JP2018104367A - Nonsolvent dental adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonsolvent dental adhesive composition that has stable properties, offers a good balance between photocurability by LED light irradiation and stability to environmental light, and shows high adhesion strength to dentin.SOLUTION: A one-agent type nonsolvent dental adhesive composition contains an acidic group-containing polymerizable monomer (A), a polymerizable monomer containing no acidic group (B), a photopolymerization initiator (C), and a polymerizable group-containing benzotriazole compound (D).SELECTED DRAWING: None

Description

  The present invention relates to a dental adhesive composition used in the field of dentistry. Specifically, it substantially contains water and an organic solvent used for bonding a hard tissue (dental material) of a tooth to a dental restoration material such as a dental composite resin, a dental compomer, and a dental resin cement. The present invention relates to a non-solvent dental adhesive composition having no single agent.

  For restoration of dental materials damaged by caries, etc. (enamel, dentin and cementum), filling restoration materials such as filling composite resins and filling compomers, and teeth such as metal alloys, porcelain and resin materials are usually used. A crown repair material is used. However, in general, the filling restorative material and the crown restorative material (both may be collectively referred to herein as “dental restorative materials”) themselves are not adhesive to the tooth. For this reason, conventionally, various adhesion systems using an adhesive have been used for adhesion between a tooth and a dental restorative material. As a conventional adhesive system, the tooth surface is etched using an acid etching material such as an aqueous phosphoric acid solution, and then the bonding material, which is an adhesive material, is applied to the tooth and dental materials. There is a so-called acid etching type (total etching type) bonding system for bonding a repair material.

  On the other hand, as a bonding system that does not use an acid etching material, there is a so-called self-etching type bonding system. Conventionally, this adhesive system is a bonding containing a crosslinkable monomer and a polymerization initiator without applying water washing after applying a self-etching primer containing acidic monomer, hydrophilic monomer and water on the surface of the tooth. A two-step adhesive system that applies materials has been the mainstream, but recently, a one-step type using a one-component dental adhesive (one-component bonding material) that combines the functions of a self-etching primer and a bonding material. The adhesive system is widely used.

  One-pack type bonding materials generally contain acidic monomers, hydrophilic monomers, crosslinkable monomers, and the like as monomer components, and water and hydrophilic volatile organic solvents are generally used.

  However, when the cavity is repaired using the one-component bonding material as described above, it is necessary to remove water or an organic solvent contained in the bonding material by air blowing before curing the cavity. It is. This is because when water or an organic solvent is present, curing failure or curing delay occurs. Therefore, a non-solvent dental adhesive composition substantially free of water and an organic solvent is desired for the purpose of omitting a process such as air blowing for removing water and an organic solvent.

  In the adhesive system as described above, a bonding material is usually applied to a portion to be repaired and photocured. Therefore, a photopolymerization initiator is used for such an adhesive system. Patent Document 1 describes a non-aqueous dental composition excellent in storage stability containing a polymerizable component, a photopolymerization initiator, and a water scavenger such as a molecular sieve. However, the bonding material using the non-aqueous dental composition described in Patent Document 1 is too light sensitive, and is less stable with respect to environmental light such as a fluorescent lamp and a dental lamp in a dental clinic room. There was a problem of shortening.

  Patent Documents 2 and 3 propose non-solvent dental adhesive compositions using a sulfonic acid group-containing polymerizable monomer and a photopolymerization initiator having a carbonyl group. However, these adhesive compositions have a problem that the amount of the photopolymerization initiator is small but the strength of the cured product is not sufficient when used as a bonding material, although the environmental light stability is not a problem. In addition, when the amount of the photopolymerization initiator is increased in order to improve curability, there is a problem that the stability against ambient light is deteriorated, and it is difficult to satisfy the two characteristics of environmental light stability and photocuring properties in a balanced manner. It was.

  On the other hand, as a photopolymerizable composition having high stability against ambient light, Patent Document 4 contains a polymerizable monomer, an α-diketone, an acylphosphine oxide, an aromatic tertiary amine, and a benzotriazole compound. It is described that the preferred weight ratio of α-diketone and acylphosphine oxide (α-diketone: acylphosphine oxide) is 1: 2.5-10.

  However, the composition described in Patent Document 4 is intended for use as a dental restoration material, not as a dental adhesive system, and is effective as a hydrophobic composition such as a dental composite resin. In a composition containing a hydrophilic component, which is an essential component for penetration of dentin into collagen and familiarity with the tooth, used in dental adhesive systems, the benzotriazole compound precipitates after storage for a short period of time. There was a problem that the property stability was low, and it was confirmed from that time that practical use in a dental adhesive system was difficult.

  Patent Document 5 proposes a dental adhesive kit using a (bis) acylphosphine oxide compound and a benzotriazole compound as a dental adhesive system having an excellent balance between photocurability by LED light irradiation and environmental light stability. ing. However, Patent Document 5 relates to a two-component adhesive material of a primer and a bonding material, and in order to dissolve the benzotriazole compound, the bonding material side is made of a composition containing an aliphatic bifunctional polymerizable monomer. In the composition containing a relatively large amount of one-component hydrophilic components, there is a problem that the property stability is low, and there is room for improvement according to a study conducted later by the present inventors. all right.

  In addition, as a UV absorber other than the benzotriazole compound, blending a benzophenone UV absorber with a resin-based dental restorative material has also been proposed (for example, Patent Document 6).

  However, benzophenone-based UV absorbers are highly soluble and have no problem with solubility in a one-component hydrophilic component, but have estrogenic activity or that the benzophenone-based UV absorber itself exhibits a yellow green color. There was a problem.

Special table 2009-522279 gazette JP, 2006-56145, A Japanese Patent Laid-Open No. 2006-69281 Japanese Patent Laid-Open No. 2004-231913 WO2015 / 052913 Japanese Patent Laid-Open No. 62-132904

  Therefore, the present invention is a non-solvent dental adhesive composition having good property stability, excellent balance between photocurability and ambient light stability by LED light irradiation, and high adhesion strength to the tooth. The purpose is to provide goods.

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６の直鎖又は分岐鎖のアルキレン基を表し、Ｒ³は水素原子又は炭素数１〜１８の直鎖又は分岐鎖の炭化水素基を表し、Ｘは水素原子、ハロゲン原子、炭素数１〜８の直鎖又は分岐鎖の炭化水素基、炭素数１〜４のアルコキシ基、シアノ基又はニトロ基を表す。）

（式中、Ｒ¹は上記と同一意味を有し、Ｒ⁴は炭素数１〜６の直鎖又は分岐鎖のアルキレン基又は炭素数１〜６の直鎖又は分岐鎖のオキシアルキレン基を表す。）
［６］前記酸性基含有重合性単量体（Ａ）が、リン酸基含有重合性単量体である、前記［１］〜［５］のいずれかの１剤型の非溶媒系歯科用接着性組成物；
［７］前記酸性基を有しない重合性単量体（Ｂ）が、下記一般式（３）で表される非対称型アクリルアミド・メタクリル酸エステル化合物（Ｂ−１）を含む、前記［１］〜［６］のいずれかの１剤型の非溶媒系歯科用接着性組成物；

