JP6995389B2 - Dental adhesive composition - Google Patents

Description

The present invention relates to novel dental adhesive compositions. More specifically, the present invention relates to a dental adhesive composition having excellent adhesiveness to a dentin and excellent storage stability when various restoration materials are used.

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, if the defect site is a small-scale tooth cavity, a composite resin is embedded in the tooth cavity to repair it, and if the defect site is large, a crown material made of ceramics, metal, or the like is coated and repaired. When repairing after demyelination, a resin core is used to form the abutment tooth as a scaffold.

Since none of these restoration materials have adhesiveness to the dentin, a dental adhesive is used between the restoration material and the dentin to secure these materials to the restoration site. And glued. Dental adhesives are generally compositions containing a polymerizable monomer component and a polymerization initiator component, and in clinical practice, various dental adhesives are currently used depending on the restoration material used. be. Further, depending on the dental adhesive used, clinical operation may be complicated.

In order to deal with such a problem, the present inventors include an acidic group-containing polymerizable monomer and a sulfur atom-containing polymerizable monomer as a dental adhesive that can be widely used for many restoration materials. We have proposed a two-component dental adhesive composition composed of one agent and a second agent containing a silane coupling agent, a borate compound and water (see Patent Document 1).

In this material, 1) the acidic group-containing polymerizable monomer adheres to the dentin, the base metal and the metal oxide, the sulfur atom-containing polymerizable monomer adheres to the noble metal, and the silane coupling agent adheres to the silica-based oxide. 2) Of the various adhesive components, acidic compounds and acid-stable compounds are used as the first agent, and acid-unstable compounds are used as the second agent. 3) The borate compound functions as a polymerization initiator that promotes polymerization and curing, so it is a useful dental adhesive in terms of improving adhesion to various adherends. Is.

Japanese Unexamined Patent Publication No. 2018-027913

Journal of the Japanese Society for Dental Science and Engineering, 2011, Vol30 No. 1, 41-46

On the other hand, in some cases in dental clinics, oxidant-based agents such as sodium hypochlorite aqueous solution are used for the purpose of cleaning and disinfecting the tooth cavity and root canal. It is known that the drug has a high cleaning and disinfecting effect on the tooth cavity and root canal, but induces adhesion inhibition due to its oxidative action.

Therefore, as a method of avoiding adhesion inhibition by the oxidant-based agent, a reducing agent such as sodium ascorbate aqueous solution or p-toluenesulfinate aqueous solution is applied to the cow tooth coronary dentin treated with the oxidant-based agent. A method for causing this to occur has been proposed (see Non-Patent Document 1). According to the document, it is reported that the action of the reducing agent causes the adhesive strength of the dental adhesive to be the same as that in the case where the oxidizing agent is not used.

However, the method of acting a reducing agent in order to avoid adhesion inhibition has a problem in that the clinical operation becomes complicated because the pretreatment operation increases.

Therefore, the present inventors mixed sodium ascorbate with the dental adhesive composition described in Patent Document 1 for the purpose of omitting the pretreatment step, and found that the adhesiveness to the dentin treated with an oxidizing agent was applied. However, it was revealed that the storage stability was also reduced.

Therefore, an object of the present invention is for dental use, which has excellent adhesiveness to dentin treated with an oxidizing agent without pretreatment such as applying a reducing agent, and has excellent storage stability. To provide an adhesive composition.

The present inventors have conducted diligent studies to solve the above problems. The dental adhesive composition described in Patent Document 1 contains an organic peroxide and a transition metal compound, and since sodium ascorbate, which is a reducing agent, reacts with these, it is treated with an oxidizing agent. It was presumed that the adhesiveness to the dentin and the storage stability were reduced.

Therefore, the present inventors have studied additives to be blended in a dental adhesive composition in order to improve the adhesiveness to the dentin treated with an oxidant-based agent, and as a result, the above-mentioned Patent Document 1 The above-mentioned dental adhesive composition itself exhibits a reducing action with respect to an oxidant-based agent, and further, the borate compound contained in the dental adhesive composition contributes to the reducing action. I got the finding. Therefore, when the dental adhesive composition described in Patent Document 1 is used for a dentin treated with an oxidant-based agent, the borate compound that should act as a polymerization initiator becomes an oxidant-based agent. It was also found that it was also consumed in the reduction of the oxidant, resulting in a decrease in the adhesive strength to the dentin treated with an oxidant-based agent.

