JP5305667B2 - Dental filling and repair kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tooth restoration material that is used by a simple operation, has excellent adhesiveness to dentin, excellently retains the excellent adhesiveness even in long-term preservation at a room temperature and hardly causes gelation etc. <P>SOLUTION: The dental filling restoration kit comprises: (A) a pretreatment agent containing (a) an acidic group-containing radically polymerizable monomer, (b) a transition metal compound of the fourth period and (c) a pretreatment agent containing water but not an amine compound; and (B) a filling restoration material which is composed of (d) an acid group-free radically polymerizable monomer, (e) an organic peroxide, (f) a photopolymerization initiator and (g) a silica-based inorganic filler, wherein the amount of the (g) the silica-based inorganic filler is 30-900 parts by mass based on 100 parts by mass of the acid group-free radically polymerizable monomer (d) and does not contain an aryl borate compound. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a filling / restoration kit for filling / restoring a tooth damaged by caries or the like in the field of dentistry.

  For the restoration of a tooth damaged by caries or the like, a curable filling / restoring material called a composite resin is used. In particular, for a caries having a relatively small cavity in the first and middle stages, a photo-curable composite resin is frequently used from the viewpoint of aesthetics, simplicity of operation and quickness.

  Such a composite resin usually comprises a polymerizable monomer, a filler, and a polymerization initiator. Conventionally, as the polymerizable monomer, a radical polymerizable monomer has been used because of its good polymerizability, and in particular, a (meth) acrylate radical polymerizable monomer has been often used. On the other hand, an inorganic filler, particularly a silica-based inorganic filler is often used as the filler.

  In the case of caries repair, adhesion between the tooth to be repaired and the composite resin is important. However, since the composite resin has almost no adhesion to the tooth, an adhesive is usually used. Such an adhesive material is cured in advance before being filled with the composite resin, thereby obtaining a high adhesive force. Among them, a photo-curing type adhesive is advantageously used because higher adhesiveness can be obtained and it can be cured at an arbitrary timing.

  However, the dentine is mainly composed of an enamel made of an inorganic material and a dentin having a high organic content and a high water content, and it has been difficult to obtain a sufficient adhesive force for both of them only with an adhesive. Therefore, prior to the application of the adhesive, there has been a need to pre-treat the tooth with a pre-treatment material.

  Conventionally, as the pretreatment, a total of three stages of treatment including application of an aqueous acidic solution / washing / drying and application of a primer after application of two steps of primer application / drying have been performed. Such an operation is not only complicated, but also has a high possibility of causing an operation error, and thus simplification of the operation has been demanded. In order to meet this demand, in recent years, a simplified system that can dispense with acidic aqueous solution, radically polymerizable monomer called water and adhesive monomer, and can eliminate application, washing and drying of acidic aqueous solution ( Hereinafter, a two-stage processing system) has been proposed and put into practical use.

  For example, as an excellent adhesive to which such a two-stage treatment system is applied, (A) a radically polymerizable monomer containing an acidic group, a + IV and / or + V valent vanadium compound, and a pretreatment material containing water. An adhesive material containing (B) a radically polymerizable monomer having no acidic group, an aryl borate compound, an organic peroxide, and a photopolymerization initiator has been proposed (see Patent Document 1). This adhesive is also intended for the restoration of extremely damaged teeth such as crown collapse, so that it can be applied to places where light is difficult to reach, such as roots, by photopolymerization with a photopolymerization initiator. It is designed to be cured using not only curing but also chemical polymerization. That is, the polymerizable monomer contained in the pretreatment material has an acidic group, and a vanadium compound is also blended. On the other hand, the arylborate compound and the organic peroxide are contained in the adhesive material. When the pretreatment material is applied to the tooth surface and then the adhesive is applied thereon, the aryl borate compound and the organic peroxide in the adhesive are contained in the pretreatment material layer. And a quaternary radical polymerization initiator composed of each of these components is formed, and it is devised to achieve strong adhesion in the vicinity of the boundary between both layers. In this two-stage treatment system, the pretreatment material is preferably formulated with an amine compound in order to improve stability in long-term storage when it is in a one-pack packaging form. Most of the examples are formulated with such amine compounds. (Hereinafter, this adhesive is also referred to as “advanced adhesive for two-stage processing system” or simply “advanced adhesive”).

  Although the preceding adhesive material of the above-mentioned two-stage processing system has excellent adhesive force, in recent years, in such dental restoration, the demand for the ease of operation is further increased. In response to this requirement, the above-described method using the preceding adhesive material requires complicated operations for applying the pretreatment material and the adhesive material, and the adhesive layer formed in this way can be used before filling with the composite resin. It is necessary to make it harden, and in treatment with a composite resin, light irradiation must be carried out twice in the mouth (adhesive photocuring and composite resin photocuring). It became more and more.

  Under these circumstances, there has been proposed a bonding material in which a composite resin is applied without applying light after the adhesive is applied, and a composite resin kit containing an acidic group-containing radical polymerizable monomer. (See Patent Document 2). However, in such an embodiment, the adhesive strength of the composite resin to the enamel and dentin cannot be satisfied to the next level, and further, by containing an acidic group-containing radical polymerizable monomer to the composite resin, There was also a problem that the basic substance derived from food was easily adsorbed to the cured body, and the filling and repairing portion was easily colored.

JP 2004-043427 A JP 2006-131621 A

  In the background described above, the present inventors, in the preceding adhesive used in the two-stage treatment system having excellent adhesion, have a large amount of inorganic filler to the extent that it is blended with a composite resin in its composition. If this is used as a composite resin, since no radical-containing monomer containing an acidic group is used, the above problem of deterioration does not occur, and the We thought that it would be possible to develop a tooth restoration material that has both adhesiveness to the surface.

  Based on the above idea, the composite resin produced by adding a large amount of silica-based inorganic filler to the preceding adhesive is the same as that used in the two-stage treatment system (acid group-containing radical polymerizable monomer, + IV and / or + V vanadium compounds, and water) are required, but the use of adhesive is no longer necessary, and after the pretreatment material is applied to the tooth surface, By the operation of filling the composite resin and irradiating with light, it was possible to perform treatment with one light irradiation. Therefore, the operation is simple, and not only the curing of the composite resin by photopolymerization, but also the above-mentioned action by chemical polymerization of the pretreatment material layer is added, so that the adhesive strength to the tooth surface is the initial production of the composite resin. Was very expensive.

  However, further research has revealed that the excellent adhesiveness of the composite resin rapidly decreases when stored at room temperature or the like. Further, when the storage period was further extended, gelation and curing were likely to occur. Therefore, the prototype composite resin has room for improvement from the viewpoint of storage stability.

  In the above background, the present invention can be used in a simple operation, has excellent adhesion to the tooth, and can retain this excellent adhesion even after long-term storage at room temperature. The purpose of this study is to develop a tooth restoration material that is less likely to become fragile.

The present inventors have intensively studied to overcome the above problems. As a result, as a filling restoration material used in combination with the pretreatment agent,
(B) d) a radical polymerizable monomer having no acidic group, e) an organic peroxide, f) a photopolymerization initiator, and g) a silica-based inorganic filler, and g) The content is d) 30 to 900 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer having no acidic group, and the above-mentioned problem is solved by using a material that does not contain an aryl borate compound. The present inventors have found that the present invention can be accomplished and have completed the present invention.