（式中、Ｚは置換基を有していてもよいＣ₁〜Ｃ₆の直鎖又は分岐鎖の脂肪族基又は芳香族基であって、前記脂肪族基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＲ⁵−、−ＣＯ−ＮＲ⁵−、−ＮＲ⁵−ＣＯ−、−ＣＯ−Ｏ−ＮＲ⁵−、−Ｏ−ＣＯ−ＮＲ⁵−及び−ＮＲ⁵−ＣＯ−ＮＲ⁵−からなる群から選ばれる少なくとも１個の結合基によって中断されていてもよい。Ｒ⁵は、水素原子又は置換基を有していてもよいＣ₁〜Ｃ₆の直鎖又は分岐鎖の脂肪族基を表す。） The present invention relates to the following inventions.
[1] An acidic group-containing polymerizable monomer (A), a polymerizable monomer having no acidic group (B), a photopolymerization initiator (C), and a polymerizable group-containing benzotriazole compound (D) Containing a one-part non-solvent dental adhesive composition;
[2] Polymerization in which the blending amount of the acidic group-containing polymerizable monomer (A) is 1 to 40% by weight with respect to the whole single-agent non-solvent dental adhesive composition and has no acidic group The blending amount of the polymerizable monomer (B) is 50 to 98% by weight, the blending amount of the photopolymerization initiator (C) is 0.1 to 5% by weight, and the polymerizable group-containing benzotriazole compound The one-component non-solvent dental adhesive composition of [1], wherein the blending amount of (D) is 0.01 to 5% by weight;
[3] The group in which the polymerizable group of the polymerizable group-containing benzotriazole compound (D) is composed of a vinyl group, a styryl group, a (meth) acryloyloxy group, a (meth) acrylamide group, and a (meth) acryloylthio group. 1 type or more non-solvent type dental adhesive composition of said [1] or [2] which is one or more types chosen from these;
[4] The one-component non-solvent dental adhesive property of [1] or [2], wherein the polymerizable group of the polymerizable group-containing benzotriazole compound (D) is a (meth) acryloyloxy group. Composition;
[5] The polymerizable group-containing benzotriazole-based compound (D) is at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). A one-component non-solvent dental adhesive composition of the above-mentioned [1] or [2];

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or a linear chain having 1 to 18 carbon atoms) A branched-chain hydrocarbon group is represented, and X represents a hydrogen atom, a halogen atom, a linear or branched hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. )

(In the formula, R ¹ has the same meaning as above, and R ⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms. .)
[6] The non-solvent dental one-agent type according to any one of [1] to [5], wherein the acidic group-containing polymerizable monomer (A) is a phosphoric acid group-containing polymerizable monomer. An adhesive composition;
[7] The above-mentioned [1], wherein the polymerizable monomer (B) having no acidic group contains an asymmetric acrylamide / methacrylic acid ester compound (B-1) represented by the following general formula (3): [6] One-solvent non-solvent dental adhesive composition according to any one of the above;

(Wherein, Z is an aliphatic group or an aromatic group of linear or branched optionally C ₁ -C ₆ optionally having a substituent, wherein the aliphatic group, -O -, - S -, - CO -, - CO -O -, - O-CO -, - NR 5 -, - CO-NR 5 -, - NR 5 -CO -, - CO-O-NR 5 -, - O-CO It may be interrupted by at least one linking group selected from the group consisting of —NR ⁵ — and —NR ⁵ —CO—NR ⁵ — R ⁵ may have a hydrogen atom or a substituent. (C ₁ -C ₆ linear or branched aliphatic group)

  According to the present invention, the one-component non-solvent system having good property stability, excellent balance between photocurability and ambient light stability by LED light irradiation, and high adhesion strength to the tooth. A dental adhesive composition is provided.

  The one-component non-solvent dental adhesive composition of the present invention comprises an acidic group-containing polymerizable monomer (A), a polymerizable monomer having no acidic group (B), a photopolymerization initiator (C And a polymerizable group-containing benzotriazole-based compound (D) as essential components. In addition, in this specification, (meth) acryl is a general term for methacryl and acryl, and the same applies to expressions similar thereto.

  The one-component non-solvent dental adhesive composition of the present invention does not contain a solvent causing curing failure or curing delay, that is, water or an organic solvent. Although there is an advantage that the step of removing the solvent can be omitted, as long as inconveniences such as poor curing and delay in curing are not caused, mixing of a trace amount of water or organic solvent (for example, 3% by mass or less per composition) is allowed. The Therefore, some ingredients are sold in a form containing water or organic solvent (for example, colloidal silica). In such a case, water or organic solvent is removed to an acceptable limit. It is used for the preparation of the composition.

  Hereinafter, each component used in the present invention will be described.

Acidic group-containing polymerizable monomer (A)
The acidic group-containing polymerizable monomer (A) has an acid etching effect and a primer treatment effect, and is a component that provides a decalcifying action and a penetrating action. The acidic group-containing polymerizable monomer (A) can be polymerized and also imparts a curing action. By containing the acidic group-containing polymerizable monomer (A), adhesion to the tooth and adhesion durability are improved.

  The acidic group-containing polymerizable monomer (A) in the present invention has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. And a polymerizable monomer having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group or a styrene group. Specific examples of the acidic group-containing polymerizable monomer (A) are given below. In the present specification, methacryloyl and acryloyl are collectively referred to as (meth) acryloyl.

  Examples of phosphoric acid group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate. 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydro Genphosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyl Xiundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydrogen phosphate, bis [2- (Meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meta ) Acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydeci ] Hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate Bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate and acid chlorides, alkali metal salts and ammonium salts thereof.

  Examples of pyrophosphate group-containing polymerizable monomers include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis [6- (meth) acryloyl pyrophosphate. Oxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate and acid chlorides, alkali metal salts and ammonium salts thereof.

  Examples of the thiophosphate group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl dihydrogen thiophosphate, 3- (meth) acryloyloxypropyl dihydrogen thiophosphate, 4- (meth) acryloyloxybutyl dihydro Genthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8- (meta ) Acrylyloxyoctyl dihydrogenthiophosphate, 9- (meth) acryloyloxynonyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyl dihydrogenthio Sulfate, 11- (meth) acryloyloxyundecyl dihydrogen thiophosphate, 12- (meth) acryloyl oxide decyl dihydrogen thiophosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen thiophosphate, 20- (meth) ) Acrylyloxyicosyl dihydrogenthiophosphate and acid chlorides, alkali metal salts and ammonium salts thereof.

  Examples of the phosphonic acid group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl phenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth) acryloyloxyhexyl-3. -Phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexylphosphonoacetate, 10- (meth) acryloyloxydecylphosphonoacetate and their Examples include acid chlorides, alkali metal salts, and ammonium salts.

  Examples of the sulfonic acid group-containing polymerizable monomer include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth) acrylate.

  Examples of the carboxylic acid group-containing polymerizable monomer include a polymerizable monomer having one carboxy group in the molecule and a polymerizable monomer having a plurality of carboxy groups in the molecule.

  Examples of the polymerizable monomer having one carboxy group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (meth) acryloyl tyrosine, N- (Meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meta ) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) a Leroy oxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydro Gemma rate and acid halides.

  Examples of the polymerizable monomer having a plurality of carboxy groups in the molecule include 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 10 -(Meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 13- ( (Meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxybutyl trimellitate Tate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (Meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 ′-(meth) acryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate and acid anhydrides thereof or And acid halides.

  Among these acidic group-containing polymerizable monomers, phosphoric acid groups or pyrophosphoric acid group-containing (meth) acrylic monomers are preferable because they exhibit better adhesiveness to teeth, and in particular, phosphoric acid A group-containing (meth) acrylic monomer is preferred. Among them, divalent phosphorus having an alkyl group or alkylene group having 6 to 20 carbon atoms as a main chain in the molecule in that it exhibits high decalcification in the absence of an organic solvent and high adhesion. An acid group-containing (meth) acrylic monomer is more preferred, and a divalent phosphate group containing an alkylene group having 8 to 12 carbon atoms as the main chain in the molecule such as 10-methacryloyloxydecyl dihydrogen phosphate (Meth) acrylic monomers are most preferred.

  The acidic group-containing polymerizable monomer (A) may be used alone or in combination of two or more. Adhesiveness may be lowered when the amount of the acidic group-containing polymerizable monomer (A) is too large or too small. Therefore, the compounding amount of the acidic group-containing polymerizable monomer (A) is the total weight of the one-part non-solvent dental adhesive composition (hereinafter referred to as “one-part non-solvent dental adhesive composition”). Is based on the photopolymerization initiator, polymerization accelerator, polymerization inhibitor, filler, etc.), preferably in the range of 1-40 wt%, more preferably in the range of 3-38 wt%, A range of 5 to 28% by weight is most preferred.

