JP2014009219A - Dental adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental adhesive composition containing a polymerizable monomer, which has high affinity of a dental adhesive material component with respect to dentine, and stably exhibits high adhesive strength to the dentine.SOLUTION: The dental adhesive composition contains (A) a polymerizable monomer component, (B) a polymer having a zwitterionic group in a side chain, and (C) water. The dental adhesive composition can be effectively used for a dental pretreatment material, a dental adhesive material, and a dental adhesive composite resin.

Description

  The present invention relates to a dental adhesive composition used in the field of dentistry. More specifically, the present invention relates to a dental adhesive composition for bonding a dental restoration made of a composite resin or the like and a tooth substance.

  In the case of a tooth cavity damaged by caries or the like, if it is a relatively small cavity in the first mid-term, direct restoration by composite resin is often performed from the viewpoint of aesthetics, simplicity of operation and quickness. . On the other hand, prosthetics made of metal, ceramics, or dental resin are often used for repairing relatively large cavities.

  Since these dental restorations such as composite resins and prosthetics do not have adhesiveness to the tooth, an adhesive composed of a polymerizable monomer composition is used together to adhere this to the tooth. . Thus, the polymerizable monomer used in such an adhesive is usually composed mainly of a methacrylate monomer, but its adhesive strength to the tooth is not sufficient, for example, for bonding a composite resin. In many cases, the adhesive strength has not been reached to overcome the internal stress generated upon curing of the composite resin, that is, the tensile stress generated at the interface between the tooth and the composite resin. Furthermore, the adhesive strength that can withstand the force applied by occlusion is often not reached. Therefore, in order to improve the adhesive strength of these adhesives, the following pretreatment is performed on the tooth surface during use. That is, 1) Apply a pretreatment material for etching treatment to hard tooth (mainly enamel mainly composed of hydroxyapatite), and 2) To penetrate and promote the adhesive in the tooth A primer, which is a pretreatment material, is applied.

  Here, as the pretreatment material for the former etching treatment, an acid aqueous solution for decalcifying the tooth surface is generally used, and an aqueous solution of phosphoric acid, citric acid, maleic acid or the like is used.

  On the other hand, the latter primer requires the adhesive to penetrate and harden into the fine gaps between the rough enamel surface by decalcification of the aqueous acid solution and the sponge-like collagen fibers exposed on the dentin surface after decalcification. Therefore, a hydrophilic monomer having a good affinity with the above-mentioned tooth substance such as hydroxyethyl methacrylate, or a polymerizable monomer composition mainly composed of an organic solvent or the like is used. The primer itself usually does not contain a polymerization initiator, but it contains a radical generated by the adhesive during the photo-curing reaction of the adhesive for composite resin applied thereon. The polymerizable monomer is cured by polymerization.

  As described above, since the affinity of the dental adhesive to the tooth substance is poor and the adhesive force is not sufficient, the dental adhesive is generally used after being treated with the pretreatment material. Therefore, it is desired to develop a dental adhesive exhibiting sufficient adhesive strength without using a pretreatment material, and a dental adhesive material that can significantly improve the adhesion strength when used in combination with a pretreatment material. From this point of view, various studies have been conducted on dental adhesives, and the adhesive strength is improved by including a polymer component in the adhesive and forming a uniform adhesive layer (see Patent Document 1). , An adhesive that has desirable rheological properties by combining a carboxylic acid functional polymer and an acid derivative substituted with a polymerizable ethylenically unsaturated group (see Patent Document 2), or a poly-lower alkyl Examples include (meth) acrylates that have improved adhesive strength (see Patent Document 3). However, these contain a polymer in the adhesive material to form a uniform adhesive material layer, and although there is an effect of improving a certain adhesive strength, the affinity of the adhesive material itself to the tooth substance is effectively improved. However, there was room for further improvement from the viewpoint of adhesive strength.

  By the way, in recent years, a polymer having a zwitterionic group in the side chain has attracted attention as a raw material for drugs and cosmetics. As an example of applying the polymer having a zwitterionic group in the side chain to a dental application, a dental polymerizable composition containing a polymerizable monomer and a polymer having a zwitterionic group in the side chain Is known (Patent Document 4). However, Patent Document 4 only shows that the use of a polymer having a zwitterionic group in the side chain has a high effect of suppressing adsorption of proteins, plaques, and the like. In a specific embodiment, a combined system of a polymer having a zwitterionic group in the side chain and water is not described. That is, Patent Document 4 does not predict anything about how a dental adhesive containing a polymer having a zwitterionic group in a side chain can improve the affinity with a tooth and increase the adhesive strength. In addition, there is no suggestion of using water and the polymer in combination.

JP 2007-56027 A JP 2006-89484 A JP 2010-202625 A JP 2007-217516 A

  The purpose of the present invention is to develop a dental adhesive composition containing a polymerizable monomer that enhances the affinity of the adhesive component to the tooth and exhibits higher adhesion to the tooth than in the past. And

  The inventors of the present invention have made extensive studies to overcome the above technical problems. As a result, it has been found that the adhesive strength can be drastically improved by blending a polymerizable monomer, a polymer having a zwitterionic group in the side chain, and water, thereby completing the present invention. It came.

  That is, the present invention provides a dental adhesive comprising (A) a polymerizable monomer component, (B) a polymer having a zwitterionic group in the side chain, and (C) water. Composition.

  A dental adhesive composition containing a polymerizable monomer component, a polymer having a zwitterionic group in the side chain, and water further stably exhibits high adhesive strength to teeth. It is possible to make it.

