JP2019151595A - Dental composition - Google Patents

Abstract

To provide a novel dental composition with excellent storage stability.SOLUTION: A dental composition contains (A) a silane coupling agent represented by the formula (1), (B) an acidic compound, (C) an organic solvent and (D) water in the same package. The composition is suitable as a dental adhesive or dental primer. [Vis a methyl group or H; Wis O or an imino group; Ris a C1-30 divalent hydrocarbon group; X, Yand Zindependently represent a C1-30 hydrocarbon group, a C1-30 alkoxy group, or a group represented by the formula (1s) (R, Rand Rindependently represent a C1-30 hydrocarbon group or a C1-30 alkoxy group); where, at least one of X, Yand Zis the group represented by the formula (1s)].SELECTED DRAWING: None

Description

  The present invention relates to a novel dental composition. In detail, it is related with the novel dental composition which contains a silane coupling agent, an acidic compound, an organic solvent, and water in the same package.

  As a dental composition used for dental treatment, one containing a silane coupling agent is known. Mainly mentioned are primers used for bonding of teeth and dental restorative materials, and bonding materials.

  For example, in dental restoration materials, dental ceramics are often used for prostheses, and organic composites containing inorganic compounds and polymerizable monomers are often used for dental cements and composite resins. In order to adhere such a prosthesis and dental cement, composite resin, etc., a dental composition containing a silane coupling agent is used (for example, see Patent Documents 1 to 4).

  The mechanism by which a dental composition containing a silane coupling agent works effectively is considered as follows. That is, when a hydrolyzable group such as an alkoxy group of a silane coupling agent is hydrolyzed, a silanol group is generated and bonded to the surface of the prosthesis. On the other hand, the polymerizable group (reactive group) of the silane coupling agent is polymerized with the polymerizable monomer in the dental cement so that the prosthesis, the dental cement, and the composite resin are bonded. In order to bond by this mechanism, an acid, a base, and / or water are required to generate silanol groups of the silane coupling agent.

  Patent Document 1 describes a silane coupling agent containing a silane coupling agent, an acidic compound, and water. Patent Document 1 discloses that each component is included in a specific ratio. And it is shown that the storage of each component is determined in consideration of storage stability in the combination, and each component is mixed and used immediately, or a silane coupling agent, an acidic compound, and water. Is described.

  Similarly, Patent Document 2 proposes an adhesive composition that does not contain water and that separates a silane coupling agent and an acid.

  As described above, normally, the silane coupling agent and the acid, base, and / or water that hydrolyzes the silane coupling agent are generally stored separately. However, when these are separated, it is necessary to mix the separated parts at the time of actual use, and the operability is complicated. Moreover, if it is not sufficiently mixed, the silane coupling agent is not hydrolyzed, and the effect may not be fully exhibited, and there is room for improvement.

Japanese Patent Laid-Open No. 2002-265312 JP 2003-230574 A JP 2007-277114 A JP 2017-218407 A

  In order to improve the above points, a one-component type dental composition has also been developed (see, for example, Patent Documents 3 and 4). In patent document 3, in the photopolymerization, it is set as the one liquid type using the material which generate | occur | produces an acid or a base. Moreover, in patent document 4, it is set as the one-component type using the alkali metal salt of aryl borate.

  However, these inventions have room for improvement in the following points. That is, in the invention described in Patent Document 3, since it is necessary to generate an acid or a base by light irradiation, there is room for improvement in that workability is inevitably lowered. Moreover, in the invention described in Patent Document 4, since there is no acid, there is room for improvement in terms of low adhesion to base metals, teeth, and the like. As described above, there is no dental composition that contains at least a silane coupling agent, an acidic compound, and water and contains these in the same package.

  Accordingly, an object of the present invention is a dental composition containing at least a silane coupling agent, an acidic compound, and water, which does not exist in the past, and contains these in the same package, and the improvement in adhesion is Of course, it is to provide a composition having excellent storage stability.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. In particular, the type of silane coupling agent was examined. That is, the dental composition was examined for a silane coupling agent that exhibits sufficient adhesiveness and is excellent in storage stability even when coexisting with an acidic compound and water. As a result, it has been found that the above problem can be solved by using a specific silane coupling agent having a siloxane bond in the molecule, and the present invention has been completed.

That is, the present invention
(1) The following formula (1)

{Where,
V ¹¹ is a methyl group or a hydrogen atom,
W ¹¹ is an oxygen atom or an imino group,
R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms,
X ¹¹ , Y ¹¹ , and Z ¹¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or the following formula (1s)

(In the formula, R ¹² , R ¹³ , and R ¹⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.)
A group represented by
However, at least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a group represented by the formula (1s). } A first silane coupling agent represented by the following formula (2)

{Where,
V ²¹ is a methyl group or a hydrogen atom,
W ²¹ is an oxygen atom or an imino group,
R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, and X ²¹ and Z ²¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or the following: Formula (2s)

(In the formula, R ²² , R ²³ , and R ²⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.)
It is group shown by these. }
At least one (A) silane coupling agent selected from the second silane coupling agent represented by the formula (hereinafter sometimes referred to simply as “component (A)”),
(B) an acidic compound (hereinafter sometimes simply referred to as “component (B)”),
(C) an organic solvent (hereinafter sometimes simply referred to as “component (C)”), and (D) water (hereinafter sometimes simply referred to as “component (D)”).
Is a dental composition containing the same in the same package.

  The present invention can take the following aspects.

  (2) The dental composition of (1) containing 50 to 500 parts by mass of the (D) water per 100 parts by mass of the (A) silane coupling agent.

  (3) The above (1) or (2), wherein the (B) acidic compound contains (B1) an acidic group-containing polymerizable monomer (hereinafter sometimes simply referred to as “component (B1)”). Dental composition.

