it was pulled at a crosshead speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation), and the tooth and the composite resin were Tensile bond strength was measured. The tensile bond strength between the tooth and the composite resin was measured for each of four test pieces for each example or each comparative example. The average value of the four times of tensile adhesive strength was used as the adhesive strength of the corresponding Example or Comparative Example.

(3) Method for measuring adhesive strength of 1.5 mm thick composite resin In the same manner as the method for measuring adhesive strength of 0.5 mm thick composite resin, instead of paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm, Using a paraffin wax having a hole having a thickness of 1.5 mm and a diameter of 8 mm, an adhesive test piece having a composite resin thickness of 1.5 mm was produced. And the adhesive strength was measured by the method similar to the adhesive strength measuring method of 0.5 mm thickness composite resin.

(4) Method for measuring adhesive strength of 2.5 mm thick composite resin In the same manner as the method for measuring adhesive strength of 0.5 mm thick composite resin, instead of paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm, An adhesive test piece having a composite resin thickness of 2.5 mm was prepared using paraffin wax having a hole with a thickness of 2.5 mm and a diameter of 8 mm. And the adhesive strength was measured by the method similar to the adhesive strength measuring method of 0.5 mm thickness composite resin.

(5) Basic measurement of inorganic compound Phosphoric acid is added to a solution in which distilled water and ethanol are mixed at a volume ratio of 1: 1, and a pH meter (main body: ion meter IM20E, electrode: GST-5721S, both at 23 ° C.) Toa DKK Co., Ltd.) was measured to prepare a dispersion medium for measurement. In a beaker having a bottom area of 706.5 mm ^{2 in} the inner space, 20 g of the dispersion and 1.0 g of a basic inorganic compound are placed, and at 23 ° C., a stirrer having a diameter of 8 mm and a length of 20 mm is used. The mixture was stirred with a stirrer at 200 rpm for 2 minutes. The pH of the dispersion immediately after stirring for 2 minutes was measured with a pH meter immersed in the liquid, and a value obtained by subtracting the pH value of the dispersion medium alone from the pH value of the dispersion at this time was defined as the pH difference. Table 1 shows measured values and pH differences in various inorganic base compounds.

(6) Method for measuring eluted ions 0.2 g of the above dispersion was weighed into a 100 ml sample tube and diluted to 1% by mass using IPA. This liquid was filtered with a syringe filter, and the presence or absence of elution of metal ions was confirmed using ICP (inductively coupled plasma) emission spectroscopic analysis.

(7) Preparation of composite resin For 6.0 g BisGMA, 3.0 g 3G and 1.0 g 14G, 0.05 g BTPO, 0.05 g DMBE, 0.01 g HQME and 0.003 g BHT was added and stirred in the dark until uniform, to form a matrix. The obtained matrix was mixed with 15.5 g of F1 and 8.0 g of AO in an agate mortar and degassed under vacuum to obtain a photocurable composite resin CR1 having a filler filling rate of 61.7%. Obtained. Other composite resins (CR2 to CR40) were prepared in the same procedure as shown in Tables 2 and 3.

(8) Preparation of primer 5.0 g of PM, 5.0 g of HEMA, 0.003 g of BHT and 10.0 g of distilled water were stirred in the dark until uniform to obtain primer P1. Other primers (P2 to P18) were prepared in the same procedure as shown in Tables 4 and 5.

  Using the composite resins and primers described in Table 6, Table 7, and Table 8, the dental filling and repair kits of each example were used, and the adhesion test was performed on each example and comparative example. The results are shown in Table 6, Table 7, and Table 8.

Comparative Examples A1 to A3, Examples 4 to 9, 11, Comparative Example A12, and Examples 13 to 13 using a composite resin containing an acidic group-free polymerizable monomer, a tertiary amine compound, and a basic inorganic material 28, Comparative Examples A29 to A31 and Examples 32 to 50 were measured. Moreover, in Comparative Examples A1-A3, Examples 4-9, 11, Comparative Example A12, and Examples 13-18, the same primer was used, and in Examples 19-28, the kind of primer was changed and measured. All the results showed good adhesive strength even when the thickness of the composite resin was large (1.5 mm) for both enamel and dentin. In Comparative Examples A29 to A31 and Examples 32 to 43, the same primer was used, and in Examples 44 to 50, the type of primer was changed for measurement. All the results showed good adhesive strength when the composite resin thickness was 2.5 mm for both enamel and dentin.