That is, the present invention includes (A) a) an acidic group-containing radical polymerizable monomer, b) a transition metal compound in the fourth period, and c) a pretreatment agent containing water and not containing an amine compound,
(B) d) radical polymerizable monomer having no acidic group, e) organic peroxide, f) photopolymerization initiator, and g) silica or silica and a metal oxide of group 2-14. inorganic filler is a composite oxide comprising consist (hereinafter, silica-based inorganic filler also called), the g) radical polymerizable monomer 100 parts by mass of the content has no d) acidic group-free machine filler to It is a dental filling / restoration kit comprising 30 to 900 parts by mass and a filling / restoration material not containing an aryl borate compound.

  According to the dental filling / restoration kit of the present invention, (A) after treating the tooth with the pretreatment agent, (B) filling the filling restorative material directly on this and photocuring it, The cured body can be adhered to the tooth. Therefore, it is easy to operate, and its adhesive strength is sufficiently strong in both enamel and dentin compared to conventional composite resins that are used after applying adhesive and photocuring it. become. And this high adhesive force is satisfactorily maintained even when the filling / restoring material is stored at room temperature for a long time, gelation hardly occurs, and there is little discoloration after curing.

  Thus, in the dental filling / restoration kit of the present invention, the reason why the adhesive strength and the filling / restoring material have excellent storage stability is presumed as follows. That is, first, in the tooth restoration material applied on the pretreatment material, the organic peroxide contained therein elutes into the pretreatment material layer, and the transition metal compound contained in this layer and the organic treatment material are dissolved. The oxide reacts and functions as a radical polymerization initiator. As a result, the pretreatment material layer is cured by chemical polymerization, and strong adhesion near the boundary between the tooth restoration material and the cured body is achieved.

  In addition, when the amine compound is added to the pretreatment material as in the prior art, the above-described high adhesive strength cannot be obtained. This is presumably because the amine compound is coordinated with the transition metal in the transition metal compound, thereby reducing the activity of the transition metal compound.

  On the other hand, when an aryl borate compound is blended in the tooth restoration material, extremely high adhesive strength can be obtained as described above. However, in a curable composition in which a large amount of inorganic filler is blended, the aryl borate is selected depending on its acid point. Since the compound is activated and reacts gradually with the organic peroxide, the adhesive strength is reduced during storage at room temperature or the like, and gelation and curing are likely to occur during long-term storage. On the other hand, when an acidic group-containing radical polymerizable monomer is blended in the tooth restoration material, the acidic group and the organic peroxide in the acidic group-containing radical polymerizable monomer are not included even if the aryl borate compound is not included. Since the oxide reacts, as a result, the adhesive strength decreases with time. Therefore, in the present invention, since the aryl borate compound and the acidic group-containing radical polymerizable monomer are not blended in the filling / restoring material, such reduction or gelation of the organic peroxide hardly occurs. It is presumed that the storage stability will be excellent.

  The (A) pretreatment material used for the dental filling / restoration kit of the present invention comprises a) an acidic group-containing radical polymerizable monomer, b) a fourth-period transition metal compound, and c) water, and The composition does not contain an amine compound. Hereinafter, the (A) pretreatment material will be described.

  a) The acidic group-containing radical polymerizable monomer (hereinafter sometimes simply referred to as “acidic monomer”) is not particularly limited, and known radical polymerizable monomers having an acidic group can be used. Preferably, a compound in which an aqueous solution or aqueous suspension comprising 10 parts by mass of the monomer and 90 parts by mass of water has a pH of 4.5 or less, more preferably 4 or less is used.

Such an acidic monomer includes at least one acidic group in one molecule, or an acid anhydride structure in which two of the acidic groups are dehydrated or condensed, or an acid halide group in which the hydroxyl group of the acidic group is substituted with a halogen, and at least 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. Here, the acidic group refers to a group in which an aqueous solution or aqueous suspension of a radical polymerizable monomer having the group exhibits acidity. Examples of the acidic group include a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphinico group {═P (═O) OH}, a phosphono group {—P (═O) (OH) ₂ }, and the like. In addition, examples in which these groups are acid anhydrides or acid halides are exemplified.

  Also, the radically polymerizable unsaturated group is not particularly limited and may be any known group. Specifically, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, (meth) acryloylthio derivative group such as (meth) acryloyl group, vinyl group, allyl group, styryl group Etc. are exemplified.

  In the pretreatment material of the present invention, the acidic monomer has a decalcification effect on the tooth and a high permeability improvement effect on the tooth, and the adhesion of the filling restoration material to the tooth is good. Further, it acts to activate the reaction between a transition metal compound, which will be described later, and b) an organic peroxide blended in the filling restoration material.

  The acidic monomer is not particularly limited as long as it is a compound having at least one acidic group and radically polymerizable unsaturated group as described above. However, it is less polymerizable, easy to handle, easily available, and less harmful to living organisms. From the viewpoint, vinyl sulfonic acid, vinyl phosphonic acid, (meth) acrylic acid, or the following general formulas (1) to (3),

{In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C 2-30 divalent organic residue, W represents an oxygen atom, a sulfur atom or NH, and Z represents —COOH. , —SO ₃ H, —O—P (═O) (OH) ₂ , —P (═O) (OH) ₂ , or —O—P (═O) (OH) (OR ₃ ) [where R ₃ is an alkyl group having 1 to 10 carbon atoms in the main chain or an aryl group having 6 to 14 carbon atoms constituting the ring, and the alkyl group or aryl group includes a halogen atom, a hydroxyl group, a cyano group, a nitro group, An alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, or 2 to 2 carbon atoms 5 may be substituted with 5 acyloxy groups], m and n are each independently 1 to 1 An integer, m + n coincides with the valence of R _2}

{Wherein R ₁ ′ and R ₁ ″ each independently represents a hydrogen atom or a methyl group, and R ₂ ′ and R ₂ ″ each independently represent a C 1-30 divalent to hexavalent organic residue, W ′ and W ″ each independently represent an oxygen atom, a sulfur atom or NH, m ′ and m ″ each independently represent an integer of 1 to 5, (m ′ + 1) represents the valence of R ₂ ′, (M ″ +1) matches the valence of R ₂ ″. }

{In the formula, R ₄ represents a bond or a divalent organic residue having 1 to 20 carbon atoms, Z ′ represents —COOH, —SO ₃ H, —O—P (═O) (OH) ₂ , — P (═O) (OH) ₂ , or —O—P (═O) (OH) (OR ₃ ) [wherein R ₃ is a carbon constituting an alkyl group having 1 to 10 carbon atoms in the main chain or a ring. The number of the aryl group is 6 to 14, and the alkyl group or aryl group is a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number. 2-5 alkynyl group, C1-C5 alkoxyl group, C2-C5 acyl group, or C2-C5 acyloxy group may be substituted. Show. }
Or an acid anhydride obtained by dehydrating condensation within a molecule or between molecules can be preferably used.

In the general formula (1) or (2), R ₁ , R ₁ ′ and R ₁ ″ are a hydrogen atom or a methyl group, and W, W ′ and W ″ are each an oxygen atom, a sulfur atom or NH. Indicates.