  (4) Further, (E) a dental compound according to any one of the above (1) to (3), which contains a fluorine compound having a fluorine atom in the molecule (hereinafter sometimes simply referred to as “(E) component”). Composition.

  (5) A dental adhesive composition comprising the dental composition according to any one of (1) to (4).

  (6) A dental primer composition comprising the dental composition according to any one of (1) to (4).

  According to the present invention, even when (A) a silane coupling agent, (B) an acidic compound, and (D) water are present in the same system (in the same package), the storage stability is good, And it has high adhesiveness.

  The dental composition of the present invention contains the components (A) to (D) and other components such as the component (E) blended as necessary in the same package. Since the component (A), the component (B), and the component (D) are present in the same system, the component (A) can be sufficiently hydrolyzed and its effects can be sufficiently exerted. it can. As a result, after mixing in the same package, not only can be used as a one-component type for direct use, but also a multi-component type (for example, a mixture of the dental composition of the present invention and other components) (2 liquid type) can also be used.

  In addition, in the present invention, the specific component (A) having a siloxane bond in the molecule is used while having the above effects, and therefore, the storage stability is excellent. In addition, the effect of storage stability can be further enhanced by further blending the component (E).

  The present invention is a dental composition containing the components (A) to (D) as essential components and containing them in the same package. In the following, description will be given in order.

<(A) Silane coupling agent; (A) component>
The component (A) used in the present invention is at least one selected from the first silane coupling agent and the second silane coupling agent. First, the first silane coupling agent will be described.

(First silane coupling agent)
In the present invention, the first silane coupling agent is
Following formula (1)

{Where,
V ¹¹ is a methyl group or a hydrogen atom,
W ¹¹ is an oxygen atom or an imino group,
R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms,
X ¹¹ , Y ¹¹ , and Z ¹¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or the following formula (1s)

(Where
R ¹² , R ¹³ and R ¹⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. )
A group represented by
However, at least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a group represented by the formula (1s). } It is a silane coupling agent shown by this.

In the formula ^{(1), R 11} is a divalent hydrocarbon group having 1 to 30 carbon atoms. Among these, in view of excellent storage stability and adhesiveness, an alkylene group having 1 to 10 carbon atoms is preferable, and more specifically, carbon numbers such as a methylene group, an ethylene group, a trimethylene group, and a propylene group. Is preferably an alkylene group of 1 to 3.

In the formula (1), V ¹¹ is a methyl group or a hydrogen atom. Among them, a methyl group is preferable in consideration of excellent adhesiveness.

In the formula (1), W ¹¹ is an oxygen atom or an imino group (—NH—).

In the formula (1), X ¹¹ , Y ¹¹ , and Z ¹¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a group represented by the formula (1s). is there. At least one of X ¹¹ , Y ¹¹ and Z ¹¹ is a group represented by the formula (1s).

In X ¹¹ , Y ¹¹ , and Z ¹¹ , examples of the hydrocarbon group having 1 to 30 carbon atoms include saturated hydrocarbon groups such as alkyl groups having 1 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include straight-chain and branched alkyl groups having 1 to 10 carbon atoms, and among them, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

In X ¹¹ , Y ¹¹ and Z ¹¹ , the hydrocarbon group having 1 to 30 carbon atoms may be an unsaturated hydrocarbon group having 1 to 30 carbon atoms. Of these, unsaturated hydrocarbon groups having 1 to 10 carbon atoms are preferable in order to exert an excellent effect in adhesiveness, and groups having a polymerizable group at the end such as a vinyl group and an allyl group are preferable.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , the alkoxy group having 1 to 30 carbon atoms is preferably an alkoxy group having 1 to 10 carbon atoms in order to exert an excellent effect, specifically, a methoxy group Ethoxy group, propoxy group, isopropoxy group, butoxy group.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , at least one of them must be a group represented by the following formula (1s).

In the formula, each of R ¹² , R ¹³ , and R ¹⁴ is a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms.

In R ¹² , R ¹³ , and R ¹⁴ , the hydrocarbon group having 1 to 30 carbon atoms and the alkoxy group having 1 to 30 carbon atoms are the same as the groups described above for X ¹¹ , Y ¹¹ , and Z ¹¹ . Group, and a hydrocarbon group is preferable from the viewpoint of storage stability.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , at least one may be a group represented by the formula (1s), and two or all three may be groups represented by the formula (1s). . Among these, two or three are preferable in consideration of excellent storage stability and adhesiveness.

  A commercially available thing can be used for the 1st silane coupling agent shown by said Formula (1). Among them, specific examples of suitable compounds can improve storage stability, and thus (methacryloxymethyl) bis (trimethylsiloxy) methylsilane, methacryloxypropyltris (vinyldimethylsiloxy) silane, and methacryloxypropyl. Tris (trimethylsiloxy) silane, methacryloxytris (trimethylsiloxy) silane, 3-methacryloxypropylbis (trimethylsiloxy) methylsilane, (3-acryloxypropyl) methylbis (trimethylsiloxy) silane, (3-acryloxypropyl) tris (Trimethylsiloxy) silane is mentioned.

(Secondary silane coupling agent)
In the present invention, the second silane coupling agent is
Following formula (2)

{Where,
V ²¹ is a methyl group or a hydrogen atom,
W ²¹ is an oxygen atom or an imino group,
R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms,
X ²¹ and Z ²¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or the following formula (2s)

(Where
R ²² , R ²³ , and R ²⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. ). }
It is a silane coupling agent shown by these.

In the formula (2), R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, and is the same group as that described for R ¹¹ , and a suitable group is also the same as R ^11. .