  Furthermore, in addition to the above effects, the dental adhesive of the present invention forms a strong adhesive layer due to the polymer effect of the polymer having a zwitterionic group in the side chain. The performance can be greatly improved. Therefore, since the adhesive layer can be easily formed with a uniform thickness immediately after the solvent removal by air blow, the adhesive layer is thin even if it is filled with a dental restoration such as a composite resin when the adhesive layer is not sufficiently cured. It is difficult for the adhesive layer to be broken at the part, there are few technique errors, and high adhesive strength can be obtained. Therefore, the dental adhesive of the present invention is extremely useful as an adhesive excellent in the adhesive strength between a tooth substance and a dental restoration such as a composite resin.

  The dental adhesive composition of the present invention comprises (A) a polymerizable monomer component, (B) a polymer having a zwitterionic group in the side chain, and (C) water. The dental adhesive composition is characterized. Hereinafter, each component contained in the dental adhesive composition of the present invention will be described in detail sequentially.

  The (A) polymerizable monomer contained in the dental adhesive composition will be described. The polymerizable monomer of the present invention has at least one polymerizable group in the molecule. Examples of the polymerizable unsaturated group present in the molecule include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. In particular, a compound having an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group is preferable from the viewpoint of curing speed.

  As the polymerizable monomer that can be used in the present invention, a known compound can be used without any limitation as long as it has at least one polymerizable unsaturated group in the molecule. Specific examples include methyl (meth) acrylate (meaning methyl acrylate or methyl methacrylate; the same shall apply hereinafter), ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth). Acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meta ) Acrylate, mono (meth) acrylate monomers such as 2- (meth) acryloxyethyl acetylacetate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethyl Glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2,2′-bis [4- (meth) acryloyloxyethoxyphenyl ] Propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, Polyfunctional (meta) such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate ) Acrylate monomers, etc. It can be mentioned.

  The compounding amount of the polymerizable monomer (A) in the dental adhesive composition of the present invention is preferably 10% by mass or more, and more preferably 20% by mass or more in order to obtain high adhesiveness. .

  The adhesive composition of the present invention can contain (A1) an acidic group-containing polymerizable monomer in (A) the polymerizable monomer component. Here, the (A1) acidic group-containing polymerizable monomer has at least one polymerizable unsaturated group and at least one acidic group in the molecule. A publicly known thing can be used as an acidic group, and the following can be mentioned as an acidic group which exists in a molecule of a compound of (A1) acidic group content polymerization monomer ingredient. . An acid anhydride group is also included in the acid group as a hydrolyzed acid group.

  In addition, (A1) polymerizable unsaturated group present in the molecule of the acidic group-containing polymerizable monomer component compound includes acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl. And a group such as a styryl group.

  Examples of compounds that can be suitably used as the (A1) acidic group-containing polymerizable monomer component used in the present invention include vinylphosphonic acids in which a phosphate group is directly bonded to a vinyl group in addition to the compound represented by the following formula: Acrylic acid, methacrylic acid, vinyl sulfonic acid and the like.

In the above compounds, R1 represents a hydrogen atom or a methyl group. These compounds can be used alone or in admixture of two or more. Among them, a group having a high decalcifying action on teeth (mainly due to having a phosphate group having strong acidity) and a group having a high adhesion to teeth -OP (= O) (OH) ₂ It is preferable to use a polymerizable monomer containing a phosphate group such as a group (—O—) ₂ P (═O) OH.

  The (A1) acidic group-containing polymerizable monomer component is preferably a compound having an acryloyl group, methacryloyl group, acrylamide group, or methacrylamide group as a polymerizable unsaturated group from the viewpoint of curing speed.

  (A1) When mix | blending an acidic group containing polymerizable monomer component, the content rate of the (A1) acidic group containing polymerizable monomer component in (A) polymerizable monomer is enamel and dentin. From the viewpoint of adhesive strength to both, it is preferably 5% by mass or more, and preferably 10 to 60% by mass from the viewpoint of balance between demineralization of tooth, penetration into tooth and strength.

  Furthermore, it is also possible to polymerize by mixing a polymerizable monomer other than the polymerizable monomer. Examples of these other polymerizable monomers include fumaric acid ester compounds such as dimethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, α-methylstyrene derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, allyl diglycol carbonate; amino group-containing (meth) acrylate monomers such as dimethylaminoethyl methacrylate; 10-mercaptodecyl (meth) Thiouracil group-containing (meth) acrylate monomers such as acrylate and 6-methacryloyloxyhexyl-2-thiouracil-5-carboxylate; silane coupling agents such as methacryloyloxypropyltrimethoxysilane It can gel. These polymerizable monomers can be used alone or in admixture of two or more.

  Next, the polymer which has (B) zwitterionic group in a side chain contained in the dental adhesive composition will be described. Here, the zwitterionic group is a functional group having a positively charged atomic group and a negatively charged atomic group, and a locally polar functional group is electrically It is neutral.

  As the zwitterionic group contained in the polymer having a zwitterionic group in the side chain that can be used in the present invention, known ones can be used without any limitation. As a specific example, positively charged atomic groups include onium cations such as lower alkyl ammonium groups and lower alkyl phosphonium groups, and negatively charged atomic groups include phosphate groups and sulfone groups. Acid anions such as acid groups and carboxyl groups can be mentioned.

  As the zwitterionic group of the polymer having such a zwitterionic group in the side chain, those represented by the following general formula (1) and / or (2) are preferable.

Wherein n and m are integers from 1 to 4, R ² to R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, A is a nitrogen atom or phosphorus atom, and B ⁻ is Represents any substituent represented by formula (3).)

(In the formula, R ⁵ is an alkyl group having 1 to 4 carbon atoms.)
In particular, the compound represented by the following general formula (4) or (5) is more preferable from the viewpoint of easy interaction with the peptide bond of collagen.

(A represents a nitrogen atom or a phosphorus atom, and B ⁻ represents any substituent represented by the following general formula (6).)