As a result of examining the amount of the borate compound contained in the dental adhesive composition based on these findings, the amount of the borate compound contained in the adhesive composition was increased to treat the dental adhesive composition with an oxidizing agent. It was found that high adhesive strength to the tooth substance was developed.

On the other hand, it was also found that increasing the blending amount of the borate compound reduces the adhesive durability to the metal oxide-based ceramics. Therefore, as a result of further studies, the number of borate compounds contained in the dental adhesive composition is increased, and the amount of the acidic group-containing polymerizable unit contained in the polymerizable monomer in the adhesive composition is increased. We have found that the above problems can be solved without impairing the adhesive durability to metal oxide-based ceramics by setting the molar ratio of the body to the borate compound in a specific range, and have completed the present invention.

That is, the present invention is a dental adhesive composition for dentin treated with an oxidant-based agent, which comprises (a1) an acidic group-containing polymerizable monomer and (A) a polymerizable monomer. , (B) Borate compound, (C) Organic peroxide, (D) Transition metal compound, (E) Water, and (F) Organic solvent, relative to 100 parts by mass of the dental adhesive composition. The content of the (B) borate compound is 0.9 to 4.0 parts by mass, and the content of the (a1) acidic group-containing monomer with respect to 100 parts by mass of the (A) polymerizable monomer is contained. The amount is 3 to 30 parts by mass, and the content of the (a1) acidic group-containing monomer with respect to 1 mol of the (B) borate compound is 2.5 to 8.0 mol . The characteristic dental adhesive composition.

The above-mentioned dental adhesive composition of the present invention can preferably take the following aspects.
(1) Each mol of the (B) borate compound contains 0.5 to 1.5 mol of the (C) organic peroxide.
(2) The transition metal compound (D) is contained in an amount of 0.13 parts by mass to 0.50 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer.
(3) Do not contain a reducing agent for (C) organic peroxide and (D) transition metal compound.
Further, these dental adhesive compositions are suitably prepared by the combination shown in (4) below.
(4) The dental adhesive composition is composed of a combination of a first partial composition and a second partial composition in a state in which the first partial composition is physically inaccessible. It is composed of a mixture of the first partial composition and the second partial composition, and the first partial composition includes at least the (a1) acidic group-containing polymerizable monomer and the (D) transition. The combination comprising a metal compound, wherein the second partial composition comprises at least the (B) borate compound and the (C) organic peroxide.

The dental adhesive composition of the present invention exhibits high adhesiveness to various restoration materials and high storage stability. In particular, it provides excellent adhesion to dentin treated with an oxidizing agent without pretreatment such as treating the dentin with a reducing agent such as an aqueous solution of sodium ascorbate or an aqueous solution of p-toluenesulfinate. Have. Therefore, the dental adhesive composition of the present invention can be used with high versatility as an adhesive material in dental clinics using various restoration materials.

As described above, the reason why the dental adhesive composition of the present invention was able to achieve both adhesiveness and storage stability to the dentin treated with an oxidant-based agent is not clear in detail, but the present inventors have. I guess as follows. That is, since the borate compound used in the dental adhesive composition of the present invention does not have a reducing ability by itself, it does not decompose organic peroxides in the dental adhesive composition and has high storage stability. It is presumed to indicate. On the other hand, the borate compound reacts with an acid component such as an acidic group-containing polymerizable monomer in the dental adhesive composition, and it is presumed that the product at this time exhibits a reducing action on an oxidant-based drug. To. Therefore, the dental adhesive composition of the present invention contains the amount of the borate compound contained in the dental adhesive composition and the acidic group-containing polymerizable monomer contained in the polymerizable monomer. It is presumed that by setting the ratio with the borate compound in a specific range, it has excellent adhesiveness to the dentin treated with an oxidant-based agent without pretreatment and also has high storage stability. To.