In the formula (2), V ²¹ is a methyl group or a hydrogen atom. Among them, a methyl group is preferable in consideration of excellent adhesiveness.

In the formula (2), W ²¹ is an oxygen atom or an imino group (—NH—).

In the formula (2), X ²¹ and Z ²¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a group represented by the formula (2s).

In X ²¹ and Z ²¹ , examples of the hydrocarbon group having 1 to 30 carbon atoms include the same groups as those described above for X ¹¹ , Y ¹¹ and Z ¹¹ , and preferred groups are also the same.

Similarly, in X ²¹ and Z ²¹ , examples of the alkoxy group having 1 to 30 carbon atoms include the same groups as those described above for X ¹¹ , Y ¹¹ , and Z ¹¹ , and preferred groups are also the same. It is.

Furthermore, in the group represented by the formula (2s), R ²² , R ²³ , and R ²⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. These hydrocarbon groups having 1 to 30 carbon atoms and alkoxy groups having 1 to 30 carbon atoms are the same groups as those described for R ¹² , R ¹³ , and R ¹⁴ (X ¹¹ , Y ¹¹ , and Z ¹¹ ). And is preferably a hydrocarbon group from the viewpoint of storage stability.

In X ²¹ and Z ²¹ , both are preferably groups represented by the formula (2s) in order to improve storage stability and adhesiveness.

  A commercially available thing can be used for the 2nd silane coupling agent shown by said Formula (2). Among these, 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane may be mentioned from the viewpoint that the storage stability can be further improved if a suitable compound is specifically exemplified.

(Amount of component (A))
In the present invention, the component (A) is at least one silane coupling agent selected from the first silane coupling agent and the second silane coupling agent. (A) A component can also be used 1 type or in combination of 2 or more types. When two or more types are used in combination, the reference mass is the total amount thereof.

  In the present invention, the mixing ratio of the component (A) in the dental composition is not particularly limited, but is preferably in the range of 0.1 to 70% by mass, and more preferably in the range of 1 to 50% by mass. If the blending ratio is less than 0.1% by mass, sufficient adhesive strength and storage stability may not be obtained, and if it exceeds 70% by mass, the curability may be lowered and the adhesive strength may be lowered.

<(B) acidic compound; (B) component>
In the present invention, the acidic compound (B) functions as an acid catalyst that promotes hydrolysis of the component (A) and promotes dehydration condensation between the component (A) and a silanol group on the surface of the adherend.

  The component (B) means an aqueous solution dissolved and / or dispersed in water at a concentration of 1 mol / L, or a substance having a pH of 5 or less in an aqueous dispersion. Examples of the component (B) include known compounds such as inorganic acids such as hydrochloric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid and citric acid. In addition, an acidic compound can be used 1 type or in combination of 2 or more types. When two or more types are used in combination, the reference mass is the total amount thereof.

  Furthermore, teeth (dentin, enamel), base metals (iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, etc. or alloys containing these as main components), and metals such as zirconium and oxygen From the point of improving the adhesiveness to metal oxides (such as zirconia ceramics) containing as a main component, an acidic group-containing polymerizable monomer (hereinafter sometimes simply referred to as “component (B1)”) is used. Is preferred. Therefore, by selecting the components to be used, the dental composition of the present invention is a dental adhesive composition used for repairing by adhering a base metal or metal oxide prosthesis and a tooth. It can be suitably used as a product.

((B1) acidic group-containing polymerizable monomer; (B1) component)
The acidic group-containing polymerizable monomer is not particularly limited as long as it is a compound having at least one acidic group and at least one polymerizable unsaturated group in one molecule, and a known compound can be used.

Here, an acidic group is a group in which an aqueous dispersion medium or aqueous suspension of a polymerizable monomer having the group exhibits acidity, and not only a simple acidic group but also two of the acidic groups are dehydrated and condensed. It may be an acid anhydride structure or an acid halide group in which an acidic group is halogenated. Specifically, a phosphinico group {= P (═O) OH}, a phosphono group {—P (═O) (OH) ₂ }, a carboxyl group {—C (═O) OH}, a dihydrogen phosphate monoester Group {—O—P (═O) (OH) ₂ }, hydrogen phosphate diester group {(—O—) ₂ P (═O) OH}, sulfo group (—SO ₃ H), and acid anhydride skeleton {-C (= O) -OC (= O)-} and the like.

  Among the specific groups as described above, the stability to water is high, and the dissolution of the smear layer on the tooth surface and the tooth decalcification can be carried out gently, so that the carboxyl group, dihydrogen phosphate monoester group, hydrogen phosphate A diester group is more preferred. Among these, the dihydrogen phosphate monoester group and the hydrogen phosphate diester group having the highest effect are most preferable.

  Specific examples of the polymerizable monomer having a dihydrogen phosphate monoester group or a hydrogen phosphate diester group include 2- (meth) acryloyloxyethyl dihydrogen phosphate and bis [2- (meth) acryloyloxy. Ethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 6- (meth) acryloyloxyhexylphenyl hydrogen phosphate, 10- (meth) Acryloyloxydecyl dihydrogen phosphate, 1,3-di (meth) acryloylpropane-2-dihydrogen phosphate, 1,3-di (meth) acryloylpropane-2-phenylhydrogen phosphate , Bis [5- {2- (meth) acryloyloxy} heptyl] hydrogen phosphate, and the like.

  Specific examples of the polymerizable monomer having a carboxyl group include acrylic acid, methacrylic acid, 4- (meth) acryloxyethyl trimellitic acid, and 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid. 1,4-di (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, etc. Is mentioned.

  Specific examples of the polymerizable monomer having a sulfo group include 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, and vinylsulfonic acid. Etc.