Polymerizable monomer having no acidic group (B)
As the polymerizable monomer having no acidic group (B), a radical polymerizable monomer having no acidic group and having a polymerizable group is preferable, and from the viewpoint of easy radical polymerization, the polymerizable group is (Meth) acrylic groups and / or (meth) acrylamide groups are preferred. The polymerizable monomer (B) having no acidic group contributes to the improvement of the coating property, mechanical strength, and adhesiveness of the dental adhesive.

  As the polymerizable monomer (B) having no acidic group, acidic groups other than the following asymmetric acrylamide / methacrylic acid ester compound (B-1) and asymmetrical acrylamide / methacrylic acid ester compound (B-1) are used. The polymerizable monomer (B-2) which does not have is mentioned.

Asymmetric acrylamide / methacrylic acid ester compound (B-1)
The asymmetric acrylamide / methacrylic acid ester compound (B-1) is represented by the following general formula (3) (hereinafter, the asymmetric acrylamide / methacrylic acid ester compound represented by the following general formula (3) is asymmetric type). Acrylamide / methacrylic acid ester compound (B-1)).

（式中、Ｚは置換基を有していてもよいＣ₁〜Ｃ₆の直鎖又は分岐鎖の脂肪族基又は芳香族基であって、前記脂肪族基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＲ⁵−、−ＣＯ−ＮＲ⁵−、−ＮＲ⁵−ＣＯ−、−ＣＯ−Ｏ−ＮＲ⁵−、−Ｏ−ＣＯＮＲ⁵−及び−ＮＲ⁵−ＣＯ−ＮＲ⁵−からなる群より選ばれる少なくとも１個の結合基によって中断されていてもよい。Ｒ⁵は、水素原子又は置換基を有していてもよいＣ₁〜Ｃ₆の直鎖又は分岐鎖の脂肪族基を表す。）

(Wherein, Z is an aliphatic group or an aromatic group of linear or branched optionally C ₁ -C ₆ optionally having a substituent, wherein the aliphatic group, -O -, - S -, - CO -, - CO -O -, - O-CO -, - NR 5 -, - CONR 5 -, - NR 5 -CO -, - CO-O-NR 5 -, - O-CONR ⁵ - and -NR ⁵ -CO-NR ⁵ - which may be interrupted by at least one bonding group selected from the group consisting .R ⁵ is optionally C ₁ may have a hydrogen atom or a substituent It represents a linear or branched chain aliphatic group of -C _6.)

Z is a site for adjusting the hydrophilicity of the asymmetric acrylamide / methacrylic acid ester compound (B-1). The C ₁ -C ₆ aliphatic group optionally having a substituent represented by Z is a saturated aliphatic group (an alkylene group, a cycloalkylene group (for example, 1,4-cyclohexylene group, etc.)). , An unsaturated aliphatic group (alkenylene group, alkynylene group) may be used, and a saturated aliphatic group (alkylene group) is preferable from the viewpoint of availability or production and chemical stability. Z is preferably a linear or branched C _{1 to} C ₄ aliphatic group which may have a substituent, from the viewpoint of adhesion to teeth and polymerization curability, and has a substituent. It is more preferably a linear or branched C _{2 to} C ₄ aliphatic group that may be used.

Examples of the C ₁ -C ₆ alkylene group include a methylene group, a methylmethylene group, an ethylene group, a 1-methylethylene group, a 2-methylethylene group, a trimethylene group, a 1-ethylethylene group, and a 2-ethylethylene group. 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, 1-butylethylene group, 2- Butylethylene group, 1-ethyl-1-methylethylene group, 1-ethyl-2-methylethylene group, 1,1,2-trimethylethylene group, 1,2,2-trimethylethylene group, 1-ethyltrimethylene group 2-ethyltrimethylene group, 3-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, , 3-dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3-dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyl Tetramethylene group, pentamethylene group, 1-butylethylene group, 2-butylethylene group, 1-methyl-1-propylethylene group, 1-methyl-2-propylethylene group, 2-methyl-2-propylethylene group, 1,1-diethylethylene group, 1,2-diethylethylene group, 2,2-diethylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 2- Ethyl-1,1-dimethylethylene group, 2-ethyl-1,2-dimethylethylene group, 1,1,2,2-tetramethylethylene group, 1-propyl Propyltrimethylene, 2-propyltrimethylene, 3-propyltrimethylene, 1-ethyl-1-methyltrimethylene, 1-ethyl-2-methyltrimethylene, 1-ethyl-3-methyltrimethylene Methylene group, 2-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 2-ethyl-3-methyltrimethylene group, 3-ethyl-1-methyltrimethylene group, 3-ethyl 2-methyltrimethylene group, 3-ethyl-3-methyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group Group, 1,2,3-trimethyltrimethylene group, 1,3,3-trimethyltrimethylene group, 2,2,3-trimethyltrimethylene group, 2,3,3-trimethyl Rutrimethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 3-ethyltetramethylene group, 4-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1 , 3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, 2,4-dimethyltetramethylene group, 3,3-dimethyltetramethylene Methylene group, 3,4-dimethyltetramethylene group, 4,4-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 4-methylpentamethylene group, 5 -Methyl pentamethylene group, hexamethylene group, etc. Group, ethylene group, 1-methylethylene group, 2-methylethylene group, trimethylene group, 1-ethylethylene group, 2-ethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1- A methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group and tetramethylene group are preferred, and a methylmethylene group, ethylene group, 1-methylethylene group, 2-methylethylene group, trimethylene group, 1-ethyl Ethylene group, 2-ethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group More preferred.

  Examples of the aromatic group optionally having a substituent represented by Z include an aryl group and an aromatic heterocyclic group. As the aromatic group, an aryl group is preferable to an aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring. As the aryl group, for example, a phenyl group is preferable. Examples of aromatic heterocyclic groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, triazole, pyran, and pyridine. Groups, pyridazine groups, pyrimidine groups, pyrazine groups, and 1,3,5-triazine groups. Of the aromatic groups, a phenyl group is particularly preferred.

The aliphatic group in R ⁵ may be any of a saturated aliphatic group (alkyl group) and an unsaturated aliphatic group (alkenyl group, alkynyl group), and is easy to obtain or manufacture and has chemical stability. From the viewpoint, a saturated aliphatic group (alkyl group) is preferable. Examples of the C ₁ -C ₆ linear or branched alkyl group in R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2- Examples include dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, and the like, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A butyl group or the like is preferable.

R ⁵ is more preferably a hydrogen atom or a linear or branched C _{1 to} C ₄ alkyl group which may have a substituent, a linear or optionally substituted hydrogen atom or substituent. Even more preferred are branched C ₁ -C ₃ alkyl groups.

  When the aliphatic group of Z is interrupted by the linking group, the number of linking groups is not particularly limited, but may be about 1 to 10, preferably 1, 2, or 3. More preferably one or two. In the formula (3), it is preferable that the aliphatic group of Z is not interrupted by the continuous linking group. That is, it is preferable that the bonding group is not adjacent. Examples of the linking group include -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, and -CO-O-. More preferred is at least one linking group selected from the group consisting of NH-, -O-CO-NH- and -NH-CO-NH-, -O-, -S-, -CO-, -NH-, Particularly preferred is at least one linking group selected from the group consisting of —CO—NH— and —NH—CO—.

The substituent in the formula (3) is not particularly limited, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxy group, hydroxy group, amino group, C ₁ -C ₆ alkyl group in mono- or di-substituted amino group, an acyl group, an acyloxy group, an amide group, C ₁ -C ₆ alkoxycarbonyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkyl group is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), C ₁ -C ₆ alkyl group are more preferable. Wherein C ₁ -C ₆ alkoxycarbonyl group, a C ₁ -C ₆ alkoxy group, the C ₁ -C ₆ alkylthio group and a C ₁ -C ₆ alkyl group, substituted by 1, 2 or 3 halogen atoms May be. Specific examples of the alkyl group include the same as those described for R ⁵ , and a linear or branched C _{1 to} C ₄ alkyl group is preferable. The number of substituents is not particularly limited, and may be about 1 to 8, preferably 1, 2, or 3.

