JP6851611B2 - Two-component dental adhesive composition - Google Patents

Description

The present invention relates to a two-component dental adhesive composition.

In the field of dental clinics, various restoration materials are used for the parts that have been damaged due to caries or accidents. For example, a composite resin is used for a small tooth cavity, and a crown material made of ceramics, metal, or the like is used for a large defect site. In addition, when repairing after demyelination, a resin core is used to form abutment teeth as a scaffold.

Various adhesives are used to bond these materials to the dentin. For example, in general, a photopolymerization type bonding material is used for a composite resin, a dental cement and its pretreatment material (primer) are used for a crown material, and a photopolymerization catalyst and a photopolymerization catalyst are used for a resin core. A dual cure type bonding material containing a chemical polymerization catalyst is used. However, when the adhesive is used properly for each case, the clinical operation becomes complicated.

Therefore, in order to deal with such a problem, a dental primer composition that exhibits sufficient adhesiveness to any of dentin, metal, and ceramics has been proposed (for example, Patent Document 1 and the like). Here, Patent Document 1 describes a primer composition in which a coupling agent, a sulfur atom-containing polymerizable compound, an acidic group-containing polymerizable compound, a polymerizable monomer, an organic solvent and water are mixed, or the primer composition. On the other hand, it is disclosed that the primer composition to which a polymerization accelerator is further added has obtained excellent adhesive strength for all of dentin, metal and ceramics.

Japanese Unexamined Patent Publication No. 2002-265312

On the other hand, a dental adhesive that exhibits excellent adhesiveness to various dental materials such as dentin, metal, and ceramics is required to be able to maintain excellent adhesiveness even after long-term storage.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a two-component dental adhesive composition having excellent adhesiveness to various dental materials and excellent storage stability.

The above object is achieved by the following invention. That is,
The two-component dental adhesive composition of the present invention has a first agent and a second agent encapsulated with each other, and has (A) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer. It contains at least five components consisting of a monomer, (C) silane coupling agent, (D) borate compound, and (E) water, and the first agent contains (A) an acidic group among the above five components. It contains only a polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer, and the second agent contains (C) a silane coupling agent, (D) a borate compound, and (E) among the above five components. ) only water is included, the first agent is an organic peroxide containing first, total polymerizable containing at least (a) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer The compounding ratio of the (A) acidic group-containing polymerizable monomer to 100 parts by mass of the monomer is 5 parts by mass to 30 parts by mass.

Another embodiment of the two-component dental adhesive composition of the present invention comprises, as (A) an acidic group-containing polymerizable monomer, an acidic group-containing polymerizable monomer represented by the following general formula (A1). , The acidic group-containing polymerizable monomer represented by the general formula (A2) and the acidic group-containing polymerizable monomer represented by the general formula (A1) and the acidic group-containing monomer represented by the general formula (A2) are used. The blending ratio of the acidic group-containing polymerizable monomer represented by the general formula (A2) to the total amount of the polymerizable monomer is preferably 3% by mass to 40% by mass.

[In the general formula (A1), ^RA11 represents a hydrogen atom or a methyl group, and W ¹ is an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-C _6). H ₄ -) ^{represents, R A21} is, (i) a bond, (ii) 2 to 6 monovalent hydrocarbon group having 1 to 30 carbon atoms, or a (iii) from 1 to 30 carbon atoms, an ether It represents a 2-6 valent organic residue containing at least one bond selected from a bond and an ester bond, where X ¹ represents a monovalent acidic group. Further, m1 represents an integer of 1 to 4, and n1 represents an integer of 1 to 6-m1. Here, m1 + n1 represents the valence of ^RA21.
In the general formula (A2), ^RA11 and ^RA12 independently represent a hydrogen atom or a methyl group, and W ¹ and W ² independently represent an oxycarbonyl group (-COO-) and an iminocarbonyl group (-COO-). -CONH-), or a phenylene group (-C ₆ H ₄ -) ^{represents, R A21} and ^{R A22} each independently, (i) a bond, (ii) 2 to 6 valent 1 to 30 carbon atoms A hydrocarbon group of, or (iii) having 1 to 30 carbon atoms and representing a 2 to 6 valent organic residue containing at least one bond selected from an ether bond and an ester bond, where X ¹ is monovalent. It represents an acidic group and X ² represents a divalent acidic group. Further, m1 and m2 independently represent an integer of 1 to 4, n1 represents an integer of 1 to 6-m1, and n2 represents an integer of 1 to 6-m2. Here, m1 + n1 represents the valence of ^{R A21,} m2 + n2 represents the valence of ^{R A22.} ]

Another embodiment of the two-component dental adhesive composition of the present invention is a long-chain phosphate group-containing polymerizable monomer represented by the following general formula (A1) as (A) acidic group-containing polymerizable monomer. It is preferable to use a monomer and a short-chain phosphate group-containing polymerizable monomer represented by the following general formula (A2).

[In the general formula (A1), ^RA11 represents a hydrogen atom or a methyl group, and W ¹ is an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-C ₆ H). ₄ -) represents, R ^A21 is carbon atoms in the main chain is 6-14 divalent to hexavalent chain hydrocarbon group or a main chain at least one of bonds selected from ether bond and an ester bond Represents a 2- to 6-valent chain organic residue containing in and having a main chain of 6 to 14 atoms.
X ¹ represents a phosphoric acid dihydrogen monoester group {-O-P (= O) (OH) ₂ } or a phosphono group {-P (= O) (OH) ₂ }. Further, m1 represents an integer of 1 to 4, and n1 represents an integer of 1 to 6-m1. Here, m1 + n1 represents the valence of ^RA21.
In the general formula (A2), ^RA11 and ^RA12 independently represent a hydrogen atom or a methyl group, and W ¹ and W ² independently represent an oxycarbonyl group (-COO-) and an iminocarbonyl group (-COO-). -CONH-), or a phenylene group (-C ₆ H ₄ -) ^{represents, R A21} and ^{R A22} each independently, carbon atoms in the main chain is 2 to 4 2 to 6 valent chain hydrocarbon group, or represents a divalent to hexavalent chain organic residue atoms of the main chain is 2 to 4 together with at least one binding is selected from an ether bond and an ester bond in the main chain, X ¹ is It represents a monovalent acidic group, where X ² represents a hydrogen phosphate diester group {(−O−) ₂ P (= O) OH} or a phosphinic group {= P (= O) OH}. Furthermore, m1 and m2 each independently represent an integer of 1 to 4, m1 + n1 represents the valence of ^{R A21,} m2 + n2 represents the valence of ^{R A22,} n1 represents an integer of 1 to 6-m1, n2 represents an integer of 1 to 6-m2. ]

In another embodiment of the two-component dental adhesive composition of the present invention, it is preferable that the (C) silane coupling agent is a compound represented by the following general formula (C1).

[In the general formula (C1), X is an oxygen atom or a nitrogen ^{atom, R C1} is a methyl group or a hydrogen ^{atom, R C2} is an alkylene group having 1 to 10 carbon ^atoms, R ^{C3, R C4} And ^RC5 are independently alkyl groups having 1 to 10 carbon atoms or alkoxyl groups having 1 to 10 carbon atoms.
Provided ^that at least one group selected from R ^{C3, R C4} and ^{R C5} is alkoxy group having 2 to 4 carbon atoms. ]

In another embodiment of the two-component dental adhesive composition of the present invention, in the general formula (C1), ^RC3 , ^RC4 and ^RC5 are independently alkoxyl groups having 2 to 4 carbon atoms. Is preferable.

In another embodiment of the two-component dental adhesive composition of the present invention, it is preferable that the (D) borate compound is an alkali metal salt of tetraaryl borate.

In another embodiment of the two-component dental adhesive composition of the present invention, at least one of the first agent and the second agent further contains (F) an organic solvent, and (F) the organic solvent is at normal pressure. It contains at least a low boiling organic solvent having a boiling point of 50 ° C. to 65 ° C. and a high boiling point organic solvent having a boiling point of 75 ° C. to 90 ° C. at normal pressure, and (A) an acidic group-containing polymerizable monomer and (B). ) The blending ratio of the low boiling point organic solvent to 100 parts by mass of the total polymerizable monomer containing at least the sulfur atom-containing polymerizable monomer is 200 parts by mass to 400 parts by mass, and 100 parts by mass of the total polymerizable monomer. The blending ratio of the high boiling point organic solvent with respect to the amount is preferably 25 parts by mass to 120 parts by mass.

In another embodiment of the two-component dental adhesive composition of the present invention, the first agent further contains (F) an organic solvent, and the blending ratio of the (F) organic solvent in the first agent is from 30% by mass to 30% by mass. It is preferably 90% by mass.

In another embodiment of the two-component dental adhesive composition of the present invention, the second agent further contains (F) an organic solvent, and the compounding ratio of the (F) organic solvent in the second agent is 10% by mass or more. It is preferably 99% by mass.

In another embodiment of the two-component dental adhesive composition of the present invention, the first agent and the second agent each further contain (F) an organic solvent, relative to the total amount of the first agent and the second agent. (F) The ratio of the total amount of the organic solvent is preferably 63% by mass to 85% by mass.

As described above, according to the present invention, it is possible to provide a two-component dental adhesive composition which is excellent in adhesiveness to various dental materials and also excellent in storage stability.

<Two-component dental adhesive composition>
The two-component dental adhesive composition of the present embodiment has a first agent and a second agent encapsulated with each other, and has (A) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerization. It contains at least five components consisting of a sex monomer, (C) a silane coupling agent, (D) a borate compound, and (E) water. The first agent contains only (A) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer among the five components shown in (A) to (E) above. The second agent contains only (C) a silane coupling agent, (D) a borate compound, and (E) water among the five components shown in (A) to (E) above.

Of the five components shown in (A) to (E) above, the first agent does not contain the components shown in (C) to (E) in principle, but is shown in (C) to (E). It is permissible that the component is unavoidably contained in a very small amount in the form of impurities or the like. Similarly, among the five components shown in (A) to (E) above, the second agent does not contain the components shown in (A) to (B) in principle, but in (A) to (B). It is permissible that the indicated component is inevitably contained in a very small amount in the form of impurities or the like.

Here, (A) the acidic group-containing polymerizable monomer mainly contains dentin (dental dentin, enamel), base metal (iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, etc.) or these. Improves adhesion to metal oxides (zirconia ceramics, alumina, titania, etc.) containing oxygen as the main component and metals such as zirconium (alloys contained as the main component), and (B) sulfur atom-containing polymerizable single amount The body mainly improves adhesion to precious metals (gold, platinum, palladium, silver, etc. or alloys containing these as main components), and (C) silane coupling agent is silica mainly containing silicon oxide as a component. Based oxides (porcelain, silica particles, silica-based glass ceramics, silica-based glass, etc.) and composite resin materials (resin matrix, and inorganic fillers containing silica-based oxides such as silica particles and silica-based glass fibers as components, Improves adhesion to composite materials). Therefore, the two-component dental adhesive composition of the present embodiment can be applied to any of various dental materials such as dentin, metal (base metal and noble metal), metal oxide, silica-based oxide, and composite resin material. However, it can exhibit excellent adhesiveness.

