JP2009215254A - Dental filling repairing kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental filling repair kit curing a pre-treating material and a filling repair material by light irradiation only once, further improving adhesive strength between a tooth and the filling repair material, hardly influencing the adhesive strength between the tooth and the filling repair material by thickness of the filling repair material, and exhibiting excellent aesthetic properties. <P>SOLUTION: The dental filling repair kit includes (A) the filling repair material containing (a) an acidic group-non-containing radically polymerizable monomer, (b) an amine compound containing (b1) an aliphatic amine compound and (b2) an aromatic tertiary amine compound, (c) a photopolymerization initiator, and (d) a filler, and (B) the pre-treating material containing (e) an acidic group-containing radically polymerizable monomer, and (f) water. The dental filling repair kit works such that by directly filling a cavity with the filling repair material (A) is directly filled in a cavity where the pre-treating material (B) has been applied and the applied pre-treating material is not cured. <P>COPYRIGHT: (C)2009,JPO&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 with each other, 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. Therefore, similarly, the adhesive force between the filling / restoring material and the pretreatment material is not yet sufficient from an actual clinical point of view, 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 this object, the present inventor has conducted extensive research, and as a result, after pretreatment using a radically polymerizable monomer containing an acidic group and a pretreatment material containing water, an aliphatic amine compound and an aromatic A filling restoration material containing an acid group-free radical polymerizable monomer to which an amine compound containing a tertiary amine compound was added was filled in the cavity and cured by irradiation with visible light. Even if the filling restorative material is polymerized by only one light irradiation, a stable and high adhesive force is developed between the tooth and the filling restorative material, and further, the adhesion between the tooth and the filling restorative material depends on the thickness of the filling restorative material. The present inventors have found that the force is hardly influenced and the filling / restoring material is difficult to be colored, thereby completing the present invention.

  In particular, the present invention provides (a) an acid group-free radical polymerizable monomer, (b1) an aliphatic amine compound and (b2) an aromatic tertiary amine compound (b) an amine compound, (c) (A) a filling restoration material containing a photopolymerization initiator and (d) a filler, and (e) a pretreatment material containing (e) an acidic group-containing radical polymerizable monomer and (f) water. (A) The filling / restoring material is a dental filling / restoring kit in which (B) the pretreatment material is applied and the applied pretreatment material is directly filled into the uncured cavity.

  According to the present invention, the pretreatment material and the filling material are filled by filling the restoration material containing an amine compound containing an aliphatic amine compound and an aromatic tertiary amine compound on the pretreatment material applied to the tooth. At the contact interface with the restoration material, a neutralization reaction occurs between the aliphatic amine compound having a relatively high basicity and the acidic group of the radically polymerizable monomer containing the acidic group in the pretreatment material. Is weakened, and a reduction in 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, at the interface between the filling / restoring material and the pretreatment material, movement of the radical polymerizable monomer to both occurs, and the two layers become compatible. At that time, since the amine compound containing the aliphatic amine compound and the aromatic tertiary amine compound is also transferred from the filling restoration material side to the pretreatment material side, it depends on the inclusion of the aromatic tertiary amine compound. The effect of promoting photopolymerization extends not only to the contact interface between the pretreatment material and the filling / restoring material, but also to the inside of the pretreatment material layer.

  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.

  Another embodiment of the present invention is a dental filling / restoration kit in which the (b1) aliphatic amine compound is an aliphatic tertiary amine compound.

  The effects of the present invention are easily manifested, and discoloration of the composite resin is unlikely to occur, so the use of an aliphatic tertiary amine compound increases the neutralization effect of acidic groups due to its relatively high basicity. In addition, the storage stability of the filling / restoring material can be further improved.

  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 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 restorative material is more difficult to peel off from the tooth.

  Another invention of the present invention is a dental filling / restoration kit in which (B) the pretreatment material further contains a photopolymerization initiator.