  Specific examples of the asymmetric acrylamide / methacrylic acid ester compound (B-1) are not particularly limited, and examples thereof include the following.

Among these, from the viewpoint of adhesiveness and polymerization curing against tooth, asymmetrical acrylamide methacrylate Z is a straight or branched chain aliphatic group of good C ₂ -C ₄ may have a substituent Ester compound (B-1) is preferred, N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N- (1-ethyl- (2-methacryloyloxy) ethyl) acrylamide, N- (2- (2-methacryloyloxyethoxy) ethyl) acrylamide is more preferable, and N-methacryloyloxyethylacrylamide and N-methacryloyloxypropylacrylamide are the most from the viewpoint of high hydrophilicity related to the penetration of dentin into the collagen layer. preferable.

A polymerizable monomer having no acidic group other than the asymmetric acrylamide / methacrylic acid ester compound (B-1) (B-2)
A polymerizable monomer (B-2) having no acidic group other than the asymmetric acrylamide / methacrylic acid ester compound (B-1), for example, n (n is a natural number of 1 or more) olefinic double bonds The monomer having the above is expressed as an n-functional monomer, and is divided into three groups: a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher monomer.

(I) Monofunctional monomer Monofunctional monomers include methyl (meth) acrylate, iso-butyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N -Dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate (Meth) acrylate polymerizable monomers such as acrylate and erythritol mono (meth) acrylate; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, etc. ) Acrylamide polymerizable monomer; (meth) acryloyl oxide decyl pyridinium bromide, (meth) acryloyl oxide decyl pyridinium chloride, (meth) acryloyl oxide decyl pyridinium bromide, (meth) acryloyloxy hexadecyl pyridinium chloride Ride, and the like. Among these, 2-hydroxyethyl (meth) acrylate and N, N-diethyl (meth) acrylamide are preferable.

(Ii) Bifunctional monomer Examples of the bifunctional monomer include aromatic compound-based bifunctional polymerizable monomers and aliphatic compound-based bifunctional polymerizable monomers.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy-2-). Hydroxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2,2-bis ( 4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2- (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) propane, 2- (4- (Meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyl Examples include oxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, and the like. Among these, 2,2-bis [4- (3- (methacryloyloxy-2-hydroxypropoxy) phenyl] propane is preferable.

  Examples of aliphatic compound-based bifunctional polymerizable monomers include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, 2,2,4-trimethylhexamethylene Screw (2-car Ba carbamoyloxy ethyl) dimethacrylate (commonly known as "UDMA"), and the like. Among these, glycerol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate preferable.

(Iii) Trifunctional or higher monomers Monofunctional or higher monomers include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2 , 4-Trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxa Heptane Etc.

  These polymerizable monomers (B) having no acidic group are used alone or in combination of two or more. The content of the polymerizable monomer (B) having no acidic group is a one-part non-solvent dental adhesive composition from the viewpoint of obtaining a good balance between penetration into teeth and adhesion durability. Is preferably in the range of 50 to 98% by weight, more preferably 60 to 96% by weight, and most preferably in the range of 70 to 93% by weight.

  The one-component non-solvent dental adhesive composition of the present invention contains an asymmetric acrylamide / methacrylic acid ester compound (B-1) among the polymerizable monomers (B) having no acidic group. It is preferable to do. The asymmetric acrylamide / methacrylic acid ester compound (B-1) may be blended alone or in combination of two or more. The blending amount of the asymmetric acrylamide / methacrylic acid ester compound (B-1) is not particularly limited as long as the effect of the present invention is exhibited, but based on the total weight of the one-agent non-solvent dental adhesive composition, The range of 1 to 60% by weight is preferable, the range of 2 to 50% by weight is more preferable, the range of 3 to 40% by weight is further preferable, and the range of 5 to 30% by weight is most preferable. The blending amount of the asymmetric acrylamide / methacrylic acid ester compound (B-1) does not exceed the blending amount of the polymerizable monomer (B) having no acidic group.

Photopolymerization initiator (C)
The dental adhesive of the present invention preferably contains a photopolymerization initiator (C) from the viewpoint of curability. A well-known photoinitiator can be used for the photoinitiator (C) used for this invention. A photoinitiator (C) may mix | blend 1 type individually, and may mix | blend 2 or more types in combination.

  Photopolymerization initiators (C) include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones , Benzoin alkyl ether compounds, α-amino ketone compounds, and the like.

  Among the (bis) acylphosphine oxides, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) ) Phosphonate and the like. Examples of bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl)- 4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,5,6-to Methyl) -2,4,4-trimethylpentyl phosphine oxide and the like.

  The water-soluble acylphosphine oxides preferably have alkali metal ions, alkaline earth metal ions, pyridinium ions, or ammonium ions in the acylphosphine oxide molecule. For example, water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

  Specific examples of the water-soluble acylphosphine oxides include monomethylacetylphosphonate sodium salt, monomethyl (1-oxopropyl) phosphonate sodium salt, monomethylbenzoylphosphonate sodium salt, monomethyl (1-oxobutyl) phosphonate sodium salt, Monomethyl (2-methyl-1-oxopropyl) phosphonate sodium salt, acetylphosphonate sodium salt, acetylmethylphosphonate sodium salt, methyl 4- (hydroxymethoxyphosphinyl) -4-oxobutanoate sodium salt, Methyl 4-oxo-phosphonobutanoate mononatrium salt, acetylphenylphosphinate sodium salt, (1-oxopropyl) pentylphosphinate sodium salt, Tyl 4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentyl phosphinate sodium salt, acetylethyl phosphinate sodium salt, methyl (1,1-dimethyl) methyl phosphinate sodium (1,1-dimethoxyethyl) methyl phosphinate sodium salt, (1,1-diethoxyethyl) methyl phosphinate sodium salt, methyl 4- (hydroxymethylphosphinyl) -4-oxobutanoate Lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (2-methyl) -1,3-thiazolidin-2-yl) phospho Ito sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium salt, acetyl phosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1 , 1-diethoxyethyl) methylphosphonite sodium salt, methyl (2-methyloxathiolan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolane-2- Yl) phosphinate sodium salt, methyl (1,1-dipropoxyethyl) phosphinate sodium salt, (1-methoxyvinyl) methyl phosphinate sodium salt, (1-ethylthiovinyl) methyl phosphinate sodium salt, methyl (2-methylperhydro-1,3-diazin-2-yl) Phosphinate sodium salt, methyl (2-methylperhydro-1,3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, methyl (2-Methyl-1,3-thiazolidin-2-yl) phosphinate / sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate / sodium salt, acetylmethylphosphinate oxime / Natrium salt, acetylmethylphosphine -O-benzyloxime sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate sodium salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenylhydrazone ethyl) phosphinate・ Natri Salt, [1- (2,4-dinitrophenylhydrazono) ethyl] methyl phosphinate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate Sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formylmethyl phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, (1,1-dimethoxypropyl) methylphosphinate / dodecylguanidine salt, (1,1-dimethoxypropyl) methylphosphinate / isopropylamine salt, acetylmethylphosphinate thiosemicarbazone / sodium salt, (1 1-dimethoxyethyl) methyl phosphinate / 1,3,5-tributyl-4-methylamino-1,2,4-triazolium salt, (1,1-dimethoxyethyl) methyl phosphinate / 1-butyl-4-butyl Aminomethylamino-3,5-dipropyl-1,2,4-triazolium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4 , 6-trimethylbenzoylphenylphosphine oxide ammonium salt and the like. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is also mentioned.

  Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  Examples of the thioxanthone or quaternary ammonium salt of thioxanthone include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxo-9H-thioxanthen-4-yloxy)- N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxo-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-1- Propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy-3- (3, 4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-prop Aminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (1 , 3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride and the like can be used.

  Among these thioxanthones or quaternary ammonium salts of thioxanthones, a particularly suitable thioxanthone is 2-chlorothioxanthen-9-one, and a particularly preferred quaternary ammonium salt of thioxanthones is 2- Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the α-diketone include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. Is mentioned. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  Examples of the coumarin compound include 3,3′-carbonylbis (7-diethylaminocoumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3 -Benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p- Nitrobenzoyl) coumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [F] Coumarin, 3-carboxycoumarin, 3-carboxy- -Methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin , 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- ( 4-methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3- (3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6-methoxy) Coumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3 -(2-benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazoloyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) Coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3′-carbonylbis (7-dibutylaminocoumarin), 3, 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6 , 7-Tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, 10- (2-benzothiazoyl)- 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, etc. Examples thereof include compounds described in Japanese Patent No. 3109 and Japanese Patent Application Laid-Open No. 10-245525.

  Among the above-mentioned coumarin compounds, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

  Examples of the anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-hydroxyanthraquinone, and the like. .

  Examples of the benzoin alkyl ether compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the α-aminoketone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Among these photopolymerization initiators (C), it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds. As a result, a dental adhesive having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

  The blending amount of the photopolymerization initiator (C) is based on the total weight of the one-part non-solvent dental adhesive composition from the viewpoint of curability of the one-part non-solvent dental adhesive composition. Based on the range, 0.1 to 5% by weight is preferable, 0.5 to 4% by weight is more preferable, and 0.8 to 3% by weight is most preferable.

  In the one-component non-solvent dental adhesive composition of the present invention, a tertiary amine can be used as a polymerization accelerator as desired. The tertiary amine used in the present invention may be an aliphatic amine or an aromatic amine.

  Examples of the aliphatic tertiary amine include N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N -Ethyl diethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine and the like. Among these, 2- (dimethylamino) ethyl methacrylate and triethanolamine are more preferably used from the viewpoints of curability and storage stability of the one-component non-solvent dental adhesive composition.

  Examples of the aromatic tertiary amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N- Bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N , N-bis (2-hydroxyethyl) -4-tert-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N -Dimethylamino) methyl benzoate, 4- (N, N-dimethylamino) benzoic acid n-butoxyethyl, 4- (N, N-dimethylamino) benzoic acid 2- (methacryloyloxy) ethyl, 4- (N, N-dimethylamino) benzophenone, 4- (N, N-dimethylamino) benzoic acid butyl and the like. Among these, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N) from the viewpoint of imparting excellent curability to the one-component non-solvent dental adhesive composition. -Dimethylamino) ethyl benzoate, 4- (N, N-dimethylamino) benzoic acid n-butoxyethyl and at least one selected from the group consisting of 4- (N, N-dimethylamino) benzophenone are preferably used. . A tertiary amine may be blended alone or in combination of two or more.

  The amount of these tertiary amines is preferably in the range of 0.05 to 10% by weight, based on the total weight of the one-component non-solvent dental adhesive composition, preferably 0.1 to 7% by weight. A range is more preferable, and a range of 0.5 to 5% by weight is most preferable.

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６の直鎖又は分岐鎖のアルキレン基を表し、Ｒ³は水素原子又は炭素数１〜１８の直鎖又は分岐鎖の炭化水素基を表し、Ｘは水素原子、ハロゲン原子、炭素数１〜８の直鎖又は分岐鎖の炭化水素基、炭素数１〜４のアルコキシ基、シアノ基又はニトロ基を表す。）

（式中、Ｒ¹は上記と同一意味を有し、Ｒ⁴は炭素数１〜６の直鎖又は分岐鎖のアルキレン基又は炭素数１〜６の直鎖又は分岐鎖のオキシアルキレン基を表す。） Polymerizable group-containing benzotriazole compound (D)
The polymerizable group-containing benzotriazole compound (D) functions as a stabilizer against ambient light. Examples of the polymerizable group include a vinyl group, a styryl group, a (meth) acryloyloxy group, a (meth) acrylamide group, and a (meth) acryloylthio group, and a (meth) acryloyloxy group is preferable. The polymerizable group-containing benzotriazole compound (D) used in the present invention is represented by the following alkanol phenol type polymerizable group-containing benzotriazole compound represented by the following general formula (1), and the following general formula (2). Examples include sesamol type polymerizable group-containing benzotriazole compounds. The “alkanolphenol type polymerizable group-containing benzotriazole compound” means a derivative from a compound in which an alkanolphenol is bonded to the nitrogen atom at the 2-position of the benzotriazole ring. The “sesamol type polymerizable group-containing benzotriazole compound” means a derivative from a compound in which sesamol is bonded to the nitrogen atom at the 2-position of the benzotriazole ring.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or a linear chain having 1 to 18 carbon atoms) A branched-chain hydrocarbon group is represented, and X represents a hydrogen atom, a halogen atom, a linear or branched hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. )

(In the formula, R ¹ has the same meaning as above, and R ⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms. .)

Examples of the linear or branched alkylene group having 1 to 6 carbon atoms of R ² include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1, 2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group Group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n- Butylene 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene Group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n -A propylene group etc. are mentioned.

Examples of the linear or branched hydrocarbon group having 1 to 18 carbon atoms of R ³ include, for example, a linear or branched alkyl group having 1 to 18 carbon atoms, and a linear or branched chain group having 2 to 18 carbon atoms. An alkenyl group is mentioned, A C1-C18 linear or branched alkyl group is preferable. Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, 2-methylpropyl group, and t-butyl group. N-pentyl group, isopentyl group, s-pentyl group, neopentyl group, t-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group (isohexyl group), 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethyl Butyl group, 1,3-dimethylbutyl group, 1,4-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethyl Til group, 1-ethyl-2-methyl-propyl group, 1,1,2-trimethylpropyl group, n-heptyl group, 2-methylhexyl group, n-octyl group, isooctyl group, t-octyl group, 2- Ethylhexyl group, 3-methylheptyl group, n-nonyl group, isononyl group, 1-methyloctyl group, 2-ethylheptyl group, n-decyl group, 1-methylnonyl group, n-undecyl group, 1,1-dimethylnonyl Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-octadecyl group and the like. Examples of the alkenyl group having 2 to 18 carbon atoms include vinyl group, allyl group (2-propenyl group), 1-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1- Examples include pentenyl group, 4-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group, 1-decenyl group, 1-undecenyl group, 1-dodecenyl group and the like.

Examples of the linear or branched hydrocarbon group having 1 to 8 carbon atoms of X include those having 1 to 8 carbon atoms among the hydrocarbon groups of R ³ . Examples of the alkoxy group having 1 to 4 carbon atoms of X include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, and a t-butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formula (1), R ² is preferably a linear or branched alkylene group having 1 to 4 carbon atoms. In the general formula (1), R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Further, in the general formula (1), X is preferably a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group.

  Although it does not restrict | limit especially as said alkanol phenol type polymeric group containing benzotriazole type compound, As a specific substance name, 2- [2-hydroxy-5- (methacryloyloxymethyl) phenyl] -2H -Benzotriazole, 2- [2-hydroxy-5- (acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5 -(Acryloyloxypropyl) phenyl]- H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxybutyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxybutyl) phenyl] -2H-benzotriazole, 2 -[2-hydroxy-5- (methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy- 3-t-butyl-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-butyl-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 2 -[2-hydroxy-5- (methacryloyloxy) Ethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2-hydroxy-5- ( Methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2-hydroxy-5 -(Methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2-hydroxy -5- (methacryloyloxyethyl) phenyl] -5-t-butyl 2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-t-butyl-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl ] -5-nitro-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. Moreover, these alkanol phenol type polymeric group containing benzotriazole type compounds can also be used individually by 1 type, and can also use 2 or more types together.