In addition to this, the (D) borate compound functions as a polymerization accelerator that promotes polymerization curing of the mixed composition after mixing the first agent and the second agent, and thus has adhesiveness to various adherends. Has a function to further improve. In addition to this, chemically polymerizable dental compositions containing organic peroxides and amine compounds (eg resin cement) and dentin, metals (base and noble metals), metal oxides, silica-based oxides, composites When a dental material such as a resin material is bonded to a dental material using the two-component dental adhesive composition of the present embodiment, the (D) borate compound becomes (A) an acidic group-containing polymerizable monomer. It is also possible to suppress a decrease in the polymerization activity of the chemically polymerizable dental composition due to the above, and to suppress a significant decrease in the adhesive strength.

Further, (E) water decalcifies the surface of the dentin in the presence of (A) an acidic group-containing polymerizable monomer, which is one of the acid components, to improve the adhesiveness to the dentin and to improve the adhesiveness to the dentin. (C) In the presence of a silane coupling agent, it also has a function of improving the adhesiveness to silica-based oxides and composite resin materials. Further, in the two-component dental adhesive composition of the present embodiment, the first agent and the second agent are mixed and applied to the surface of the adherend to obtain the above-mentioned components and the adherend. Adhesiveness is exhibited by the progress of the interaction with and the chemical polymerization due to the interaction of each component described above.

On the other hand, the mixed composition obtained by mixing the five components shown in (A) to (E) at once is a dentin, a base metal, a noble metal, a metal oxide, a silica-based oxide, and a composite resin immediately after mixing. Although it can exhibit excellent adhesiveness to any of the materials, gelation progresses when it is stored for a long period of time, and eventually it cannot be used as an adhesive. The progress of gelation of the mixed composition is considered to be due to the interaction of any two or more of the five components shown in (A) to (E), but the details are unknown. However, as a result of trial and error, the present inventors have added the five components shown in (A) to (E) to (A) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer. By storing the first agent containing (C) a silane coupling agent, (D) a borate compound and (E) a second agent containing water in separate forms, it is excellent for various dental materials. It was found that the adhesiveness can be ensured and excellent storage stability can be obtained.

If necessary, the first agent contains other components other than (A) acidic group-containing polymerizable monomer and (B) sulfur atom-containing polymerizable monomer (however, the above (C) to (E). ) May be further contained, and the second agent may contain (C) a silane coupling agent, (D) a borate compound and (E) other components other than water, if necessary. (However, the components corresponding to the above (A) and (B) are excluded) may be further contained. The details of the first agent and other components that can be further added to the second agent will be described later. Further, it is particularly preferable that the second agent does not contain any other acid component other than the (A) acidic group-containing polymerizable monomer. When the second agent contains an acid component, the acid component promotes the hydrolysis of hydrolyzable groups such as the alkoxy group constituting the (C) silane coupling agent during storage, or the (D) borate compound. This is because the storage stability of the second agent tends to be significantly lowered due to the decomposition reaction.

Here, "the second agent does not contain an acid component" means that the second agent does not substantially contain an acid component, and it is particularly preferable that the second agent does not contain an acid component at all. In other words, as long as it does not adversely affect the adhesive strength and storage stability after long-term storage, it is permissible if a very small amount of acid component is contained as an impurity or the like. The "acid component" means a substance having a pH of 4 or less in an aqueous solution or an aqueous dispersion dissolved and / or dispersed in water at a concentration of 1 mol / L. Examples of the "acid component" include any known acid component such as an inorganic acid such as hydrochloric acid and nitric acid and an organic acid such as acetic acid and sulfonic acid. Filling surface-modified with a polymerizable monomer containing an acidic group such as a phosphoric acid group, a phosphonic acid group, a sulfonic acid group or a carboxyl group, and an acidic group such as a phosphoric acid group, a phosphonic acid group, a sulfonic acid group or a carboxyl group. Materials and the like can be mentioned.

Further, the two-component dental adhesive composition of the present embodiment is stored in a state of being packaged in a first agent and a second agent at the time of storage. Here, the form of the sachet is not particularly limited as long as the composition constituting the first agent and the composition constituting the second agent do not come into contact with each other and mix with each other during storage, but usually, a syringe, etc. The first agent and the second agent are separately stored in various containers such as bags and bottles. On the other hand, at the time of use, it is usual that the first agent and the second agent are mixed to prepare a mixed composition, and then this mixed composition is applied to the surface of an adherend such as a tooth substance. It is also possible to mix the first agent and the second agent on the surface of the adherend by simultaneously applying the first agent and the second agent to the surface of the adherend or sequentially applying them separately. ..

Regarding the mixing ratio of the first agent and the second agent (first agent / second agent) when the two-component dental adhesive composition of the present embodiment is used, the adhesiveness and operability are significantly impaired. Although it can be appropriately selected within the range that does not exist, the mixing ratio (first agent / second agent) is 1/5 to 5/1 in terms of volume ratio from the practical viewpoints such as handleability and ease of product packaging. It is preferably in the range, more preferably in the range of 1/3 to 3/1, or more preferably in the range of 1/5 to 5/1 in terms of mass ratio, and more preferably in the range of 1/3 to 3/1. .. In addition, usually, the user of the two-component dental adhesive composition of the present embodiment is a mixing ratio determined by the developer, manufacturer or seller of the two-component dental adhesive composition of the present embodiment ( Hereinafter, the first agent and the second agent are mixed according to the "designated mixing ratio"). The actual mixing ratio at the time of use is allowed to deviate from the specified mixing ratio as long as the adhesiveness and operability are not significantly impaired. For example, when the specified mixing ratio is used as a reference (100%). The actual mixing ratio at the time of use may be in the range of 33% to 300%, preferably in the range of 50% to 200%.

The designated mixing ratio can be displayed on the mixing ratio information display medium. Examples of the mixing ratio information display medium include i) a product package consisting of a paper box and the like, ii) a paper medium and / or a product instruction manual provided as electronic data, and iii) the first agent and the second agent, respectively. Containers to be stored in a sealed state (bottles, syringes, packaging bags, etc.), iv) Product catalogs provided as paper media and / or electronic data, v) Sent to product users by e-mail or mail separately from the product. You can use the correspondence etc. Further, the designated mixing ratio may be provided to the product user in a manner that the product user can recognize by a mode other than those shown in i) to v) above.

Regarding the component X and the component Y used in the two-component dental adhesive composition of the present embodiment, a part of the component X and the component Y is contained in the first agent, and the rest is contained in the second agent. In this case, the blending ratio Z of the component Y based on the blending amount of the component X disclosed in the present specification means that the first agent and the second agent are mixed as described below. That is, it means that the first agent and the second agent are mixed at a mixing ratio that satisfies the blending ratio Z.

Next, details of each component used in the two-component dental adhesive composition of the present embodiment will be described.

(A) Acidic group-containing polymerizable monomer The acidic group-containing polymerizable monomer blended in the first agent contains one or more acidic groups and one or more polymerizable unsaturated groups in the molecule. Means a compound having. Here, as the acidic group, the phosphinic group {= P (= O) OH}, the phosphono group {-P (= O) (OH) ₂ }, the carboxyl group {-C (= O) OH}, and the diphosphate group hydrogen monoester group {-O-P (= O) (OH) 2}, hydrogen phosphate diester group _{{(-O-) 2 P (=} O) OH}, sulfo group _(-SO 3 H), or, Examples thereof include groups showing acidity in an aqueous solution such as an organic group having an acid anhydride skeleton {-C (= O) -OC (= O)-}. Examples of the polymerizable unsaturated group include an acryloyl group, a metaacrylloyl group, an acrylamide group, a metaacrylamide group, and a styryl group.

The acidic group-containing polymerizable monomer is not particularly limited as long as it is a compound having one or more acidic groups and one or more polymerizable unsaturated groups in the molecule, but adhesion to dentin or base metal. From the viewpoint of strength, the compound represented by the following general formula (A1) or (A2) can be preferably used.

In the general formula (A1), ^RA11 represents a hydrogen atom or a methyl group, and W ¹ is an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-C ₆ H). ₄ -) ^{represents, R A21} is, (i) a bond, (ii) 2 to 6 monovalent hydrocarbon group having 1 to 30 carbon atoms, or a (iii) from 1 to 30 carbon atoms, an ether bond And represents a 2-6 valent organic residue containing at least one bond selected from ester bonds, where X ¹ represents a monovalent acidic group.

Further, m1 represents an integer of 1 to 4, and n1 represents an integer of 1 to 6-m1. Here, m1 + n1 represents the valence of ^RA21.

Note that when ^{W 1} is a oxycarbonyl group or imino ^group, as ^{R A21,} (ii) a hydrocarbon group, or, (iii) an organic residue, one of is selected. ^Moreover, if the bond is selected as ^{R A21,} a m1 = n1 = 1.

In the general formula (A2), ^RA11 and ^RA12 independently represent a hydrogen atom or a methyl group, and W ¹ and W ² independently represent an oxycarbonyl group (-COO-) and an iminocarbonyl group (-COO-). -CONH-), or a phenylene group (-C ₆ H ₄ -) ^{represents, R A21} and ^{R A22} each independently, (i) a bond, (ii) 2 to 6 valent 1 to 30 carbon atoms A hydrocarbon group of, or (iii) having 1 to 30 carbon atoms and representing a 2 to 6 valent organic residue containing at least one bond selected from an ether bond and an ester bond, where X ¹ is monovalent. It represents an acidic group and X ² represents a divalent acidic group.

Further, m1 and m2 independently represent an integer of 1 to 4, n1 represents an integer of 1 to 6-m1, and n2 represents an integer of 1 to 6-m2. Here, m1 + n1 represents the valence of ^{R A21,} m2 + n2 represents the valence of ^{R A22.}

Note that when ^{W 1} is a oxycarbonyl group or imino ^group, as ^{R A21,} (ii) a hydrocarbon group, or, (iii) any organic residue are selected, ^{W 2} is an oxycarbonyl group or iminocarbonyl for ^groups, as ^{R A22,} (ii) a hydrocarbon group, or may be selected one of (iii) an organic residue. ^In the case of ^{R A21} is a bond, a m1 = n1 = ^1, in the case of ^{R A22} is a bond, is m2 = n2 = 1.

In formula (A1) and (A2), X ¹ and X ² are as long as the acidic group according to the definition, although its structure is not particularly limited, preferred examples are as follows.

In the general formulas (A1) and (A2), ^{the structures of RA21} and ^RA22 are not particularly limited, and (i) a bond, (ii) a hydrocarbon group, or (iii) an organic residue is adopted. However, specific examples of suitable groups are as follows. Here, in ^{the specific examples of RA21} and ^RA22 shown below, p1, p2, and p3 are each independently an integer of 0 to 10, and p1 + p2 + p3 is 1 or more.

