JP7426211B2 - Dental adhesive composition - Google Patents

Description

The present invention relates to dental adhesive compositions.

To restore tooth structure (enamel, dentin, and cementum) that has been damaged by caries, etc., we usually use filling restoration materials such as composite resin for filling and compomer for filling, as well as tooth materials such as metal alloys, porcelain, and resin materials. A crown repair material is used. However, in general, filling restorative materials and crown restorative materials (in this specification, both may be collectively referred to as "dental restorative materials") themselves do not have adhesive properties to tooth structure. For this reason, conventionally, various bonding systems using adhesives have been used to bond tooth substance and dental restorative materials. Conventionally widely used adhesive systems include an acid etching type adhesive system (total etching type) and an adhesive system that does not use an acid etching material (self etching type). Recently, a one-step bonding system using a one-component dental adhesive (one-component bonding material) that has both the functions of a self-etching primer and a bonding material has been widely used.

Such one-component bonding materials generally contain acidic monomers, hydrophilic monomers, crosslinkable monomers, etc. as monomer components. , (meth)acrylate compounds are commonly used.

A one-component bonding material is required to have excellent adhesion to tooth tissue, especially dentin. On the other hand, Patent Document 1 reports that excellent adhesion to dentin can be obtained over a long period of time by using a specific polymerizable monomer having a fluorocarbon group. Further, in Patent Document 2, a dental composition containing a polymerizable monomer having a fluorocarbon group and two or more polymerizable groups, a hydrophilic polymerizable monomer, and a polymerization initiator has excellent water repellency. It has been reported that it not only expresses this, but also has excellent adhesion properties due to its good compatibility with tooth structure and adhesive materials. Furthermore, Non-Patent Document 1 reports that a filling composite resin using a polymerizable monomer having a fluorocarbon group, an ethylene glycol skeleton, and two or more polymerizable groups exhibits excellent curability. .

International Publication No. 2011/121966 Japanese Patent Application Publication No. 2003-81731

Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 1999, vol. 36, Issue 3, pages 373-388

However, in the dental compositions disclosed in Patent Documents 1 and 2, the decrease in adhesiveness from the initial adhesive strength was suppressed to some extent in the adhesive durability test due to the high water repellency caused by the fluorocarbon group. However, the permeability of the composition into dentin was poor, and there was room for further improvement in initial adhesion and dentin cohesive failure rate. Further, although it has been confirmed that the composition of Non-Patent Document 1 has excellent curability, it did not have adhesiveness to tooth structure.

Therefore, an object of the present invention is to provide a dental adhesive composition that can obtain high adhesiveness (initial adhesive strength and adhesive durability) to dentin and exhibits a high dentin cohesive failure rate. .

As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by a dental adhesive composition containing a specific polymerizable monomer having a fluorocarbon group and an ether bond. Based on this finding, the present invention was completed after further studies.

（上記式中、Ｒ₁は－Ｏ－、－ＮＨ－、又は－ＣＨ₂Ｏ－を表し、Ｒ₂はＨ、Ｆ、又はＣＨ₃を表し、Ｘは下記一般式（３）又は（４）で表される基であり、Ｙは－ＣＨ₂－、－ＣＦ₂－、及び－Ｏ－からなる群から選ばれる１種以上を含む基であり、Ｙにおいて、－ＣＨ₂－の数は０～１０であり、－ＣＦ₂－の数は１～１０であり、－Ｏ－の数は１～１０である。）

（式中、Ｒ₁は上記式（２）と同一意味を有し、Ｒ₃はＨ、又はＣＨ₃を表し、Ｒ₄は－Ｏ－、－ＮＨ－、又は－ＮＨＣＯ－を表す。）
［３］前記重合性単量体（Ａ）が一般式（１）で表される重合性単量体であり、Ｘが一般式（３）で表される基である、［２］に記載の歯科用接着性組成物。
［４］Ｒ₃がＨである、［２］又は［３］に記載の歯科用接着性組成物。
［５］Ｙにおける－ＣＦ₂－の数が２～９である、［２］～［４］のいずれかに記載の歯科用接着性組成物。
［６］Ｙにおける－Ｏ－の数が２～９である、［２］～［５］のいずれかに記載の歯科用接着性組成物。
［７］Ｙが－ＣＦ₂－ＣＦ₂－を含む、［２］～［６］のいずれかに記載の歯科用接着性組成物。
［８］前記重合性単量体（Ａ）が有するエーテル結合の数が１～１０である、［１］～［７］のいずれかに記載の歯科用接着性組成物。
［９］前記重合性単量体（Ａ）が有するフッ素原子の数が２～２０である、［１］～［８］のいずれかに記載の歯科用接着性組成物。
［１０］酸性基を有しない親水性重合性単量体（Ｄ）をさらに含む、［１］～［９］のいずれかに記載の歯科用接着性組成物。
［１１］酸性基を有しない疎水性重合性単量体（Ｅ）（ただし、重合性単量体（Ａ）に該当するものを除く）をさらに含む、［１］～［１０］のいずれかに記載の歯科用接着性組成物。
［１２］前記重合開始剤（Ｃ）が、光重合開始剤（Ｃ－１）である、［１］～［１１］のいずれかに記載の歯科用接着性組成物。
［１３］前記酸性基含有重合性単量体（Ｂ）が、リン酸基含有重合性単量体である、［１］～［１２］のいずれかに記載の歯科用接着性組成物。
［１４］前記重合性単量体（Ａ）の含有量が、重合性単量体の全量１００質量部において、０．５～４０質量部である、［１］～［１３］のいずれかに記載の歯科用接着性組成物。
［１５］［１］～［１４］のいずれかに記載の歯科用接着性組成物からなる、歯科用ボンディング材。 That is, the present invention relates to the following.
[1] Polymerizable monomer (A) having a fluorocarbon group, two or more olefinic double bonds, and one or more ether bond, acidic group-containing polymerizable monomer (B), and polymerization initiator A dental adhesive composition containing (C).
[2] The dental adhesive composition according to [1], wherein the polymerizable monomer (A) contains the polymerizable monomer represented by the following general formula (1) or (2).