Examples of the linear or branched alkylene group having 1 to 6 carbon atoms of R ⁴ include the same as those exemplified for R ² . Examples of the linear or branched oxyalkylene group having 1 to 6 carbon atoms of R ⁴ include oxymethylene group, oxyethylene group, oxytrimethylene group, oxypropylene group, oxy-1-ethylethylene group, oxy- 1,2-dimethylethylene group, oxybutylene group, oxytetramethylene group, 1,2-oxybutylene group, 1,3-oxybutylene group, 2,3-oxybutylene group, oxypentylene group, oxyhexylene group Etc.

In the general formula (2), R ⁴ is preferably a linear or branched alkylene group having 1 to 4 carbon atoms or a linear or branched oxyalkylene group having 1 to 4 carbon atoms.

  Although it does not restrict | limit especially as said sesamol type polymerizable group containing benzotriazole type compound, As a specific substance name, 2- [2- (6-hydroxybenzo [1,3] dioxole-5- Yl) -2H-benzotriazol-5-yl] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] ethyl acrylate, 3 -[2- (6-Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] propyl methacrylate, 3- [2- (6-hydroxybenzo [1,3] dioxole- 5-yl) -2H-benzotriazol-5-yl] propyl acrylate, 4- [2- (6-hydroxybenzo [1,3] di Xol-5-yl) -2H-benzotriazol-5-yl] butyl methacrylate, 4- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] Butyl acrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1, 3] dioxol-5-yl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole -5-yl} propanoyloxy] ethyl methacrylate, 2- [3- {2- (6-hydroxybenzo [1,3] di Xol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] ethyl acrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H- Benzotriazol-5-yl} propanoyloxy] butyl methacrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyl Oxy] butyl acrylate, 2- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] ethyl methacrylate, 2- [3 -{2- (6-Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy C] ethyl acrylate, 2- (methacryloyloxy) ethyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5 carboxylate, 2- (acryloyloxy) ethyl 2- ( 6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate, 4- (methacryloyloxy) butyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl ) -2H-benzotriazole-5-carboxylate, 4- (acryloyloxy) butyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate, and the like. It is done. These sesamol type polymerizable group-containing benzotriazole compounds may be used alone or in combination of two or more.

  The compounding amount of the polymerizable group-containing benzotriazole compound (D) is one-part non-solvent dental adhesive composition from the viewpoint of solubility in the one-part non-solvent dental adhesive composition. Is preferably in the range of 0.01 to 5% by weight, more preferably in the range of 0.05 to 4% by weight, and most preferably in the range of 0.10 to 3% by weight.

  In the case of using the one-component non-solvent dental adhesive composition according to the present invention, in order to achieve both high curability and ambient light stability, the types and blending ratios of components (C) and (D) Is preferably selected as appropriate. If the content of the component (C) is excessive, sufficiently high curability can be obtained, but the ambient light stability may deteriorate even if a large amount of the component (D) is added. On the other hand, when the content of the component (C) is too small, the environmental light stability is good, but the photocurability is lowered, and high adhesive strength tends to be difficult to be obtained, and the non-solvent having an excellent property balance It may be difficult to obtain a dental adhesive composition. On the other hand, when the content of the component (D) is excessive, the ambient light stability is improved, but the photocurability is lowered, and high adhesive strength may not be obtained, and the content of the component (D) is too low. If so, the effect of improving ambient light stability may not be obtained. From such a viewpoint, the preferred weight ratio ((C) / (D)) of the components (C) and (D) is the adhesiveness, photocuring characteristics, and environmental light stability of the non-solvent dental adhesive composition. From the viewpoint of improvement, 0.50 to 100 is preferable, 0.55 to 50 is more preferable, and 0.60 to 10 is more preferable.

  The single-agent non-solvent dental adhesive composition can also contain a fluoride as long as the effects of the present invention are not impaired. The fluoride may be any material that can dissolve in water and release fluorine ions. Specifically, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, Magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, aluminum fluoride, manganese fluoride (II), iron fluoride (II), iron fluoride (III), cobalt fluoride (II), fluoride Copper (II), zinc fluoride, attimone fluoride (III), lead fluoride (II), silver fluoride (I), cadmium fluoride, tin fluoride (II), tin fluoride (IV), fluoride Diamine silver, ammonium fluoride, sodium hydrogen fluoride, ammonium hydrogen fluoride, potassium hydrogen fluoride, sodium fluorophosphate, potassium hexafluorotitanate, sodium hexafluorosilicate Potassium, sodium hexafluorophosphate, hexafluoro tin (IV) sodium, hexafluoro stannate (IV) alanine, pentafluoro stannate (II), sodium, potassium hexafluorozirconate, and the like.

  Depending on the embodiment, it is preferable to further add a filler to the one-component non-solvent dental adhesive composition. Such fillers are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene. Chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. These may be used alone or in combination of two or more. Can be used as a mixture. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoints of handling property and mechanical strength of the obtained one-component non-solvent dental adhesive composition, the average particle size of the organic filler is preferably 0.001 to 50 μm, 0.001 to More preferably, it is 10 μm.

  Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and glass ceramic. , Aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. . These can also be used individually by 1 type or in mixture of 2 or more types. The shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoints of handling property and mechanical strength of the obtained one-component non-solvent dental adhesive composition, the average particle size of the inorganic filler is preferably 0.001 to 50 μm, preferably 0.001 to 10 μm. It is more preferable that

  Examples of the shape of the inorganic filler include an amorphous filler and a spherical filler. From the viewpoint of improving the mechanical strength of the dental bonding material (B), it is preferable to use a spherical filler as the inorganic filler. Here, the spherical filler is a particle in a direction perpendicular to the maximum diameter, in which the filler is photographed with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded. It is a filler having an average uniformity obtained by dividing the diameter by the maximum diameter of 0.6 or more. The average particle diameter of the spherical filler is preferably 0.1 to 5 μm. When the average particle size is less than 0.1 μm, the filling rate of the spherical filler in the one-component non-solvent dental adhesive composition may be lowered, and the mechanical strength may be lowered. On the other hand, when the average particle diameter exceeds 5 μm, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.

  In order to adjust the fluidity of the one-component non-solvent dental adhesive composition, the inorganic filler is used after surface treatment with a known surface treatment agent such as a silane coupling agent as necessary. Also good. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The organic-inorganic composite filler used in the present invention is obtained by adding a monomer compound to the above-mentioned inorganic filler in advance, forming a paste, polymerizing, and pulverizing. Examples of the organic-inorganic composite filler include TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized). The shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoints of handling property and mechanical strength of the obtained one-part non-solvent dental adhesive composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm. More preferably, the thickness is 001 to 10 μm.

  The blending amount of the filler used in the present invention is not particularly limited, and is preferably in the range of 0.1 to 30% by weight based on the total weight of the one-component non-solvent dental adhesive composition, A range of ˜15 wt% is more preferred, and a range of 0.8 to 5 wt% is most preferred.

  The one-component non-solvent dental adhesive composition may be blended with a fluoride ion releasing substance in order to impart acid resistance to the tooth. Fluorine ion-releasing substances include fluorine glasses such as fluoroaluminosilicate glass; metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride; methyl methacrylate and methacryl Fluorine ion releasing polymers such as copolymers with acid fluoride; fluorine ion releasing substances such as cetylamine hydrofluoride are exemplified.

  In addition, the one-component non-solvent dental adhesive composition contains a pH adjuster, a polymerization inhibitor, a thickener, a colorant, a fluorescent agent, a fragrance and the like as long as the effects of the present invention are not impaired. May be. Also, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan may be added. Good.