In the general formula (A1), ^{the case where RA21} is a bond means that m1 = n1 = 1 and the group W ¹ and the group X ¹ are directly bonded. Further, when ^{W 1} is a oxycarbonyl group or imino group ^{as R A21,} (ii) a hydrocarbon group, or, (iii) an organic residue, one of is selected.

In the general formula ^(A2), the case of ^{R A21} is a bond, a m1 = n1 = 1, and refers to a state where the group ^{W 1} and group ^{X 2} is directly bonded. Further, when ^{W 1} is a oxycarbonyl group or imino group ^{as R A21,} (ii) a hydrocarbon group, or, (iii) an organic residue, one of is selected. ^Similarly, the case of ^{R A22} is a bond, a m2 = n2 = 1, and refers to a state where the group ^{W 2} and group ^{X 2} is directly bonded. Also, if ^{W 2} is an oxycarbonyl group or imino group ^{as R A22,} (ii) a hydrocarbon group, or, (iii) an organic residue, one of is selected.

Preferred specific examples of the acidic group-containing polymerizable monomer represented by the general formulas (A1) and (A2) are shown below. Note that in the embodiment shown below, Ph represents a phenyl ^{group, R A11} are the same as those shown in formula (A1) or (A2).

In addition, q1, q2, and q3 in the compound shown in the lowermost row are independently integers of 0 to 2. The compound is often obtained as a mixture of compounds having different q1, q2, and q3, and the average sum of q1, q2, and q3 in the mixture is 3.5.

Examples of the acidic group-containing polymerizable monomer include vinyl phosphonic acids, acrylic acid, methacrylic acid, vinyl sulfonic acid and the like, in addition to those described above.

Among the acidic group-containing polymerizable monomers exemplified above, the phosphinic group {= P (= O) OH} and the phosphono group {-P (= O) ( OH) ₂ }, carboxyl group {-C (= O) OH}, dihydrogen phosphate monoester group {-OP (= O) (OH) ₂ }, hydrogen phosphate diester group {(-O-) _{It is particularly preferable to use one having 2} P (= O) OH} from the viewpoint of adhesive strength.

Among the acidic group-containing polymerizable monomers exemplified above, the acidic group-containing polymerizable monomer represented by the general formula (A1) is selected from the viewpoint of adhesiveness to dentin, base metal and metal oxide. It is preferable to use a long-chain phosphate group-containing polymerizable monomer having a molecular structure described below. ^{That is, (ii) a hydrocarbon group or (iii) an organic residue is selected as RA21} represented by the general formula (A1), where the (ii) hydrocarbon group has 6 to 14 carbon atoms in the main chain. It is preferably a 2- to 6-valent chain hydrocarbon group, and the (iii) organic residue contains at least one bond selected from an ether bond and an ester bond in the main chain and has the number of atoms in the main chain. It is preferably a 2- to 6-valent chain organic residue having a value of 6 to 14. ^{Here, as a specific example of RA21} in the long-chain phosphoric acid group-containing polymerizable monomer, an alkylene group having 6 to 14 carbon atoms (preferably 6 to 10) in the main chain can be mentioned. Further, X ¹ is preferably a phosphoric acid dihydrogen monoester group {-O-P (= O) (OH) ₂ } or a phosphono group {-P (= O) (OH) ₂ }.

Further, in the two-component dental adhesive composition of the present embodiment, only the acidic group-containing polymerizable monomer represented by the general formula (A1) may be used as the acidic group-containing polymerizable monomer. It is possible to use only the acidic group-containing polymerizable monomer represented by the general formula (A2), or the acidic group-containing polymerizable monomer represented by the general formula (A1) and the general formula ( It can also be used in combination with the acidic group-containing polymerizable monomer represented by A2).

In order to further improve the adhesiveness and adhesive durability, an acidic group-containing polymerizable monomer represented by the general formula (A1) and an acidic group-containing polymerizable monomer represented by the general formula (A2) are used in combination. In this case, from the viewpoint of the blending ratio of the acidic group-containing polymerizable monomer, the acidic group-containing polymerizable monomer represented by the general formula (A1) and the acidic group-containing polymerizable single amount represented by the general formula (A2). The blending ratio of the acidic group-containing polymerizable monomer represented by the general formula (A2) to the total amount (100% by mass) of the body is preferably 3% by mass to 40% by mass, and 5% by mass to 30% by mass. It is more preferable to set it to%. If the blending ratio of the acidic group-containing polymerizable monomer represented by the general formula (A2) is less than 3% by mass, the effect of improving the adhesiveness by improving the reactivity with the borate compound may not be sufficiently obtained, and 40% by mass. If it exceeds%, the adhesive durability against base metals and metal oxides may decrease.

On the other hand, from the viewpoint of the molecular structure of the acidic group-containing polymerizable monomer, the above-mentioned long-chain phosphate group-containing polymerizable monomer is used as the acidic group-containing polymerizable monomer represented by the general formula (A1). As the acidic group-containing polymerizable monomer represented by the general formula (A2), it is preferable to use a short-chain phosphate group-containing polymerizable monomer having a molecular structure described below. That is, (ii) a hydrocarbon group or (iii) an organic residue is independently selected as ^RA21 and ^RA22 represented by the general formula (A2), where the (ii) hydrocarbon group is the main chain. It is preferably a 2- to 6-valent chain hydrocarbon group having 2 to 4 carbon atoms, and the (iii) organic residue has at least one bond selected from an ether bond and an ester bond as the main chain. It is preferably a 2- to 6-valent chain organic residue containing 2 to 4 atoms in the main chain. ^{Here, specific examples of RA21} and ^RA22 in the short-chain phosphoric acid group-containing polymerizable monomer include an alkylene group having 2 to 4 carbon atoms in the main chain. Further, X ² is preferably a phosphate hydrogen diester group {(−O−) ₂ P (= O) OH} or a phosphinico group {= P (= O) OH}. When a long-chain phosphate group-containing polymerizable monomer and a short-chain phosphate group-containing polymerizable monomer are used in combination, these phosphate group-containing polymerizable monomers and a borate compound are used. Since the reactivity is improved, it becomes easy to further improve the adhesiveness.

Further, in the two-component dental adhesive composition of the present embodiment, 100 parts by mass of a total polymerizable monomer containing at least an acidic group-containing polymerizable monomer and a sulfur atom-containing polymerizable monomer is used. When this is done, the blending ratio of the acidic group-containing polymerizable monomer is preferably 5 parts by mass to 30 parts by mass, and more preferably 10 parts by mass to 20 parts by mass. If the blending ratio is less than 5 parts by mass, sufficient adhesive strength to the dentin may not be obtained, and if it exceeds 30 parts by mass, the adhesive durability to base metals and metal oxides may decrease.

Above all, in order to further improve the adhesive durability against base metals and metal oxides, the following formulations are preferable. Specifically, when the (A) acidic group-containing polymerizable monomer contains an acidic group-containing polymerizable monomer represented by the general formula (A2), the total polymerizable monomer is 100 parts by mass. The amount of the acidic group-containing polymerizable monomer represented by the general formula (A2) is preferably 1 part to 10 parts by mass, and more preferably 1 part to 5 parts by mass.

In the specification of the present application, the "totally polymerizable monomer" means all kinds of polymerizable monomers used as constituents of the two-component dental adhesive composition of the present embodiment. For example, when only (A) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer are used as the polymerizable monomer, the “totally polymerizable monomer” is These two types of polymerizable monomers are meant, and the amounts of "totally polymerizable monomers" are (A) the amount of the acidic group-containing polymerizable monomer and (B) the sulfur atom-containing polymerizable single amount. It means the total amount with the amount of body. Further, as a constituent component of the two-component dental adhesive composition of the present embodiment, in addition to (A) an acidic group-containing polymerizable monomer and (B) a sulfur atom-containing polymerizable monomer, (G) is further added. When other polymerizable monomers are used, the "totally polymerizable monomer" means these three types of polymerizable monomers, and the amount of the "totally polymerizable monomer" is (A). ) It means the total amount of the amount of the acidic group-containing polymerizable monomer, (B) the amount of the sulfur atom-containing polymerizable monomer, and (G) the amount of other polymerizable monomers. In the specification of the present application, the silane coupling agent having a polymerizable group described later is not classified as a “polymerizable monomer”. Therefore, even when a silane coupling agent having a polymerizable group is used as a constituent component of the two-component dental adhesive composition of the present embodiment, the amount of "totally polymerizable monomer" is not sufficient. , The amount of silane coupling agent having a polymerizable group is not included.

(B) Sulfur atom-containing polymerizable monomer The sulfur atom-containing polymerizable monomer blended in the first agent constitutes an acidic group containing a sulfur atom (however, a sulfur atom such as a sulfo group) in the molecule. It means a compound having one or more radically polymerizable groups (excluding the sulfur atom). Here, examples of the radically polymerizable group include groups containing an ethylenically unsaturated double bond such as a metaacryloyl group and a styryl group. Further, the sulfur atom is contained in the molecule in a form that does not form an acidic group such as a sulfo group, and forms a partial structure in the molecule such as> C = S,> CSC <, etc. Therefore, it is contained in a form constituting a partial structure other than the acidic group.

The sulfur atom-containing polymerizable monomer contains a sulfur atom (excluding the sulfur atom constituting an acidic group containing a sulfur atom such as a sulfo group) and one or more radically polymerizable groups in the molecule. The compound is not particularly limited as long as it has, but is a compound capable of producing a mercapto group by the remutability represented by the following general formulas (B1) to (B5); a disulfide compound represented by the following general formulas (B6) to (B9); Examples thereof include chain or cyclic thioether compounds represented by the following general formulas (B10) to (B11).

In the general formula ^{(B1) ~ (B11),} R B1 is a hydrogen atom or a methyl ^{group, R B2} is a divalent saturated hydrocarbon group having 1 to 12 carbon _{atoms, -CH 2 -C 6 H 4 -CH} 2 -Group,-(CH ₂ ) _o- Si (CH ₃ ) ₂ OSi (CH ₃ ) _2- (CH ₂ ) _p -group (where o and p are integers 1 to 5, respectively), or- CH ₂ CH ₂ OCH ₂ CH ₂ − group, Z ¹ is −OC (= O) − group, −OCH ₂ − group, or −OCH ₂ −C ₆ H ₄ − group (however, any of these). In the group Z ¹ , the rightmost carbon atom is bonded to the carbon forming an unsaturated double bond adjacent to the ^{group Z 1 , and the leftmost oxygen atom is bonded to the group RB2} ), and Z ² is −. OC (= O) - group (provided that the carbon atom at the right end in the radical Z ² is attached to the carbon to form an unsaturated double bond adjacent to the group Z ^2, the left end of the oxygen atoms bonded to the group R ^B2 (), -C ₆ H ₄ -group, or a bond (here, when group Z ² is a bond, an unsaturated double bond adjacent to ^{group RB2} and group Z ^{2 is formed.} Y is -S-, -O-, or -N ( ^RB3 )-(where R ^B3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). It is.).