(In the above formula, R ₁ represents -O-, -NH-, or -CH ₂ O-, R ₂ represents H, F, or CH ₃ , and X represents the following general formula (3) or (4). Y is a group containing one or more selected from the group consisting of -CH ₂ -, -CF ₂ -, and -O-, and in Y, the number of -CH ₂ - is 0 ~10, the number of -CF ₂ - is 1 to 10, and the number of -O- is 1 to 10.)

(In the formula, R ₁ has the same meaning as the above formula (2), R ₃ represents H or CH ₃ , and R ₄ represents -O-, -NH-, or -NHCO-.)
[3] The polymerizable monomer (A) is a polymerizable monomer represented by general formula (1), and X is a group represented by general formula (3), described in [2] dental adhesive composition.
[4] The dental adhesive composition according to [2] or [3], wherein R ₃ is H.
[5] The dental adhesive composition according to any one of [2] to [4], wherein the number of -CF ₂ - in Y is 2 to 9.
[6] The dental adhesive composition according to any one of [2] to [5], wherein the number of -O- in Y is 2 to 9.
[7] The dental adhesive composition according to any one of [2] to [6], wherein Y contains -CF ₂ -CF ₂ -.
[8] The dental adhesive composition according to any one of [1] to [7], wherein the polymerizable monomer (A) has 1 to 10 ether bonds.
[9] The dental adhesive composition according to any one of [1] to [8], wherein the polymerizable monomer (A) has 2 to 20 fluorine atoms.
[10] The dental adhesive composition according to any one of [1] to [9], further comprising a hydrophilic polymerizable monomer (D) having no acidic group.
[11] Any one of [1] to [10] further containing a hydrophobic polymerizable monomer (E) that does not have an acidic group (excluding those that fall under the polymerizable monomer (A)) The dental adhesive composition described in .
[12] The dental adhesive composition according to any one of [1] to [11], wherein the polymerization initiator (C) is a photopolymerization initiator (C-1).
[13] The dental adhesive composition according to any one of [1] to [12], wherein the acidic group-containing polymerizable monomer (B) is a phosphoric acid group-containing polymerizable monomer.
[14] Any one of [1] to [13], wherein the content of the polymerizable monomer (A) is 0.5 to 40 parts by mass based on 100 parts by mass of the total amount of polymerizable monomers. The dental adhesive composition described.
[15] A dental bonding material comprising the dental adhesive composition according to any one of [1] to [14].

According to the present invention, a dental adhesive composition is provided that has high adhesiveness (initial adhesive strength and adhesive durability) to dentin and exhibits a high dentin cohesive failure rate. Further, according to the present invention, the cured product of the dental adhesive composition has sufficient mechanical strength.

The dental adhesive composition of the present invention comprises a polymerizable monomer (A) having a fluorocarbon group, two or more olefinic double bonds, and one or more ether bond, and an acidic group-containing polymerizable monomer. (B) and a polymerization initiator (C). In this specification, (meth)acrylic is a general term for methacrylic and acrylic, and the same applies to similar expressions. In this specification, the upper and lower limits of numerical ranges (content of each component, value calculated from each component, each physical property, etc.) can be combined as appropriate.

Although it is not clear why the dental adhesive composition of the present invention has high adhesive properties (initial adhesive strength and adhesive durability) to dentin and exhibits a high dentin cohesive failure rate, it is explained below. It is estimated as follows. That is, the polymerizable monomer (A) having a fluorocarbon group, two or more olefinic double bonds, and one or more ether bonds not only has high water repellency due to the fluorocarbon group, but also has one or more Since it also has a certain degree of hydrophilicity due to the presence of ether bonds, it is thought that its ability to penetrate into dentin is improved. Furthermore, since it has a plurality of olefinic double bonds, which are polymerizable groups, it is thought that the decrease in curability that might be caused by the introduction of an ether bond (oxygen atom) is suppressed. Therefore, it is considered that the dental adhesive composition of the present invention containing the polymerizable monomer (A) exhibited excellent initial adhesive strength, adhesive durability, and dentin cohesive failure rate.

That is, the dental adhesive composition of the present invention has high water repellency due to the fluorocarbon group, penetration effect into the tooth substance due to the presence of one or more ether bonds, and has two or more olefinic double bonds. By containing the polymerizable monomer (A) that has a well-balanced three properties of excellent curability, the composition as a whole has properties that contribute to adhesive properties such as hydrophilicity, hydrophobicity, and mechanical strength. It is considered that this composition showed excellent initial adhesive strength, adhesive durability, and dentin cohesive failure rate because the composition had an excellent balance of the following.

Each component used in the dental adhesive composition of the present invention will be explained below.

[Polymerizable monomer (A) having a fluorocarbon group, two or more olefinic double bonds, and one or more ether bonds]
The dental adhesive composition of the present invention comprises a polymerizable monomer (A) (hereinafter simply "polymerizable monomer") having a fluorocarbon group, two or more olefinic double bonds, and one or more ether bonds. body (A)). In the present invention, the use of a polymerizable monomer (A) is the core of the technology, and by combining such a polymerizable monomer (A) with other components, the dental adhesive composition can be applied to dentin. High adhesiveness (initial adhesive strength and adhesive durability) and high dentin cohesive failure rate can be achieved. One type of polymerizable monomer (A) may be used alone, or two or more types may be used in combination.