Comparative Examples A1 to A3, Examples 4 to 6
Measurements were made using composite resins having different types and contents of basic inorganic materials. The primer layer applied to the teeth is filled with a composite resin containing a tertiary amine compound and a basic inorganic material, so that the basicity is relatively high at the contact interface between the primer layer and the composite resin. Neutralization reaction occurs between the inorganic material and the acidic group of PM, which is an acidic group-containing radical polymerizable monomer in the primer layer, the acid of the acidic group is weakened, and the polymerization effect of the tertiary amine compound is enhanced. Can be increased. For this reason, not only the primer layer but also the polymerization of the composite resin in contact with the primer layer is easily completed. As a result, even when any basic inorganic material was used, stable adhesive strength was exhibited both when the thickness of the composite resin was 0.5 mm and when the thickness was 1.5 mm.

Examples 7-9, 11, Comparative Example A12
Measurement was performed using composite resins having different types of tertiary amine compounds and photopolymerization initiators. When any tertiary amine compound and photopolymerization initiator were used, stable adhesive strength was exhibited in both cases where the composite resin had a thickness of 0.5 mm and 1.5 mm. However, in Examples 8 and 9, since CQ and BN, which are α-diketone photopolymerization initiators, were used, the adhesive strength was slightly reduced as compared with the other examples.

Examples 13 and 14
Example 13 and Example 14 were evaluated in which the same composition ratio as in Comparative Example A1 was used and the type of the acid group-free and water-soluble radical polymerizable monomer was changed. Example 13 using a polyfunctional radical polymerizable monomer rather than Example 14 using HEMA which is a monofunctional radical polymerizable monomer as an acid group-free and water-soluble radical polymerizable monomer The adhesive strength was better regardless of the thickness of the composite resin. In particular, when the thickness of the composite resin was 1.5 mm, Example 13 had higher adhesive strength to dentin than Example 14.

Examples 15-17
The compositions of Comparative Example A1 were evaluated for Examples 15 to 17 in which the content ratio of the acidic group-free and water-soluble radical polymerizable monomer was changed. Example 16 and Example 17 containing an acid group-free and water-soluble radical polymerizable monomer are more preferable than Example 15 containing no acid group-free and water-soluble radical polymerizable monomer. The adhesive strength was good regardless of the thickness of the composite resin.

Example 18
Example 18 in which the filler content ratio was changed with the composition of Example 4 was evaluated. Good adhesive strength was exhibited regardless of the thickness of the composite resin.

Examples 24 and 25
Example 24, in which MF, which is a polyvalent metal ion-eluting filler, was added to the primer, and Example 25, in which surface-treated fumed silica and MF were added as inorganic fillers, were evaluated. As a result, in the test piece having a composite resin thickness of 0.5 mm, the adhesive strength to dentin was improved in Example 24 as compared with Example 20 in which MF was not added. Furthermore, Example 25 also improved the durability of adhesion to enamel and dentin. Further, in the test piece having a composite resin thickness of 1.5 mm, the adhesion strength to the enamel and dentin was improved in both Example 24 and Example 25 as compared with Example 20.

Examples 21-23
The evaluation was performed by changing the kind of the acid group-containing radical polymerizable monomer and the content of the acid group-free radical polymerizable monomer in the primer. As a result, Example 21 in which the acidic group of the acidic group-containing radical polymerizable monomer is a phosphate ester used MAC-10 in which the acidic group of the acidic group-containing radical polymerizable monomer is a carboxyl group. Compared with Example 22, the adhesive strength to the enamel was good regardless of the thickness of the composite resin. Further, Example 23 containing the radical polymerizable monomer not containing an acidic group had higher adhesive strength than Examples 21 and 22 regardless of the thickness of the composite resin.

Example 26
Example 26 was evaluated in which a photopolymerization initiator and two types of fillers were added to the primer. Compared to Example 20, Example 26, to which both a filler and a polymerization initiator were added, showed good adhesive strength almost the same as that of Example 25 described above, regardless of the thickness of the composite resin.