Hereinafter, embodiments for carrying out the present invention will be described in detail. In the following description, it is assumed that the numerical range of "X to Y" includes X and Y, that is, "X to Y" means "X or more and Y or less."

The dental adhesive composition of the present invention is a dental adhesive composition for dentin treated with an oxidizing agent and contains (a1) an acidic group-containing polymerizable monomer (A). The dental adhesive composition containing a polymerizable monomer, (B) a borate compound, (C) an organic peroxide, (D) a transition metal compound, (E) water, and (F) an organic solvent. The content of the (B) borate compound with respect to 100 parts by mass of the total amount is 0.9 to 4.0 parts by mass, and the content of the (a1) acidic group with respect to 100 parts by mass of the (A) polymerizable monomer is contained. The content of the monomer is 3 to 30 parts by mass, and the content of the (a1) acidic group-containing monomer is 2.5 to 8.0 mol with respect to 1 mol of the (B) borate compound. The dental adhesive composition is characterized by the above .
Hereinafter, each component constituting the dental adhesive composition of the present invention will be described in detail.

<(A) Polymerizable monomer>
The (A) polymerizable monomer in the dental adhesive composition of the present invention is a compound having at least one radically polymerizable unsaturated group in one molecule. The dental adhesive composition according to the present embodiment is cured by radical polymerization of (A) the polymerizable monomer. Further, the (A) polymerizable monomer includes (a1) an acidic group-containing polymerizable monomer and (a2) an acidic group-free polymerizable monomer.

<(A1) Acidic group-containing polymerizable monomer>
The (a1) acidic group-containing polymerizable monomer is not particularly different from the acidic group-containing polymerizable monomer used in conventional dental adhesives, and has at least one radical polymerizable property in one molecule. It is composed of an acidic polymerizable monomer containing at least one acidic group in addition to the unsaturated radical.

(A1) 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 as main components. Improves adhesion to alloys) and metal oxides (zirconia ceramics, alumina, titanium, etc.) containing metals such as zirconium and oxygen as main components. (A1) The acidic group-containing polymerizable monomer has an effect of decalcifying the dentin and a high effect of improving the permeability to the dentin, and makes the filling restoration material have good adhesiveness to the dentin.

(A1) Examples of the radically polymerizable unsaturated group contained in the acidic group-containing polymerizable monomer include an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, and a styryl group. Among these, the polymerizable unsaturated group is preferably an acryloyl group and / or a metaacryloyl group from the viewpoint of adhesiveness to the filling material.

(A1) The acidic group contained in the acidic group-containing polymerizable monomer is a group in which the aqueous dispersion medium or water suspension of the polymerizable monomer having the group exhibits acidity, and is only an acidic group. Instead, it may be an acid anhydride structure in which two of the acidic groups are dehydrated and condensed, or an acid halide group in which the acidic group is halogenated.

Specifically, (a1) the acidic group contained in the acidic group-containing polymerizable monomer includes a phosphono group {-P (= O) (OH) ₂ }, a carboxyl group {-C (= O) OH}, and the like. Phosphoric acid dihydrogen monoester group {-O-P (= O) (OH) ₂ }, phosphate hydrogen diester group {(-O-) ₂ P (= O) OH}, sulfo group (-SO _3H ) , And the acid anhydride skeleton {-C (= O) -OC (= O)-} and the like.

Specific examples of the polymerizable monomer having a phosphono group include vinylphosphonic acid and p-vinylbenzenephosphonic acid.

Specific examples of the polymerizable monomer having a carboxyl group include acrylic acid, methacrylic acid, 4- (meth) acryloxyethyltrimellitic acid, and 11- (meth) acryloyloxy-1,1-undecanecarboxylic acid. , 1,4-Di (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, etc. Can be mentioned.

Specific examples of the polymerizable monomer having a sulfo group include 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, and vinylsulfonic acid. And so on.