In the general formula (1) or (3), Z and Z ′ are —COOH, —SO ₃ H, —O—P (═O) (OH) ₂ , —P (═O) (OH) ₂ , Or —O—P (═O) (OH) (OR ₃ ), wherein R ₃ is an alkyl group having 1 to 10 carbon atoms in the main chain or an aryl group having 6 to 14 carbon atoms constituting the ring, Preferably, the main chain is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms constituting a ring, and the alkyl group or aryl group includes a halogen atom, a hydroxyl group, a nitro group, a cyano group, An alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, or 2 to 2 carbon atoms It may be substituted with 5 acyloxy groups. Further, it may be substituted with a plurality of the same or different substituents.

Examples of the alkyl group having 1 to 10 carbon atoms in the main chain of R ₃ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, and an n-decyl group. Examples of the group substituted with the substituent include chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 6-hydroxy Hexyl group, 2-cyanoethyl group, i-propyl group, i-butyl group, t-butyl group, 1-methylpropyl group, 2-ethylhexyl group, 2-propenyl group, cis- or trans-2-butenyl group, 2 -Propynyl group, methoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxybutyl group, 3-oxabutyl group, 4-oxapentyl group Examples include 3-oxapentyl group, 2-acetyloxyethyl group, 3-acetyloxypropyl group, 2-propionyloxyethyl group, 3-acetyloxy-2-hydroxypropyl group, 2-ethyl-3-hydroxypentyl group, etc. Is done.

  Examples of the aryl group having 6 to 14 carbon atoms constituting the ring include a phenyl group, 1- or 2-naphthyl group, 1-, 2- or 9-anthranyl group, and the alkyl group is the substituent. O-, m- or p-chlorophenyl group, o-, m- or p-bromophenyl group, o-, m- or p-hydroxyphenyl group, 3-hydroxy-2-naphthyl group, o as substituted -, M- or p-nitrophenyl group, o-, m- or p-cyanophenyl group, o-, m- or p-methylphenyl group, o-, m- or p-butylphenyl group, 3, 4 -Dimethylphenyl group, 2,4-dimethylphenyl group, o-, m- or p-styryl group, o-, m- or p- (2-propynyl) phenyl group, o-, m- or p-methoxyphenyl A group, o-, m- or p-ethoxy Examples include nyl group, 2-, 3- or 4-acetylphenyl group, 2-, 3- or 4-acetyloxyphenyl group, 4-hydroxy-3-methylphenyl group, 4-methyl-2-nitrophenyl group, etc. Is done.

  Further, the pretreatment material used in the present invention has an acid anhydride structure in which these Z or Z ′ and acidic groups such as ═P (═O) —OH group in the general formula (2) are dehydrated and condensed. A compound can also be used suitably. When taking the acid anhydride structure, the compound represented by the general formula (1) or (3) may be dehydrated and condensed in the molecule, or the compound represented by the general formula (1) to (3) or Two molecules selected from vinyl sulfonic acid, vinyl phosphonic acid, and (meth) acrylic acid may be dehydrated and condensed between molecules. When an acid anhydride structure dehydrated and condensed between molecules is taken, it may be a compound having a structure in which the same acid is dehydrated or condensed, or a compound having a structure in which different acids are dehydrated and condensed. From the viewpoint of synthesis and availability, the compound having an acid anhydride structure is preferably a compound having a structure in which dehydration condensation is carried out within the molecule or a compound having a structure in which two identical acid molecules are subjected to dehydration condensation.

R ₂ , R ₂ ′ and R ₂ ″ in the above general formula (1) or (2) all represent a bivalent to hexavalent organic residue having 1 to 30 carbon atoms. The organic residue is not particularly limited. A known group may be used, and the structure may include a bond other than a carbon-carbon bond such as an ether bond, an ester bond, an amide bond, a sulfonyl bond, a urethane bond, and a thioether bond, and further a halogen atom, You may have a substituent which does not contain carbon atoms, such as a hydroxyl group, an amino group, a cyano group, and a nitro group.

  Specific examples of the organic residue include the following.

R ₄ in the general formula (3) represents a bond or a divalent organic residue having 1 to 20 carbon atoms. The organic residue is not particularly limited, and the structure may contain a bond other than a carbon-carbon bond such as an ether bond, an ester bond, an amide bond, a sulfonyl bond, a urethane bond, or a thioether bond, and further a halogen atom. And may have a substituent not containing a carbon atom such as a hydroxyl group, an amino group, a cyano group, or a nitro group. As the organic residue of the group is specifically exemplified for the aforementioned R ^2, include a divalent group having 1 to 20 carbon atoms.

  Specific examples of the acidic group-containing radical polymerizable monomer represented by the general formula (1) are as follows.

(In the above compounds, R ₁ represents a hydrogen atom or a methyl group)
Specific examples of the acidic monomer represented by the general formula (2) are as follows.

(In each of the above compounds, R ₁ ′ and R ₁ ″ each independently represents a hydrogen atom or a methyl group)
Specific examples of the acidic monomer represented by the general formula (3) are as follows.

  Specific examples of the acid monomer having an acid anhydride structure are as follows.

(In the above compounds, R ₁ represents a hydrogen atom or a methyl group)
These acidic monomers may be used alone or in combination of two or more.

  Among these acidic group-containing radically polymerizable monomers, the compound represented by the above general formula (1) or (2) or the general formula (1) is shown from the viewpoint of ease of handling, synthesis and availability. A compound having an acid anhydride structure obtained by dehydration condensation in the molecule is preferable (in the case of a compound having an acid anhydride structure, n is 2 or more as the compound represented by the general formula (1)).

Furthermore, Z is —O—P (═O) (OH) among the compounds represented by the general formula (1) in that higher adhesive strength can be obtained not only for tooth enamel but also for base metals. _{The use} of a compound represented by ₂ or —O—P (═O) (OH) (OR ₃ ) or a compound represented by the general formula (2) is preferred.

  Further, from the viewpoint of good polymerizability and low possibility of elution from a cured product after curing, a compound in which W, W ′ and W ″ are oxygen atoms, that is, a radical polymerizable group is a (meth) acryloxy group. It is preferable that it is a compound which is.

  These acidic monomers may be used by mixing a plurality of types.

  The blending amount of the acidic monomer in the pretreatment material of the present invention is not particularly limited, but in order to obtain high adhesiveness, 5 to 100 mass in 100 mass parts of all polymerizable monomers of the pretreatment material. Parts, preferably 10 to 80 parts by mass.

  The b) fourth period transition metal compound used in the A) pretreatment material of the present invention is a group 3-12 metal compound of the fourth period of the periodic table, specifically scandium (Sc). , Titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn) metal compounds It is. By compounding these metal compounds in the pretreatment material, an organic peroxide and a radical polymerization initiator contained in the filling restoration material described later are formed at the adhesion interface, and the adhesion between the adherend surface and the filling restoration material Can be made extremely good. Each of the above transition metal elements can have a plurality of valences, but can be added to the pretreatment material of the present invention as long as it can exist stably. For example, Sc (III), Ti (IV), V (III to V), Cr (II, III, VI), Mn (II to VII), Fe (II, III), Co (II, III), Ni (II), Cu (I, II), Zn (II). Specific examples of such compounds include + III-valent scandium compounds such as scandium (III) iodide, + VI-valent titanium compounds such as titanium (IV) chloride, titanium (IV) tetraisopropoxide, and + VI-valent vanadium compounds. Divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), Bis (maltolate) oxovanadium (IV), etc., vanadium pentoxide (V), sodium metavanadate, etc. as a + V-valent vanadium compound, chromium (II) chloride as a + II-valent chromium compound, chromium chloride as a + III-valent chromium compound (III) etc. are selected as + VI valent chromium compounds. Romic acid, chromate, etc. are manganese acetate (II), manganese naphthenate (II), etc. as + II-valent manganese compounds, and iron iron (II) acetate, iron chloride (II), etc. as + II iron compounds, As the + III iron compound, iron acetate (III), iron (III) chloride, etc., as the + II cobalt compound, cobalt (II) acetate, cobalt (II) naphthenate, etc., as the + II valent nickel compound, nickel (II) chloride Etc., copper chloride (I), copper bromide (I), etc. as + I copper compound, copper chloride (II), copper acetate (II) etc. as + II copper compound, zinc chloride (II) as + II zinc compound, Examples thereof include zinc (II) acetate. Among these, V (IV, V), Mn (II), Fe (II, III), and Co (II) are preferable, and among them, higher adhesive strength can be obtained, so + IV and / or + V valent vanadium compounds. Is more preferable. Most preferred is a + IV valent vanadium compound.