Here, examples of the polymerizable compound capable of producing a mercapto group by tautomerism represented by the general formulas (B1) to (B5) include the following compounds.

Examples of the disulfide compounds represented by the general formulas (B6) to (B9) include the following compounds.

Further, examples of the chain or cyclic thioether compound represented by the general formulas (B10) to (B11) include the following compounds.

The sulfur atom-containing polymerizable monomer may be used alone or in combination of two or more. Further, from the viewpoint of storage stability of the first agent containing a sulfur atom-containing polymerizable monomer, the sulfur atom-containing polymerizable monomer is a polymerizable compound or disulfide that can generate a mercapto group due to tautomerism. It is preferably a compound, and from the viewpoint of adhesive strength, a compound capable of producing a mercapto group by tautomerism is most preferable. When two or more types are used in combination, the blending ratio of the sulfur atom-containing polymerizable monomers is based on the total amount of all types of sulfur atom-containing polymerizable monomers.

The blending ratio of the sulfur atom-containing polymerizable monomer is not particularly limited, but is preferably 0.001 to 30 parts by mass with respect to 100 parts by mass of the total polymerizable monomer. It is more preferably 01 to 10 parts by mass. If the blending ratio is less than 0.001 part by weight, it may not be sufficiently obtained for the noble metal, and if it exceeds 30 parts by mass, the curability may be lowered and the adhesive strength may be lowered.

(C) Silane Coupling Agent As the silane coupling agent to be blended in the second agent, known ones can be used without limitation. For example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methokiethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysisilane, γ -Methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltri (trimethylsiloxy) silane, ω-methacryloxydecyltrimethoxysilane, γ-methacryloxypropylpenta Methyldisiloxane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, γ-isocyanapropyl Examples thereof include triethoxysilane, γ-ureidopropyltriethoxysilane, and hexamethyldisilazane.

The silane coupling agent preferably has a polymerizable group such as a (meth) acrylic group from the viewpoint of adhesiveness to the silica-based oxide and the composite resin material. Further, from the viewpoint of storage stability of the second agent containing the silane coupling agent, it is particularly preferable to use the compound represented by the following general formula (C1).

In the general formula (C1), X is an oxygen atom or a nitrogen ^{atom, R C1} is a methyl group or a hydrogen ^{atom, R C2} is an alkylene group having 1 to 10 carbon ^atoms, R ^{C3, R C4} and ^RC5 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms. Provided ^that at least one group selected from R ^{C3, R C4} and ^{R C5} is alkoxy group having 2 to 4 carbon atoms.

Further, from the viewpoint of further improving the adhesion of silica-based oxide and to the composite resin material, it is preferred none of the R ^C3, R ^C4 and R ^C5 is an alkoxy group. The alkoxy group preferably has 2 to 4 carbon atoms, and most preferably 2. By setting the number of carbon atoms of the alkoxy group to 2 or more, it becomes easier to obtain excellent adhesive strength even if the second agent is stored for a long period of time and then mixed with the first agent. Further, by setting the number of carbon atoms of the alkoxy group to 4 or less, it becomes easy to further improve the adhesive strength from the time immediately after adjusting the second agent. ^Thus, R ^{C3, R C4} and ^{R C5} are each independently more preferably an alkoxyl group having 2 to 4 carbon atoms.

Among the silane coupling agents represented by the general formula (C1), γ-methacryloxypropyltriethoxysisilane is particularly suitable.

Further, the above-mentioned silane coupling agent may be used alone or in combination of two or more. When two or more kinds of silane coupling agents are used in combination, the blending ratio of the silane coupling agents is based on the total mass of all kinds of silane coupling agents. When a silane coupling agent having a polymerizable group such as γ-methacryloxypropyltriethoxysisilane is used as the silane coupling agent, the silane coupling agents having a polymerizable group are (A) and (B). ) And (G) are not classified into any of the polymerizable monomers, and it is regarded as (C) a silane coupling agent, and the blending ratio is calculated.

The blending ratio of the silane coupling agent is not particularly limited, but is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the total polymerizable monomer, and 1 part by mass to 20 parts by mass. It is more preferable to use parts by mass. If the blending ratio is less than 0.1 parts by weight, it may not be sufficiently obtained for the silica-based oxide and the composite resin material, and if it exceeds 30 parts by mass, the curability may be lowered and the adhesive strength may be lowered.

(D) Borate compound As the borate compound to be blended in the second agent, any known borate compound can be used without limitation, but it is preferable to use an aryl borate compound having an aryl group in the molecule. Examples of the aryl borate compound include an aryl borate compound having 3 or 4 aryl groups in one molecule.

Examples of the triarylborate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, and monoalkyltri (3). , 5-Bistryfluoromethyl) phenylboron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltri (P-Nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) ) Boron, monoalkyltri (m-butyloxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron, monoalkyltri (m-octyloxyphenyl) boron (alkyl groups are n-butyl group, n-octyl) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium Examples thereof include salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts and the like.

Examples of the tetraarylborate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis (3,5-bistrifluoromethyl). ) Phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis ( m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyl) Oxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium Salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. Can be mentioned.

Among the arylborate compounds listed above, a tetraarylborate compound is preferable, and an alkali metal salt of tetraarylborate is more preferable, from the viewpoint of storage stability of the second agent.

The borate compound may be used alone or in combination of two or more. When two or more types are used in combination, the blending ratio of the borate compounds is based on the total mass of all types of borate compounds.

The borate compound has a function as a polymerization accelerator as described above. In addition to the borate compound, the polymerization accelerator includes (a) organic peroxides such as benzoyl peroxide, (b) azo compounds such as azobisbutyronitrile, and (c) sodium benzenesulfinate. Sulfinates, (d) amines (secondary amines such as N-methylaniline or tertiary amines such as triethylamine), (e) α-diketones such as camphorquinone, (f) 2,4- Thioxanthones such as diethylthioxanthone, α-aminoacetophenones such as (g) 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1, (h) bis (2,6-dimethoxybenzoyl)- Acylphosphine oxides such as 2,4,4-trimethylpentylsulfinoxide, barbituric acids such as (i) 5-butylbarbituric acid, pigments such as (j) 3-thienoyl coumarin, (k). Photoacid generators such as 2,4,6-tris (trichloromethyl) -s-triazine, (l) organic borons such as triphenylborane, tributylborane, or tributylborane oxide, (m) iron chloride, Transitional metal compounds such as copper chloride, iron nitrate and iron citrate are also included.

However, as a result of trial and error by the present inventors, in a two-component composition in which a polymerization accelerator other than the borate compound and the components shown in (A) to (C) and (E) are combined instead of the borate compound. Adhesion to at least one of the adherends selected from dentin, base metal, noble metal, metal oxide, silica-based oxide, composite resin material is insufficient, or instead of the borate compound, the above ( When the polymerization accelerators shown in a) to (m) are used, both adhesiveness and storage stability can be sufficiently achieved even if the combination of the components to be blended in the first agent and the second agent is changed in various ways. I couldn't. However, in the two-component dental adhesive composition of the present embodiment, for the purpose of further improving the adhesiveness, the polymerization accelerators shown in (a) to (m) above may be added as necessary together with the borate compound. It may be used together.

The blending ratio of the borate compound is not particularly limited, but is preferably 0.1 part by mass to 15 parts by mass with respect to 100 parts by mass of the total polymerizable monomer, and 1 part by mass to 10 parts by mass. It is more preferable to make a part. If the blending ratio is less than 0.1 parts by weight, the polymerization curing reaction is not sufficiently promoted, and in particular, the adhesive strength of dentin may be lowered. Since the amount of the compound is increased, the curability may be lowered and the adhesive strength may be lowered.

(E) Water The water to be blended in the second agent is preferably substantially free of harmful impurities from the viewpoint of storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water and distilled water. Etc. can be used.

The mixing ratio of water is preferably 5 parts by mass to 50 parts by mass, and more preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass of the total polymerizable monomer. If the blending ratio is less than 5 parts by weight, sufficient adhesive strength to the dentin, silica-based oxide and composite resin material may not be obtained. On the other hand, if the blending ratio exceeds 50 parts by mass, water tends to remain after air blowing, and the adhesive strength may decrease. Furthermore, the storage stability of the silane coupling agent may decrease, and in particular, the adhesive strength of the silica-based oxide may decrease.

The preferable blending ratios of the (C) silane coupling agent, (D) borate compound, and (E) water in the second agent are not particularly limited, but it is preferable to satisfy the following blending ratios. That is, the blending ratio of the (D) borate compound to 100 parts by mass of the (C) silane coupling agent is preferably 1 part by mass to 300 parts by mass, more preferably 10 parts by mass to 200 parts by mass, and 10 parts by mass to 150 parts by mass. Is even more preferable. By setting the blending ratio of the borate compound (D) to 1 part by mass to 300 parts by mass, the storage stability of the second agent itself, particularly the storage stability of the silane coupling agent can be further improved. From the same viewpoint, the mixing ratio of (E) water to 100 parts by mass of (C) silane coupling agent is preferably 20 parts by mass to 1500 parts by mass, more preferably 25 parts by mass to 1250 parts by mass, and 100 parts by mass. ~ 850 parts by mass is more preferable.

(F) Organic Solvent An organic solvent may be further added to at least one of the first agent and the second agent constituting the two-component dental adhesive composition of the present embodiment, if necessary. As the organic solvent, any known organic solvent can be used without limitation, but usually, it is preferable to use a highly volatile organic solvent having a boiling point of less than 100 ° C.

Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, 1,4-dioxane and tetrahydrofuran; ethyl acetate and formic acid. Esters such as ethyl; aromatic solvents such as toluene, xylene, benzene; hydrocarbon solvents such as pentane, hexane, heptane, octane; chlorine solvents such as methylene chloride, chloroform, 1,2-dichloroethane; trifluoro Fluorine-based solvents such as ethanol can be mentioned. Among these, acetone, toluene, ethanol, isopropyl alcohol and the like are particularly preferably used for reasons such as solubility and storage stability. The organic solvent may be used alone or in combination of two or more. When two or more kinds are used in combination, the blending ratio of the organic solvent is based on the total mass of all kinds of organic solvents.

The organic solvent may be added only to the first agent, may be added only to the second agent, or may be added to both the first agent and the second agent. Further, as the organic solvent (a) added to the first agent, only one kind of organic solvent may be used, or two or more kinds may be used in combination. This also applies to the second agent. Further, (b) when an organic solvent is added to each of the first agent and the second agent, the organic solvent used for the first agent and the organic solvent used for the second agent are the same but different. You may.