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) acryloyloxyethyl]. Hydrogenphosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate, 6- (meth) acryloyloxyhexyl dihydrogenphosphate, 6- (meth) acryloyloxyhexylphenylhydrogenphosphate, 10- (meth) acryloyloxy Decyldihydrogen phosphate, 1,3-di (meth) acryloyl propane-2-dihydrogen phosphate, 1,3-di (meth) acryloyl propane-2-phenylhydrogen phosphate, bis [5- {2-( Meta) Acryloyloxyethoxycarbonyl} heptyl] Hydrogen phosphate and the like.

Among the above-mentioned polymerizable monomers having an acidic group, the carboxyl group, the dihydrogen phosphate monoester group, because they are highly stable to water and can dissolve the smear layer on the tooth surface and decalcify the teeth slowly. A polymerizable monomer having at least one group selected from the hydrogen phosphate diester group is preferable, and the polymerizable monomer having at least one group selected from the dihydrogen phosphate monoester group or the hydrogen phosphate diester group is preferable. The monomer is most preferable.

Among the polymerizable monomers having an acidic group as described above, examples of particularly preferable monomers include compounds of the following formulas.

(In the formula, R is a hydrogen atom or a methyl group.)
Only one kind of these acidic group-containing polymerizable monomers may be used, or two or more kinds thereof may be used in combination.

Further, in the dental adhesive composition according to the present embodiment, (A) the total of the polymerizable monomers, that is, (a1) the acidic group-containing polymerizable monomer and (a2) the acidic group-free polymerizable monomer. When the total amount of the monomers is 100 parts by mass, (a1) the mixing ratio of the acidic group-containing polymerizable monomer needs to be 3 parts by mass to 30 parts by mass. (A1) If the blending ratio of the acidic group-containing polymerizable monomer is less than 3 parts by mass, the effect of improving the adhesiveness by improving the reactivity with the borate compound becomes insufficient, and if it exceeds 30 parts by mass, the base metal and the metal oxide It is not preferable because it reduces the adhesive durability against the metal. From the viewpoint of adhesiveness to various restoration materials, the blending ratio of (a1) acidic group-containing polymerizable monomer is (a1) acidic group-containing polymerization when (A) the polymerizable monomer is 100 parts by mass. It is preferable to contain 10 parts by mass to 28 parts by mass of the sex monomer. When a plurality of acidic group-containing polymerizable monomers are used, the total amount of the acidic group-containing polymerizable monomers used may be within the above range.

<(A2) Acidic group-free polymerizable monomer>
The (a2) acidic group-free polymerizable monomer in the dental adhesive composition of the present invention is a compound that does not contain an acidic group and contains one or more radically polymerizable unsaturated groups in one molecule. If so, a known compound can be used without particular limitation. Here, examples of the radically polymerizable unsaturated group include those similar to the radically polymerizable unsaturated group contained in the (a1) acidic group-containing polymerizable monomer, but from the viewpoint of adhesiveness, an acryloyl group. , Methacloyl group, acrylamide group, methacrylamide group and the like are preferable.

Suitable specific examples of the (a2) acidic group-free polymerizable monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, and 2-cyanomethyl (a2). Monofunctional such as meth) acrylate, benzyl methacrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and glyceryl mono (meth) acrylate. Sexually polymerizable monomer; 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. Glycoldi (meth) acrylate, 2,2'-bis [4- (meth) acryoyloxyethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2 '-Bis [4- (meth) acryloyloxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2'-bis {4- [2-hydroxy-3- (meth) acryloyloxypropoxy] phenyl} propane, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethyl propanetri (meth) acrylate, neopentyl glycol di (meth) acrylate , 1,6-bis (methacrylethyloxycarbonylamino) -2,2,4-trimethylhexane, 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane, urethane (meth) acrylate , Polyfunctional polymerizable monomers such as epoxy (meth) 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 done.

Among the above-mentioned (a2) acidic group-free polymerizable monomers, polyfunctional polymerizable monomers are preferably used from the viewpoint of adhesiveness to dentin and adhesive durability. Specific examples of preferably used polyfunctional polymerizable monomers are 2,2'-bis {4- [2-hydroxy-3- (meth) acryloyloxypropoxy] phenyl} propane and 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.