In the polymerizable monomer (A), from the viewpoint of adhesiveness and adhesive durability, the number of ether bonds (-O-) is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5. . Further, the number of fluorine atoms in the polymerizable monomer (A) is preferably 2 to 20, more preferably 2 to 16, and even more preferably 2 to 12.

（上記式中、Ｒ₁は－Ｏ－、－ＮＨ－、又は－ＣＨ₂Ｏ－を表し、Ｒ₂はＨ、Ｆ、又はＣＨ₃を表し、Ｘは下記一般式（３）又は（４）で表される基であり、Ｙは－ＣＨ₂－（メチレン基）、－ＣＦ₂－（ジフルオロメチレン基）、及び－Ｏ－からなる群から選ばれる１種以上を含む基であり、Ｙにおいて、－ＣＨ₂－の数は０～１０であり、－ＣＦ₂－の数は１～１０であり、－Ｏ－の数は１～１０である。） Examples of the polymerizable monomer (A) include polymerizable monomers represented by the following general formula (1) or (2).

(In the above formula, R ₁ represents -O-, -NH-, or -CH ₂ O-, R ₂ represents H, F, or CH ₃ , and X represents the following general formula (3) or (4). is a group represented by, Y is a group containing one or more selected from the group consisting of -CH ₂ - (methylene group), -CF ₂ - (difluoromethylene group), and -O-, and in Y , the number of -CH ₂ - is 0 to 10, the number of -CF ₂ - is 1 to 10, and the number of -O- is 1 to 10.)

（式中、Ｒ₁は上記式（２）と同一意味を有し、Ｒ₃はＨ、又はＣＨ₃を表し、Ｒ₄は－Ｏ－、－ＮＨ－、又は－ＮＨＣＯ－を表す。）

(In the formula, R ₁ has the same meaning as the above formula (2), R ₃ represents H or CH ₃ , and R ₄ represents -O-, -NH-, or -NHCO-.)

In general formulas (1) and (2), two X's may be the same or different. In Y in general formula (1) or (2), a methylene group, a difluoromethylene group, and an ether bond may be arbitrarily combined. Y is a group containing one or more selected from the group consisting of a methylene group, a difluoromethylene group, and an ether bond, and may contain other divalent functional groups; , and an ether bond. Furthermore, in order to achieve both permeability and water repellency, it is preferable that methylene groups, difluoromethylene groups, and ether bonds are not bonded more than twice in succession. Further, Y more preferably contains -CF ₂ -CF ₂ -, and even more preferably contains -CF ₂ -CF ₂ -O-. Y is linear or branched, preferably linear. In general formulas (1) and (2), X is preferably a group represented by general formula (3).

In general formula (3), R ₃ is preferably H from the viewpoint of higher curability. R ₄ is preferably -O- or -NH-, and more preferably -O- since it exhibits higher hydrophilicity and improves penetration into dentin. In general formula (4), R ₁ is preferably -O- or -NH-, and -O- is preferable because it shows higher hydrophilicity and improves the penetration effect into dentin. More preferred.

Among the polymerizable monomers (A), the polymerizable monomer represented by formula (1) is preferably used from the viewpoint of exhibiting excellent initial adhesive strength, adhesive durability, and dentin cohesive failure rate. As the polymerizable monomer (A), among them, the number of -CH ₂ - contained in Y is 0 to 10, the number of -CF ₂ - is 1 to 10, and the number of -O- is 1 to 10. It is preferable that the number of -CH ₂ - is 0 to 8, the number of -CF ₂ - is 2 to 9, and it is more preferable that the number of -O- is 2 to 9, and the number of -CH ₂ - is 2 to 9. More preferably, the number of -CF ₂ - is 3 to 7, and the number of -O- is 3 to 7. In Y, the total number of -CH ₂ -, -CF ₂ -, and -O- is preferably 2 to 30, more preferably 4 to 26, and even more preferably 6 to 20. Further, the number of carbon atoms contained in Y is preferably 1 to 18, more preferably 2 to 15, and even more preferably 3 to 12.

In the polymerizable monomer represented by formula (1), all X are groups represented by general formula (3), Y includes -CF ₂ -CF ₂ -, and - contained in Y Compounds in which the number of CH ₂ - is 0 to 8, the number of -CF ₂ - is 2 to 9, and the number of -O- is 2 to 9 are preferred, and each X is a group represented by the general formula (3). , Y is linear, contains -CF ₂ -CF ₂ -O-, the number of -CH ₂ - contained in Y is 0 to 6, the number of -CF ₂ - is 3 to 7, - A compound in which the number of O- is 3 to 7 is more preferable, in which each X is a group represented by the general formula (3), R ₄ is -O- or -NH-, and Y is a linear and contains -CF ₂ -CF ₂ -O-, the number of -CH ₂ - contained in Y is 0 to 6, the number of -CF ₂ - is 3 to 7, and the number of -O- is 3 to 7 A compound in which Y contains 3 to 12 carbon atoms is more preferable, where X is a group represented by general formula (3), R ₃ is H, and R ₄ is -O- or -NH-, Y is linear, contains -CF ₂ -CF ₂ -O-, the number of -CH ₂ - contained in Y is 0 to 6, and the number of -CF ₂ - is 3 ~7, compounds in which the number of -O- is 3 to 7 and Y contains 3 to 12 carbon atoms are particularly preferred. The polymerizable monomer represented by formula (2) is the same as the preferred X and Y of the polymerizable monomer represented by formula (1) above, and R ₂ is H or F. Compounds are preferred.