  A plurality of types of transition metal compounds in the fourth period may be used in combination.

  In the following description, for the sake of simplicity, the transition metal compound in the fourth period is indicated when simply referred to as a transition metal compound unless otherwise specified.

The blending amount of the transition metal compound in the pretreatment material of the present invention is not particularly limited, but in order to obtain high adhesion, a larger blending amount is preferable, while a smaller blending amount is storage stable. Since it is excellent in property, it is preferable that it is 0.001-10 mass parts with respect to 100 mass parts of all the polymerizable monomers in a pretreatment material, and it is more preferable that it is 0.05-3 mass parts. Most preferably, it is 0.1 to 1 part by mass. Water as the component c) used in the pretreatment material (A) of the present invention is substantially free of impurities harmful to storage stability, biocompatibility and adhesiveness. It is preferably not contained, and examples thereof include deionized water and distilled water.

  The amount of the water is not particularly limited, but is preferably 5 to 9150 parts by mass with respect to 100 parts by mass of the total polymerizable monomer in the pretreatment material constituting the pretreatment material. More preferably, it is 15-110 mass parts.

  Furthermore, the pretreatment material of the present invention can contain (h) a polyvalent metal ion-eluting filler. The polyvalent metal ions eluted from the polyvalent metal ion-eluting filler can improve the adhesion to the tooth and the physical properties of the cured product by ion-crosslinking the polymer of the acidic group-containing polymerizable monomer. it can. Furthermore, by partially neutralizing the acidic groups of the acidic group-containing polymerizable monomer, storage stability is improved, and high adhesive strength is exhibited even after long-term storage.

  Here, the polyvalent metal ion is a divalent or higher valent metal ion capable of binding to the acidic group other than the transition metal of the fourth period. As a representative example, calcium, Metal ions such as strontium, barium, aluminum, lanthanum, and lanthanoid. Among these, from the viewpoint of adhesive strength, it is more preferable that trivalent ions such as aluminum are contained as at least a part. The polyvalent metal ion-eluting filler may contain a monovalent metal ion such as sodium, but if the monovalent metal ion is contained in a large amount, the polyvalent metal ion ion Since it also affects the reactivity of crosslinking, the monovalent metal ion is preferably as low as possible, and is usually preferably 10 mol% or less of the polyvalent metal ion content. % Or less is particularly desirable. Further, the amount of polyvalent metal ions eluted after 24 hours when 0.1 g of filler was immersed in 10 ml of a 10 wt% maleic acid aqueous solution at a temperature of 23 ° C. was 5.0 to 500 meq / g-filler. Is preferred. More preferably, it is 10-100 meq / g-filler. The amount of polyvalent metal ions at this time can also be measured by ICP emission spectroscopic analysis or atomic absorption analysis. The amount of polyvalent metal ions eluted after 24 hours under the above conditions is hereinafter also referred to as “24 hours eluted ion amount”. In addition, the amount of polyvalent metal ions (meq / g) represents the amount of ionic crosslinking by polyvalent metal ions per 1 g of the polyvalent metal ion-eluting filler in milliequivalents. It can be calculated by calculating the sum of the values obtained by multiplying each polyvalent metal ion concentration (mmol / g) eluted from the hit by the valence of each metal ion.

  The polyvalent metal ion-eluting filler of component (h) is not particularly limited as long as it satisfies the above conditions. In the present invention, glass having a chain-like, layer-like, or network-like skeleton containing a polyvalent metal ion in the gap between the skeletons is preferably used.

  Preferable examples include glasses having a chain-like, layer-like, and network-like skeleton for containing polyvalent metal ions, such as oxide glass and fluoride glass. Examples of the oxide glass include those made of aluminosilicate glass, borosilicate glass, soda lime glass, and the like, and examples of the fluoride glass include zirconium fluoride glass. In addition, the polyvalent metal ion-eluting filler made of these glasses becomes porous particles having a network-like structure after the polyvalent metal ions are eluted, and has an action of improving the strength of the primer layer. .

  Among the above polyvalent metal ion-eluting fillers, those made of aluminosilicate glass are more preferably used in terms of improving the strength of the cured product, and further from fluoroaluminosilicate glass that gradually releases fluoride ions that reinforce the tooth structure. Is most preferably used.

  The elution characteristics of polyvalent metal ions in the polyvalent metal ion-eluting filler can be controlled by the blending ratio of each element. For example, if the content of polyvalent metal ions such as aluminum and calcium is increased, these elution amounts generally increase, and the elution amount of polyvalent metal ions can be changed by changing the content of sodium and phosphorus. Therefore, the elution characteristics of polyvalent metal ions can be controlled relatively easily.

  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 to 16; fluorine, 2 to 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 polyvalent metal ion-eluting filler that can be used in the present invention is not particularly limited, and may be pulverized particles or spherical particles obtained by normal pulverization. You can also mix the particles.

  In addition, the polyvalent metal ion-eluting filler that is the component B of the present invention preferably has an average particle diameter of 0.01 μm to 5 μm, more preferably 0.05 μm to 5 μm, from the viewpoint of facilitating the production of the primer. Most preferred is 3 μm, and more preferably in the range of 0.1 μm to 2 μm.

  Further, the blending amount of the polyvalent metal ion-eluting filler may be determined in a timely manner according to the polyvalent metal ion elution amount, and is not particularly limited as long as the pretreatment material has a tooth decalcification ability (pH 3 or less), Preferably 1-50 mass parts is preferable with respect to 100 mass parts of all the radically polymerizable monomers in a pretreatment material, More preferably, it is 3-30 mass parts.

  In the pretreatment material of the present invention, for various purposes, it is possible to blend other than the above-described components within a range that does not impair the performance as the pretreatment material. However, as described above, the amine compound is not contained from the viewpoint of improving the adhesive strength. Here, the term “containing no amine compound” means that the compound does not substantially contain an amine compound. For example, in a range that does not affect the effect, for example, an extremely small amount of impurities as other components, etc. Specifically, it is allowed to be contained in an amount of 0.1% by mass or less.

  Examples of such other components include a water-soluble organic solvent, a radical polymerizable monomer having no acidic group, a polymerization inhibitor, a photopolymerization initiator, an inorganic filler, and an α-hydroxycarbonyl compound.