Example 27
Example 27 was evaluated in which an aromatic tertiary amine compound was included in the primer. In Example 27, the adhesion strength to enamel and dentin was improved regardless of the thickness of the composite resin.

Example 28
With the composition of Example 20, the adhesive strength when the composite resin thickness was 2.5 mm was evaluated for both enamel and dentin. Example 28 had low adhesion strength to enamel and dentin.

Comparative Example A29 to Comparative Example A31, Example 32
Measurements were made using composite resins having different basic inorganic material contents. As a result, as compared with Example 28, Comparative Example A29 to Comparative Example A31 and Example 32 included a composite resin containing hydroperoxide and a primer containing a vanadium compound. In a 5 mm test piece, the adhesion strength to enamel and dentin was improved. In Example 32 using FASG capable of eluting polyvalent metal ions, the adhesive strength was higher.

Examples 33-35
Measurement was performed using composite resins having different hydroperoxide contents. As a result, Example 35 containing a large amount of hydroperoxide had higher adhesive strength than Examples 33 and 34.

Examples 36-39
Measurement was performed using composite resins having different types of hydroperoxide and photopolymerization initiator. When any hydroperoxide and photopolymerization initiator was used, stable adhesive strength was exhibited when the composite resin had a thickness of 2.5 mm. However, in Examples 38 and 39, CQ and BN, which are α-diketone photopolymerization initiators, were used, respectively. Therefore, the adhesive strength was slightly reduced as compared with Examples 36 and 37.

Examples 40, 43
Examples 40 and 43 in which the filler content ratio was changed with the composition of the same acidic group-free radical polymerizable monomer were evaluated. As a result, good adhesive strength was exhibited.

Examples 41 and 42
Evaluation of Examples 41 and 42 having the same composition of a radical polymerizable monomer having no acidic group as in Example 40 and adding CQ which is a different kind of photoacid generator and α-diketone photopolymerization initiator. did. Since the α-diketone photopolymerization initiator is activated by the action of the photoacid generator, the primer and the composite resin can be bonded with good strength.

Examples 44 and 45
Measurement was performed using primers having different vanadium compound contents. As a result, compared with Example 32, Examples 44 and 45 containing a large amount of vanadium compound had higher adhesive strength than Example 32.

Examples 47, 48
Example 47, in which MF, which is a polyvalent metal ion-eluting filler, was added to the primer, and Example 48, in which surface-treated fumed silica and MF were added as inorganic fillers, were evaluated. As a result, in the test piece having a composite resin thickness of 2.5 mm, both Example 47 and Example 48 showed improved adhesion strength to enamel and dentin as compared to Example 46.

Examples 49, 50
Examples 49 and 50 in which the kind of the organic solvent was changed with the composition of the primer to which the photopolymerization initiator and two kinds of fillers were added were evaluated. As a result, good adhesive strength was exhibited.

Comparative examples B 1 and B 2
Comparative example in which the type of primer is changed using a composite resin that contains a radical polymerizable monomer that does not contain an acidic group and does not contain a tertiary amine compound and a basic inorganic material. B 1 and Comparative Example B 2 were evaluated. In Comparative Example B1 and Comparative Example B2 , compared with Comparative Example A3 and Example 27, when the composite resin thickness was 0.5 m, the respective adhesive strengths were not substantially changed. When the thickness was 1.5 mm, the respective adhesive strengths were greatly reduced.

Comparative examples B3 and B4
Comparison of different types of primers using a composite resin that contains an acid group-free radical polymerizable monomer, a tertiary amine compound, and no basic inorganic material. Example B3 and Comparative Example B4 were evaluated. In Comparative Example B3 and Comparative Example B4 , compared with Comparative Example A3 and Example 27, when the composite resin thickness was 0.5 m, the respective adhesive strengths were not substantially changed. When the thickness was 1.5 mm, the respective adhesive strengths were greatly reduced.

Comparative Example B 5
Comparison of different types of primers using a composite resin that contains a radical polymerizable monomer that does not contain an acidic group, a basic inorganic material, and no tertiary amine compound. Example B5 was evaluated. Comparative Example B 5, as compared to Example 27, the thickness of the composite resin 0.5 m, although each adhesive strength was not substantially changed, the thickness of the composite resin 1.5 mm, each adhesive The strength was greatly reduced.