(A2) As the acidic group-free polymerizable monomer, only one type may be used, or two or more types may be used in combination. The blending ratio of the (a2) acidic group-free polymerizable monomer is based on the total of (a1) the acidic group-containing polymerizable monomer and (a2) the acidic group-free polymerizable monomer, and (a1) the acidic group. When the total amount of the (a1) acidic group-containing polymerizable monomer and (a2) acidic group-free polymerizable monomer is 100 parts by mass, which is the balance excluding the contained polymerizable monomer, (a1). a2) The blending ratio of the acidic group-free polymerizable monomer is 70 parts by mass to 97 parts by mass. From the viewpoint of adhesiveness to various restoration materials, it is preferable to contain (a1) 10 parts by mass to 28 parts by mass of the acidic group-containing polymerizable monomer, and as a result, (a2) the acidic group-free polymerizable monomer. Is preferably contained in an amount of 72 parts by mass to 90 parts by mass. When two or more types of (a2) acidic group-free polymerizable monomers are used in combination, the total amount of (a2) acidic group-free polymerizable monomers may be within the above range.

<(B) Borate compound>
The borate compound in the dental adhesive composition of the present invention has two functions of a reducing agent precursor and a polymerization initiator. As described above, it is presumed that the borate compound reacts with the acid component and is converted into a borane compound to function as a reducing agent. Therefore, it is presumed that the generated borane compound restores the adhesiveness by decomposing the components of the oxidant-based drug on the surface of the dentin. On the other hand, the borane compound functions as a polymerization initiator because it generates radicals by reacting with (C) an organic peroxide and (D) a transition metal compound.

As the borate compound to be blended in the dental adhesive composition of the present invention, any known borate compound can be used without limitation, but from the viewpoint of storage stability, an aryl borate having an aryl group in the molecule. It is preferable to use a compound. The arylborate compound is a compound in which at least one aryl group is bonded to a boron atom, and an arylborate compound having 3 or 4 aryl groups in one molecule is preferable.

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 dental adhesive composition.

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

The blending ratio of the borate compound in the dental adhesive composition of the present invention is
1) When the total amount of the dental adhesive composition is 100 parts by mass, (B) the borate compound is 0.9 to 4 parts by mass, and 2) (B) per mol of the borate compound is (a1) acidic. It is necessary to contain 2.5 to 8.0 mol of the group-containing polymerizable monomer. By setting the blending ratio of the borate compound in the above range, it is possible to have excellent adhesiveness to the dentin treated with an oxidant-based agent without pretreatment and to have high storage stability.

If the blending ratio of the borate compound to the total amount of the dental adhesive composition is less than 0.9 parts by mass, the borane compound produced when applied to the dentin treated with an oxidizing agent-based agent is consumed by the agent, and thus the polymerization is carried out. It does not function sufficiently as an initiator and the adhesive strength decreases, and when the blending ratio of the borane compound exceeds 4.0 parts by mass, the borate compound which is the polymerization initiator becomes excessive in the adhesive layer, so that the curability decreases. It is not preferable because the adhesive strength is reduced.

From the viewpoint of adhesiveness and storage stability, it is preferable that the borate compound (B) is 1.1 to 3.0 parts by mass when the total amount of the dental adhesive composition is 100 parts by mass.

Further, when the amount of (a1) acidic group-containing polymerizable monomer per 1 mol of (B) borate compound is less than 2.5 mol, the acid group is contained due to the salt formability of the acidic group-containing polymerizable monomer and the borate compound. It is not preferable because the polymerizable monomer is insufficient and the adhesive durability to the metal oxide-based ceramics is lowered. Further, when the amount of the acidic group-containing polymerizable monomer exceeds 8.0 mol, the amount of the acidic group-containing polymerizable monomer in the dental adhesive composition becomes excessive, and the adhesive durability against base metals and metal oxides becomes excessive. It is not preferable because it decreases.