  When the dental filling / restoration kit having such a composition is employed, the photopolymerization of the pretreatment material and the filling / restoration material can be sufficiently advanced. Therefore, the adhesive force between the tooth and the filling restorative 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 and an amine compound containing an aliphatic amine compound and an aromatic tertiary amine compound, and the primer contains an acid group-containing radical polymerizable monomer. Contains the body.

(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 the amine compound described below, so the acidic group and the amine compound described below cause a neutralization reaction, and the amine in the composite resin immediately after the production of the composite resin. The effect of promoting the polymerization of the compound is reduced. On the other hand, if the composite resin does not contain an acidic group as in this embodiment, the neutralization reaction between the acidic group and the amine compound described below is performed before filling the composite cavity into the dental cavity. Do not wake up. Furthermore, since the composite resin contains an aliphatic amine having a relatively high basicity in addition to the aromatic tertiary amine having a high polymerization promoting effect, as shown in the present embodiment, after filling the composite resin, At the contact interface between the primer and the composite resin, the aliphatic amine is preferentially neutralized, and the aromatic tertiary amine that has not undergone the neutralization reaction enhances the polymerization promotion effect of the photopolymerization initiator inside the primer and composite resin. Can do. 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 radically 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 Examples thereof include fluorine-containing (meth) acrylates such as H, 6H-decafluorohexyl methacrylate and 1H, 1H, 7H-dodecafluoroheptyl methacrylate, and (meth) acrylates represented by the following formulas (a) to (g).

In addition, R < ¹ > in each said formula 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.

  Moreover, among the above-mentioned acidic group-free radical polymerizable monomers, bifunctional radical polymerizable monomers are preferable 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 added to move from the composite resin side to the primer side, so that the primer can be polymerized more efficiently. Will be able to.

  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, in order to suppress the water absorption and improve the adhesive strength between the tooth and the composite resin while facilitating the movement of the photopolymerization initiator, 100 parts by mass of the radical polymerizable monomer containing no acidic group is used. Of these, a composite resin containing 3 to 30 parts by mass of an acidic group-free and water-soluble radical polymerizable monomer is preferable. 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) Amine Compound In the present embodiment, the (b) amine compound includes (b1) an aliphatic amine compound and (b2) an aromatic tertiary amine compound. By using both of these types of amine compounds in combination, a much better bond strength can be obtained compared to the case of using only one of them. When the primer described below and the composite resin are brought into contact with each other, first, the intermediate is preferentially placed between the relatively basic aliphatic amine compound and the acidic group of the acidic group-containing radical polymerizable monomer in the primer described later. A sum reaction occurs. For this reason, the aromatic tertiary amine compound is less likely to cause a neutralization reaction with the acidic group, and can prevent the effect of promoting the polymerization from being reduced. Therefore, the aromatic tertiary amine compound can exhibit a sufficient polymerization promoting effect as a photopolymerization initiator.

(B1) Aliphatic amine compound In the aliphatic amine compound, all organic groups bonded to the nitrogen atom are aliphatic groups (however, they may have a substituent). The compound is preferably a highly basic aliphatic amine having a pKa value in a 25 ° C. water of the corresponding ammonium salt of 7 or more, preferably 7.5 or more. In the present embodiment, as the aliphatic amine compound, any of primary amines, secondary amines and tertiary amines can be used, but the primary and secondary amines are volatile. In addition to the problems such as the reduction in the expression of the effects of the present invention and the generation of odor, the composite resin may be discolored when subjected to air oxidation, especially for dental use. Non-problematic tertiary amines are preferably used.