  Among the polymerizable monomers having an acidic group as described above, a particularly preferable monomer is exemplified by a compound represented by the following formula.

上記式で示される酸性基含有重合性単量体において、Ｒは、水素原子、またはメチル基である。

In the acidic group-containing polymerizable monomer represented by the above formula, R is a hydrogen atom or a methyl group.

  Moreover, these acidic group-containing polymerizable monomers may be used in combination of two or more as required. When two or more kinds are used in combination, the reference mass is the total amount thereof. As a matter of course, when the acidic group-containing polymerizable monomer and other acidic compound are used in combination, the mass of the basic acidic compound is the total amount thereof.

  The (B) acidic compound of the present invention can also include a polymer obtained by polymerizing the (B1) acidic group-containing polymerizable monomer.

((B) Compounding amount of acidic compound)
In the present invention, the blending amount of the component (B) is not particularly limited, but is preferably in the range of 1 to 10000 parts by mass with respect to 100 parts by mass of the component (A), and 10 to 1000 parts by mass. The range of is more preferable. If the compounding amount of the acidic compound is less than 1 part by mass, the adhesiveness may decrease, and if the compounding amount exceeds 10,000 parts by mass, the adhesiveness after storage decreases (storage stability decreases). There is a case.

<(C) Organic solvent; (C) component>
In the present invention, any known organic solvent can be used without limitation, and can be appropriately selected depending on the purpose of the dental composition. In particular,
Alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol;
Ketones such as acetone and methyl ethyl ketone;
Ethers such as ethyl ether, 1,4-dioxane and tetrahydrofuran;
Esters such as ethyl acetate and ethyl formate;
Aromatic solvents such as toluene, xylene, benzene;
Hydrocarbon solvents such as pentane, hexane, heptane, octane;
Chlorinated solvents such as methylene chloride, chloroform, 1,2-dichloroethane;
Fluorine solvents such as trifluoroethanol are exemplified.

  Among these, acetone, ethanol, isopropyl alcohol and the like are particularly preferably used for reasons such as solubility and storage stability. Said organic solvent can also be used 1 type or in combination of 2 or more types. When two or more kinds of organic solvents are used, the reference amount is the total amount thereof.

  The blending ratio of the organic solvent in the dental composition corresponds to the remainder other than the components (A) and (B), the component (D) described in detail below, and other components blended as necessary. To do. Therefore, what is necessary is just to determine the mixture ratio of (C) component suitably with the mixture ratio of another component. Especially, the mixture ratio of (C) component has the preferable inside of the range of 5-99 mass%, when the whole quantity of a dental composition is 100 mass%, and the inside of the range of 10-95 mass% is more preferable. When the (C) organic solvent in the dental composition is less than 5% by mass, the concentration of (A) the silane coupling agent and (D) water increases, so that the storage stability tends to decrease. In addition, when (C) the organic solvent exceeds 99% by mass, the concentration of (A) the silane coupling agent is so dilute that adhesive strength (adhesiveness) may not be sufficiently obtained.

<(D) Water; (D) Component>
In the present invention, (D) water is preferably substantially free of harmful impurities from the viewpoints of storage stability, biocompatibility, and adhesiveness, and examples include deionized water and distilled water. .

  What is necessary is just to determine the compounding quantity of water suitably according to the other component to be used, the use of the dental composition obtained, etc. Especially, the blending amount of water is preferably in the range of 10 to 2000 parts by mass and more preferably in the range of 50 to 500 parts by mass with respect to 100 parts by mass of the (A) silane coupling agent. When the blending amount of the component (D) is less than 10 parts by mass, the adhesive strength tends to decrease, and when it exceeds 2000 parts by mass, the water cannot be removed by air blow and remains to inhibit adhesion. (A) Hydrolysis of the silane coupling agent is promoted too much and storage stability tends to decrease.

  In the present invention, if the above component (A), component (B), component (C), and component (D) are contained in the same package, only these four components may be included, and further performance is exhibited. In addition, other components can be contained. “Contained in the same package” means that each component is present in a container such as the same bag. Next, other components that can be used in the present invention will be described.

<Other ingredients>
<(E) Fluorine compound having fluorine atom in molecule; (E) component>
In the present invention, (E) a fluorine compound having a fluorine atom in the molecule may be blended. The component (E) is not particularly limited as long as it is a fluorine compound that can be used for dentistry. By blending the component (E), the storage stability can be further enhanced.

  The component (E) preferably releases fluorine ions when dissolved in the dental composition. Specific examples of the component (E) include sodium fluoride, potassium fluoride, lithium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, copper fluoride, and fluoride. Metal fluoride salts such as zirconium, aluminum fluoride and titanium fluoride and quaternary ammonium salts such as tetramethylammonium fluoride and tetraethylammonium fluoride tetra-n-butylammonium are used.

  The reason why the storage stability is improved by blending the component (E) is not clear, but the present inventors estimate as follows. First, fluorine ions generated from the component (E) cleave the siloxane bond of the condensate obtained by dehydration condensation of silanol groups of the silane coupling agent (A). And since a silanol group can be produced | generated again, it is thought that the condensation of silanol groups during storage is suppressed and the state where many silanol groups exist is maintained. As a result, when using the dental composition, it is predicted that the silanol group easily acts on the surface of the adherend and the adhesiveness is not lowered.