  Among the zwitterionic groups, those represented by the general formula (4) are more preferred, and in this case, the onium cation is preferably a lower alkyl ammonium group from the viewpoint of chemical stability.

  The main chain of the polymer having a zwitterionic group in the side chain of the present invention is not particularly limited as long as it is a known main chain. For example, polyethylene, polystyrene, polysulfone, polyether, polyurethane, polyester, poly (meta ) Acrylate, poly (meth) acrylamide and the like. In particular, when a (meth) acrylate-based polymerizable monomer is used as the polymerizable monomer component (A), it is easy to uniformly dissolve and disperse in the adhesive composition of the present invention, and good adhesiveness is obtained. Since the main chain is poly (meth) acrylate, a polymer having a zwitterionic group represented by the following general formula (7) or (8) in the side chain is preferably used.

  The polymer preferably has a linear structure from the viewpoint of compatibility with the polymerizable monomer component.

(In the above formula, R ¹ represents hydrogen or a methyl group. N and m are integers from 1 to 4, R ² to R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms. A is nitrogen. atom or a phosphorus atom, B ^- represents any of the substituents represented by the following general formula (9)).

(In the formula, R ⁵ is an alkyl group having 1 to 4 carbon atoms.)
A polymer having a zwitterionic group may be a polymerizable monomer having only a zwitterionic group, or a polymer having no zwitterionic group and a polymerizable monomer having a zwitterionic group. It can be obtained according to a known polymer production method using a polymerizable monomer as a raw material.

  Here, the polymerizable monomer having a zwitterionic group and the polymerizable monomer not containing any zwitterionic group both contain a polymerizable unsaturated group. As the polymerizable unsaturated group, acryloyl Examples thereof include a group, a methacryloyl group, an acrylamide group, a methacrylamide group, a vinyl group, an allyl group, an ethynyl group, and a styryl group. From the viewpoint of ease of polymerization, the polymerizable unsaturated group contained in the polymerizable monomer having a zwitterionic group and the polymerizable monomer not containing any zwitterionic group is preferably the same.

  As the polymerizable monomer having a zwitterionic group, a known monomer having a zwitterionic group can be used. As the polymerizable monomer having a zwitterionic group, a zwitterionic group can be used. Two or more different types may be used. Specific examples of the polymerizable monomer having a zwitterionic group when the polymerizable unsaturated group of the polymerizable monomer having a zwitterionic group is an acryloyl group or a methacryloyl group include 2- ( Methacryloyloxy) ethyl-2- (trimethylammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl-2- (trimethylphosphonio) ethyl phosphate, {(methacryloyloxy) ethyl-dimethylammonioethyl} -methyl phosphate, (Methacryloyloxy) ethyl-dimethylammonioethylsulfate, (methacryloyloxy) ethyl-dimethylammonioethylcarboxylic acid, {(methacryloyloxy) ethyl-dimethylphosphonioethyl} -methylphosphate, (methacryloyloxy) ethyl-dimethyl Suho niobium ethyl sulfate, (methacryloyloxy) ethyl - include dimethyl phosphonate niobium carboxylate and the like.

  Any polymerizable monomer that is copolymerized with a polymerizable monomer having a zwitterionic group can be any known monomer that is copolymerizable with the polymerizable monomer having a zwitterionic group. A polymerizable monomer that does not contain an ionic ionic group can be used, and among them, a polymerizable monomer that does not have an ionic group is preferable in order to sufficiently exhibit the effects of the present invention.

  A polymerizable monomer having no zwitterionic group suitable for copolymerization when the polymerizable unsaturated group of the polymerizable monomer having a zwitterionic group is an acryloyl group or a methacryloyl group For example, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, ethoxyethyl (meth) acrylate, alkyl ether (meth) acrylates such as butoxyethyl (meth) acrylate, acetyloxyethyl (meth) acrylate, propionoxyethyl (meth) acrylate, butanoneoxyethyl (meth) acrylate , Examples include acetoacetoxyethyl (meth) acrylate.

Further, the molecular weight of the polymer having a zwitterionic group in the side chain of the present invention is not particularly limited, but gel permeation chromatography (hereinafter, referred to as “durability”) from the viewpoint of durability and ease of handling in a solution. A polymer having a number average molecular weight in the range of 1 × 10 ³ to 1 × 10 ⁶ in terms of polystyrene-equivalent molecular weight measured by GPC) is preferable. The higher the molecular weight, the better the durability.However, if the molecular weight is too high, the viscosity of the adhesive composition becomes too high and the operability is inferior. It will not melt. Moreover, when molecular weight is small, the hardening body intensity | strength of adhesive composition will fall.

  The number of zwitterionic groups of the polymer having a zwitterionic group in the side chain of the present invention is not particularly limited, but the zwitterionic group is sufficient in that the effects of the present invention are sufficiently exhibited. It is preferable that the monomer component having a content of at least 10 mol% or more, preferably 50 mol% or more.

  The blending amount of the polymer having a zwitterionic group in the side chain is not particularly limited, but it exerts high adhesive strength on the tooth, and on the tooth surface immediately after removing the solvent by air blow. In terms of being able to form an adhesive layer with a uniform thickness, 0.01 to 50 parts by mass is preferable per 100 parts by mass of the polymerizable monomer component. 20 parts by mass is more preferable. When the blending amount is too large, polymerization of the polymerizable monomer becomes insufficient, and the strength of the cured product is lowered.