Specific examples of the polymerizable monomer represented by formula (1) are shown below.

Specific examples of the polymerizable monomer represented by formula (2) are shown below.

The content of the polymerizable monomer (A) is not particularly limited, but if the content is too small, there is a possibility that the effect of improving the adhesiveness of the polymerizable monomer (A) cannot be obtained. On the other hand, if the content is too large, the curability may decrease and adhesive performance may not be exhibited. Therefore, the content of the polymerizable monomer (A) is preferably 0.5 to 40 parts by mass, and 0.5 to 34 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer components in the dental adhesive composition. parts by weight is more preferable, and 1 to 23 parts by weight is even more preferable.

[Acidic group-containing polymerizable monomer (B)]
The acidic group-containing polymerizable monomer (B) has an acid etching effect and a primer treatment effect, and is a component that provides a deashing effect and a penetrating effect. Moreover, the acidic group-containing polymerizable monomer (B) is polymerizable and also provides a curing action. By containing the acidic group-containing polymerizable monomer (B), adhesiveness and adhesive durability to tooth substance are improved.

The acidic group-containing polymerizable monomer (B) 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, a carboxylic acid group, and an acryloyl Examples include polymerizable monomers having at least one polymerizable group such as a methacryloyl group, a vinyl group, or a styrene group. Specific examples of the acidic group-containing polymerizable monomer (B) are listed below.

Examples of the phosphoric acid group-containing polymerizable monomer include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, and 5-(meth)acryloyloxybutyl dihydrogen phosphate. (meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxyheptyldihydrogen phosphate, ) Acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl 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-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10- (meth)acryloyloxydecyl] 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 their acid chlorides, alkali metal salts, ammonium salts, and other phosphoric acid group-containing (meth)acrylics Examples include monomers.

Examples of the pyrophosphate group-containing polymerizable monomer 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 their acid chlorides, alkali metal salts, ammonium salts, etc. containing pyrophosphate groups Examples include (meth)acrylic monomers.

Examples of the thiophosphoric acid group-containing polymerizable monomer include 2-(meth)acryloyloxyethyldihydrogenthiophosphate, 3-(meth)acryloyloxypropyldihydrogenthiophosphate, and 4-(meth)acryloyloxybutyldihydrogenthiophosphate. , 5-(meth)acryloyloxypentyldihydrogenthiophosphate, 6-(meth)acryloyloxyhexyldihydrogenthiophosphate, 7-(meth)acryloyloxyheptyldihydrogenthiophosphate, 8-(meth)acryloyloxyoctyldihydrogen Thiophosphate, 9-(meth)acryloyloxynonyldihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyundecyldihydrogenthiophosphate, 12-(meth)acryloyloxy Examples include dodecyldihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyicosyldihydrogenthiophosphate, 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, 6-(meth)acryloyloxyhexyl-3 -phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate and these Examples include acid chlorides, alkali metal salts, and ammonium salts.

Examples of the sulfonic acid group-containing polymerizable monomer include 2-(meth)acrylamido-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 monomer having multiple carboxy groups in the molecule.

Examples of polymerizable monomers having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloyl aspartic acid, O-(meth)acryloyltyrosine, N- (meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyl-p-aminobenzoic acid, ) Acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, Examples include 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, and acid halides thereof.

Examples of polymerizable monomers having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, and 10-dicarboxylic acid. -(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-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, Examples include 4-dicarboxybenzoyloxy)propyl succinate and their acid anhydrides or acid halides.

Among these acidic group-containing polymerizable monomers (B), phosphoric acid group- or pyrophosphoric acid group-containing (meth)acrylic monomers are preferred because they exhibit better adhesion to tooth structure, and are particularly preferred. , phosphoric acid group-containing (meth)acrylic monomers are preferred. Among them, divalent phosphorus having an alkyl group or alkylene group with 6 to 20 carbon atoms as the main chain in the molecule is particularly effective in showing high deashing properties and high adhesive properties in the absence of organic solvents. Acid group-containing (meth)acrylic monomers are more preferable, and divalent phosphoric acid group-containing (meth)acrylic monomers having an alkylene group having 8 to 12 carbon atoms as the main chain in the molecule such as 10-methacryloyloxydecyl dihydrogen phosphate are more preferred. Most preferred are meth)acrylic monomers.

The acidic group-containing polymerizable monomer (B) may be used alone or in combination of two or more. If the content of the acidic group-containing polymerizable monomer (B) is too much or too little, the adhesiveness may deteriorate. Therefore, the content of the acidic group-containing polymerizable monomer (B) is preferably in the range of 1 to 50 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer components in the dental adhesive composition. The range of 1 to 30 parts by weight is more preferable, and the range of 1 to 20 parts by weight is even more preferable.

[Polymerization initiator (C)]
The polymerization initiator (C) used in the present invention can be selected from polymerization initiators used in general industry, and among them, polymerization initiators used in dental applications are preferably used. As the polymerization initiator (C), in particular, at least one selected from the group consisting of a photopolymerization initiator (C-1) and a chemical polymerization initiator (C-2) can be used.

Examples of the photopolymerization initiator (C-1) include (bis)acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, Examples include coumarins, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds. One type of photopolymerization initiator (C-1) may be used alone, or two or more types may be used in combination.

Among these photopolymerization initiators (C-1), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides and α-diketones. As a result, the dental adhesive composition has excellent photocurability in the visible light region and near ultraviolet region, and exhibits sufficient photocurability even when using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp. You can get things.

Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 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, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, potassium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, ammonium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, etc. It will be done.