  When water solubility of the acidic monomer or non-acidic monomer described later is low, the pretreatment material can be easily made into a uniform solution or a long-time stable emulsion by adding a water-soluble organic solvent. It becomes extremely easy to treat the surface without unevenness.

  Specific examples of such a water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2. -Propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2 -Dimethyl-1-propanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-he Ptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, Alcohol, propargyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, abiethinol, 1,2-ethanediol, 1,2-propanediol, 1 , 2-butanediol, 2,3-butanediol, 2-methyl-2,4-pentanediol, alcohols such as 1,2,6-hexanetriol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 1,3-dioxolane, tetrahydrofuran, dimethoxyethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis 2-methoxyethyl) ether, ether compounds such as bis (2-ethoxyethyl) ether, ketone compounds such as acetone and methylethylketone, phosphate esters such as hexamethylphosphoric triamide, acids such as dimethylformamide and dimethylacetamide Examples thereof include water-soluble organic solvents such as amide compounds, carboxylic acid compounds such as acetic acid and propionic acid, and sulfur oxide compounds such as dimethyl sulfoxide and sulfolane.

  Among these water-soluble organic solvents, it is most preferable to use a water-soluble organic solvent having high safety for a living body such as ethanol, isopropanol, or acetone in view of harmful effects on the living body.

  These water-soluble organic solvents may be used alone or in combination with different types. Although the compounding quantity of the said water-soluble organic solvent is not restrict | limited in particular, It is preferable that it is 20-300 mass parts with respect to 100 mass parts of all the polymerizable monomers in a pretreatment material, and 50-150. More preferred is part by mass.

  Furthermore, you may mix | blend monomers other than the said acidic monomer, ie, the radically polymerizable monomer (henceforth a non-acidic monomer) which does not have an acidic group.

  The radical polymerizable group in the non-acidic monomer is the same as the group exemplified in the description of the acidic monomer.

  Specific examples of the non-acidic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl Non-having one polymerizable unsaturated group such as (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloxyethyl propionate, 2-methacryloxyethyl acetoacetate Water-soluble (meth) acrylate monomers {hereinafter referred to as water-insoluble monofunctional non-acidic monomers}; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) Acrylate, polyethylene Water-soluble (meth) acrylate monomers such as glycol mono (meth) acrylate and ethoxylated undecenol (meth) acrylate {hereinafter referred to as water-soluble monofunctional non-acidic monomers}; Nonaethylene glycol di (meth) acrylate , Decaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, etc. Bodies {hereinafter referred to as water-soluble bifunctional non-acidic monomers}; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, Lopylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl 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, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylol methane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Aliphatic (meth) acrylate monomers having a plurality of polymerizable unsaturated groups, such as lithitol hexa (meth) acrylate and urethane di (meth) acrylate, 2,2-bis ((meth) acryloxyphenyl) propane 2,2-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis Aromatic (meth) acrylate-based units having a plurality of polymerizable unsaturated groups such as (4- (meth) acryloxypolyethoxyphenyl) propane and 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane Polymerizable unsaturated groups such as monomers (hereinafter referred to as water-insoluble polyfunctional non-acidic monomers together with both aliphatic and aromatic) (meth) Monomer having a (meth) acrylamide group as a polymerizable unsaturated group such as a monomer having a kryloxy group, diacetone acrylamide, N-methylol (meth) acrylamide, monomethyl fumarate, diethyl fumarate, fumaric acid Fumarate compounds such as diphenyl, styrene derivatives such as styrene, divinylbenzene, α-methylstyrene, allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, allyl diglycol carbonate, vinyl acetate, 4-vinyl Examples include pyridine, N-vinyl pyrrolidone, and ethyl vinyl ether.

  Among these, a monomer having a methacryloyloxy group or an acryloyloxy group is particularly preferable in terms of adhesiveness and ease of handling.

  Among these monomers having a methacryloyloxy group or an acryloyloxy group, it is preferable to add water-soluble non-acidic monomers from the viewpoint of improving the permeability of the pretreatment material to the tooth, and water-soluble monofunctional non-acidic Monomers are more preferred. Particularly preferred is 2-hydroxyethyl (meth) acrylate.

  On the other hand, from the viewpoint of adhesion durability, it is preferable to blend a water-insoluble polyfunctional non-acidic monomer. Among them, triethylene glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane di (meth) acrylate, 2,2-bis [ 4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] propane and 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane are more preferred.

  When these water-insoluble polyfunctional non-acidic monomers are included in the primer, in combination with water-soluble non-acidic monomers, the polymerizable monomer is prevented from causing phase separation with water. Are preferably used.

  The blending amount of these non-acidic monomers is not particularly limited, but is preferably 0.1 to 95 parts by mass in 100 parts by mass of all polymerizable monomers of the pretreatment material, and 20 to 90 parts by mass. It is more preferable that

  These radically polymerizable monomers can be used alone or in admixture of two or more.

  The polymerization inhibitor is preferably added in an amount that does not significantly affect the adhesive strength in order to prevent gelation when the pretreatment material of the present invention is stored and to improve storage stability. Specific examples of such a polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butylcresol and the like. The general blending amount of the polymerization inhibitor is 0.00001 to 5 parts by mass, more preferably about 0.001 to 1 part by mass with respect to 100 parts by mass of the total polymerizable monomer in the pretreatment material. .

  Further, the (A) pretreatment material of the present invention can provide a high adhesive force even if it does not contain a polymerization initiator in addition to the above-mentioned b) transition metal compound, but there is no problem even if it contains a polymerization initiator. Examples of such polymerization initiators include chemical polymerization initiators, thermal polymerization initiators, and photopolymerization initiators. Particularly preferred is a photopolymerization initiator.

  Examples of the photopolymerization initiator include α-diketones, benzoin alkyl ethers, thioxanthone derivatives, benzophenone derivatives, acylphosphine oxide derivatives and the like which will be described later. Of these, acylphosphine oxide derivatives are preferable, and bisacylphosphine oxide derivatives are more preferable. Most preferred is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

  The photopolymerization initiators can be blended not only alone but also in combination of a plurality of types as required.

  The blending amount of the photopolymerization initiator is not particularly limited and may be appropriately determined according to the blending ratio of other components to be blended. In the case of an α-diketone or acylphosphine oxide, a pretreatment material is used. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of all the radically polymerizable monomers to comprise, More preferably, it is 0.1-10 mass parts.

  In addition, the pretreatment material in the present invention may contain a filler to be described later. Examples of the filler include inorganic fillers and organic fillers. Of these, inorganic fillers are preferable, and fumed silica is preferable.

  The fillers as described above can be blended not only individually but also in combination of a plurality of types as necessary.

  The blending amount of the filler is not particularly limited, and may be appropriately determined according to the blending ratio of other components to be blended, etc., but with respect to 100 parts by mass of all radical polymerizable monomers constituting the pretreatment material. , Preferably it is 0.1-40 mass parts, More preferably, it is 1-20 mass parts.

  In addition, an α-hydroxycarbonyl compound may be added to the pretreatment material of the present invention for the purpose of improving the activity of the transition metal compound. Examples of the α-hydroxycarbonyl compound include α-hydroxycarbonyls such as lactic acid, tartaric acid, glycolic acid, citric acid and malic acid and esters thereof, and α-hydroxyketones such as hydroxyacetone, acetoin and benzoin.

  The α-hydroxycarbonyl compounds as described above can be blended not only individually but also in combination of a plurality of types as necessary.