  In the present invention, the blending amount of the component (E) is not particularly limited, but is preferably in the following range in consideration of storage stability and adhesiveness. Specifically, it is preferable that the number of moles of fluorine ions in (E) is 0.001 to 6 moles with respect to 1 mole of the hydrolyzable group in the (A) silane coupling agent, It is preferably ˜3 mol, and more preferably 0.1 to 1.5. When there are too many compounding quantities of the said (E) component, many hydrolysable groups in (A) component will be fluorinated, and there exists a possibility that it cannot participate in adhesion | attachment. On the other hand, when there are too few compounding quantities of the said (E) component, the compounding effect of the said (E) component will not fully be exhibited, but there exists a possibility that storage stability may fall. In addition, the hydrolyzable group in the said (A) component points out the group which has the coupling | bond part of Si-O which hydrolyzes in a 1st and 2 silane coupling agent. For example, in the case of (methacryloxymethyl) bis (trimethylsiloxy) methylsilane, which is the first silane coupling agent, if 1 mol of (methacryloxymethyl) bis (trimethylsiloxy) methylsilane, 2 mol of hydrolyzable groups Will exist. In the case of 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane, which is the second silane coupling agent, 1 mol of 1,3-bis (3-methacryloxypropyl) tetrakis (trimethyl) If it is siloxy) disiloxane, 5 mol of hydrolyzable groups will be present.

  In addition, although the said range is preferable, the compounding quantity of (E) component will be 0.0005-50000 mass with respect to (A) component with respect to 100 mass parts of (A) component if converted normally by mass. Part, preferably 0.05 to 20000 parts by mass, and more preferably 0.05 to 10000 parts by mass.

  In addition, the dental composition of the present embodiment contains known compounds used for dental compositions such as polymerizable monomers having no acidic group, fillers, photopolymerization initiators, polymerization inhibitors. Can be blended. Next, these compounds will be described.

<Other components; polymerizable monomer having no acidic group>
Examples of the polymerizable monomer having no acidic group (hereinafter sometimes referred to simply as “acidic group-free polymerizable monomer”) include α-cyanoacrylic acid, (meth) acrylic acid, α-halogen. Esters of organic acids such as fluorinated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, (meth) acrylamide and (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl Derivatives and styrene derivatives are exemplified. Of these, (meth) acrylic acid esters are preferred. Specific examples of the polymerizable monomer having no acidic group are shown below. In the following description, an n-functional monomer is a monomer having n olefinic double bonds (functional groups). Examples of the acidic group-free polymerizable monomer include monofunctional, bifunctional, and trifunctional or higher polymerizable monomers. Hereinafter, the monofunctional polymerizable monomer having no acidic group is simply referred to as “monofunctional polymerizable monomer”, and the bifunctional polymerizable monomer having no acidic group is simply referred to as “ In some cases, the trifunctional or higher functional monomer having no acidic group is hereinafter simply referred to as “polyfunctional polymerizable monomer”.

<Other components; non-acidic group-containing polymerizable monomer; monofunctional polymerizable monomer>
In the present invention, examples of the monofunctional polymerizable monomer include the following compounds. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) ) Acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide and the like.

<Other components; non-acidic group-containing polymerizable monomer; bifunctional polymerizable monomer>
In the present invention, examples of the bifunctional polymerizable monomer include the following compounds. Specifically, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2 -Bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3- (Meta) acrylic Oxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, [2,2,4-trimethylhexamethylenebis (2-carbamoyl) Oxyethyl)] dimethacrylate and the like.

<Other components; non-acidic group-containing polymerizable monomer; polyfunctional polymerizable monomer>
In the present invention, examples of the polyfunctional polymerizable monomer include the following compounds. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N ′-(2,2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane Etc.

  The above acidic group-free polymerizable monomers can be used in appropriate combination depending on the intended use of the dental composition. These acidic group-free polymerizable monomers are used in one kind or in combination of plural kinds. When a plurality of types are used, the reference blending amount is the total amount thereof.

<Other components; blending amount of non-acidic group-containing polymerizable monomer>
In the present invention, since the blending amount of the acidic group-free polymerizable monomer is not an essential component, it may not be included as a matter of course, but in order to apply to various uses, the following blending amount is satisfied. It is preferable. Specifically, the blending amount of the acidic group-free polymerizable monomer is preferably 1 to 90000 parts by mass, and preferably 10 to 50000 parts by mass with respect to 100 parts by mass of component (A). . In addition, what is necessary is just to determine an optimal compounding quantity suitably according to the intended use of the dental composition.

  In addition, when blending an acidic group-free polymerizable monomer, depending on the intended use, the monofunctional polymerizable monomer, the bifunctional polymerizable monomer, and the polyfunctional polymerizable monomer It is preferable to use the body in combination.

<Other components; filler>
In the present invention, a filler can also be blended. As a filler, it can use in the range which does not inhibit the effect of this invention among well-known organic fillers and inorganic fillers.

  Specific examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane trimethacrylate copolymer, polyvinyl chloride. , Polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, polycarbonate and the like. These organic fillers do not contain acidic groups.

  Specific examples of inorganic fillers include quartz, amorphous silica, silica zirconia, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, carbonized. Examples thereof include silicon, boron carbide, calcium carbonate, hydroxyapatite, and calcium phosphate.

  Further, these inorganic fillers are preferably treated with a surface treatment agent typified by a silane coupling agent. Thereby, it becomes easy to improve the mechanical strength and water resistance by improving the compatibility with the polymerizable monomer. The surface treatment method may be performed by a known method, and examples of the surface treatment agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ -Chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylate Silane, N- phenyl--γ- aminopropyltrimethoxysilane, hexamethyldisilazane or the like is preferably used.

  The said filler can be used individually or in combination of 2 or more types. When two or more types are used, the reference blending amount is the total amount thereof.

  Since the said filler is not an essential component, it does not need to be contained in the dental composition of this invention. However, when using the said filler, it is preferable that the compounding quantity of the said filler shall be 1-50000 mass parts with respect to 100 mass parts of said (A) component, and it is preferable to set it as 10-30000 mass parts. . In addition, what is necessary is just to determine an optimal compounding quantity suitably according to the intended use of the dental composition.