Among (bis)acylphosphine oxides, 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)phenyl Examples include phosphine oxide, bis(2,3,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like.

Furthermore, examples of (bis)acylphosphine oxides include compounds described in JP-A No. 2000-159621.

Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine It is particularly preferred to use a sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide as the photopolymerization initiator (C-1).

Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenequinone, etc. . Among these, camphorquinone is particularly preferred from the viewpoint of having a maximum absorption wavelength in the visible light region.

As the chemical polymerization initiator (C-2), organic peroxides are preferably used. The organic peroxide used as the chemical polymerization initiator (C-2) is not particularly limited, and any known one can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates, and the like. The chemical polymerization initiator (C-2) may be used alone or in combination of two or more.

Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.

Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. can be mentioned.

Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

Examples of the dialkyl peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 1,3-bis( Examples include t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, and the like.

Examples of peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. (peroxy)butane, 2,2-bis(t-butylperoxy)octane, 4,4-bis(t-butylperoxy)valeric acid n-butyl ester, and the like.

Examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-Amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3, Examples include 3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleate.

Examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propyl Examples include peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, diallylperoxydicarbonate, and the like.

Among these organic peroxides, hydroperoxides are preferably used as the chemical polymerization initiator (C-2) in view of the overall balance between safety and storage stability. Among them, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are particularly preferably used as the chemical polymerization initiator (C-2).

The content of the polymerization initiator (C) in the dental adhesive composition of the present invention is not particularly limited, but from the viewpoint of curability of the resulting composition, etc. The amount of the polymerization initiator (C) is preferably in the range of 0.01 to 10 parts by weight, more preferably in the range of 0.05 to 7 parts by weight, and even more preferably in the range of 0.1 to 5 parts by weight. In addition, if the content of the polymerization initiator (C) exceeds 10 parts by mass, if the polymerization performance of the polymerization initiator itself is low, sufficient adhesive strength may not be obtained, and furthermore, dental adhesive This may lead to precipitation from the chemical composition.

[Hydrophilic polymerizable monomer (D) without acidic group]
The hydrophilic polymerizable monomer (D) that does not have an acidic group is preferably a radical monomer that does not have an acidic group and has a polymerizable group, and from the viewpoint of easy radical polymerization, the polymerizable group is (meth). ) Acrylic group and/or (meth)acrylamide group are preferred. The hydrophilic polymerizable monomer (D) having no acidic group means one having a solubility in water of 10% by mass or more at 25°C, preferably one having a solubility of 30% by mass or more, and More preferred are those that can be dissolved in water in any proportion. The hydrophilic polymerizable monomer (D) that does not have an acidic group not only promotes the penetration of the components of the dental adhesive composition into the tooth structure, but also penetrates into the tooth structure and absorbs organic components in the tooth structure. Adheres to (collagen). The hydrophilic polymerizable monomer (D) having no acidic group is preferably one having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, or an amide group. Hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-( Hydrophilic monofunctional (meth)acrylate polymerizable monomers such as (meth)acryloyloxy)ethyltrimethylammonium chloride and polyethylene glycol di(meth)acrylate (those with 9 or more oxyethylene groups); N - Methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, Diacetone (meth)acrylamide, 4-(meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl(meth)acrylamide, and monofunctional (meth)acrylamide monomers represented by the following general formula (5), etc. Examples include hydrophilic monofunctional (meth)acrylamide polymerizable monomers.

（式（５）中、Ｒ₅及びＲ₆はそれぞれ独立して、置換基を有していてもよい直鎖状又は分岐鎖状の炭素数１～３のアルキル基であり、Ｒ₇は水素原子又はメチル基である。）

(In formula (5), R ₅ and R ₆ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms which may have a substituent, and R ₇ is hydrogen atoms or methyl groups.)

The substituent for R ₅ and R ₆ is a linear or branched alkyl group having 1 to 4 carbon atoms or a halogen atom. Examples of the alkyl group having 1 to 3 carbon atoms for R ₅ and R ₆ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

Among these hydrophilic polymerizable monomers (D) without acidic groups, from the viewpoint of adhesiveness to tooth structure, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, diacetone ( Meth)acrylamide and hydrophilic monofunctional (meth)acrylamide monomers are preferred, and 2-hydroxyethyl (meth)acrylate, a monofunctional (meth)acrylamide monomer represented by general formula (5) is more preferable. The hydrophilic polymerizable monomer (D) having no acidic group may be used singly or in combination of two or more.

Furthermore, among the monofunctional (meth)acrylamide monomers represented by general formula (5), N,N-dimethylacrylamide and N,N-diethylacrylamide are more preferable from the viewpoint of storage stability; , N-diethylacrylamide is most preferred.

If the amount of the hydrophilic polymerizable monomer (D) not having an acidic group in the present invention is too small, the penetration effect into the tooth structure may be reduced. Therefore, the content of the hydrophilic polymerizable monomer (D) having no acidic group is in the range of 10 to 80 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components in the dental adhesive composition. Preferably, the range is from 15 to 70 parts by weight, more preferably from 20 to 60 parts by weight, and particularly preferably from 25 to 50 parts by weight.

[Hydrophobic polymerizable monomer (E) without acidic group]
The hydrophobic polymerizable monomer (E) that does not have an acidic group is preferably a radically polymerizable monomer that does not have an acidic group and has a polymerizable group. The group is preferably a (meth)acrylic group and/or a (meth)acrylamide group. The hydrophobic polymerizable monomer (E) having no acidic group means one having a solubility in water at 25°C of less than 10% by mass, such as an aromatic compound-based bifunctional monomer, a fat, etc. Crosslinkable monomers such as difunctional monomers and trifunctional or higher functional monomers based on group compounds are exemplified (excluding those falling under the polymerizable monomer (A)). The hydrophobic polymerizable monomer (E) having no acidic group improves the mechanical strength, handleability, etc. of the cured product of the dental adhesive composition.