  In this embodiment, specific examples of the aliphatic group bonded to the nitrogen atom described above include linear or branched groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and an i-butyl group. Examples include branched alkyl groups having 1 to 6 carbon atoms; groups having a carbon-carbon double bond such as ethenyl group (vinyl group), propenyl group, and allyl group. The substituent bonded to the aliphatic group is a hydroxyl group (the substituted aliphatic group includes 2-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 2,3-dihydroxypropyl group). A halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; an acyloxy group having 1 to 3 carbon atoms such as an acetyloxy group, an acryloyloxy group, or a methacryloyloxy group; a methoxy group, an ethoxy group, or a propyloxy group An alkoxyl group having 1 to 3 carbon atoms such as carbonyl group, carbonyloxy group, alkenyl group, or cyano group. Among them, an aliphatic group in which the carbon atom bonded to the nitrogen atom is a saturated carbon atom is preferable, and since the volatility is lower, the aliphatic group further has a hydroxy group or a methacryloxy group as a substituent. Is preferred.

  In this embodiment, specific examples of the aliphatic amine compound suitably used in the present invention include aliphatic amines such as ethanolamine, 2-ethylhexylamine, n-butylamine, n-hexylamine, and n-octylamine. Primary amine compounds; aliphatic secondary amine compounds such as diethanolamine, diethylamine, dibutylamine, diallylamine, diisopropylamine, di-2-ethylhexylamine, di-n-octylamine; triethylamine, tributylamine, triallylamine, N , N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzyl Examples include aliphatic tertiary amine compounds such as amine, dimethylethanolamine, diethylethanolamine, dipropylethanolamine, triethanolamine, tri (isopropanol) amine, tri (2-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. Furthermore, N, N-dimethylaminoethyl methacrylate, dimethylethanolamine, methyldiethanolamine, or triethanolamine is used because it is relatively hydrophilic and can be quickly neutralized with an acidic group-containing radical polymerizable monomer. Is particularly preferred.

  In the present embodiment, when the amount of the aliphatic amine compound described above is too small, a sufficient neutralizing effect is not exhibited. On the other hand, when the amount is too large, as described above, the strength of the cured filling restoration material decreases. In addition, the amine compound may be eluted from the cured filling restoration material, which is not desirable. Usually, 0.1 to 10 parts by weight, particularly 0.2 to 7 parts by weight, most preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the radically polymerizable monomer not containing an acidic group in the composite resin. The range of parts is preferred.

(B2) Aromatic tertiary amine compound The aromatic tertiary amine compound as a component used in combination with the aliphatic amine compound described above includes at least one aromatic group on the nitrogen atom of the amino group, An aromatic tertiary amine which is an amine compound having at most 2 aliphatic groups bonded thereto and has a pKa value of 6 or less in 25 ° C. water of the corresponding ammonium salt is preferable. 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 an alkyl group having 1 to 6 carbon atoms, and particularly an unsubstituted C 1 to 3 alkyl group. 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.

  These aromatic tertiary amines may be used alone or in combination of two or more compounds as necessary.

  In the present embodiment, the aromatic tertiary amine compound is generally added within a range of 0.1 to 10 times the photopolymerization initiator used. More preferably, 0.01 to 10 parts by weight, particularly 0.02 to 5 parts by weight, most preferably 0.2 to 3 parts by weight based on 100 parts by weight of the non-acidic group-containing radical polymerizable monomer in the composite resin. It is preferable to be in the range of parts by mass.

  In addition, as the aliphatic amine compound (b1) and the aromatic tertiary amine compound (b2), the compounds exemplified above can be used singly or in combination of two or more. It is preferable to use both together so that the mass ratio (b1) :( b2) is in the range of 3:97 to 97: 3, preferably 10:90 to 75:25, particularly 20:80 to 60:40. It is.

(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 the above-mentioned photopolymerization initiator, (b) an amine compound including an aliphatic amine compound (b1) and an aromatic tertiary amine compound (b2), particularly the latter aromatic tertiary amine compound (b2). It is particularly preferable to use an acyl phosphine oxide compound that exhibits a polymerization promoting effect 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.

  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 radically polymerizable monomers in a primer.

(D) 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, an inorganic filler, an organic filler, or an inorganic-organic composite filler can be appropriately used.