<Other components; Photopolymerization initiator>
In the present invention, as the photopolymerization initiator, a photosensitizer that generates radicals by light irradiation can be used. Examples of photosensitizers for ultraviolet rays include benzoin compounds such as benzoin, benzoin methyl ether and benzoin ethyl ether, benzophenone compounds such as acetoin benzophenone, p-chlorobenzophenone and p-methoxybenzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, Acylphosphine oxides such as 2,3,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 3,3′- Coumarins such as carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6 Examples include halomethyl group-substituted s-triazine derivatives such as -tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine. A photosensitizer that initiates polymerization with visible light is preferably used because it does not require ultraviolet rays harmful to the human body. Examples of these include α-diketones such as benzyl, camphorquinone, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-doctrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, naphthoquinone and the like. Can be mentioned. Preferably, camphor quinone is used.

  These photosensitizers (photopolymerization initiators) can be used alone or in combination of two or more. When two or more types are used, the reference blending amount is the total amount thereof.

  It is also preferable to use a photopolymerization accelerator in combination with the photosensitizer. In particular, when a tertiary amine is used as a photopolymerization accelerator, it is more preferable to use a compound in which an aromatic group is directly substituted with a nitrogen atom. Examples of photopolymerization accelerators include Ν, Ν-dimethylaniline, Ν, Ν-diethylaniline, Ν, ｎ-di-n-butylaniline, Ν, Ν-dibenzylaniline, Ν, Ν-dimethyl-p-toluidine, Ν, Ν-dimethyl-m-toluidine, Ν, Ν-diethyl-p-toluidine, p-bromo-Ν, Ν dimethylaniline, m-chloro Ν, Ν-dimethylaniline, p-dimethylaminobenzaldehyde, p- Dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid aminoester, Ν, Ν-dimethyl anthranilic acid methyl ester, Ν, Ν-dihydroxyethylaniline, Ν, Ν- Dihydroxyethyl-p-toluidine, p-dimethylaminostyrene, Ν, Ν-dimethyl-3,5-xylidine , 4-dimethylaminopyridine, Ν, Ν-dimethyl-α-naphthylamine, Ν, Ν-dimethyl-β-naphthylamine, and the like. Among these photopolymerization accelerators, at least one kind can be selected and used, and two or more kinds can also be mixed and used.

  These photopolymerization accelerators can be used alone or in combination of two or more. When two or more types are used, the reference blending amount is the total amount thereof.

  The addition amounts of the photopolymerization initiator and the photopolymerization accelerator can be appropriately determined. Usually, it is preferable to use an effective amount of a photopolymerization initiator and a photopolymerization accelerator. Among them, the total amount of the polymerizable monomer component in the dental composition, that is, when the component (A) contains a radical polymerizable group, the compound, when the acidic group-containing polymerizable monomer is included as an acidic compound. Is a photopolymerization initiator when the acidic group-containing polymerizable monomer and the acidic group-free polymerizable monomer are used, the total amount of the acidic group-free polymerizable monomer is 100 parts by mass. It is preferable to use 0.001-30 mass parts, and it is more preferable to set it as 0.1-10 mass parts. The blending amount of the photopolymerization accelerator is preferably 0.001 to 30 parts by mass, preferably 0.1 to 10 parts by mass when the total amount of the polymerizable monomer component is 100 parts by mass. Is more preferable.

<Other components; chemical polymerization initiator>
As the chemical polymerization initiator used in the dental adhesive composition of the present embodiment, any known chemical polymerization initiator can be used without limitation. Examples of such chemical polymerization initiators include a combination of organic peroxides and amines, a combination of organic peroxides, amines and sulfinates, a combination of acidic compounds and arylborate compounds, and a fourth period transition metal. Examples include a combination of a compound and an organic peroxide, a combination of an organic peroxide and a thiourea derivative, and a chemical polymerization initiator such as barbituric acid and alkylborane.

Examples of the organic peroxide include various peroxides classified into ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate. These may be used alone or in combination of two or more.
As the amines, secondary or tertiary amines are preferable, and specific examples thereof include N-methylaniline, N-methyl-p-toluidine and the like as secondary amines. N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl -P-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dihydroxy Tyl-p-toluidine, 4-dimethylaminopyridine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N -Dimethylstearylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2,2 '-(n-butylimino) diethanol and the like. These may be used alone or in combination of two or more.

  As the aryl borate compound, a known compound can be used as long as it has at least one boron-aryl bond in one molecule, but it has high storage stability, ease of handling, and availability. An aryl borate compound having four boron-aryl bonds in one molecule is most preferable because of its ease of use. Specific examples of aryl borate compounds having four boron-aryl bonds in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoro). Methyl) phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (M-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p- Octyloxyphenyl) boron, tetra Scan (m-octyloxyphenyl) salt of a boron compound such as boron can be cited. As a cation forming a salt with a boron compound, a metal ion, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion may be used. it can. These may be used alone or in combination of two or more.

  As the thiourea derivative, a compound having a thiourea skeleton can be used without particular limitation, and includes a thiourea compound and a mercaptobenzimidazole compound described later, and can be appropriately selected according to the purpose. For example, the thiourea compound includes ethylenethiourea, N, N′-dimethylthiourea, 1- (2-pyridyl) -2-thiourea, 1- (2-tetrahydrofurfuryl) -2-thiourea, 1- Examples include acetyl-2-thiourea. Examples of the mercaptobenzimidazole compound include 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzimidazole, 2-mercapto-5-ethoxybenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5- Examples include ethyl benzimidazole. These may be used alone or in combination of two or more.