Examples of aromatic compound-based difunctional 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-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)propane ethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)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 (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl ) propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (those with an average number of added moles of ethoxy group of 2.6, commonly known as "D-2.6E"), 2,2-bis(4-methacryloyloxypolyethoxyphenyl) -(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane is preferred.

Examples of aliphatic compound-based bifunctional monomers include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate. (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-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2 -carbamoyloxyethyl) di(meth)acrylate, N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropylamide, and the like. Among these, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as "3G"), 1,10-decanediol di(meth)acrylate (commonly known as "DD"), 2,2,4-trimethylhexamethylene bis (2-Carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA") and N-methacryloyloxyethyl acrylamide (commonly known as "MAEA") are preferred.

Examples of trifunctional or higher-functional monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth) Acrylate, 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxyheptane, and the like. Among these, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.

Among the above-mentioned hydrophobic polymerizable monomers (E) that do not have acidic groups, aromatic compound-based bifunctional monomers and aliphatic compound-based bifunctional monomers are preferred from the viewpoint of mechanical strength and handleability. Polymeric monomers are preferably used. Examples of aromatic compound-based bifunctional monomers include 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), and 2,2- Bis(4-methacryloyloxypolyethoxyphenyl)propane (having an average number of added moles of ethoxy groups of 2.6, commonly known as "D-2.6E") is preferred. Examples of aliphatic compound-based bifunctional monomers include triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as "3G"), 1,10-decanediol di(meth)acrylate (commonly known as "DD"), 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA") and N-methacryloyloxyethyl acrylamide (commonly known as "MAEA") are preferred.

Among the hydrophobic polymerizable monomers (E) without acidic groups, Bis-GMA, D-2.6E, DD, and MAEA are more preferred from the viewpoint of adhesive strength and mechanical strength of the cured product. Bis-GMA and MAEA are more preferred.

The hydrophobic polymerizable monomer (E) having no acidic group may be used alone or in combination of two or more. If the content of the hydrophobic polymerizable monomer (E) having no acidic group is too small, the mechanical strength of the cured product may decrease. Therefore, the content of the hydrophobic polymerizable monomer (E) having no acidic group is 10 to 80 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components in the dental adhesive composition. The range is preferably from 15 to 70 parts by weight, more preferably from 20 to 60 parts by weight, and particularly preferably from 25 to 50 parts by weight.

The dental adhesive composition of the present invention preferably further contains a filler. Such fillers can be broadly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. One type of filler may be used alone, or two or more types may be used in combination. Examples of cases in which two or more types are used in combination include cases in which fillers having different materials, particle size distributions, shapes, etc. are used in combination. As the filler, commercially available products can be used.

Examples of organic filler materials include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, Examples include polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. One type of organic filler may be used alone, or two or more types may be used in combination. The shape of the organic filler is not particularly limited.

Examples of 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, 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. Can be mentioned. One type of inorganic filler may be used alone, or two or more types may be used in combination.

There is no particular restriction on the shape of the inorganic filler, and examples of the inorganic filler include amorphous fillers and spherical fillers. From the viewpoint of improving the mechanical strength of the cured product, it is preferable to use a spherical filler as the inorganic filler. Here, the term spherical filler refers to particles observed in a unit field of view when photographed with a scanning electron microscope (SEM) that are rounded, and the particle diameter in the direction perpendicular to the maximum diameter is the maximum diameter. The filler can have an average uniformity divided by the diameter of 0.6 or more. When using a spherical filler as the inorganic filler, the average particle diameter is 0.1 μm, since the filling rate of the spherical filler in the dental adhesive composition does not decrease and the mechanical strength of the cured product can be maintained. The average particle diameter is preferably 5 μm or less because the surface area is sufficient to maintain the mechanical strength of the cured product.

In order to adjust the fluidity of the dental adhesive composition, the inorganic filler may be used after being previously subjected to surface treatment with a known surface treatment agent such as a silane coupling agent, if necessary. Examples of such surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like.

As the organic-inorganic composite filler, one obtained by adding a monomer compound to the above-mentioned inorganic filler in advance, making it into a paste, polymerizing it, and pulverizing it can be used. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler are mixed, polymerized, and then pulverized) can be used. The shape of the organic-inorganic composite filler is not particularly limited.

The particle size of the filler is not particularly limited, and the average particle size can be appropriately selected. From the viewpoint of the handling properties of the obtained dental adhesive composition and the mechanical strength of the cured product, the average particle diameter of the filler is preferably 0.001 μm or more, and preferably 50 μm or less, More preferably, it is 10 μm or less. In addition, in this specification, the average particle diameter of a filler means the average particle diameter of primary particles of a filler (average primary particle diameter).

The average particle diameter of the filler can be determined by a laser diffraction scattering method or by observing particles with an electron microscope. Specifically, a laser diffraction scattering method is convenient for measuring the particle size of particles of 0.1 μm or more, and electron microscopy is convenient for measuring the particle size of ultrafine particles of less than 0.1 μm. A laser diffraction scattering method may be used to determine whether or not it is 0.1 μm or more.

In the laser diffraction scattering method, for example, measurement is performed using a laser diffraction particle size distribution measuring device (for example, "SALD-2300" manufactured by Shimadzu Corporation) using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium. The average particle size can be determined.