  The blending amount of the α-hydroxycarbonyl compound is not particularly limited and may be appropriately determined according to the blending ratio of other components to be blended, etc., but the total radical polymerizable monomer constituting the pretreatment material is 100 masses. Preferably it is 0.01-10 mass parts with respect to a part, More preferably, it is 0.1-5 mass parts.

  In addition to the above-mentioned components, the pretreatment material in the present invention may contain conventionally known components, such as a thickener, a polymerization regulator, an ultraviolet absorber, and phosphoric acid. Examples thereof include inorganic acids such as acetic acid, organic acids such as acetic acid, water-insoluble organic solvents, dyes, pigments, and antibacterial agents.

  The preparation method of the pre-treatment material is not particularly limited, and each component obtained by measuring a predetermined amount may be mixed to obtain a uniform solution or emulsion. Moreover, as long as it does not mix | blend the arbitrary component which becomes unstable by making it into the same packaging like the organic peroxide mentioned later, it is possible to preserve | save as a one-pack packaging which mixed everything. Needless to say, it may be stored in two or more packages as necessary, and mixed at the time of use, for example, in the case of blending components that are difficult to pack in the same package.

  The dental filling / restoration kit of the present invention has (B) a filling restorative material having the following composition on the adherend surface treated with the pretreatment material in the tooth restoration part, that is, d) an acidic group. A radically polymerizable monomer, e) an organic peroxide, f) a photopolymerization initiator, and g) a silica-based inorganic filler, the content of the g) silica-based inorganic filler being d) having an acidic group A filling restorative material having a composition that is 30 to 900 parts by mass and does not contain an aryl borate compound is filled with respect to 100 parts by mass of the non-radically polymerizable monomer, and this is used after being photocured. At the time of curing the (B) filling / restoring material, not only the above-mentioned f) photocuring of the material by the action of the photopolymerization initiator but also e) the organic peroxide contained in the filling / restoring material is pretreated. Due to the elution into the material layer, the compound and the transition metal compound in the pretreatment material layer interact with each other to form a radical polymerization initiator, and chemical polymerization of the pretreatment material layer also occurs. . As a result, the vicinity of the boundary between the cured body of the filling and restorative material and the pretreatment material layer becomes stronger, and the cured body of the filling and restorative material adheres to the tooth with high strength. Hereinafter, the (B) filling / restoring material will be described.

  d) Examples of the non-acidic radical polymerizable monomer (non-acidic monomer) include the same non-acidic monomers exemplified as optional components in the pretreatment material of the present invention. Such non-acidic monomers can be used in combination of a plurality of types.

  In addition, when the radical polymerizable monomer used for the filling / restoring material has an acidic group, the acidic group reacts with an organic peroxide described later to promote deterioration of the filling / restoring material, and the long-term It becomes difficult to save.

  These non-acidic monomers may be appropriately selected and blended depending on other components, their blending amount, application and purpose as long as they can be used as a filling restoration material. In particular, a water-insoluble polyfunctional non-acidic monomer is preferably included. In particular, it is preferable that a water-insoluble polyfunctional non-acidic monomer having a hydroxy group or a urethane bond is contained in the same molecule. Examples of such water-insoluble polyfunctional non-acidic monomers include 2,2-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] propane and urethane di (meth) acrylate.

On the other hand, as described above, the filling / restoring material of the present invention contains an organic peroxide, which will be described later, and the organic peroxide is eluted in the pretreatment material layer, so that the transition metal compound in the pretreatment material and It functions as a polymerization initiator by the action of.
Whereas the pretreatment agent is a layer having a relatively high hydrophilicity, the filling / restoring material has a high hydrophobicity, so that the organic peroxide can be dissolved into the pretreatment material layer more quickly. It is preferable to add a water-soluble non-acidic monomer to the filling restorative material to improve the affinity between them. In particular, it is an embodiment in which a water-soluble bifunctional non-acidic monomer is blended in the filling / restoring material.

  In the case of adding a water-soluble non-acidic monomer to the filling / restoring material, from the viewpoint of water resistance of the filling / restoring material, when the total radical polymerizable monomer constituting the filling / restoring material is 100 parts by mass, The acidic monomer is 30 parts by mass or less, more preferably 20 parts by mass or less.

  (B) In the filling / restoring material, e) the organic peroxide is not particularly limited, and any conventionally known one can be used without any limitation. As typical organic peroxides, known hydroperoxides, peroxyketals, ketone peroxides, alkylsilyl peroxides, diacyl peroxides, peroxyesters, and the like can be used.

  More specifically, as hydroperoxides, P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5 -Dihydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.

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

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

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

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

  Examples of peroxyester esters include t-butyl peroxyneodecanoate and cumyl peroxyneodecanoate.

  The organic peroxide to be used may be selected in a timely manner depending on the structure and amount of the non-acidic monomer used in combination and the inorganic filler described later. Among them, hydroperoxide, peroxyketal, Ketone peroxides and alkylsilyl peroxides are preferred, and hydroperoxides are most preferred.

  The blending amount of the organic peroxide is not particularly limited, but is preferably 0.01 to 20 parts by mass, more preferably 0 with respect to 100 parts by mass of all radical polymerizable monomers constituting the filling / restoring material. 0.1 to 10 parts by mass, most preferably 0.5 to 5 parts by mass.

  Moreover, f) a photoinitiator is mix | blended with the (B) filling restoration material of this invention. By blending a photopolymerization initiator, the filling restoration material is cured by light irradiation.

  The photopolymerization initiator is not particularly limited, and known photopolymerization initiators of radical polymerizable monomers can be used.

  Examples of the photopolymerization initiator include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9,10- Α-diketones such as phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether, 2,4-diethoxythioxanthone, 2-chlorothioxanthone, Thioxanthone derivatives such as methylthioxanthone, benzophenone derivatives such as benzophenone, p, p′-dimethylaminobenzophenone, p, p′-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6- Methoxy) -2,4,4-trimethylpentyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) such acylphosphine oxide derivatives such as phenylphosphine oxide are exemplified.

  Furthermore, in addition to the photopolymerization initiator, a reducing compound may be used in combination. As such a reducing compound, an aromatic tertiary amine compound is preferably used. Examples of such aromatic tertiary amine compounds include 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, ethyl 3-dimethylaminobenzoate, And dimethylamino-p-toluidine, diethylamino-p-toluidine, p-tolyldiethanolamine and the like. Of these, 4-dimethylaminobenzoic acid and 4-dimethylaminobenzoic acid esters are preferred.

  The photopolymerization initiators as described above can be blended not only individually but also in combination of a plurality of types as necessary.

  Further, it is known that when an electron acceptor is further used in addition to the photo radical polymerization initiator / reducing compound, the polymerization activity is increased. As such an electron acceptor, halomethyl group-substituted s-triazine derivatives and diaryliodonium salt compounds which are photoacid generators are preferable.

  Specific examples of representative halomethyl group-substituted s-triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s- And triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and the like.

  Examples of diaryliodonium salt compounds include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methylphenyliodonium, Bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyloxyphenylphenyliodonium, p-phenoxyphenylphenyliodonium, bis Cations such as (p-dodecylphenyl) iodonium, chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate And diaryl iodonium salt compounds comprising anions such as tetrakispentafluorophenylborate, tetrakispentafluorophenyl gallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate.