  The dental adhesive composition of the present invention is further characterized by containing (C) water. By containing water, the affinity of the dental adhesive composition for the tooth substance is improved. The reason is presumed as follows. In other words, the peptide chain contained in collagen, which is a dentin component of the tooth, has a structure in which it is woven alternately by being positively and negatively charged locally. It is considered that local bonds of zwitterions are dissociated when water bonds are born and water is interposed, and the bonds are further strengthened by interaction of the zwitterionic groups with the peptide chains. Such water is generally removed by air blowing before the adhesive composition is cured when the adhesive composition of the present invention is applied to the tooth surface. The blending amount of water per part by weight is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 25 parts by weight in order to sufficiently ion-dissociate the zwitterionic group.

  In addition, when (D) a water-soluble organic solvent or an amphiphilic polymerizable monomer is used, water separation is prevented and a uniform composition is obtained, which is preferable in terms of adhesive strength. As the amphiphilic polymerizable monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or the like is used, and the preferred blending amount of the amphiphilic monomer is a viewpoint of water absorption. To 55 parts by mass or less, preferably 50 parts by mass or less, based on 100 parts by mass of the polymerizable monomer component.

  Moreover, the water-soluble organic solvent which shows water solubility and has volatility at room temperature can be used. The term “water-soluble” as used herein means that the solubility in water at 20 ° C. is 20 g / 100 ml or more, and preferably at 20 ° C., it is compatible with water at an arbitrary ratio. Moreover, volatility means that the boiling point in 760 mmHg is 100 degrees C or less, and the vapor pressure in 20 degrees C is 1.0 KPa or more. Examples of such volatile water-soluble organic solvents include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of toxicity to a living body, ethanol, isopropyl alcohol and acetone are preferable, and isopropyl alcohol and acetone are particularly preferable from the viewpoint of compatibility with a polymer having a zwitterionic group in the side chain.

  In addition, these water-soluble organic solvents are also used by removing by air blowing before the adhesive composition is cured when the adhesive composition of the present invention is applied to the tooth surface, similarly to the water. Is done.

  The compounding amount of these water-soluble organic solvents is usually in the range of 2 to 400 parts by mass, more preferably 5 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer component.

  The dental adhesive composition of the present invention is usefully used for dental adhesion in dental applications. In particular, it is useful as a dental adhesive or a dental adhesive composite resin used when adhering a dental restoration such as a composite resin or prosthesis to a tooth, in which case (E) polymerization initiation An effective amount of the agent is blended. The polymerization initiator is classified into a chemical polymerization type and a photopolymerization type, and may be appropriately selected according to the purpose. It is also possible to use a dual cure type in which a photopolymerization initiator and a chemical polymerization initiator are used in combination, and polymerization can be initiated by either photopolymerization or chemical polymerization.

  A photopolymerization initiator is suitably used for a dental adhesive or a dental adhesive composite resin for adhering a composite resin to a tooth. Representative photopolymerization initiators include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9, Α-diketones such as 10-phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether, 2,4-diethoxythioxanthone and 2-chlorothioxan Thioxanthone derivatives such as Son, methylthioxanthone, benzophenone, benzophenone derivatives such as p, p'-dimethylaminobenzophenone, p, p'-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 - Toxibenzoyl) -2,4,4-trimethylpentylphosphine oxide, acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and aryl borate compounds / dyes / photoacid generators The system which becomes is mentioned. Among these, an α-diketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a photopolymerization initiator composed of a combination of an aryl borate compound / dye / photoacid generator are particularly preferable. is there.

  As the α-diketone, camphorquinone and benzyl are preferable. As the acylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are preferable. Although these α-diketones and acyl phosphine oxides exhibit photopolymerization activity alone, they are used in combination with amine compounds such as ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, and dimethylaminoethyl (meth) acrylate. It is preferable to obtain higher polymerization activity. In addition, as a photopolymerization initiator of an aryl borate compound / dye / photoacid generator system, an aryl borate compound such as tetraphenyl boron sodium salt is used as a dye, and 3,3′-carbonylbis (7-diethylamino) coumarin is used as a dye. Substitution of halomethyl group such as 2,4,6-tris (trichloromethyl) -s-triazine, using a coumarin dye such as 3,3'-carbonylbis (4-cyano-7-diethylaminocoumarin) as a photoacid generator Those using s-triazine derivatives or diphenyliodonium salt compounds can be particularly preferably used.

  On the other hand, a chemical polymerization initiator is suitably used for a dental adhesive (hereinafter also referred to as dental resin cement) for adhering a dental restoration such as a prosthesis to a tooth. Typical chemical polymerization initiators include combinations of organic peroxides and amines, organic peroxides, combinations of amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acid, alkylboranes. And the like, and the like.

  Examples of compounds suitable for use in the chemical polymerization initiator are as follows. Examples of the organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, Examples include acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like. These can be used alone or in combination of two or more.

  As the amines, secondary or tertiary amines are preferable, and specific examples thereof include N-methylaniline, N-methyl-p-toluidine and the like as secondary amines. N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl -P-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylan Ranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N dimethylhexyl Amine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2,2 ′-(n-butylimino ) Examples include diethanol.

  Any aryl borate can be used as long as it has at least one boron-aryl bond in one molecule, but it has high storage stability, ease of handling, and availability. From the viewpoint of ease of use, aryl borates having four boron-aryl bonds in one molecule are most preferable. Specific examples of aryl borates having four boron-aryl bonds in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl). ) Phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis ( m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyl) Oxyphenyl) boron, tetrakis ( - it can be mentioned salts of boron compounds such as octyloxy phenyl) boron. As a cation forming a salt with a boron compound, a metal ion, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion may be used. it can.

  Among the above chemical polymerization initiators, a chemical polymerization initiator obtained by using a combination of an acidic compound and an aryl borate in combination with a + IV and / or + V vanadium compound is particularly suitable because of its high polymerization activity. Furthermore, the combined use of the above organic peroxide is most preferable because the polymerization activity can be further enhanced.