In electron microscopy, for example, a photograph of particles is taken using a scanning electron microscope (for example, "S-4000 model" manufactured by Hitachi, Ltd.), and the number of particles (200 or more) observed within a unit field of view of the photograph is measured. The average particle diameter can be determined by measuring the particle diameter using image analysis type particle size distribution measuring software (such as "Macview" manufactured by Mountec Co., Ltd.). At this time, the particle diameter of the particles is determined as the arithmetic mean value of the longest length and the shortest length of the particles, and the average particle diameter is calculated from the number of particles and their particle diameters.

The filler content in the dental adhesive composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the dental adhesive composition. , more preferably 1.0% by mass or more, more preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less.

In addition, the dental adhesive composition may contain a pH adjuster, a polymerization inhibitor, a thickener, a coloring agent, a fluorescent agent, a fragrance, and the like within a range that does not impede the effects of the present invention. In addition, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecyl ammonium chloride, and triclosan may be added. good.

Known dyes and pigments may be added to the dental adhesive composition of the present invention.

The dental adhesive composition of the present invention can be used, for example, as a dental bonding material, a self-adhesive dental composite resin, a dental cement, a pit and fissure filling material, a moving tooth fixing material, an orthodontic adhesive, etc. Among these, it is suitably used as a dental bonding material. At this time, the dental adhesive composition of the present invention may be used as a two-part type (two-component type, two-paste type) in which the components are divided into two parts.

Among dental bonding materials, one-component bonding materials require all processes of deashing, infiltration, and hardening to be performed in one step with one component. Therefore, when the dental adhesive composition of the present invention is used as a one-component bonding material, it is preferable to contain water as a solvent from the viewpoint of emphasizing permeability. On the other hand, from the viewpoint of emphasizing curability, the dental adhesive composition preferably contains an appropriate amount of the hydrophobic polymerizable monomer (E), and from the viewpoint of obtaining a uniform solution, the dental adhesive composition preferably contains the hydrophobic polymerizable monomer (E) in an appropriate amount. It is preferable that an organic solvent is included as the solvent. In a more preferred embodiment, the solvent is used in the form of a mixed solvent of water and an organic solvent. In such an embodiment, the content of water in the mixed solvent is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples. Furthermore, not all combinations of features described in the embodiments are essential to the solution of the present invention. The various components used in the following Examples and Comparative Examples, their abbreviations, structures, and test methods are as follows.

[Polymerizable monomer (A) having a fluorocarbon group, two or more olefinic double bonds, and one or more ether]

DA-F3EO:

DA-F4EO:

[Acidic group-containing polymerizable monomer (B)]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Polymerization initiator (C)]
CQ: Camphorquinone BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[Hydrophilic polymerizable monomer (D) without acidic group]
HEMA: 2-hydroxyethyl methacrylate

[Hydrophobic polymerizable monomer (E) without acidic group]
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane

〔others〕
DABE: Ethyl 4-(N,N-dimethylamino)benzoate (polymerization accelerator)
DEPT: N,N-di(2-hydroxyethyl)-p-toluidine (polymerization accelerator)
BHT: 2,6-di-t-butyl-4-methylphenol (stabilizer (polymerization inhibitor))
Water: Purified water EtOH: Ethanol R972: Nippon Aerosil Co., Ltd., fine particle silica "AEROSIL (trademark registered) R 972", average particle size: 16 nm
8FMA: Octafluoropentyl methacrylate

8FDA: 1H, 1H, 6H, 6H-PERFLUORO-1,6-HEXANEDIOL DIACRYLATE (manufactured by Exfluor Research)

[Tensile adhesive strength to dentin]
The labial surface of a bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain a sample in which the flat surface of dentin was exposed. The obtained sample was further polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. An adhesive tape having a thickness of about 150 μm and having a round hole of 3 mm in diameter was attached to the smooth surface after drying to define the adhesion area.

The dental bonding materials prepared in each of the Examples and Comparative Examples were applied to the above-mentioned round holes using a brush, left for 10 seconds, and then the surface was blown with air. Subsequently, the applied dental bonding material was cured by irradiating it with light for 10 seconds using a dental LED light irradiator (manufactured by Morita Co., Ltd., trade name "Pencure 2000").

The surface of the obtained cured dental bonding material is filled with a composite resin for dental fillings (manufactured by Kuraray Noritake Dental Co., Ltd., trade name: "Clear Fill (registered trademark) AP-X"), and a release film (polyester) is applied. coated with. Next, a slide glass was placed on top of the release film and pressed against it to smooth the surface coated with the composite resin. Subsequently, the composite resin was irradiated with light for 20 seconds through the release film using the LED light irradiator "PenCure 2000" to cure the composite resin.

A stainless steel cylindrical rod (made by Kuraray Noritake Dental Co., Ltd., trade name "Panavia (registered trademark) 21") was applied to the surface of the obtained composite resin for dental filling. (diameter 7 mm, length 2.5 cm) one end surface (circular cross section) was adhered. After adhesion, the sample was allowed to stand at room temperature for 30 minutes, and then immersed in distilled water to obtain an adhesion test sample. Twenty samples for the adhesion test were prepared and left for 24 hours in a thermostat kept at 37°C. For 10 of the 20 samples, in order to evaluate the initial adhesive strength, the tensile adhesive strength was measured immediately after the samples were allowed to stand for 24 hours. For the remaining 10 pieces, in order to evaluate their adhesive durability, they were further subjected to 4,000 thermal cycles in which each cycle consisted of immersing them in cold water at 4°C and hot water at 60°C for 1 minute, and then their tensile adhesive strength was determined. was measured.