  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 a kind of the inorganic filler used in the present invention, a known one can be appropriately selected and used. For example, periodic groups I, II, III, IV, transition metals or their oxides or hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, silicates or mixtures or composite salts thereof Etc. can be selected.

Some inorganic fillers have a strong acid point on the surface, and the above-mentioned aliphatic amine may be adsorbed. Therefore, the inorganic filler is preferably an inorganic filler that does not exhibit a bluish purple coloration due to 4-phenylazodiphenylamine, which is an acid-base indicator, in anhydrous toluene.

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.

  Specific examples of typical inorganic fillers include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Furthermore, cation-eluting fillers such as hydroxides such as calcium hydroxide and strontium hydroxide, oxides such as zinc oxide, silicate glass, and fluoroaluminosilicate glass can also be suitably used. In particular, polyvalent metal ions eluted from fluoroaluminosilicate glass are ion-crosslinked with a polymer of a radical polymerizable monomer having an acidic group, thereby improving the adhesion to teeth and the physical properties of the cured product. Can do.

  Among the above-mentioned inorganic fillers, inorganic fillers composed of metal oxide particles such as silica, alumina or zirconia, or composite metal oxide particles such as silica-titania or silica-zirconia can be suitably used. Moreover, these can also be used in combination of 2 or more types.

  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. In addition, a material having a large number of strong acid points on the surface is preferable because it can satisfy the acid point measurement test using 4-phenylazodiphenylamine. 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 the surface treatment of inorganic fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxy). (Ethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-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 inorganic filler or the inorganic-organic composite filler can be performed.

  The refractive index of the filler mentioned above is not specifically 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. Further, 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.

(E) 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 comprises 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.

(F) 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 included 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. 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 300 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 50-150 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, inorganic fillers are preferably used, and it is particularly preferable to use fumed silica or fluoroaluminosilicate glass that can improve the adhesion to the tooth and the physical properties of the cured body. 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 1-40 mass parts with respect to 100 mass parts of bodies.

  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.

  Further, 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 1 paste of the composite resin and More preferably, it is packaged as a one-component 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 1 and 2, and the compositions of the prepared primers are shown in Table 3, respectively. Tables 4 and 5 show the compositions of the dental filling / restoration kits, the initial adhesion test results, and the adhesion durability test results of the filled parts in the examples and comparative examples, 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

[Aliphatic tertiary amine compounds]
“DMEM”: N, N-dimethylaminoethyl methacrylate “MDEOA”: N-methyldiethanolamine “TEOA”: triethanolamine

[Aliphatic secondary amine compound]
“DEOA”: Diethanolamine

[Aliphatic primary amine compound]
“EOA”: Ethanolamine

[Aromatic tertiary amine compounds]
“DMBE”: ethyl pN, N-dimethylaminobenzoate “TMPT”: N, N-dimethyl-p-toluidine

[Photopolymerization initiator]
“CQ”: camphorquinone “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

[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 “MF”: Fluoro Aluminosilicate 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.), and then 1 g of pulverized powder. The filler surface was modified with 20 g of 5.0N hydrochloric acid for 20 minutes.

(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 thereon, and a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Co., Ltd.) is used to irradiate visible light for 30 seconds 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) 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 DMEM, 0.05 g DMBE, 0.01 g HQME and 0.003 g of BHT were added, and the mixture was stirred until it became uniform in the dark to form a matrix. The obtained matrix and 16.3 g of F1 were mixed in an agate mortar and defoamed under vacuum to obtain a photocurable composite resin CR1 having a filler filling rate of 62%. Other composite resins (CR2 to CR23) were produced in the same procedure as shown in Tables 1 and 2.

(5) 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 P13) were prepared in the same procedure as shown in Table 3.

  A dental filling / restoration kit for each example was prepared using the composite resin and primer described in Table 4, and an adhesion test was conducted for each example. The results are shown in Table 4.