The organic solvent used is an organic solvent having a boiling point of 50 ° C. to 65 ° C. at normal pressure (1 atm) (hereinafter, may be referred to as "low boiling point organic solvent") and normal pressure (1 atm). It is preferable to use at least an organic solvent having a boiling point of 75 ° C. to 90 ° C. (hereinafter, may be referred to as “high boiling point organic solvent”). In this case, it is preferable to use 200 parts by mass to 400 parts by mass of the low boiling point organic solvent and 25 parts by mass to 120 parts by mass of the high boiling point organic solvent with respect to 100 parts by mass of the totally polymerizable monomer.

By setting the blending amount of the low-boiling organic solvent and the high-boiling organic solvent with respect to 100 parts by mass of the fully polymerizable monomer within the above range, the metal, ceramics, hybrid resin, CAD / CAM resin block, etc. When the two-component dental adhesive composition of the present embodiment is bonded together with the dental resin cement, it is easy to prevent the prosthesis from being adhered in a floating state. Become.

The low boiling point organic solvent and the high boiling point organic solvent may be added to only one of the first agent and the second agent, respectively, or may be added to both of them. Examples of the low boiling point organic solvent include acetone (boiling point: 56.5 ° C.), and examples of the high boiling point organic solvent include isopropyl alcohol (boiling point: 82.4 ° C.) and ethanol (boiling point: 78.4 ° C.). ℃) and the like. As a matter of course, the low boiling point organic solvent and the high boiling point organic solvent may be used alone or in combination of two or more. When two or more kinds are used in combination, the blending ratio of the low boiling point organic solvent and the high boiling point organic solvent is based on the total mass of each organic solvent.

When an organic solvent is added to the first agent and the second agent, it is preferable to adjust each agent so as to satisfy the following ratios. That is, when an organic solvent is added to the first agent, the content of the organic solvent in the first agent is preferably in the range of 30% by mass to 90% by mass, more preferably in the range of 50% by mass to 70% by mass. .. Similarly, when an organic solvent is added to the second agent, the content of the organic solvent in the second agent is preferably in the range of 10% by mass to 99% by mass, more preferably in the range of 30% by mass to 90% by mass. preferable. By setting the content of the organic solvent in the first agent and the second agent within the above range, the storage stability of each agent was improved, and the mixture of the first agent and the second agent and the adhesive surface were coated. The thickness of the coating film made of the two-component dental adhesive composition of the present embodiment can be easily controlled.

Further, when each of the first agent and the second agent further contains an organic solvent, the ratio of the total amount of the organic solvent to the total amount of the first agent and the second agent is preferably 63% by mass to 85% by mass, 65. Particularly preferably, it is by mass% to 80% by mass. When the ratio of the total amount of the organic solvent to the total amount of the first agent and the second agent is less than 63% by mass, the operation time is sufficient due to the progress of the chemical polymerization after mixing the first agent and the second agent. May not be secured. When the ratio of the total amount of the organic solvent to the total amount of the first agent and the second agent exceeds 85% by mass, the coating film composed of the two-component dental adhesive composition of the present embodiment applied to the adhesive surface. The thickness may be reduced and the adhesiveness may be reduced. Further, by setting the ratio of the total amount of the organic solvent to the total amount of the first agent and the second agent within the above range, the mixing of the first agent and the second agent becomes easy.

(G) Other Polymerizable Monomer The two-component dental adhesive composition of the present embodiment contains (A) an acidic group-containing polymerizable monomer and an acidic group-containing polymerizable monomer from the viewpoint of adhesiveness to dentin and adhesive durability. It is preferable to further use (G) other polymerizable monomer other than (B) the sulfur atom-containing polymerizable monomer.

The other polymerizable monomer does not contain an acidic group and a sulfur atom (excluding the sulfur atom constituting an acidic group containing a sulfur atom such as a sulfo group) in the molecule, and has one or more. A known compound can be used without particular limitation as long as it is a compound containing a polymerizable unsaturated group. Here, examples of the polymerizable unsaturated group include those similar to those of the polymerizable unsaturated group contained in the acidic group-containing polymerizable monomer, but from the viewpoint of adhesiveness, an acryloyl group, a metaacrylloyl group, etc. An acrylamide group, a metaacrylamide group and the like are preferable.

Suitable specific examples of other polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, and benzyl. Monofunctional polymerizable single amount of methacrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, etc. Body: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, 2,2'-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2'-bis [4 -(Meta) acryloyloxyethoxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2'-bis {4- [2-hydroxy-3- (meth) acryloyloxypropoxy] phenyl} propane, 1,4-butanediol di ( Meta) Acrylate, 1,6-Hexanediol Di (Meta) Acrylate, 1,9-Nonandiol Di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Neopentyl Glycoldi (Meta) Acrylate, 1,6- Bis (methacrylethyloxycarbonylamino) -2,2,4-trimethylhexane, 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane, urethane (meth) acrylate, epoxy (meth) Polyfunctional polymerizable monomers such as acrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate; fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; styrene, divinylbenzene, α-methylstyrene , Styrene such as α-methylstyrene dimer, α-methylstyrene derivative; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate can be mentioned.

Among the other polymerizable monomers described above, a polyfunctional polymerizable monomer is preferably used from the viewpoint of adhesiveness to the dentin and adhesive durability. Specific examples of preferably used polyfunctional polymerizable monomers are 2,2'-bis {4- [2-hydroxy-3- (meth) acryloyloxypropoxy] phenyl} propane, triethylene glycol. Methacrylate, 2,2-bis [(4- (meth) acryloyloxypolyethoxyphenyl) propane], 1,6-bis (methacrylethyloxycarbonylamino) -2,2,4-trimethylhexane, 1,6-bis Examples thereof include (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane and trimethylpropantrimethacrylate.

As the other polymerizable monomer, only one type may be used, or two or more types may be used in combination. Other polymerizable monomers may be used alone or in combination of two or more. When two or more kinds are used in combination, the blending ratio of the other polymerizable monomers is based on the total mass of the total polymerizable monomers. Further, (G) and other polymerizable monomers can be added to either or both of the first agent and the second agent, but it is usually preferable to add them only to the first agent. ..

The blending ratio of the other polymerizable monomers is not particularly limited, but (A) an acidic group polymerizable monomer and (B) sulfur with respect to 100 parts by mass of the total polymerizable monomer. It is the amount excluding the atom-containing polymerizable monomer. From the viewpoint of sufficiently ensuring the adhesiveness improving effect derived from the acidic group-containing polymerizable monomer and the sulfur atom-containing polymerizable monomer, the blending ratio of the other polymerizable monomers is a total polymerizable single amount. It is preferably 40 parts by mass to 95 parts by mass, and more preferably 70 parts by mass to 90 parts by mass with respect to 100 parts by mass of the body.

(H) Organic Peroxide and (I) Degradation Accelerator The two-component dental adhesive composition of the present embodiment contains, if necessary, an organic peroxide for the purpose of further improving the polymerization activity. And the decomposition accelerator thereof are also suitable. In this case, it becomes easier to improve the adhesive strength to the dentin in particular.

Known compounds can be used as the organic peroxide without limitation, but typical examples thereof include ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates. Can be mentioned. Specific examples of these organic peroxides include the following.

Here, examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.

Examples of peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 1,1-bis (t-). Butyl peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-) Butyl peroxy) butane, n-butyl 4,4-bis (t-butyl peroxy) valerate, 2,2-bis (4,5-di-t-butyl peroxycyclohexyl) propane can be mentioned.

Hydroperoxides include P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl. Hydroperoxide can be mentioned. Examples of dialkyl peroxides include α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylkumi. Examples thereof include ruper oxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3 and the like.

Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and dichloromethane. Oxides, m-toroil benzoyl peroxide, benzoyl peroxide and the like can be mentioned.

Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, and G. Examples thereof include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, and di (3-methyl-3-methoxybutyl) peroxydicarbonate.

Peroxyesters include α, α-bis (neodecanoyl peroxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-. Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivarate, t-butylperoxypivarate, 1 , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy2-ethylhexanoate, t-butylperoxy2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmono Carbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-tor) Oil peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane , T-Butylperoxyacetate, t-Butylperoxy-m-toluole benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate and the like.

In addition to these, t-butyltrimethylsilyl peroxide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can be preferably used. Only one type of these organic peroxides may be used, or two or more types may be used in combination, but from the viewpoint of polymerization activity, it is particularly preferable to use hydroperoxides.

From the viewpoint of further improving the polymerization activity, it is more preferable to use the organic peroxide together with a decomposition accelerator that promotes the decomposition of the organic peroxide. The decomposition accelerator is not particularly limited as long as it is a compound having an action of promoting the decomposition of the organic peroxide in the coexistence of the borate compound, but in particular, the vanadium compound, iron compound, copper compound, molybdenum compound and manganese exemplified below It is preferable to use a metal compound selected from the group consisting of a compound, a cobalt compound and a tungsten compound.

Here, specific examples of the metal compound include vanadium compounds such as vanadium oxide (V), vanadium acetylacetonate oxide, sodium vanadate, vanadium oxytrichloride, iron (III) chloride, iron (III) acetylacetonate, and the like. Iron compounds such as iron naphthenate (III) and iron citrate (III), copper compounds such as copper chloride (II), copper citrate (II), copper (II) acetylacetonate, copper stearate (II), etc. Molybdenum compounds such as molybdenum oxide (VI) and molybdenum molybdenum acetylacetonate, manganese compounds such as manganese oxide (IV) and manganese naphthenate, cobalt compounds such as cobalt naphthenate and cobalt (III) acetylacetonate, tungsten oxide (VI) ), Tungstate compounds such as sodium tungstate and silicotungstate.

From the viewpoint of storage stability, the organic peroxide is preferably added to the second agent. The reason for this is that when an organic peroxide is added to the first agent, the organic peroxide and the (B) sulfur atom-containing polymerizable monomer react during storage to cause gelation. This is because the storage stability is lowered. Further, when a decomposition accelerator is also used in combination, it is preferable to add a decomposition accelerator to the first agent in order to suppress the decomposition of the organic peroxide during storage.

The amount of the organic peroxide to be blended is not particularly limited, but from the viewpoint of polymerization activity, 0.1 mol to 10 mol is preferable, and 0.5 mol to 5 mol is more preferable with respect to 1 mol of the borate compound. The amount of the decomposition accelerator used is not particularly limited, but from the viewpoint of polymerization activity, 0.001 mol to 1 mol is preferable with respect to 1 mol of the organic peroxide, and 0.05 mol to 0.1 mol is more preferable. preferable.

(J) Film Strengthening Agent When bonding is performed using the two-component dental adhesive composition of the present embodiment, a mixed composition obtained by mixing the first agent and the second agent on the surface of the first adherend is used. A film is formed, and the first adherend and the second adherend are adhered to each other through this film. Then, the adhesion between the first adherend and the second adherend is usually carried out at a stage before the coating film cured by chemical polymerization is completely cured. For this reason, if the strength of the coating film at the time of adhesion is low, the coating film may be crushed between these adherends at the time of adhesion and the coating film may become extremely thin, resulting in a significant decrease in the adhesive strength. Therefore, a film strengthening agent may be used in order to suppress such variations in adhesive strength and to facilitate stable and high adhesive strength at the time of adhesion.