  In the fourth period transition metal compound, the transition metal of the fourth period is a metal element belonging to Group 3 to 12 of the fourth period of the periodic table. Specifically, scandium (Sc), titanium (Ti), vanadium ( V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). Each of these transition metal elements can have a plurality of valences, but can have a valence that can exist stably, for example, Sc (III), Ti (IV), V (III to V), Cr (II, III, VI), Mn (II to VII), Fe (II, III), Co (II, III), Ni (II), Cu (I, II), Zn (II) are at least organic peroxidized. And used as a chemical polymerization initiator.

  Specific examples of such a fourth period transition metal compound include scandium iodide (III), titanium (IV) chloride, titanium (IV) tetraisopropoxide, divanadium tetroxide (IV), vanadium acetylacetonate. (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide ( V), chromium (III) chloride, chromic acid (VI), chromate (VI), manganese (II) acetate, iron (II) acetate, iron (III) acetate, cobalt (II) acetate, cobalt naphthenate ( II), nickel chloride (II), copper chloride (I), copper bromide (I), copper chloride (II), copper acetate (II), copper sulfate (II) Copper acetylacetonate (II), mention may be made of zinc acetate (II) or the like, it can also be used in combination of two or more thereof in combination.

  The amount of the chemical polymerization initiator added can be appropriately determined according to the type of chemical polymerization initiator used. Usually, it is preferable to use an effective amount of a chemical polymerization initiator. Among them, the total amount of the polymerizable monomer component in the dental composition, that is, when the component (A) contains a radical polymerizable group, the compound, when the acidic group-containing polymerizable monomer is included as an acidic compound. In the case of using an acidic group-containing polymerizable monomer and an acidic group-free polymerizable monomer, when the total amount of the acidic group-free polymerizable monomer is 100 parts by mass, a chemical polymerization initiator It is preferable to use 0.001-30 mass parts, and it is preferable to use 0.1-10 mass parts.

  When a chemical polymerization initiator is used, it usually becomes a multi-component type in which the reaction components are packaged and the dental composition of the present invention and other components are mixed and used. However, the dental composition of the present invention is used in combination with other restorative materials such as dental bonding materials, composite resins, compomers, resin cores, resin cements, resin-reinforced glass ionomer cements, denture base resins, and the like. Is. Therefore, it can also be used as a one-pack type by adding one of the reaction components of the chemical polymerization catalyst to the restoration material.

<Other components; polymerization inhibitor>
In this invention, the well-known polymerization inhibitor which can be used for a dental material can also be mix | blended. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene and the like. Among these polymerization inhibitors, at least one kind can be selected and used, and two or more kinds can also be mixed and used.

  The said polymerization inhibitor can be used individually or in combination of 2 or more types. When two or more types are used, the reference blending amount is the total amount thereof.

  Since the polymerization inhibitor is not an essential component, it may not be included in the dental composition of the present invention. However, when using the said polymerization inhibitor, it is preferable to use 0.0001-10 mass parts of polymerizable inhibitors when the whole quantity of the said polymerizable monomer component shall be 100 mass parts.

  In addition, the dental composition of this invention can mix | blend the silane coupling agent which can be used for dental materials other than the said (A) component in the range which does not inhibit the effect of this invention. However, in consideration of storage stability, the silane coupling agent is preferably only the component (A).

  The dental composition of the present invention has high adhesiveness and excellent storage stability. Therefore, although a preservation | save state is not specifically limited, It is preferable to preserve | save within the same package in the range of 0-25 degreeC. If it is this temperature range, even if it preserve | saves for 100 days or more, the adhesive fall can be suppressed. The upper limit of the number of storage days is not particularly limited, but is 1000 days in the temperature range of 0 to 10 ° C.

  Since the dental composition of the present invention contains the component (A), the component (B), and the component (D) in the same package, these components can be easily mixed. Therefore, hydrolysis of the component (A) can be sufficiently caused. As a result, after mixing in the same package, not only can be used as a one-component type for direct use, but also a multi-component type (for example, a mixture of the dental composition of the present invention and other components) (2 liquid type) can also be used.

  In the case of a multi-component type, the other material used in combination with the dental composition of the present invention is not particularly limited, and may be appropriately determined according to the intended use. For example, when a chemical polymerization initiator is added to the dental composition of the present invention, it is used as a chemical polymerization dental composition by mixing with another material to which a component that reacts with the chemical polymerization initiator is added. It is also possible to do.

<Preferred use of dental composition (adhered body)>
The dental composition of the present invention can be used for various adherends. Specifically, the main components are ceramics such as zirconia ceramics, silica-based ceramics (such as porcelain), tooth (dentin, enamel), iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, etc. Base metals containing, precious metals containing gold, platinum, palladium, silver, etc. as the main component, resin hardened bodies containing dispersed fillers such as silica particles or silica-zirconia particles (hard resin teeth, hybrid resins, CAD / CAM resin blocks), etc. It can be used for bonding to various dental materials.

  Among such applications to adhere to the adherend, since it is excellent in adhesion to a cured resin containing ceramics or silica-based particles, it is preferably used as a ceramic primer and an adhesive for multipurpose adhesion.

  Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

<Abbreviation of substance>
Hereinafter, abbreviations of substances used in Examples and Comparative Examples will be described.