  Specific examples of the vanadium compound include divanadium tetraoxide (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (Maltrate) oxo vanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V) and the like can be mentioned.

  The (E) polymerization initiator of the present invention can be blended not only alone but also in combination of a plurality of types as required. These compounding amounts are preferably in the range of 0.01 to 10 parts by mass when the polymerizable monomer is 100 parts by mass. If the amount is less than 0.01 parts by mass, the curability of the adhesive tends to be reduced. Conversely, if the amount exceeds 10 parts by mass, the strength of the cured product of the adhesive tends to decrease. As for the said compounding quantity of a polymerization initiator, it is more preferable that it is the range of 0.1-8 mass parts.

  You may make the dental composition of this invention contain a filler as needed. Here, as the filler, conventionally known silica-based inorganic filler, organic filler, and inorganic-organic composite filler can be used without any 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 the composite oxide particles, the silica component is preferably contained at least 10 mol% or more, preferably 50 mol% or more.

  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. The method for producing the silica-based inorganic filler is not limited at all, and a spraying method, a sol-gel method, a flame melting method, and the like can be used. When applying the dental adhesive composition of this invention to a dental adhesive, the filler by a flame melting method is preferable. Moreover, when applying the dental adhesive composition of this invention to a dental adhesive composite resin, the filler by a sol gel method is preferable and a spherical filler is more preferable.

  As such a silica-based inorganic filler, those subjected to silane coupling treatment can be suitably used. Specific examples of silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane , Vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropyl Methyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, hexamethyldisilazane, 11-methacryloxy undecyl trimethoxysilane, 11-methacryloxy-undecyl methyl dimethoxy silane.

  Examples of the organic filler include polyalkyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polyalkyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene- Examples thereof include particles made of an organic polymer such as a styrene copolymer, and polyalkyl methacrylate is particularly preferably used.

  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 these fillers when used for a dental adhesive is in the range of 2 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer component. If the amount is less than 2 parts by mass, a sufficient strength improving effect cannot be obtained.

  Moreover, the compounding quantity of the filler in case the adhesive composition of this invention is used as a dental resin cement or a dental adhesive composite resin is 100-2000 with respect to 100 mass parts of (A) polymerizable monomer components. It is the range of mass parts. Here, the dental adhesive composite resin is a composite in which a polymerizable monomer composition for adhering to the above-mentioned tooth substance is contained in the composite resin and directly bonded to the tooth without using a bonding material. In this case, if the blending amount of the filler is less than 100 parts by weight, sufficient strength as a composite resin cannot be obtained.

  Furthermore, the dental composition of the present invention includes an organic thickener, a polymerization inhibitor, a polymerization regulator, an ultraviolet absorber, a dye, a charge, as long as the performance is not deteriorated as required regardless of the application. Various additives such as an inhibitor, a pigment, and a fragrance can be added.

  According to the use of the dental adhesive composition, if a preferable composition is shown, in the case of a dental adhesive, (A) a polymerizable monomer component, (B) a polymer component having a zwitterionic group in the side chain, The composition contains (C) water, (D) a water-soluble organic solvent component, (E) a polymerization initiator component, and a filler component. The blending ratio of each component is 0.01 to 50 parts by mass of the polymer component (B) having a zwitterionic group in the side chain with respect to 100 parts by mass of the (A) polymerizable monomer component. C) Water 0.01-50 parts by mass, (D) Water-soluble organic solvent component 2-400 parts by mass, (E) Polymerization initiator component 0.01-10 parts by mass, Filler component 2- The amount is preferably 100 parts by mass.

  When the dental adhesive composition is used for a one-pack type (self-etching type) dental adhesive, the preferred composition is (A) a polymerizable monomer component, and (B) a zwitterionic group side. The composition contains a polymer component in the chain, (C) water, (D) a water-soluble organic solvent component, (E) a polymerization initiator component, and a filler component. The blending ratio of each component is (B) zwitterionic group with respect to 100 parts by mass of (A) polymerizable monomer component (A1) containing 5% by mass or more of (A1) acidic group-containing polymerizable monomer. In the side chain is 0.01 to 50 parts by mass, (C) 0.01 to 50 parts by mass of water, (D) 2 to 400 parts by mass of the water-soluble organic solvent component, and (E ) The polymerization initiator component is 0.01 to 10 parts by mass, and the filler component is preferably 2 to 100 parts by mass.

  Furthermore, when the use of the dental adhesive composition is a dental pretreatment material, preferred compositions are (A) a polymerizable monomer component, (B) a polymer component having a zwitterionic group in the side chain, The composition contains (C) water and (D) a water-soluble organic solvent component. The blending ratio of each component is (B) zwitterionic group with respect to 100 parts by mass of (A) polymerizable monomer component (A1) containing 5% by mass or more of (A1) acidic group-containing polymerizable monomer. It is preferable that it is 0.01-50 mass parts of polymer components which have a side chain, (C) 0.01-50 mass parts of water, and (D) 2-400 mass parts of water-soluble organic solvent components. It is.

  When the use of the dental adhesive composition is a dental adhesive composite resin, (A) a polymerizable monomer component, (B) a polymer component having a zwitterionic group in the side chain, (C) water, (E) It becomes a composition containing a polymerization initiator component and a filler component. The blending ratio of each component is (B) zwitterionic group with respect to 100 parts by mass of (A) polymerizable monomer component (A1) containing 5% by mass or more of (A1) acidic group-containing polymerizable monomer. Is a polymer component having a side chain of 0.01 to 50 parts by mass, (C) water is 0.01 to 10 parts by mass, (E) a polymerization initiator component is 0.01 to 10 parts by mass, and a filler. The component is preferably 100 to 2000 parts by mass.