<One-agent type non-solvent dental adhesive composition>
The one-component non-solvent dental self-etching composition of the present invention is a liquid or paste composition, and is usually stored and stored in one package containing all the above-described components as one package. The

  The one-component non-solvent dental adhesive composition of the present invention is a non-solvent dental adhesive composition for bonding a tooth and a filling restorative material such as a filling compomer and a filling composite resin. However, it can also be used in combination with binders such as resin cement, glass ionomer cement, zinc phosphate cement, polycarboxylate cement, silicate cement, and zinc oxide Eugenol cement. Furthermore, it can be used as a dentinal tubule sealing material for the purpose of suppressing the hypersensitivity by applying to the fissure and fissure as it is without using the filling restoration material. .

  In addition, for example, when the restoration material breaks in the oral cavity, it can also be used for materials other than dental materials such as metal, porcelain, and dental composite resin hardened material. It may be used in combination with a metal adhesion primer for dental use, a dental porcelain adhesion primer, an acid etching material, and a hypochlorite-containing tooth surface cleaning agent.

  In a preferred embodiment of the one-component non-solvent dental adhesive composition of the present invention, the polymerizable monomer (B) having no acidic group is an asymmetric acrylamide / methacrylic acid ester compound (B- 1) and a polymerizable monomer (B-2) having no acidic group other than the asymmetric acrylamide / methacrylic acid ester compound (B-1) and having no acidic group ( An embodiment (X-1) in which B-2) includes an aromatic compound-based bifunctional polymerizable monomer may be mentioned.

  Moreover, as other suitable embodiment, it contains an acidic group containing polymerizable monomer (A) as a polymerizable monomer component and a polymerizable monomer (B) having no acidic group, and contains an acidic group. The polymerizable monomer (A) is a phosphoric acid group-containing polymerizable monomer, and the polymerizable monomer (B) having no acidic group is an asymmetric acrylamide / methacrylic acid ester compound (B-1), A polymerizable monomer (B-2) having no acidic group other than the asymmetric acrylamide / methacrylic acid ester compound (B-1), and having no acidic group (B-2) Embodiment (X-2) in which contains an aromatic compound-based bifunctional polymerizable monomer.

  Furthermore, as another suitable embodiment, it contains an acidic group-containing polymerizable monomer (A) as a polymerizable monomer component and a polymerizable monomer (B) having no acidic group, and contains an acidic group. The polymerizable monomer (A) is a phosphoric acid group-containing polymerizable monomer, and the polymerizable monomer (B) having no acidic group is an asymmetric acrylamide / methacrylic acid ester compound (B-1), A polymerizable monomer (B-2) having no acidic group other than the asymmetric acrylamide / methacrylic acid ester compound (B-1), and having no acidic group (B-2) Embodiment (X-3) in which includes a monofunctional monomer and an aromatic compound-based bifunctional polymerizable monomer.

  Furthermore, as another preferred embodiment, the acidic group-containing polymerizable monomer (A) is a phosphoric acid group-containing polymerizable monomer, and the polymerizable monomer (B) having no acidic group is An asymmetric acrylamide / methacrylic acid ester compound (B-1) and a polymerizable monomer (B-2) having no acidic group other than the asymmetric acrylamide / methacrylic acid ester compound (B-1), The polymerizable monomer (B-2) having no acidic group is the bifunctional polymerization of the polymerizable monomer (B-2) having no acidic group with a monofunctional monomer and an aromatic compound. And a polymerizable group-containing benzotriazole compound (D) selected from the group consisting of a compound represented by the general formula (1) and a compound represented by the general formula (2) Embodiment (X-4) is mentioned.

  In any of the preferred embodiments (X-1), (X-2), (X-3) and (X-4) described above, the types and amounts of the respective components are determined based on the description of the present specification. It can be changed as appropriate, and arbitrary components can be added or deleted. In any of the preferred embodiments (X-1), (X-2), (X-3) and (X-4) described above, the single-agent non-solvent dental adhesive composition Each component and each characteristic (environmental light stability, photocuring time, shear bond strength, etc.) can be appropriately changed and combined.

  The present invention includes embodiments in which the above-described configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention are exhibited.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following Example. Abbreviations used below are as follows. In addition, not all combinations of features described in the embodiments are essential to the solution means of the present invention. Various components used in the following examples and comparative examples, their abbreviations, structures, and test methods are as follows.

[Acid group-containing polymerizable monomer (A)]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate

ＭＡＰＡ：Ｎ−メタクリロイルオキシプロピルアクリルアミド（下記式（５）で表される化合物）

〔非対称型アクリルアミド・メタクリル酸エステル化合物（Ｂ−１）以外の酸性基を有しない重合性単量体（Ｂ−２）〕
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＤＥＡＡ：Ｎ，Ｎ−ジエチルアクリルアミド
Ｂｉｓ−ＧＭＡ：２，２−ビス〔４−（３−（メタクリロイルオキシ−２−ヒドロキシプロポキシ）フェニル〕プロパン
ＵＤＭＡ：２，２，４−トリメチルヘキサメチレンビス（２−カルバモイルオキシエチル）ジメタクリレート [Polymerizable monomer having no acidic group (B)]
[Asymmetric acrylamide / methacrylic acid ester compound (B-1)]
MAEA: N-methacryloyloxyethylacrylamide (compound represented by the following formula (4))

MAPA: N-methacryloyloxypropylacrylamide (compound represented by the following formula (5))

[Polymerizable monomer (B-2) having no acidic group other than asymmetric acrylamide / methacrylic acid ester compound (B-1)]
HEMA: 2-hydroxyethyl methacrylate DEAA: N, N-diethylacrylamide Bis-GMA: 2,2-bis [4- (3- (methacryloyloxy-2-hydroxypropoxy) phenyl] propane UDMA: 2,2,4- Trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate

[Photopolymerization initiator (C)]
CQ: dl-camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BAPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Polymerizable group-containing benzotriazole compound (D)]
MA-BNT1: 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole (compound represented by the following formula (6))

MA-BNT2: 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] ethyl methacrylate (compound represented by the following formula (7))

[Benzotriazole compounds other than polymerizable group-containing benzotriazole compounds (D)]
BNT: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (compound represented by the following formula (8))

[Tertiary amine]
DABE: ethyl 4- (N, N-dimethylamino) benzoate DEPT: N, N-bis (2-hydroxyethyl) -p-toluidine

[Filler]
R972: “AEROSIL (registered trademark) R972” manufactured by Nippon Aerosil Co., Ltd. (hydrophobic fumed silica, average particle size: 16 nm)

[Others]
BHT: 2,6-di-t-butyl-4-methylphenol (stabilizer (polymerization inhibitor))

  A one-component non-solvent bonding material having the composition shown in Table 1 was prepared. The numerical value of each component in a table | surface shows a weight part. The contents of each Example and Comparative Example are as follows, and the evaluation methods are described below.

<Examples 1-3>
MDP, HEMA, Bis-GMA, CQ, DABE, DEPT, BHT, inorganic filler R972, non-solvent bonding material in which MA-BNT1 is mixed in a weight ratio shown in Table 1 as a polymerizable group-containing benzotriazole compound (D) Was prepared. Using this bonding material, the ambient light stability test, the photocuring time measurement, the property stability test method, and the ultradent shear bond strength test method (ISO 29022: 2013 Notched shear bond strength test) described later. The stability, photocuring time, and property stability were evaluated, and the shear bond strength to dentin was measured. The results are shown in Table 1.

<Examples 4 to 11>
As shown in Table 1, a non-solvent bonding material was prepared in the same manner as in Example 1 except that the type and amount of each component were changed. Each characteristic was evaluated similarly to Example 1 about each obtained bonding material. The results are shown in Table 1.

<Comparative Example 1>
A non-solvent bonding material was prepared in the same manner as in Example 5 except that the polymerizable group-containing benzotriazole compound (D) was not included. Each characteristic of the obtained bonding material was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative example 2>
A non-solvent bonding material was prepared in the same manner as in Example except that the benzotriazole compound BNT that was not the polymerizable group-containing benzotriazole compound (D) was used instead of MA-BNT1. Each characteristic of the obtained bonding material was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Ambient light stability test]
In a dark room, under a xenon lamp in which a color temperature conversion film and an ultraviolet filter are inserted, place a mixing dish (product number “# 912 (TB)” manufactured by Kuraray Noritake Dental Co., Ltd.) at a height of 8000 lux. One drop of the bonding material was dropped. After exposing the sample to light for a certain period of time, remove the mixing dish on which the sample has been dropped from the irradiation area, immediately inspect the sample for physical uniformity, and set the time for maintaining the uniformity as the operation margin time. It was.