Comparative Example B 6
Acidic group-containing radical polymerizable monomer using a composite resin containing a tertiary amine compound and a basic inorganic material was assessed for Comparative Example B 6 obtained by blending a primer having the same composition as in Example 27. As a result, first, when the thickness of the composite resin was 1.5 mm, the adhesive strength was greatly reduced as compared with the case where the thickness of the composite resin was 0.5 m. Moreover, the adhesive strength with respect to dentin was falling compared with Example 27 irrespective of thickness.

Comparative examples B7 and B8
As the radical polymerizable monomer, a composite resin containing a radical polymerizable monomer not containing an acidic group, containing a hydroperoxide, and not containing a tertiary amine compound and a basic inorganic material is used. Comparative Example B 7 and Comparative Example B 8 with different values were evaluated. Comparative Example B 7 and Comparative Example B 8, as compared to Example 32 and Example 47, the thickness of the composite resin 2.5 m, adhesive strength to enamel and dentin was reduced. In particular, the decrease in adhesion strength to dentin was significant.

Comparative examples B9 , B10
As a radical polymerizable monomer, a composite resin containing a radical polymerizable monomer that does not contain an acidic group, a hydroperoxide and a tertiary amine compound, and no basic inorganic material is used. Comparative Example B 9 and Comparative Example B 10 with different values were evaluated. Comparative Example B 9 and Comparative Example B 10, as compared to Example 32 and Example 47, the thickness of the composite resin 2.5 m, adhesive strength to enamel and dentin was reduced. In particular, the decrease in adhesion strength to dentin was significant.

Claims (6)

(A) radical polymerizable monomer containing no acidic group, (b) an aromatic tertiary amine compound having a pKa value of 7.0 or less , (c) a photopolymerization initiator, (d) the following formula (1) (A) a filling restoration material containing a trivalent or higher metal ion-eluting basic inorganic material having a pH value difference value of 0.05 or more and (e) a filler;
(F) a pretreatment material containing an acidic group-containing radical polymerizable monomer and (g) water;
And (B) the pretreatment material is applied, and the applied pretreatment material is directly filled into an uncured cavity. Filling repair kit.
Formula (1) pH value difference value = S (pH) -R (pH)
[In the above formula (1), S (pH) is phosphoric acid in a solution in which distilled water and ethanol are mixed at a volume ratio of 1: 1 in a beaker having a bottom area of 706.5 mm ^{2 in} the inner space. Was added dropwise to 20 g of an acidic solution adjusted to pH 2.50 ± 0.03 at 23 ° C., and 1.0 g of the trivalent or higher metal ion-eluting basic inorganic compound was added, and the length was 8 mm in diameter. The pH value at 23 ° C. of the dispersion S immediately after stirring for 2 minutes at a rotation speed of 200 rpm at 23 ° C. using a 20 mm stirrer is shown.
R (pH) represents the pH value at 23 ° C. of Dispersion R prepared in Dispersion S that does not contain the trivalent or higher metal ion-eluting basic inorganic compound. ] (A) the filling restorative material, the (a) to acidic group-free radically polymerizable monomer of 100 parts by weight of the (d) 3 or more valences of metal ions eluting basic inorganic materials at least 3 parts by weight The dental filling / restoration kit according to claim 1, comprising:   100 parts by weight of the (a) acidic group-free radical polymerizable monomer comprises (a1) 3 to 30 parts by weight of an acidic group-free and water-soluble radical polymerizable monomer. The dental filling / restoration kit according to claim 1 or 2. The dental filling / restoration kit according to any one of claims 1 to 3 , wherein the (d) trivalent or higher metal ion-eluting basic inorganic material is fluoroaluminosilicate glass. The dental filling / restoration kit according to any one of claims 1 to 4 , wherein the photopolymerization initiator (c) comprises an acyl phosphine oxide polymerization initiator. The dental treatment according to any one of claims 1 to 5 , wherein the (B) pretreatment material further comprises a vanadium compound, and the (A) filling restoration material further comprises a hydroperoxide. Filling repair kit.