  Evaluation of Examples 1-27 using a polymerizable resin containing no acidic group and a composite resin containing an amine compound containing an aliphatic amine compound and an aromatic tertiary amine compound was performed. Moreover, in Examples 1-15, the same primer was used, and in Examples 16-27, the kind of primer was changed and evaluated. All the evaluation results showed good adhesive strength even when the thickness of the composite resin was large (1.5 mm) with respect to both enamel and dentin.

Examples 1-10
Evaluation was made using composite resins having different types and blending amounts of aliphatic amine compounds and aromatic tertiary amine compounds. By filling a composite resin containing an aliphatic amine compound and an aromatic tertiary amine compound on the primer layer applied to the tooth, the contact interface between the primer layer and the composite resin has a relatively high basicity. It is thought that the acid of the acidic group is weakened by the neutralization reaction between the aliphatic amine compound and the acidic group of PM which is a radical polymerizable monomer containing acidic group in the primer layer. The polymerization promoting effect of the group III tertiary amine compound can be enhanced. 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 aliphatic amine compound and aromatic tertiary amine compound were used, stable adhesive strength was obtained in both cases where the composite resin thickness was 0.5 mm and 1.5 mm. Indicated. However, in Example 5 and Example 6, an aliphatic primary amine compound and an aliphatic secondary amine compound were used, respectively, and in Example 7, CQ, which is an α-diketone photopolymerization initiator, was used. Since it was used, the adhesive strength was slightly reduced as compared with other examples.

Examples 11 and 12
Example 11 and Example 12 were evaluated in which the same composition ratio as in Example 1 was used and the kind of the radically polymerizable monomer not containing an acidic group and water-soluble was changed. BPE-1300, which is a polyfunctional radical polymerizable monomer, is used as a water-soluble radical polymerizable monomer that does not contain an acidic group, as compared with Example 9 using HEMA, which is a monofunctional radical polymerizable monomer. The used Example 11 had better adhesive strength regardless of the thickness of the composite resin. In particular, Example 11 had higher adhesion strength to dentin than Example 12.

Example 13
Example 13 in which the kind and composition of the radical group-free monomer containing no acidic group was changed was evaluated. Good adhesive strength was exhibited regardless of the thickness of the composite resin.

Examples 14-16
The compositions of Example 1 were evaluated for Examples 14 to 16 in which the content ratio of the acid group-free and water-soluble radical polymerizable monomer was changed. Example 15 and Example 16 containing an acid group-free and water-soluble radical polymerizable monomer are more preferred than Example 14 containing no acid group-free and water-soluble radical polymerizable monomer. The adhesive strength was good regardless of the thickness of the composite resin.

Examples 26 and 28
Example 26, in which MF, which is a polyvalent metal ion-eluting filler, was added to the primer, and Example 28, 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 26 as compared with Example 20 in which MF was not added. Furthermore, Example 28 also improved the durability of adhesion to enamel and dentin. In addition, 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 26 and Example 28 as compared with Example 20.

Examples 22-24
The evaluation was carried out by changing the type of acidic group-containing radical polymerizable monomer in the primer. As a result, Example 22 in which the acidic group of the acidic group-containing radical polymerizable monomer is a phosphoric ester has a part of MAC-10 in which the acidic group of the acidic group-containing radical polymerizable monomer is a carboxyl group. The adhesive strength was better than that of Example 23 used, regardless of the thickness of the composite resin. Further, Example 24 using only MAC-10 as the acidic group-containing radical polymerizable monomer had lower adhesive strength than Examples 22 and 23 regardless of the thickness of the composite resin.

Examples 27 and 29
Example 27 in which a polymerization initiator was contained in the primer and Example 29 in which a polymerization initiator and two kinds of inorganic fillers were added were evaluated. Compared to Example 20, Example 27 improved the adhesion strength to dentin regardless of the thickness of the composite resin. In addition, Example 29 to which both the inorganic filler and the polymerization initiator were added showed good adhesive strength almost the same as that of Example 28 described above, regardless of the thickness of the composite resin.