  The operation allowance time under ambient light is generally 20 seconds or longer for one-part non-solvent dental adhesive compositions, and can be used without problems in clinical practice. Preferably, it is most preferably 30 seconds or longer.

[Method for measuring photocuring time]
0.015 g of a non-solvent bonding material was dropped into a 4 mm hole washer adhered on a glass preparation. Immerse the non-solvent bonding material in the washer with a thermocouple (Okazaki Seisakusho, product code “SKC / C”) connected to a recorder (Yokogawa Seisakusho, product code “Type 3066”). Were irradiated with light using a dental LED light irradiator (trade name “VALO” manufactured by Ultradent Co., Ltd.). The time from the start of light irradiation to the generation of an exothermic peak top due to curing was defined as photocuring time (seconds).

[Property stability]
A non-solvent bonding material that had no particular problems with properties after preparation was allowed to stand under conditions of refrigeration (2 to 8 ° C.) for 3 months. Thereafter, the non-solvent bonding material was taken out and returned to room temperature, and the stability was evaluated by property changes such as precipitation. In the evaluation, the case where no precipitation was observed and there was no change in properties immediately after the preparation was evaluated as ◯, and the case where there was obvious precipitation was evaluated as x.

(Ultradent method shear adhesion test)
The lip surface of bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain samples in which the flat surface of dentin was exposed. A tape was affixed to the bottom of a 15-hole mold (15-hole mold, manufactured by Ultradent, φ35 mm × height 25 mm), and teeth were fixed thereon. The gypsum was filled in the mold and allowed to stand for about 30 minutes to cure the gypsum. The sample was taken out from the mold, polished with # 600 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to a size (φ2.38 mm or more) that can secure the adherend surface, and washed with water for 5 minutes with ultrasonic waves. .

  The non-solvent bonding materials of each Example and Comparative Example were applied to the adherend surface of the sample using a brush, left standing for 10 seconds, and then dried by air blowing the surface. Then, the applied bonding material was hardened by irradiating light for 10 seconds with a dental LED light irradiator (trade name “VALO” manufactured by Ultradent Co., Ltd.).

  A 2.38 mm CR filling mold (Bonding Mold Insert, manufactured by Ultradent Co.) is attached to a dedicated tool (Bonding Clamp, manufactured by Ultradent Co., Ltd.), and the mold is lowered to the part where the non-solvent bonding material has been treated. Close contact with the surface. A composite resin for dental filling (trade name “Clearfill AP-X” (registered trademark), manufactured by Kuraray Noritake Dental Co., Ltd.) is filled into the mold hole so that the thickness is within 1 mm, and then AP- X was filled in the mold (up to about 2/3 of the mold and about 2 mm thick), and irradiated with light for 20 seconds in the standard mode using the irradiator “VALO”. The sample was removed from the mold, and 10 samples were prepared as test samples for adhesion test. Next, the test sample for adhesion test was immersed in distilled water in a sample container, left in a thermostat set at 37 ° C. for 24 hours, then taken out and measured for adhesive strength. The adhesive strength (shear adhesive strength) is measured by attaching a test sample for adhesion test to a dedicated holder (Test Base Clamp, manufactured by Ultradent), a dedicated jig (Crosshead Assembly, manufactured by Ultradent), and a universal testing machine (Shimadzu Corporation). And the crosshead speed was set to 1 mm / min. The numerical value of the adhesive strength was the average value of the measured values for the ten adhesion test samples.

  As shown in Table 1, the one-component non-solvent bonding materials (Examples 1 to 11) according to the present invention contain a polymerizable group-containing benzotriazole compound (D) as an environmental light stabilizer. Therefore, it is excellent in environmental light stability. In addition, there is no delay in photocuring time due to the blending of the compound, the property stability is good with no property change, and the shear bond strength is also highly adhesive to dentin. . On the other hand, the bonding material not containing the polymerizable group-containing benzotriazole compound (D) (Comparative Example 1) had poor environmental light stability. In addition, the bonding material (Comparative Example 2) containing the benzotriazole compound BNT that is not the polymerizable group-containing benzotriazole compound (D) of the present invention has poor property stability because the benzotriazole compound precipitates after storage for a certain period of time. It was. In addition, in order to confirm the influence of precipitation, in addition to the results of environmental light stability shown in Table 1, the bonding materials of Example 1 and Comparative Example 2 which were further left to stand under conditions of refrigeration (2 to 8 ° C.) for 3 months. As a result of evaluating the environmental light stability for each of these, Example 1 (30 seconds) and Comparative Example 2 (15 seconds) were confirmed. In Comparative Example 2, it was confirmed that the environmental light stability was significantly deteriorated.

  In the field of dental treatment, a one-component non-solvent dental adhesive composition according to the present invention includes a dental hard tissue (dental material), a dental composite resin, a dental compomer, a dental resin cement, and the like. It is suitably used for bonding with a dental restorative material.

Claims (7)

  Containing an acidic group-containing polymerizable monomer (A), a polymerizable monomer having no acidic group (B), a photopolymerization initiator (C), and a polymerizable group-containing benzotriazole-based compound (D); One-component non-solvent dental adhesive composition.   The amount of the acidic group-containing polymerizable monomer (A) is 1 to 40% by weight based on the total amount of the one-component non-solvent dental adhesive composition, and the polymerizable single amount having no acidic group The amount of the body (B) is 50 to 98% by weight, the amount of the photopolymerization initiator (C) is 0.1 to 5% by weight, and the polymerizable group-containing benzotriazole compound (D) The one-component non-solvent dental adhesive composition according to claim 1, wherein the compounding amount is 0.01 to 5% by weight.   The polymerizable group of the polymerizable group-containing benzotriazole compound (D) is selected from the group consisting of vinyl group, styryl group, (meth) acryloyloxy group, (meth) acrylamide group, and (meth) acryloylthio group. The one-component non-solvent dental adhesive composition according to claim 1 or 2, wherein the composition is one or more.   The single-agent non-solvent dental adhesive composition according to claim 1 or 2, wherein the polymerizable group of the polymerizable group-containing benzotriazole compound (D) is a (meth) acryloyloxy group. The polymerizable group-containing benzotriazole-based compound (D) is at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). Item 3. The one-component non-solvent dental adhesive composition according to Item 1 or 2.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or a linear chain having 1 to 18 carbon atoms) A branched-chain hydrocarbon group is represented, and X represents a hydrogen atom, a halogen atom, a linear or branched hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. )

(In the formula, R ¹ has the same meaning as above, and R ⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms. .)   The single-agent non-solvent dental adhesive according to any one of claims 1 to 5, wherein the acidic group-containing polymerizable monomer (A) is a phosphoric acid group-containing polymerizable monomer. Composition. The polymerizable monomer (B) having no acidic group includes an asymmetric acrylamide / methacrylic acid ester compound (B-1) represented by the following general formula (3). The one-component non-solvent dental adhesive composition according to Item 1.

(Wherein, Z is an aliphatic group or an aromatic group of linear or branched optionally C ₁ -C ₆ optionally having a substituent, wherein the aliphatic group, -O -, - S -, - CO -, - CO -O -, - O-CO -, - NR 5 -, - CO-NR 5 -, - NR 5 -CO -, - CO-O-NR 5 -, - O-CO It may be interrupted by at least one linking group selected from the group consisting of —NR ⁵ — and —NR ⁵ —CO—NR ⁵ — R ⁵ may have a hydrogen atom or a substituent. (C ₁ -C ₆ linear or branched aliphatic group)