  Among these photopolymerization initiators, α-diketone photopolymerization initiators and acylphosphine oxide photopolymerization initiators are particularly preferable, and acylphosphine oxide polymerization initiators are most preferable.

  The photopolymerization initiators as described above can be blended not only individually but also in combination of a plurality of types as necessary.

  The blending amount of the photopolymerization initiator is not particularly limited, and may be appropriately determined according to the blending ratio of other components to be blended. In the case of α-diketone or acylphosphine oxide, these are filled and restored. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of all the radically polymerizable monomers which comprise an agent, More preferably, it is 0.1-10 mass parts, Furthermore, an amine compound is 0 as needed. .01 to 20 parts by mass may be added. Furthermore, what is necessary is just to set it as 0.01-10 mass parts, when adding a photo-acid generator.

  The conventionally known g) silica-based inorganic filler contained in the (B) filling / restoring material of the present invention can be used without any particular limitation.

  Here, the silica-based inorganic filler refers to silica or composite oxide particles mainly composed of a metal oxide of Groups 2 to 14 of the periodic table that can be combined with silica. In the case of composite oxide particles, the silica component is preferably contained at least 10 mol% or more, preferably 50 mol% or more.

  Since such a silica-based inorganic filler has a silanol group on its surface, it can be firmly bonded by silane coupling and siloxane bonding. For this reason, the filler surface can be modified with a silane coupling agent to give strength and operability preferable as a dental filler.

  Specific examples of the silica-based inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, and strontium glass. The silica may be wet silica, but is preferably dry silica called fumed silica. Moreover, a polyvalent metal ion-eluting filler such as fluoroaluminosilicate glass can also be suitably used. Among them, silica-zirconia, barium glass, etc. having X-ray contrast properties can be preferably used.

  The particle diameter and shape of these silica-based inorganic fillers are not particularly limited, and spherical or irregular particles having an average particle diameter of 0.01 μm to 100 μm, which are generally used as dental materials, are appropriately selected depending on the purpose. Use it. Moreover, the refractive index of these fillers is not specifically limited, The thing of the range of 1.4-1.7 which the filler of a general dental curable composition has can be used without a restriction | limiting.

  Among these, from the viewpoints of operability and polishing properties, the silica-based inorganic filler is preferably spherical, and more preferably has an average particle size of 0.02 to 10 μm.

  The production method of these spherical silica-based inorganic fillers is not limited at all, and a spraying method, a sol-gel method, a flame melting method, and the like can be used, but the sol-gel method is more preferable because a filler with a uniform particle size suitable for dental use can be synthesized. .

  As such a silica-based inorganic filler, those subjected to silane coupling treatment can be suitably used. Specific examples of the silane coupling agent include methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane, 11-methacryloxyundecylmethyldimethoxysilane, and 3-glycidyloxypropyl. Such as trimethoxysilane.

  The compounding amount of these inorganic fillers is d) 30 to 900 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer having no acidic group. However, it is more preferably 70 to 700 parts by mass, and most preferably 150 to 500 parts by mass.

  By the way, a lot of acid sites exist on the surface of such a silica-based inorganic filler. Such acid sites can be reduced to some extent by the above-mentioned silane coupling treatment, but cannot be completely eliminated. Thus, in a tooth filler containing a large amount of such a surface-like silica-based inorganic filler, when an organic peroxide is blended and further an aryl borate compound is contained, as described above, Acts, resulting in a decrease in adhesive strength during storage and gelation and curing problems during long-term storage. In the present invention, such a problem is solved by not containing an aryl borate compound that is one of the causes of the problem in the filling / restoring material, but from the viewpoint of exerting the effect more remarkably. Is effective in the inorganic filler used in which the acid sites present on the surface are stronger acid sites and the abundance thereof. For this reason, as the silica-based inorganic filler to be used, a complex oxide composed of silica and a group 2-14 metal oxide is effective because the state of acid sites existing on the surface is stronger. A composite oxide composed of silica such as titania or silica-zirconia and a group 4 metal oxide is particularly effective. Considering the aforementioned X-ray contrast properties, it is most preferable to use silica-zirconia as the inorganic filler.

  In addition to the silica-based inorganic filler described above, the filler (B) of the present invention can be blended with other fillers. For example, any of inorganic fillers such as alumina, zirconia, titania, ytterbium fluoride, yttrium fluoride, and organic or organic-inorganic composite fillers can be blended.

  Organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile. -The particle | grains which consist of organic polymers, such as a styrene copolymer and an acrylonitrile-butadiene-styrene copolymer, are mentioned.

  Examples of the organic-inorganic composite filler include granular organic-inorganic composite fillers obtained by mixing these inorganic particles and a polymerizable monomer in advance, forming a paste, polymerizing, and pulverizing.

  The blending amount of the filler other than the silica-based inorganic filler is not particularly limited, but in a range where the total with the silica-based inorganic filler does not exceed 900 parts by mass, the proportion of the total amount in 100 parts by mass is 5 to 70 masses. Part, more preferably 10 to 50 parts by weight.

  In addition to the non-acidic monomer, organic peroxide, photopolymerization initiator, and inorganic filler, (B) the filling restorative material in the present invention includes various additives known as components for dental filling restorative materials. Etc. may be added as appropriate. However, as described above, the aryl borate compound is not contained from the viewpoint of lowering adhesive strength during storage and preventing gelation. Here, the phrase “containing no aryl borate compound” means that it is not substantially contained in the same manner as the amine compound in the above-mentioned pretreatment material, and specifically 0.01% by mass or less. It is allowed to be contained to the extent.

  As such other components, a polymerization inhibitor, an antioxidant, a polymerization regulator, an ultraviolet absorber, a fluorescent agent, a pigment, a dye, an antibacterial agent, a polymer thickener and the like can also be blended.

  In addition, the α-hydroxycarbonyl compound described above may be added in order to activate the transition metal compound during the pretreatment, and the blending amount thereof is the total radical polymerizable single amount constituting the filling / restoring material. Preferably it is 0.01-10 mass parts with respect to 100 mass parts of a body, More preferably, it is 0.1-5 mass parts.

  The method for producing the (B) filling / restoring material in the present invention is not particularly limited, and may be carried out in accordance with a known method for producing a filling / restoring material containing a radical polymerizable monomer and a polymerization initiator.

  As described above, the filling / restoration kit of the present invention includes (a) a pretreatment material containing a) an acidic monomer, b) a transition metal compound in the fourth period, and c) water, d) a non-acidic monomer, and e) an organic material. It comprises a peroxide compound, f) a photopolymerization initiator, and g) a filling restorative material containing an inorganic filler and no aryl borate compound. By adopting such a configuration, pre-treatment is possible even when an adhesive that requires photocuring by light irradiation is not applied in advance when filling the tooth restoration part like a conventional composite resin. The filling / restoring material can be filled and photocured directly on the coated surface of the material. Therefore, when the tooth is restored, complicated light irradiation can be completed once, and the operation is simple and quick. Moreover, the adhesive strength of the hardened body to the tooth is excellent in both enamel and dentin as already described in detail.

  Even if these components are blended differently, for example, an organic peroxide is blended in a pretreatment material, and a transition metal compound is blended in a filling restoration material, the same high adhesiveness cannot be obtained. Is added to the pretreatment material, the storage stability of the pretreatment material is deteriorated.