The film strengthening agent is not particularly limited as long as it is a substance capable of improving the strength of the film in the uncured state during the bonding work, and is, for example, a resin material such as a polymethylmethacrylate (PMMA) resin, silica particles, or silica. -Inorganic fillers such as zirconia particles, quartz and fluoroaluminosilicate glass, organic polymers such as polymethylmethacrylate, polymethylmethacrylate-polyethylmethacrylate copolymers, ethylene-vinyl acetate copolymers and styrene-butadiene copolymers. A granular organic-inorganic composite filler obtained by mixing particles (organic filler) composed of the above-mentioned inorganic particles and a polymerizable monomer, polymerizing the mixture, and pulverizing the polymer can be used. The coating strengthening agent may be used alone or in combination of two or more. When two or more types are used in combination, the blending ratio of the coating strengthening agent is based on the total mass of all types of coating strengthening agents.

The film strengthening agent can be added to at least one or both of the first agent and the second agent. However, from the viewpoint of storage stability, it is preferable to add a silica-based inorganic filler that may react with the silane coupling agent to the first agent.

The coating strengthening agent can be used within a range that does not significantly adversely affect the adhesiveness and storage stability of the two-component dental adhesive composition of the present embodiment. Therefore, when a coating strengthening agent is used, the coating strengthening agent is preferably 0.1 parts by mass to 100 parts by mass, and further 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total polymerizable monomer. It is preferably parts by mass.

(K) Other Additives In addition, other additives other than those described above can be further used in the two-component dental adhesive composition of the present embodiment, if necessary. Examples of such additives include colorants, photopolymerization initiators, polymerization inhibitors such as hydroquinone monomethyl ether, hydroquinone, and 4-talshal butylphenol. When a photopolymerization initiator is used, the two-component dental adhesive composition of the present embodiment can be adhered or cured by light irradiation.

As the photopolymerization initiator, a known photopolymerization initiator can be used without limitation. For example, a combination of α-diketones and tertiary amines, a combination of acylphosphine oxide and tertiary amines, and thioxanthone. Examples thereof include photopolymerization initiators such as a combination of class and tertiary amines and a combination of α-aminoacetophenone and tertiary amines.

Examples of α-diketones include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, 1,2-phenanthrenequinone, and 1,4-phenanthrenequinone. Examples thereof include quinone, 3,4-phenanthrenequinone, and 9,10-phenanthrenequinone.

Examples of tertiary amines include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, and N. , N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostylben, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethyl Examples thereof include stearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2'-(n-butylimino) diethanol and the like. These can be used alone or in combination of two or more.

Examples of the acylphosphine oxides include benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5. 6-Tetramethylbenzoyldiphenylphosphine oxide and the like can be mentioned.

Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

Examples of α-aminoacetophenones include 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1, 2 -Benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-dimethylamino-1-( Examples thereof include 4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1 and the like.

The photopolymerization initiator may be used alone or in combination of two or more kinds. When two or more kinds of photopolymerization initiators are used in combination, the blending ratio of the photopolymerization initiator is based on the total mass of all kinds of photopolymerization initiators. When a photopolymerization initiator is used, an effective amount of the photopolymerization initiator is used as long as the adhesiveness and storage stability of the two-component dental adhesive composition of the present embodiment are not significantly adversely affected. It is preferable to use it. Specifically, the photopolymerization initiator is preferably 0.01 parts by mass to 10 parts by mass, and 0.1 parts by mass to 8 parts by mass with respect to 100 parts by mass of the total polymerizable monomer. preferable.

When the two-component dental adhesive composition of the present embodiment is used for aesthetic treatment, the mixture of the first agent and the second agent is usually easily colored by the color of the photopolymerization initiator itself. Become. In this case, it is preferable not to add the photopolymerization type initiator to the two-component dental adhesive composition of the present embodiment. Further, when it is desired to prolong the operation time under ambient light after collecting the two-component dental adhesive composition of the present embodiment in a mixing dish, the two-component dental adhesive composition of the present embodiment is photopolymerized. It is preferable not to add the mold initiator.

<Dental treatment method>
Regarding the dental treatment method using the two-component dental adhesive composition of the present embodiment, if the two-component dental adhesive composition of the present embodiment is used for adhesion between two adherends. Although not particularly limited, typical examples thereof include the dental treatment methods described below.

That is, the first dental treatment method of the present embodiment includes the first composition applying step of applying the two-component dental adhesive composition of the present embodiment to the surface of the tooth (dental substance), and the present embodiment. A second composition that imparts a photopolymerizable dental composition containing a polymerizable monomer, a filler and a photopolymerization initiator to the surface of the tooth to which the two-component dental adhesive composition of the form has been applied. At least a step of applying light and a step of irradiating the surface of the tooth to which the two-component dental adhesive composition and the photopolymerizable dental composition of the present embodiment with light are applied are included. Here, the photopolymerizable dental composition is generally called a composite resin.

Known polymerizable monomers, fillers and photopolymerization initiators used in the photopolymerizable dental composition, including those used in the two-component dental adhesive composition of the present embodiment. Can be used in combination as appropriate.

Further, the second dental treatment method of the present embodiment is selected from the group consisting of dentin, base metal, noble metal, metal oxide, silica-based oxide, composite resin material, and a composite material in which two or more kinds thereof are combined. The first composition applying step of applying the two-component dental adhesive composition of the present embodiment to the surface of the adherend, and the subject to which the two-component dental adhesive composition of the present embodiment is applied. It comprises at least a second composition-imparting step of imparting a chemopolymerizable dental composition comprising a polymerizable monomer, a filler and a chemopolymerization initiator to the surface of the adherend. Here, the chemically heavy dental composition is generally called a resin core or a resin cement.

The polymerizable monomer used in the chemically polymerizable dental composition includes known examples of the polymerizable monomer and filler that can be used in the two-component dental adhesive composition of the present embodiment. Can be used as appropriate.

Further, as the chemical polymerization initiator, a known chemical polymerization initiator can be used, but it is preferable to use a chemical polymerization initiator containing an organic peroxide and an amine compound.

Here, examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide, dialkyl peroxides such as dit-butyl peroxide and dicumyl peroxide, acetyl peroxide, and lauroyl peroxide. , Diacyl peroxides such as benzoyl peroxide and the like. These may be used alone or in combination of two or more.

Among these organic peroxides, diacyl peroxides are preferable, and benzoyl peroxide is most preferable, from the viewpoint of polymerization activity and storage stability in combination with a tertiary amine.

Further, as the amine compound, a tertiary amine compound can be used. The tertiary amine compound is generally classified into an aromatic tertiary amine in which an aromatic group is bonded to a nitrogen atom and an aliphatic tertiary amine in which only an aliphatic group is bonded to a nitrogen atom.

Here, as the aromatic tertiary amine, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-dihydroxyethyl-p -Toluidine-based aromatic tertiary amines such as toluidine, N, N-dimethyl-3,5-xylidine; N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline , N, N-dibenzylaniline, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, N, N-dihydroxyethylaniline and other aniline aromatic tertiary amines; P-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl ester, etc. Aromatic tertiary amines with a carbonyl group attached to the aromatic ring; p-dimethylaminophenethyl alcohol, p-dimethylaminostylben, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N -Dimethyl-α-naphthylamine and the like can be mentioned.

Examples of the aliphatic tertiary amine include tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-. Examples thereof include dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2'-(n-butylimino) diethanol and the like.

The amine compound may be used alone or in combination of two or more.

When a chemically polymerizable dental composition using a chemical polymerization initiator containing an organic peroxide and an amine compound is polymerized and cured, if an acidic group-containing polymerizable monomer is present in the system, it is usually an acidic group. The acidic group of the contained polymerizable monomer neutralizes the amine compound. In this case, the polymerization activity of the chemical polymerization initiator is significantly reduced, causing curing failure.

However, a chemically polymerizable dental composition using a chemical polymerization initiator containing an organic peroxide and an amine compound on the surface of the adherend to which the two-component dental adhesive composition of the present embodiment is applied. When the above is applied, the acidic group-containing polymerizable monomer contained in the first agent of the two-component dental adhesive composition of the present embodiment does not cause the curing disorder as described above. This is because the borate compound contained in the second agent of the two-component dental adhesive composition reacts with the acidic group-containing polymerizable monomer to generate radicals, which is contained in the chemically polymerizable dental composition. This is because the polymerization activity of the chemical polymerization initiator is not inhibited.

The chemically polymerizable dental composition may further contain a photopolymerization initiator and may be a so-called dual-cure type chemically polymerizable dental composition that can be cured by either photopolymerization or chemical polymerization.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.

1. 1. Abbreviations for Substances The abbreviations for substances used in the dental adhesive compositions of Examples and Comparative Examples will be described below.

<(A) Acidic group-containing polymerizable monomer>
・ MDP: 10-methacryloxydecyldihydrogen phosphate ・ MHP: 6-methacryloxyhexyl dihydrogen phosphate ・ PM1: mono (2-methacryloxyethyl) acid phosphate ・ PM2: bis (2-methacryloxyethyl) acid phosphate -PMB2: Bis (2-methacryloxybutyl) acid phosphate

<(B) Sulfur atom-containing polymerizable monomer>
MTU-6: 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate ・ MMT-11: 2- (11-methacryloyloxyundecylthio) -5-mercapto-1,3,4-thiadiazole

<(C) Silane coupling agent>
-MPS: γ-methacryloxypropyltrimethoxysilane-MPTES: γ-methacryloxypropyltriethoxysisilane

<(D) Borate compound>
-PhB-TEOA: triethanolamine salt of tetraphenylboron-PhB-Na: sodium salt of tetraphenylboron

<(E) Organic solvent>
High boiling organic solvent IPA: Isopropyl alcohol

<(G) Other polymerizable monomers>
BisGMA: 2.2'-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane · 3G: triethylene glycol dimethacrylate · HEMA: 2-hydroxyethyl methacrylate

<Other ingredients>
-BMOV: Oxovanadium (IV) bis (maltlate)
-Perocta H: 1,1,3,3-tetramethylbutylhydroperoxide-CQ: camphorquinone-DMBE: ethyl 4-dimethylaminobenzoate-BPO: benzoyl peroxide-DEPT: N, N-dimethyl-p-toluidine PTSNa: sodium p-toluenesulfinate

2. Preparation of Dental Adhesive Composition As shown in Tables 1 to 4, each component was mixed to prepare a two-component dental adhesive composition composed of a first agent and a second agent. However, the dental adhesive composition shown in Comparative Example 11 was a one-component dental adhesive composition composed of only the first agent.

3. 3. Evaluation of adhesive strength between dentin and composite resin The anterior teeth of cows removed within 24 hours after slaughter are polished with water-resistant abrasive paper P600 under water injection, and the enamel plane is carved out so as to be parallel and flat on the lip surface. The adherend and the adherend obtained by carving out the dentin plane were prepared.