The tensile adhesive strength of the adhesive test sample was measured using a universal testing machine (product name: AG-I 100N, manufactured by Shimadzu Corporation) with the crosshead speed set at 2 mm/min, and the average value was Tensile adhesive strength.

[Dentin cohesive failure rate]
For each of the adhesion test samples for which tensile adhesion strength was measured regarding the initial adhesion strength and adhesion durability, the fracture surface after the test was visually observed, and it was found that the dentin side was destroyed in all samples. The ratio (%) of the number of samples was taken as the dentin cohesive failure rate. If the dentin cohesive failure rate is high, the permeability of the dental adhesive composition into the interior of the resin-impregnated layer is high, which can contribute to the hardenability of the interior of the resin-impregnated layer, and as a result, the adhesive interface and the inside of the resin-impregnated layer are This means that the curability of the adhesive is increased, and the bonding state of the adhesive interface is good.

[Bending strength]
Compressed air was blown onto the prepared dental adhesive compositions of Examples and Comparative Examples to evaporate the volatile organic solvent. After vacuum degassing, it is filled into a stainless steel mold (dimensions 2 mm x 2 mm x 25 mm), the top and bottom are pressed together with slide glass, and a dental LED light irradiator (manufactured by Morita Co., Ltd., product name "Pencure 2000") is used. Both sides of the slide glass were irradiated with light for 10 seconds per point, 5 points on each side, to obtain a cured product. For each example and comparative example, five cured products were produced, and after the cured products were removed from the mold, they were stored in distilled water at 37° C. for 24 hours. The cured product after storage was used as a test sample and bent using a universal testing machine (product name: AG-I 100N, manufactured by Shimadzu Corporation) under conditions of a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. The strength was measured, and the average value of the measured values of each sample was calculated and determined as the bending strength.

As shown in Table 1, the dental adhesive compositions according to the present invention (Examples 1 to 8) exhibited an initial adhesive strength of 14.0 MPa or more to dentin, and an adhesive durability of 14.5 MPa or more. It was expressed. In addition, the dentin cohesive failure rate was 80% or more for the samples in which initial adhesive strength was measured, and 60% or more in the samples in which adhesive durability was measured. It was suggested that the In contrast, the dental adhesive compositions (Comparative Examples 1 to 9) that did not contain the polymerizable monomer (A) had an initial adhesive strength of 14.0 MPa or less and an adhesive durability of 13 MPa or less to dentin. . In addition, the dentin cohesive failure rate was 60% or less for samples in which initial adhesive strength was measured, and 40% or less in samples in which adhesive durability was measured. It was suggested that this was not sufficient. In addition, regarding the bending strength, the Examples and Comparative Examples were almost the same, and the cured products of the dental adhesive compositions showed sufficient mechanical strength.

The dental adhesive composition according to the present invention is suitably used in the field of dentistry, particularly as a dental bonding material.

Claims (14)

A polymerizable monomer (A) having a fluorocarbon group, two or more olefinic double bonds, and one or more ether bond, an acidic group-containing polymerizable monomer (B), and a polymerization initiator (C) Contains
A dental adhesive composition, wherein the polymerizable monomer (A) contains a polymerizable monomer represented by the following general formula (1) or (2).

(In the above formula, R ₁ represents -O-, -NH-, or -CH ₂ O-, R ₂ represents H, F, or CH ₃ , and X represents the following general formula (3) or (4). is a group represented by, Y is a group containing one or more selected from the group consisting of -CH ₂ -, -CF ₂ -, and -O-, and Y in formula (1) is linear and Y in formula (2) is linear or branched, and in Y, the number of -CH ₂ - is 0 to 10, the number of -CF ₂ - is 1 to 10, - The number of O- is 1 to 10.)

(In the formula, R ₁ has the same meaning as in the above formula (2), * represents a bond, R ₃ represents H or CH ₃ , and R ₄ represents -O-, -NH-, or - (Represents NHCO-) The dental product according to claim 1, wherein the polymerizable monomer (A) is a polymerizable monomer represented by general formula (1), and X is a group represented by general formula (3). Adhesive composition. The dental adhesive composition according to claim 1 or 2, wherein _R3 is H. The dental adhesive composition according to any one of claims 1 to 3, wherein the number of -CF ₂ - in Y is 2 to 9. The dental adhesive composition according to any one of claims 1 to 4, wherein the number of -O- in Y is 2 to 9. The dental adhesive composition according to any one of claims 1 to 5, wherein Y contains -CF ₂ -CF ₂ -. The dental adhesive composition according to any one of claims 1 to 6, wherein the polymerizable monomer (A) has 1 to 10 ether bonds. The dental adhesive composition according to any one of claims 1 to 7, wherein the polymerizable monomer (A) has 2 to 20 fluorine atoms. The dental adhesive composition according to any one of claims 1 to 8, further comprising a hydrophilic polymerizable monomer (D) having no acidic group. The monomer according to any one of claims 1 to 9, further comprising a hydrophobic polymerizable monomer (E) having no acidic group (excluding those corresponding to the polymerizable monomer (A)). Dental adhesive composition. The dental adhesive composition according to any one of claims 1 to 10, wherein the polymerization initiator (C) is a photopolymerization initiator (C-1). The dental adhesive composition according to any one of claims 1 to 11, wherein the acidic group-containing polymerizable monomer (B) is a phosphoric acid group-containing polymerizable monomer. The dental treatment according to any one of claims 1 to 12, wherein the content of the polymerizable monomer (A) is 0.5 to 40 parts by mass based on 100 parts by mass of the total amount of polymerizable monomers. Adhesive composition for use. A dental bonding material comprising the dental adhesive composition according to any one of claims 1 to 13.