  When the dental adhesive composition is used for a dental resin cement, (A) a polymerizable monomer component, (B) a polymer component having a zwitterionic group in the side chain, (C) water, (E ) The composition contains a polymerization initiator component and a filler component. The blending ratio of each component is (B) zwitterionic group with respect to 100 parts by mass of (A) polymerizable monomer component (A1) containing 5% by mass or more of (A1) acidic group-containing polymerizable monomer. Is a polymer component having a side chain of 0.01 to 50 parts by mass, (C) water is 0.01 to 10 parts by mass, (E) a polymerization initiator component is 0.01 to 10 parts by mass, and a filler. The component is preferably 100 to 2000 parts by mass.

  In the case of dental resin cement, as the (E) polymerization initiator, a chemical polymerization type and a photopolymerization type are usually used in combination. Chemical polymerization initiators are usually composed of two or more components, and when they are used, the polymerization initiating ability is demonstrated by mixing them. Therefore, in consideration of preservability, the packaging form is divided into two or more packages. become.

  Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the present invention is not limited to these examples.

(1) Production Example 1 Synthesis of methacryloyloxyethyl phosphorylcholine polymer In a glass polymer tube, 30 g of 2-methacryloyloxyethyl phosphorylcholine (hereinafter MPC), 0.95 g (8.0 mmol) of hexyl mercaptan, azobisisobutyronitrile ( AIBN) (0.16 g, 1.0 mmol) and benzene (50 ml) were added, and the atmosphere was replaced with nitrogen after repeated freeze-degas. Heating was performed at 60 ° C., and a part of the contents was sampled after 3 hours from the start of heating, and the molecular weight of the polymer was traced using gel permeation chromatography (GPC: HLC-8020 manufactured by Tosoh Corporation). . When the number average molecular weight of the produced polymer reached 2.0 × 10 ⁴ , heating was stopped and the reaction was stopped. In addition, the solvent used for the measurement of GPC is tetrahydrofuran, and a number average molecular weight is a value of polystyrene conversion.

The polymer solution obtained as a result of the solution polymerization was poured into a hexane-diethyl ether (3: 2) mixed solution, precipitated and dried to obtain a methacryloyloxyethyl phosphorylcholine polymer (PMPC). As a result of re-analysis by GPC, the number average molecular weight was 2.1 × 10 ⁴ and the molecular weight distribution was 2.0.

(2) Production Example 2 Synthesis of copolymer of MPC and methyl methacrylate MPC 12 g, methyl methacrylate (hereinafter referred to as MMA) 18 g, hexyl mercaptan 0.95 g, AIBN 0.16 g and 50 ml of benzene were placed in a glass polymerization tube. Polymerization was carried out according to Production Example 1.

From the result of 1H-NMR of the obtained copolymer (PMPC-PMMA), the proportion of MPC in the copolymer is 25 mol%, and as a result of analysis by GPC, the number average molecular weight was 2.3 × 10 ^4. The molecular weight distribution was 2.0.

(3) Production Example 3 Synthesis of copolymer of MPC and butyl methacrylate MPC 12 g, butyl methacrylate (hereinafter referred to as BMA) 18 g, hexyl mercaptan 0.95 g, AIBN 0.16 g and 50 ml of benzene were placed in a glass polymerization tube. Polymerization was carried out according to Production Example 1.

From the result of 1H-NMR of the obtained copolymer (PMPC-PBMA), the ratio of MPC in the copolymer is 29 mol%, and as a result of analysis by GPC, the number average molecular weight is 1.9 × 10 ^4. The molecular weight distribution was 2.0.

Abbreviations and abbreviations shown in the examples are as follows.
[Polymerizable monomer]
BisGMA: 2,2-bis (4- (2-hydroxy-3-methacryloxypropoxy) phenyl) propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate [polymerizable monomer having an acidic group]
PM1: 2-methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate SPM: 2: 1 mixture of PM1 and PM2 MDP: 10-methacryloyloxydecyl dihydrogen phosphate MAC-10 : 11-methacryloyloxy 1,1-undecanedicarboxylic acid
[Volatile water-soluble organic solvent]
IPA: isopropyl alcohol [polymerization initiator]
CQ: camphorquinone DMBE: ethyl p-N, N-dimethylaminobenzoate BMOV: bis (maltolate) oxovanadium (IV)
PhBTEOA: tetraphenylboron triethanolamine salt [filler]
FS1: Silica particles by flame melting method. Average primary particle size 18 nm, treated with methyltrichlorosilane.
MSa: silica-titania spherical particles by sol-gel method, average primary particle size 0.07 μm. γ-methacryloyloxypropyltrimethoxysilane treated product.
MSb: silica-zirconia spherical particles by sol-gel method, average primary particle size 0.4 μm. γ-methacryloyloxypropyltrimethoxysilane treated product.
MS1: 1: 1 mixture of MSa and MSb
[Polymer without zwitterionic group]
PMMA: Polymethyl methacrylate (weight average molecular weight 500,000)
PBMA: Polybutyl methacrylate (weight average molecular weight 160,000)
In the following examples and comparative examples, various measurements were performed by the following methods.