Next, a double-sided tape having a hole with a diameter of 3 mm was attached to each of the polished surfaces of these two types of adherends. Subsequently, the dental adhesive compositions of Examples and Comparative Examples shown in Tables 1 to 4 are applied to the adhesive surface of the polished surface exposed from the holes of the double-sided tape, and air blown for 5 seconds. It was dried.

In the dental adhesive composition, the first agent and the second agent were mixed on a mixing dish and applied to the adhesive surface. The mixing ratio of the first agent and the second agent was set so that the blending ratio of each component shown in Tables 1 to 4 was maintained as it was. For example, in Comparative Example 14 , the first agent: 250 parts by mass and the second agent: 250 parts by mass were mixed. When the dental adhesive composition was a one-component type composed of only the first agent, only the first agent was applied to the adhesive surface.

The dental adhesive composition to be applied to the adhesive surface includes the one immediately after preparing the dental adhesive composition and the one immediately after preparing the dental adhesive composition, which is sealed in a container at 50 ° C. Two types were used after being stored in a constant temperature bath for 8 weeks. Regarding the dental adhesive compositions of Comparative Examples 8 and 11, the first agent gelled about 1 hour after the adjustment. Therefore, when the dental adhesive composition immediately after preparation is applied to the adhesive surface, the first agent is adjusted by adding a borate compound immediately before use after mixing components other than the borate compound. did. Then, in Comparative Example 8, the first agent and the second agent were mixed immediately after the preparation of the first agent and applied to the adhesive surface, and in Comparative Example 11, the first agent was immediately prepared after the preparation of the first agent. The agent was applied to the adhesive surface.

A paraffin wax having a thickness of 0.5 mm provided with a hole having a diameter of 8 mm is attached to the adhesive surface coated with the dental adhesive composition so that the hole of the paraffin wax and the hole of the double-sided tape are concentric circles. A simulated cavity was created. This simulated tooth cavity is filled with a dental composite resin (Esterite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.), lightly pressed with a polyester film, and then lighted using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Photocuring was performed by irradiation for 10 seconds. Then, a pre-polished round bar made of SUS304 (diameter 8 mm, height 18 mm) was bonded with resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.). Finally, a sample for measuring the adhesive strength was obtained by immersing in water at 37 ° C. for 24 hours. The composite resin used (Esterite Σ Quick) is a photopolymerizable composition containing camphorquinone and an amine compound.

The tensile adhesive strength of these samples was measured using an autograph (crosshead speed 2 mm / min) manufactured by Shimadzu Corporation. For each Example and Comparative Example, the measured values of the four samples were averaged and used as the measurement result. In addition, the measurement was carried out within about 1 day by pulling up the sample for measuring the adhesive strength from the water.

Tables 5 to 6 show the measurement results of the adhesive strength (initial adhesive strength) of the sample obtained by applying the dental adhesive composition immediately after preparation to the adhesive surface, and further after adjusting to the adhesive surface. Tables 7 to 8 show the measurement results of the adhesive strength (adhesive strength after long-term storage) of the sample obtained by applying the dental adhesive composition after storing in a constant temperature bath at 50 ° C. for 8 weeks. Further, the sample obtained by applying the dental adhesive composition immediately after preparation to the adhesive surface is further immersed in a water tank having a water temperature of 5 ° C and a water tank having a water temperature of 55 ° C alternately for 30 seconds each. Table 9 shows the measurement results of the adhesive strength (adhesive strength after the durability test) after the immersion treatment was set as one set and this was repeated 3000 times.

If either the first agent or the second agent was gelled in the appearance evaluation after long-term storage, which will be described later, it became difficult to apply the dental adhesive composition to the adhesive surface, so that after long-term storage. Evaluation of adhesive strength was omitted.

4. Evaluation of Adhesive Strength between Various Adhesions and Resin Cement The following seven types of adherends were prepared.
(1) An adherend obtained by polishing the bovine anterior teeth removed within 24 hours after slaughter with water-resistant abrasive paper P600 under water injection, and carving out an enamel plane so as to be parallel and flat on the lip surface.
(2) An adherend obtained by polishing the bovine anterior teeth removed within 24 hours after slaughter with water-resistant abrasive paper P600 under water injection, and carving out a dentin plane so as to be parallel and flat on the lip surface.
(3) Dental gold-silver-palladium alloy "Kinpara 12" (manufactured by Towa Giken Co., Ltd., length 10 mm x width 10 mm x thickness 3 mm) is polished with # 1500 water-resistant abrasive paper and then sandblasted. Landing.
(4) An adherend made of a base metal alloy obtained by polishing a dental cobalt-chromium alloy "Workrome" (manufactured by Towa Giken Co., Ltd., length 10 mm x width 10 mm x thickness 3 mm) with # 1500 water-resistant abrasive paper and then sandblasting.
(5) Silica-based oxide "GCERA Cosmo Tech II" (manufactured by GC Corporation, length 10 mm x width 10 mm x thickness 3 mm) is made of silica-based oxide (porcelain) sandblasted after polishing with # 1500 water-resistant abrasive paper. Adhesive body.
(6) An adherend made of a composite resin material obtained by polishing a composite resin material "Esterite Block" (manufactured by Tokuyama Dental, length 10 mm x width 10 mm x thickness 3 mm) with # 1500 water-resistant abrasive paper and then sandblasting. The "esterite block" is a composite resin material containing silica particles in the resin matrix.
(7) From metal oxide (zirconia ceramics) sandblasted after polishing zirconia ceramics "TZ-3Y-E sintered body" (manufactured by Tosoh Corporation, length 10 mm x width 10 mm x thickness 3 mm) with # 1500 water-resistant abrasive paper. The adherend.

Next, a double-sided tape having a hole with a diameter of 3 mm was attached to each of the polished surfaces of these two types of adherends. Subsequently, the dental adhesive compositions of Examples and Comparative Examples shown in Tables 1 to 4 are applied to the adhesive surface of the polished surface exposed from the holes of the double-sided tape, and air blown for 5 seconds. It was dried.

In the dental adhesive composition, the first agent and the second agent were mixed on a mixing dish and applied to the adhesive surface. The mixing ratio of the first agent and the second agent was set so that the blending ratio of each component shown in Tables 1 to 4 was maintained as it was. For example, in Example 2, the first agent: 250.1 parts by mass and the second agent: 250 parts by mass were mixed. When the dental adhesive composition was a one-component type composed of only the first agent, only the first agent was applied to the adhesive surface.

The dental adhesive composition to be applied to the adhesive surface includes the one immediately after preparing the dental adhesive composition and the one immediately after preparing the dental adhesive composition, which is sealed in a container at 50 ° C. Two types were used after being stored in a constant temperature bath for 8 weeks. Regarding the dental adhesive compositions of Comparative Examples 8 and 11, the first agent gelled about 1 hour after the adjustment. Therefore, when the dental adhesive composition immediately after preparation is applied to the adhesive surface, the first agent is adjusted by adding a borate compound immediately before use after mixing components other than the borate compound. did. Then, in Comparative Example 8, the first agent and the second agent were immediately applied to the adhesive surface after the preparation of the first agent, and in Comparative Example 11, the first agent was immediately adhered after the preparation of the first agent. It was applied to the surface.

Subsequently, a SUS304 round bar to which the adhesive surface to which the dental adhesive composition has been applied is further polished and the dental adhesive composition has been applied in advance using a dental adhesive resin cement (Estesem, manufactured by Tokuyama Dental). (Diameter 8 mm, height 18 mm) was adhered. The excess resin cement that protruded from the adhesive surface during adhesion was removed using a needle or the like. Then, the dental adhesive resin cement was chemically polymerized by leaving it in a constant temperature bath kept at a temperature of 37 ° C. and a humidity of 100% for about 1 hour. Finally, a sample for measuring the adhesive strength was obtained by immersing in water at 37 ° C. for 24 hours. The dental adhesive resin cement used contains a photopolymerization initiator and a benzoylperoxide-amine compound-based chemical polymerization initiator, and both photopolymerization and chemical polymerization are possible during polymerization curing. is there. In this adhesion test, the resin cement was cured using only chemical polymerization.

The tensile adhesive strength of these samples was measured using an autograph (crosshead speed 2 mm / min) manufactured by Shimadzu Corporation. For each Example and Comparative Example, the measured values of the four samples were averaged and used as the measurement result. In addition, the measurement was carried out within about 1 day by pulling up the sample for measuring the adhesive strength from the water.

Tables 5 to 6 show the measurement results of the adhesive strength (initial adhesive strength) of the sample obtained by applying the dental adhesive composition immediately after preparation to the adhesive surface, and further after adjusting to the adhesive surface. Tables 7 to 8 show the measurement results of the adhesive strength (adhesive strength after long-term storage) of the sample obtained by applying the dental adhesive composition after storing in a constant temperature bath at 50 ° C. for 8 weeks. Further, the sample obtained by applying the dental adhesive composition immediately after preparation to the adhesive surface is further immersed in a water tank having a water temperature of 5 ° C and a water tank having a water temperature of 55 ° C alternately for 30 seconds each. Table 9 shows the measurement results of the adhesive strength (adhesive strength after the durability test) after the immersion treatment was set as one set and this was repeated 3000 times.

If either the first agent or the second agent was gelled in the appearance evaluation after long-term storage, which will be described later, it became difficult to apply the dental adhesive composition to the adhesive surface, so that after long-term storage. Evaluation of adhesive strength was omitted.

5. Appearance evaluation after long-term storage After preparing the dental adhesive compositions of Examples and Comparative Examples shown in Tables 1 to 4, they were sealed in a container and further stored in a constant temperature bath at 50 ° C. for 8 weeks. Subsequently, the appearance of each of the container in which the first agent was sealed and the container in which the second agent was sealed taken out from the constant temperature bath was visually observed, and changes in the first agent and the second agent before and after storage were observed. The presence or absence and denaturation such as gelation were evaluated. The results are shown in Tables 7-8.

6. Measurement of operating time The operating time was measured for the dental adhesive compositions of Examples 2, 6, 7, 8 and 9. The operation time was measured according to the following procedure. First, 0.04 ml of the dental adhesive compositions of each Example and Comparative Example were collected in a mixing dish under a normal temperature and humidity environment (temperature 23 ° C., humidity 50%). In the case of a two-component dental adhesive composition, the first agent and the second agent were collected and mixed in a mixing dish at the same time. Subsequently, the collection time was set to 0 seconds, and the dental adhesive composition collected in the mixing dish after the lapse of a predetermined time was used as an adherend sample using a mini brush (cow anterior teeth removed within 24 hours after slaughter). Was applied to the surface of an enamel plane) that had been polished with water-resistant abrasive paper P600 under water injection and carved so as to be parallel and flat on the lip surface. In this application test, one set of application with a mini brush is set for each collection of the dental adhesive composition on the mixing dish, and each time the time required from collection to application is changed, a new mixture is placed on the mixing dish. The dental adhesive composition was collected and applied with a mini brush. Then, when the coating is applied, whether or not the coating property is good is determined by whether or not the dental adhesive composition can be smoothly and sufficiently stretched on the surface of the adherend sample by the mini brush, and good coating property is shown. The maximum time was taken as the operation time. The results are shown in Table 10. The guideline for the appropriate operation time is 60 seconds or more.