Example 30
Example 30 in which an aromatic tertiary amine compound was included in the primer was evaluated. In the test piece having a composite resin thickness of 0.5 mm, Example 30 showed good adhesive strength almost the same as that in Example 29 described above, but the test piece having a composite resin thickness of 1.5 mm was obtained. Then, compared with Example 29, the adhesive strength with respect to dentin improved.

Comparative Examples 1 and 2
As the radical polymerizable monomer, a composite resin containing a radical polymerizable monomer containing no acidic group and not containing an aliphatic amine compound and an aromatic tertiary amine compound was used, and the type of primer was changed. Comparative Example 1 and Comparative Example 2 were evaluated. In Comparative Example 1 and Comparative Example 2, compared with Example 1 and Example 30, when the composite resin thickness was 0.5 m, the respective adhesive strengths hardly changed, but the composite resin thickness was 1 At .5 mm, the adhesion strength of each decreased significantly.

Comparative Examples 3 and 4
As the radically polymerizable monomer, a composite resin containing an acid group-free radically polymerizable monomer, an aromatic tertiary amine compound, and no aliphatic amine compound is used, and the type of primer is changed. Comparative Example 3 and Comparative Example 4 were evaluated. In Comparative Example 3 and Comparative Example 4, compared with Example 1 and Example 30, when the composite resin thickness was 0.5 m, the respective adhesive strengths hardly changed, but the composite resin thickness was 1 At .5 mm, the adhesion strength of each decreased significantly.

Comparative Examples 5 and 6
As the radical polymerizable monomer, a composite resin containing an acid group-free radical polymerizable monomer, an aliphatic tertiary amine compound, and no aromatic tertiary amine compound is used. Comparative Example 5 and Comparative Example 6 with different values were evaluated. In Comparative Example 5 and Comparative Example 6, compared with Example 1 and Example 30, when the composite resin thickness was 0.5 m, the respective adhesive strengths were hardly changed, but the composite resin thickness was 1 At .5 mm, the adhesion strength of each decreased significantly.

Comparative Example 7
Comparison in which a primer having the same composition as Example 30 was blended using an acidic group-containing radical polymerizable monomer and a composite resin containing an amine compound containing an aliphatic amine compound and an aromatic tertiary amine compound. Example 7 was evaluated. 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 30 irrespective of thickness.

Comparative Example 8
As a radically polymerizable monomer, a composite resin containing an acidic group-free radically polymerizable monomer and containing an aromatic tertiary amine compound and not containing an aliphatic tertiary amine compound was used. Example 30 Comparative Example 8 in which a primer having the same composition as in Example 1 was blended was evaluated. As a result, when the thickness of the composite resin was 0.5 m, the adhesive strength was not greatly reduced, but when the thickness of the composite resin was 1.5 mm, the adhesive strength was greatly reduced.

  The present invention can be used in the field of dental treatment for repairing a missing tooth.

Claims (5)

(A) an acid group-free radical polymerizable monomer, (b1) an aliphatic amine compound and (b2) an aromatic tertiary amine compound (b) an amine compound, (c) a photopolymerization initiator, and ( d) a filling restorative material comprising a filler (A);
(E) an acid group-containing radically polymerizable monomer and (f) a pretreatment material containing water;
And (B) the pretreatment material is applied, and the applied pretreatment material is directly filled into an uncured cavity. Filling repair kit. The dental filling / restoration kit according to claim 1, wherein the (b1) aliphatic amine compound is an aliphatic tertiary amine compound.   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 (c) photopolymerization initiator includes an acyl phosphine oxide polymerization initiator.   The dental filling / restoration kit according to any one of claims 1 to 4, wherein the pretreatment material (B) further comprises a photopolymerization initiator.