(1) Adhesion test (a) Method I for preparing an adhesive specimen (applied when the dental adhesive composition is a dental adhesive)
Within 24 hours after slaughter, the front teeth of the cow were removed, and the enamel and dentin planes were cut out in parallel with the labial surface using # 600 emery paper in the water. Next, these surfaces were dried by blowing compressed air for about 10 seconds, and then a double-sided tape with a 3 mm diameter hole was fixed to either the enamel or dentin plane, and then the thickness was 0.5 mm. A paraffin wax having an 8 mm hole was fixed on the circular hole so as to be in the same center, thereby forming a simulated cavity. In this simulated cavity, an etching primer for two-step type composite resin (Tokuso Mac Bond II etching primer material, manufactured by Tokuyama Dental Co., Ltd.) is applied, and then the dental adhesive of the present invention is applied thereon and left for 10 seconds. Post-compressed air is blown for about 10 seconds to dry, and if necessary (when the polymerization initiator of the dental adhesive used is a photoinitiator) dental visible light irradiator (Tokuso Power Light, Tokuyama Corporation) For 10 seconds. Further, a dental composite resin (Esterite Σ, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece I.
(B) Preparation method II of adhesive test piece (applicable when the dental adhesive composition is a one-component (self-etching) dental adhesive)
(A) The one-part dental adhesive of the present invention is applied to a simulated cavity formed by the same method as the method I for producing an adhesive test piece, and left for 10 seconds, and then dried by blowing compressed air for about 10 seconds. Then, as necessary (when the polymerization initiator of the dental adhesive used was a photopolymerization initiator), the sample was irradiated with light for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Furthermore, a dental composite resin (Esterite Σ, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece II.
(C) Preparation method III of adhesive test piece (applicable when the dental adhesive composition is a dental pretreatment material)
(A) Applying the dental pretreatment material of the present invention into a simulated cavity formed by the same method as the above-mentioned method I for producing an adhesive test piece, leaving it to stand for 10 seconds, blowing compressed air for about 10 seconds, and drying, Apply a two-step composite resin adhesive (bonding material from Tokusomak Bond II, manufactured by Tokuyama Dental Co., Ltd.), and if necessary (the polymerization initiator used in the dental adhesive is a photopolymerization initiator) In some cases) light was irradiated for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Further, a dental composite resin (Esterite Σ, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece III.
(D) Preparation method IV of adhesive test piece (applicable when the dental adhesive composition is a dental adhesive composite resin)
The dental adhesive composite resin of the present invention was filled in a simulated cavity formed by the same method as (a) Method I for preparing an adhesive test piece. If necessary (when the polymerization initiator used in the dental adhesive is a photoinitiator), light is irradiated for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) for adhesion Test piece IV was produced.
(E) Adhesion test method The test piece prepared by the above method is put into a thermal shock tester, immersed in a 4 ° C water bath for 1 minute, transferred to a 60 ° C water bath, immersed for 1 minute, and returned to the 4 ° C water bath again. The operation was repeated 6000 times.

Then, a stainless steel attachment is bonded to the above test piece, and the tensile tester (Autograph, manufactured by Shimadzu Corporation) is used to pull at a crosshead speed of 2 mm / min. The tensile bond strength between the enamel or dentin and the composite resin is measured. It was measured. For each test, four tensile bond strengths were measured by the above method, and the average value was measured as the bond strength after the storage test to evaluate the storage stability.
(2) Film thickness The test piece produced by the above method was cut perpendicularly to the adherend surface using a diamond cutter to expose the cross section of the adhesion site. Under traveling water, the adhesion cross section was polished with # 3000 emery paper, and the film thickness of the adhesive layer was measured with a laser microscope (manufactured by Keyence Corporation).

Example 1
0.1 g PMPC, 46 g BisGMA as a polymerizable monomer, 34 g 3G and 20 g HEMA, 70 g IPA as a volatile organic solvent, 1.0 g CQ as a polymerization initiator, 1.5 g DMBE, A dental adhesive comprising the adhesive composition of the present invention was prepared by using 10 g of FS1 as a filler, stirring and mixing these until uniform, adding 5 g of distilled water and stirring again until uniform. Obtained. About the obtained dental adhesive, the film thickness and the adhesive strength to dentin were measured. The composition of the dental adhesive is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Examples 1 and 2)
According to the method of Example 1, dental adhesives having different compositions shown in Table 1 were prepared except that a polymer having a zwitterionic group in the side chain was not used. About the obtained dental adhesive, the film thickness and the adhesive strength to dentin were measured. The composition of the dental adhesive is shown in Table 1, and the evaluation results are shown in Table 2.

  Example 1 uses an adhesive compounded so that each component satisfies the constitution shown in the present invention, but has a sufficiently thick film thickness and exhibits high adhesive strength to dentin. It was. On the other hand, Comparative Examples 1 and 2, respectively, are a case where a polymer having a zwitterionic group in the side chain is not included, and a case where a polymer having no zwitterionic group is blended. Even in the case, the film thickness was thin and the adhesive strength was low.

(Example 2)
0.1 g PMPC, 30 g SPM as polymerizable monomer, 36 g BisGMA, 24 g 3G and 10 g HEMA, 70 g IPA as volatile organic solvent, 1.0 g CQ as polymerization initiator, .5 g of DMBE, 10 g of FS1 as a filler, and after stirring and mixing until uniform, 19 g of distilled water was added and stirring and mixing until uniform again, consisting of the adhesive composition of the present invention. A one-pack type dental adhesive was obtained. About the obtained one-pack type dental adhesive, the film thickness and the adhesive strength to dentin were measured. Table 3 shows the composition of the one-pack type dental adhesive, and Table 4 shows the evaluation results.

(Examples 3 to 14)
In accordance with the method of Example 2, one-component dental adhesives having different compositions shown in Table 3 were prepared. About each obtained one-pack type dental adhesive material, the film thickness and the adhesive strength with respect to dentin were measured using each. Table 3 shows the composition of the one-pack type dental adhesive, and Table 4 shows the evaluation results.

(Comparative Examples 3-6)
According to the method of Example 2 except that a polymer having a zwitterionic group in the side chain was not used, one-pack type dental adhesives having different compositions shown in Table 3 were prepared. About each obtained one-pack type dental adhesive material, the film thickness and the adhesive strength with respect to dentin were measured. Table 3 shows the composition of the one-pack type dental adhesive, and Table 4 shows the evaluation results.