<(A) Silane coupling agent>
MPS: γ-methacryloxypropyltrimethoxysilane (not applicable to first and second silane coupling agents).
MPTES: γ-methacryloxypropyltriethoxysilane (not applicable to first and second silane coupling agents).
・ MPTIPS: γ-methacryloxypropyltriisopropoxysilane (not applicable to primary and disilane coupling agents)
MMBSS: (methacryloxymethyl) bis (trimethylsiloxy) methylsilane (corresponding to the first silane coupling agent).
MPBSS: 3-methacryloxypropylbis (trimethylsiloxy) methylsilane (corresponding to the first silane coupling agent).
・ MMTSS: Methacryloxymethyltris (trimethylsiloxy) silane (corresponds to the first silane coupling agent)
・ MPTSS: Methacryloxypropyltris (vinyldimethylsiloxy) silane (corresponds to the first silane coupling agent)
BMPTSS: 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane (corresponding to the second silane coupling agent).

<(B) acidic compound>
<(B1) acidic group-containing polymerizable monomer>
MDP: 10-methacryloyloxydecyl dihydrogen phosphate.
PM2: bis (2-methacryloxyethyl) acid phosphate.

<Other components; (E) Fluorine compound>
NaF: sodium fluoride.
TBAF: tetra-n-butylammonium fluoride.

<Other components; non-acidic group-containing polymerizable monomer>
BisGMA: 2.2'-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane.
3G: triethylene glycol dimethacrylate.
-HEMA: 2-hydroxyethyl methacrylate.

<Other ingredients>
CQ: camphorquinone.
DMBE: ethyl 4-dimethylaminobenzoate.

Examples 1-18, Comparative Examples 1-8
Each component shown above with the compounding ratio shown in Tables 1 to 3 was mixed in the same package to prepare a dental composition. Table 1 shows the blending ratio (% by mass) of each component when the total amount of the dental composition is 100% by mass in each example and each comparative example.

  In Table 2 and Table 3, in each Example (Table 2) and each Comparative Example (Table 3), the blending ratio (part by mass) of each component of each component per 100 parts by mass of (A) silane coupling agent showed that.

  The obtained dental compositions (dental compositions of Examples and Comparative Examples) were <1. Adhesiveness was evaluated according to adhesive strength evaluation>.

<1. Adhesive strength evaluation>
As the adherend, “Noritake Super Porcelain AAA” (manufactured by Kuraray Noritake, length 15 mm × width 15 mm × thickness 3 mm), which is a dental ceramic (so-called porcelain) made of silica-based crystallized glass, is used. One side of the body was polished with # 800 water resistant abrasive paper. Thereafter, a double-sided tape having a hole with a diameter of 3 mm was attached to the polished surface of the adherend. Subsequently, the dental composition of each example and each comparative example was applied to the adhesive surface exposed from the hole of the double-sided tape of the polished surface with a microbrush, and the dental composition applied to the adhesive surface Was dried by air blowing for 5 seconds.

  Subsequently, in Examples 4 to 18 and Comparative Examples 3 to 8 to which a photopolymerization catalyst was added, the dental composition was irradiated with light for 10 seconds with a visible light irradiator (Powerlight, manufactured by Tokuyama Dental Co., Ltd.) and cured. I let you.

A paraffin wax having a diameter of 8 mm provided with a hole having a diameter of 8 mm is affixed to the adhesive surface coated with the dental composition so that the hole of the paraffin wax and the hole of the double-sided tape are concentric. Was made. This simulated cavity is filled with dental composite resin (Esthelite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.), lightly pressed with a polyester film, and then exposed to light using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Photocuring was performed by irradiation for 10 seconds. Then, a previously 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 adhesive strength was obtained by immersion 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.
As a result of measuring the adhesive strength (initial adhesive strength) of the sample obtained by applying the dental composition immediately after preparation to the adhesive surface, 2 in a thermostatic bath at 50 ° C. after preparation for the adhesive surface. Table 4 shows the measurement results of the adhesive strength (adhesive strength after storage) of the sample obtained by applying the dental composition after storage for a week.

<About the evaluation results shown in Table 4>
Examples 1-18 use the dental composition mix | blended so that the structure of this invention may be satisfied. In any case, the adhesion test results were good both at the initial stage and after storage.
On the other hand, since the dental compositions of Comparative Examples 1 to 5 use a silane coupling agent having no siloxane bond unlike (A) the silane coupling agent, (A) hydrolysis of the silane coupling agent during storage Dehydration condensation occurred and the adhesive strength was greatly reduced.
Since Comparative Examples 6, 7, and 8 did not contain (D) water, (B) acidic compound, and (A) silane coupling agent, respectively, sufficient adhesive strength could not be obtained.

Claims (6)

Following formula (1)

{Where,
V ¹¹ is a methyl group or a hydrogen atom,
W ¹¹ is an oxygen atom or an imino group,
R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms,
X ¹¹ , Y ¹¹ , and Z ¹¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or the following formula (1s)

(Where
R ¹² , R ¹³ and R ¹⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. )
A group represented by
However, at least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a group represented by the formula (1s). } A first silane coupling agent represented by the following formula (2)

{Where,
V ²¹ is a methyl group or a hydrogen atom,
W ²¹ is an oxygen atom or an imino group,
X ²¹ and Z ²¹ are each a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or the following formula (2s)

(Where
R ²² , R ²³ , and R ²⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. )
It is group shown by these. }
At least one (A) silane coupling agent selected from the second silane coupling agents represented by:
(B) an acidic compound,
(C) Organic solvent and (D) Dental composition containing water in the same package.   The dental composition according to claim 1, comprising 50 to 500 parts by mass of the (D) water per 100 parts by mass of the (A) silane coupling agent.   The dental composition according to claim 1 or 2, wherein the (B) acidic compound contains (B1) an acidic group-containing polymerizable monomer.   Furthermore, (E) The dental composition in any one of Claims 1-3 containing the fluorine compound which has a fluorine atom in a molecule | numerator.   A dental adhesive composition comprising the dental composition according to claim 1.   A dental primer composition comprising the dental composition according to claim 1.