7. Evaluation of Lifting Amount of Prosthesis The lifting amount of the prosthesis was evaluated for the dental adhesive compositions of Examples 2, 6, 7, 8 and 9. The amount of lift of the prosthesis was determined by the following procedure. First, a composite resin (Esterite Flowquick, manufactured by Tokuyama Dental) is filled in the tooth cavity using a resin model tooth in which a first-class cavity having a prominent corner is formed in the tooth cavity, and then light irradiation is performed. This cured the composite resin. Next, the surface of the model tooth on the side where the opening of the tooth cavity is formed is polished together with a composite resin (prosthesis made of a composite resin material) cured in the tooth cavity to obtain an upper surface of the prosthesis in the tooth cavity. And the surface around the tooth cavity opening of the model tooth was polished so as to be completely flush with each other (step 0 μm). Then, after polishing, the prosthesis was removed from the tooth cavity.

Next, the dental adhesive composition of each Example and each Comparative Example is applied to the inner wall surface of the tooth cavity and the surface of the prosthesis (the surface in contact with the inner wall surface of the tooth cavity), and the dental adhesive composition is further applied thereto. Resin cement for use (Estesem, manufactured by Tokuyama Dental) was applied, and then a prosthesis was inserted into the tooth cavity, and the prosthesis was attached to the model tooth. In the case of a two-component dental adhesive composition, the first agent and the second agent were mixed on a mixing dish and applied to the adhesive surface. Then, the excess dental resin cement protruding from the adhesive interface between the tooth cavity and the prosthesis was removed, and the dental resin cement was cured by irradiating with light. As a result, a sample for evaluating the amount of lift of the prosthesis was obtained. During the application of the dental adhesive composition and the dental resin cement, the temperature of the model tooth was set to the same temperature as in the oral cavity (37 ° C.). In addition, after the dental adhesive composition was applied into the tooth cavity, air blowing was performed for about 5 seconds in order to suppress the formation of a thick film at the corners of the tooth cavity.

For the obtained sample, a laser microscope was used to make a step between the surface around the cavity opening of the model tooth and the upper surface of the prosthesis about every 90 degrees along the circumferential direction of the upper surface of the prosthesis. The points were measured, and the average value of the steps at these four points was taken as the amount of lift of the prosthesis. The results are shown in Table 10. In actual clinical practice, the prosthesis is prepared with a size of 50 μm or more with respect to the tooth cavity. Therefore, if the amount of the prosthesis lifted in this test is 50 μm or less, it is judged to be good.

Claims (12)

It has a first agent and a second agent that are packaged from each other.
At least five components consisting of (A) acidic group-containing polymerizable monomer, (B) sulfur atom-containing polymerizable monomer, (C) silane coupling agent, (D) borate compound, and (E) water. Including
The first agent contains only the (A) acidic group-containing polymerizable monomer and the (B) sulfur atom-containing polymerizable monomer among the five components.
The second agent contains only the (C) silane coupling agent, the (D) borate compound, and the (E) water among the five components.
The first agent does not contain organic peroxides and does not contain organic peroxides.
The (A) acidic group-containing polymerizable single amount with respect to 100 parts by mass of the total polymerizable monomer containing at least the (A) acidic group-containing polymerizable monomer and the (B) sulfur atom-containing polymerizable monomer. A two-component dental adhesive composition characterized in that the compounding ratio of the body is 5 parts by mass to 30 parts by mass. As the (A) acidic group-containing polymerizable monomer, the acidic group-containing polymerizable monomer represented by the following general formula (A1) and the acidic group-containing polymerizable monomer represented by the following general formula (A2) In the general formula (A2) with respect to the total amount of the acidic group-containing polymerizable monomer represented by the general formula (A1) and the acidic group-containing polymerizable monomer represented by the general formula (A2). The two-component dental adhesive composition according to claim 1, wherein the compounding ratio of the indicated acidic group-containing polymerizable monomer is 3% by mass to 40% by mass.

(A1)

(A2)
[In the general formula (A1), ^RA11 represents a hydrogen atom or a methyl group, and W ¹ is an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-C _6). H ₄ -) ^{represents, R A21} is, (i) a bond, (ii) 2 to 6 monovalent hydrocarbon group having 1 to 30 carbon atoms, or a (iii) from 1 to 30 carbon atoms, an ether It represents a 2-6 valent organic residue containing at least one bond selected from a bond and an ester bond, where X ¹ represents a monovalent acidic group. Further, m1 represents an integer of 1 to 4, and n1 represents an integer of 1 to 6-m1. Here, m1 + n1 represents the valence of ^RA21.
In the general formula (A2), ^RA11 and ^RA12 independently represent a hydrogen atom or a methyl group, and W ¹ and W ² independently represent an oxycarbonyl group (-COO-) and an iminocarbonyl group (-COO-). -CONH-), or a phenylene group (-C ₆ H ₄ - represents ^{a), R a 21} and ^{R A22} are each independently, (i) a bond, a (ii) 1 to 30 carbon atoms 2-6 A valent hydrocarbon group or (iii) having 1 to 30 carbon atoms and representing a 2 to 6 valent organic residue containing at least one bond selected from an ether bond and an ester bond, where X ¹ is monovalent. Represents the acidic group of, and X ^{2 represents the divalent acidic group.} Further, m1 and m2 independently represent an integer of 1 to 4, n1 represents an integer of 1 to 6-m1, and n2 represents an integer of 1 to 6-m2. Here, m1 + n1 represents the valence of ^{R A21,} m2 + n2 represents the valence of ^{R A22.} ] As the (A) acidic group-containing polymerizable monomer, a long-chain type phosphate group-containing polymerizable monomer represented by the following general formula (A1) and a short-chain type phosphorus represented by the following general formula (A2). The two-component dental adhesive composition according to claim 1 or 2, wherein an acid group-containing polymerizable monomer is used.

(A1)

(A2)
[In the general formula (A1), ^RA11 represents a hydrogen atom or a methyl group, and W ¹ is an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-C _6). H ₄ -) represents, R ^A21 is carbon atoms in the main chain is 6-14 divalent to hexavalent chain hydrocarbon group or at least one binding is selected from an ether bond and an ester bond mainly Represents a 2- to 6-valent chain organic residue contained in the chain and having 6 to 14 atoms in the main chain.
X ¹ represents a phosphoric acid dihydrogen monoester group {-O-P (= O) (OH) ₂ } or a phosphono group {-P (= O) (OH) ₂ }. Further, m1 represents an integer of 1 to 4, and n1 represents an integer of 1 to 6-m1. Here, m1 + n1 represents the valence of ^RA21.
In the general formula (A2), ^RA11 and ^RA12 independently represent a hydrogen atom or a methyl group, and W ¹ and W ² independently represent an oxycarbonyl group (-COO-) and an iminocarbonyl group, respectively. (-CONH-), or a phenylene group (-C ₆ H ₄ -) ^{represents, R a 21} and ^{R A22} each independently, carbon atoms in the main chain is 2 to 4 2 to 6 valent linear Represents a 2-6 valent chain organic residue containing a hydrocarbon group or at least one bond selected from an ether bond and an ester bond in the main chain and having 2 to 4 atoms in the main chain. X ¹ represents a monovalent acidic group and X ² represents a hydrogen phosphate diester group {(−O−) ₂ P (= O) OH} or a phosphinic group {= P (= O) OH}. Furthermore, m1 and m2 each independently represent an integer of 1 to 4, m1 + n1 represents the valence of ^{R A21,} m2 + n2 represents the valence of ^{R A22,} n1 represents an integer of 1 to 6-m1, n2 represents an integer of 1 to 6-m2. ] The two-component dental adhesive composition according to any one of claims 1 to 3, wherein the (C) silane coupling agent is a compound represented by the following general formula (C1).

(C1)
[In the general formula (C1), X is an oxygen atom or a nitrogen ^{atom, R C1} is a methyl group or a hydrogen ^{atom, R C2} is an alkylene group having 1 to 10 carbon ^{atoms, R} C3, R ^C4 and ^RC5 are independently alkyl groups having 1 to 10 carbon atoms or alkoxyl groups having 1 to 10 carbon atoms.
Provided ^that at least one group selected from R ^{C3, R C4} and ^{R C5} is alkoxy group having 2 to 4 carbon atoms. ] The two-component dental adhesiveness according to claim 4, wherein in the general formula (C1), ^RC3 , ^RC4 and ^RC5 are each independently an alkoxyl group having 2 to 4 carbon atoms. Composition. The two-component dental adhesive composition according to any one of claims 1 to 5, wherein the borate compound (D) is an alkali metal salt of tetraarylborate. 2 according to any one of claims 1 to 6, wherein the blending ratio of the (D) borate compound with respect to 100 parts by mass of the (C) silane coupling agent is 1 part by mass to 300 parts by mass. Liquid type dental adhesive composition. The two liquids according to any one of claims 1 to 7, wherein the mixing ratio of the water (E) to 100 parts by mass of the (C) silane coupling agent is 20 parts by mass to 1500 parts by mass. Mold Dental Adhesive Composition. At least one of the first agent and the second agent further contains (F) an organic solvent.
The organic solvent (F) contains at least a low boiling point organic solvent having a boiling point of 50 ° C. to 65 ° C. at normal pressure and a high boiling point organic solvent having a boiling point of 75 ° C. to 90 ° C. at normal pressure.
The blending ratio of the low boiling point organic solvent to 100 parts by mass of the total polymerizable monomer containing at least the (A) acidic group-containing polymerizable monomer and the (B) sulfur atom-containing polymerizable monomer is 200% by mass. Parts to 400 parts by mass,
The two-component type according to any one of claims 1 to 8, wherein the blending ratio of the high boiling point organic solvent with respect to 100 parts by mass of the totally polymerizable monomer is 25 parts by mass to 120 parts by mass. Dental adhesive composition. Claims 1 to 9, wherein the first agent further contains (F) an organic solvent, and the blending ratio of the (F) organic solvent in the first agent is 30% by mass to 90% by mass. The two-component dental adhesive composition according to any one. The second agent further contains (F) an organic solvent, and the blending ratio of the (F) organic solvent in the second agent is 10% by mass to 99% by mass, according to claims 1 to 10. The two-component dental adhesive composition according to any one. The first agent and the second agent each further contain the (F) organic solvent, and the ratio of the total amount of the (F) organic solvent to the total amount of the first agent and the second agent is 63% by mass. The two-component dental adhesive composition according to any one of claims 1 to 11, wherein the content is ~ 85% by mass.