  The method of using the filling / restoration kit of the present invention is not particularly limited, and can be used in the same manner as known dental pretreatment materials and filling / restoration materials. That is, a pretreatment material is applied to a tooth surface to be bonded with a small brush, a sponge, etc., and after about 5 to 120 seconds, it is dried by air blow or the like, and then filled with a restoration material. Thereafter, the filling / restoring material may be irradiated with light and cured.

  EXAMPLES Hereinafter, although an Example is given and this invention is shown concretely, this invention is not restrict | limited at all by these Examples.

The compounds used in Examples and Comparative Examples and their abbreviations are shown below.
Abbreviation and structure [acidic monomer]
PM: Mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate
MDP; 10-methacryloxydecyl dihydrogen phosphate MAC-10; 11-methacryloyloxy-1,1-undecanedicarboxylic acid [water-insoluble non-acidic monomer]
3G; triethylene glycol dimethacrylate D2.6E; 2,2-bis [(4-methacryloyloxypolyethoxyphenyl) propane]
Bis-GMA; 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane [water-soluble non-acidic monomer]
HEMA; 2-hydroxyethyl methacrylate 14G; tetradecaethylene glycol dimethacrylate [transition metal compound]
BMOV; oxovanadium (IV) bis (maltrate)
V ₂ O ₅ ; divanadium pentoxide
NPC: Cobalt (II) naphthenate
NPM; Manganese naphthenate (II)
FeCl ₂ ; iron (II) chloride
FeCl ₃ ; iron (III) chloride
Ti (Oi-Pr) ₄ ; titanium tetraisopropoxide [organic solvent]
IPA: isopropyl alcohol acetone [organic peroxide]
TMBPO; 1,1,3,3-tetramethylbutyl hydroperoxide CHPO; cumene hydroperoxide PMPO; P-menthane hydroperoxide DHDPO; 2,5-dimethylhexane-2,5-dihydroperoxide TBSO; -Butyltrimethylsilyl peroxide [Photopolymerization initiator component]
CQ; camphorquinone
DMBE; ethyl 4-dimethylaminobenzoate BTPO; bis (2,6-dimethylbenzoyl) phenylphosphine oxide TPO; 2,6-dimethylbenzoyldiphenylphosphine oxide [aromatic amine component]
DMBE; ethyl 4-dimethylaminobenzoate DMPT; N, N-dimethylamino-p-toluidine [aliphatic amine component]
DMEM; 2-dimethylaminoethyl methacrylate MDEOA; methyldiethanolamine [others]
PBTEOA; triphenylammonium tetraphenylborate [inorganic filler]
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-methacryloyloxypropyltrimethoxy Mixture F2 hydrophobized with silane at a mass ratio of 70:30: fumed silica (average particle size 0.02 μm) surface-treated with methyltrichlorosilane [polyvalent metal ion-eluting filler]
MF: Fluoroaluminosilicate glass powder (Tokuso Ionomer, manufactured by Tokuyama Co., Ltd.) 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.) The filler surface was reformed for 20 minutes with 20 g of 5.0 N hydrochloric acid per 1 g of the pulverized powder. (Amount of ions eluted for 24 hours by ICP emission spectroscopic analysis: 25 meq / g-filler).
[Polymerization inhibitor]
BHT; dibutylhydroxytoluene HQME; hydroquinone monomethyl ether (1) Adhesive strength The anterior teeth of the bovine mandible are extracted within 24 hours after slaughter, and enamel or dentin is placed under water and parallel to the lips with # 800 emery paper. The plane was cut out. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then a double-sided tape having a hole with a diameter of 3 mm was fixed to this plane to define the bonding area. Next, a 1.5 mm thick wax with a hole of 8 mmφ was attached so as to be concentric with the double-sided tape to produce a simulated cavity. A pretreatment material was applied to the simulated cavity, left for 20 seconds, and then dried with compressed air. After drying, the photo-curable filling restoration material is filled in the simulated cavity, covered with a polypropylene sheet, and then irradiated with light for 30 seconds using a power light [manufactured by Tokuyama Dental Co., Ltd.] to give a composite resin. A test piece was prepared by polymerization polymerization.

  After the test piece produced by the above method was immersed in water at 37 ° C. for 24 hours, a metal jig was attached, and a tensile tester (Shimadzu Autograph AG5000) was used and the crosshead speed was 2 mm / min. A tensile test was performed. Eight adhesion test pieces were measured per test, and the average value was taken as the adhesive strength.

(2) Adhesive strength after storage of restoration kit In the same manner, the adhesion strength was measured using a restoration kit stored for 20 days in a 37 ° C incubator.

(3) Preparation of pretreatment material 0.1 g of BMOV and 0.003 g of BHT were dissolved in a solution comprising 5.0 g of PM, 5.0 g of HEMA, 2.0 g of water, and 8.5 g of IPA. Thus, a uniform solution was obtained and used as a pretreatment material P1. The composition ratio is shown in Table 1. Similarly, pretreatment materials P2 to P23 were prepared at the composition ratio shown in Table 1.

(4) Adjustment of Filling Restorative Material For 6.0 g BisGMA, 3.0 g 3G, and 1.0 g 14G, 0.4 g TMBPO, 0.05 g BTPO, and 0.01 g HQME, 0 Add .003 g of BHT and stir in the dark until uniform to form a matrix. The obtained matrix and F1 were mixed in an agate mortar so that the weight ratio was 104.6: 163, and defoamed under vacuum to obtain a filling restoration CR1. The composition is shown in Table 2. Similarly, filling restoration materials CR2 to CR16 were prepared at the composition ratio shown in Table 2. All the prepared restoration materials were stored in a light-shielding container.

Example 1
The tooth surface was processed using P1 as a pretreatment material, and an adhesion test was performed using CR1 as a filling restoration material. Thereafter, an adhesion test after storage was performed. The results are shown in Table 3.

Examples 2-30
A test was conducted in the same manner as in Example 1 using each pretreatment material and filling restoration material described in Table 3. The results are shown in Table 3.

Comparative Example 1
The test was conducted in the same manner as in Example 1 except that CR13 was used as the filling / restoring material. The results are shown in Table 4.

Comparative Examples 2-9
The test was performed in the same manner as in Comparative Example 1 except that the pretreatment materials and filling restoration materials described in Table 4 were used. The results are shown in Table 4.

Claims (5)

(A) a) an acidic group-containing radically polymerizable monomer, b) a transition metal compound in the fourth period, and c) a pretreatment agent containing water and not containing an amine compound;
(B) d) radical polymerizable monomer having no acidic group, e) organic peroxide, f) photopolymerization initiator, and g) silica or silica and a metal oxide of group 2-14. It made made of a complex oxide in which an inorganic filler, the g) is 30 to 900 parts by mass of the radical polymerizable monomer 100 parts by mass of the content has no d) acidic group-free machine filler, and A dental filling / restoration kit comprising a filling / restoration material containing no aryl borate compound. The dental filling / restoration kit according to claim 1, wherein (A) the pretreatment material further comprises h) a polyvalent metal ion-eluting filler. The dental filling / restoration kit according to claim 1 or 2, wherein the transition metal compound in the fourth period is a + IV and / or + V vanadium compound. e) organic peroxide, according to claim 1 or 2 dental filling restoration kit according a hydroperoxide. The dental filling / restoration kit according to claim 1, wherein the inorganic filler is a composite oxide comprising silica and a group 2-14 metal oxide.