  Examples 2 to 14 use one-component dental adhesives that are blended so that each component satisfies the configuration shown in the present invention. In any case, the film thickness is sufficiently thick. And showed high adhesive strength to dentin. In contrast, Comparative Examples 3 to 6 do not include a polymer having a zwitterionic group in the side chain, and when a polymer not having a zwitterionic group is blended, does not include water. In all cases, the film thickness was thin and the adhesive strength was low.

(Example 15)
Using 0.1 g of PMPC, 30 g of SPM as a polymerizable monomer, 36 g of BisGMA, 24 g of 3G and 10 g of HEMA, and 70 g of IPA as a volatile organic solvent, these were stirred and mixed until uniform. After that, 19 g of distilled water was added and stirred and mixed until uniform again to obtain a dental pretreatment material made of the adhesive composition of the present invention. About the obtained dental pretreatment material, the film thickness and the adhesive strength to dentin were measured. The composition of the dental pretreatment material is shown in Table 5, and the evaluation result is shown in Table 6.

(Examples 16 to 24)
According to the method of Example 15, adhesives having different compositions shown in Table 5 were prepared. About the obtained dental pretreatment material, the film thickness and the adhesive strength to dentin were measured using each. The composition of the dental pretreatment material is shown in Table 5, and the evaluation result is shown in Table 6.

(Comparative Examples 7 and 8)
Dental pretreatment materials having different compositions shown in Table 5 were prepared according to the method of Example 15 except that a polymer having a zwitterionic group in the side chain was not used. About each obtained dental pretreatment material, the film thickness and the adhesive strength with respect to dentin were measured, respectively. The composition of the dental pretreatment material is shown in Table 5, and the evaluation result is shown in Table 6.

  In Examples 15 to 24, dental pretreatment materials blended so that each component satisfies the constitution shown in the present invention were used, but in any case, the film thickness was thick and high. The adhesive strength was shown. On the other hand, Comparative Examples 7 and 8 are a case where a polymer having a zwitterionic group in the side chain is not included, and a case where a polymer having no zwitterionic group is blended. Also, the film thickness was thin and the adhesive strength was low.

(Example 25)
Using 0.1 g PMPC, 30 g SPM as the polymerizable monomer, 44 g BisGMA and 26 g 3G, 1.0 g CQ as the polymerization initiator, 1.5 g DMBE, 150 g MS1 as the filler, After stirring and mixing until uniform, 5 g of distilled water was added and stirred and mixed again until uniform, to obtain a dental adhesive composite resin made of the adhesive composition of the present invention. About the obtained adhesive adhesive composite resin, the adhesive strength with respect to dentin was measured. Table 7 shows the composition of the dental adhesive composite resin, and Table 8 shows the evaluation results.

(Examples 26 to 30)
According to the method of Example 25, dental adhesive composite resins having different compositions shown in Table 7 were prepared. About each obtained adhesive adhesive composite resin, the adhesive strength with respect to dentin was measured using each. Table 7 shows the composition of the dental adhesive composite resin, and Table 8 shows the evaluation results.

(Comparative Examples 9 and 10)
Dental adhesive composite resins having different compositions shown in Table 7 were prepared according to the method of Example 25 except that a polymer having a zwitterionic group in the side chain was not used. About the obtained adhesive adhesive composite resin, the adhesive strength with respect to dentin was measured. Table 7 shows the composition of the dental adhesive composite resin, and Table 8 shows the evaluation results.

  Examples 25-30 used the dental adhesive composite resin mix | blended so that each component might satisfy the structure shown by this invention, but showed high adhesive strength in any case.

  On the other hand, Comparative Examples 9 and 10 are a case where a polymer having a zwitterionic group in the side chain is not included, and a case where a polymer having no zwitterionic group is blended. Also, the adhesive strength showed a low value.

Claims (10)

A dental adhesive composition comprising (A) a polymerizable monomer component, (B) a polymer having a zwitterionic group in a side chain, and (C) water. (B) The positively charged atomic group and the negatively charged atomic group constituting the zwitterionic group of the polymer having a zwitterionic group in the side chain are an onium cation and an acid anion, respectively. The dental adhesive composition according to claim 1. The zwitterionic group of the polymer having the (B) zwitterionic group in the side chain is represented by the following general formula (1) and / or (2). Dental adhesive composition.

Wherein n and m are each independently an integer of 1 to 4, R ² to R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, A is a nitrogen atom or a phosphorus atom, B ⁻ Represents any substituent represented by the following general formula (3).

(In the formula, R ⁵ is an alkyl group having 1 to 4 carbon atoms.) The dental adhesive composition according to any one of claims 1 to 3, wherein the main chain of the polymer (B) having a zwitterionic group in a side chain is poly (meth) acrylate. The blending amount of the polymer (B) having a zwitterionic group in the side chain is 0.01 to 50 parts by mass per 100 parts by mass of the (A) polymerizable monomer component. The dental adhesive composition according to any one of the above. The dental adhesive composition according to any one of claims 1 to 5, wherein the polymerizable monomer component (A) comprises an acidic group-containing polymerizable monomer (A1). object. Furthermore, the dental adhesive composition as described in any one of Claims 1-6 formed by containing the water-soluble organic solvent (D). A dental pretreatment material comprising the dental adhesive composition according to any one of claims 1 to 7. Furthermore, the dental adhesive material which consists of a dental adhesive composition as described in any one of Claims 1-7 formed by containing (E) polymerization initiator. Furthermore, the dental adhesive composite resin which consists of a dental adhesive composition as described in any one of Claims 1-7 formed by containing (E) polymerization initiator.