From the viewpoint of the adhesiveness and storage stability, it is preferable to contain 2.7 to 3.8 mol of the (a1) acidic group-containing polymerizable monomer per 1 mol of the (B) borate compound.

<(C) Organic peroxide>
The dental adhesive composition of the present invention contains (C) an organic peroxide. As the organic peroxide, a known compound blended in a dental adhesive composition can be used without limitation, but typically, a ketone peroxide, a peroxyketal, a hydroperoxide, a diallyl peroxide, or a peroxide can be used. Examples thereof include oxyesters, diacyl peroxides, and peroxydicarbonates. Specific examples of these organic peroxides include the following.

Examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetate acetate 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-). Butylperoxy) 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 (4,4-di-t-butyl peroxycyclohexyl) propane can be mentioned.

Examples of 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 the dialkyl peroxide include α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylkumi. Examples thereof include ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexine 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 succinic acid peroxide. Examples thereof include oxides, m-toroil benzoyl peroxides, benzoyl peroxides and the like.

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

Examples of peroxyesters include α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-. Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 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-tol) Oil peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 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 kind of these organic peroxides may be used, or two or more kinds thereof may be used in combination, but from the viewpoint of polymerization activity, it is particularly preferable to use hydroperoxides.

The mixing ratio of the (C) organic peroxide is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer. Further, from the viewpoint of achieving both high adhesiveness to the dentin treated with an oxide-based agent and high storage stability, (B) organic peroxide is added to 0. per mol of the borate compound. It is preferably contained in an amount of 5 to 1.5 mol, more preferably 0.7 to 1.3 mol.

<(D) Transition metal compound>
The dental adhesive composition of the present invention contains (D) a transition metal compound. The transition metal compound is a metal compound of Group 3 to 12 in the 4th period of the periodic table, and specifically, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn). ), Iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), respectively. By blending these metal compounds into a dental adhesive composition, (B) a borate compound, (C) an organic peroxide and a radical polymerization initiator are formed, and they have a role of improving the adhesiveness.

Each of the above transition metal elements may have a plurality of valences, but can be added to the adhesive composition of the present invention as long as it has a valence that can exist stably. For example, Sc (III), Ti (IV), V (III-V), Cr (II, III, VI), Mn (II-VII), Fe (II, III), Co (II, III), Ni. (II), Cu (I, II), Zn (II). Specific examples of such compounds include scandium iodide (III) as the +III-valent scandium compound, titanium chloride (IV) and titanium (IV) tetraisopropoxide as the +VI-valent titanium compound, and the +VI-valent vanadium compound. As divanadium tetraoxide (IV), vanadium acetylacetonate (IV) oxide, vanadil oxalate (IV), vanadil sulfate (IV), oxobis (1-phenyl-1,3-butandionate) vanadium (IV), Bis (maltlate) oxovanadium (IV) and the like, vanadium pentoxide (V) and sodium metavanadate as + V-valent vanadium compounds, chromium (II) chloride as a +II-valent chromium compound, and chromium chloride as a +III-valent chromium compound. (III) and the like include chromium acid, chromate and the like as the + VI-valent chromium compound, manganese acetate (II) and manganese naphthenate (II) as the + II-valent manganese compound, and iron acetate as the + II iron compound (II). II), iron (II) chloride, etc., as the +III iron compound, iron (III) acetate, iron (III), etc., and as the +II cobalt compound, cobalt acetate (II), cobalt naphthenate (II), etc. , Nickel chloride (II) and the like as the +II valent nickel compound, copper (I) chloride and copper (I) as the +I copper compound, and copper (II) chloride and copper (II) acetate as the +II copper compound. , + II Zinc compounds include zinc chloride (II), zinc acetate (II) and the like. Among these, V (IV, V), Mn (II), Fe (II, III), and Co (II) are preferable, and among them, a vanadium compound having a + IV and / or + V valence can be obtained because higher adhesive strength can be obtained. Is more preferable. Most preferably, it is a + IV vanadium compound.

A plurality of types of these transition metal compounds in the fourth period may be used in combination.
Is done.

From the viewpoint of polymerization activity, the blending ratio of the transition metal compound is preferably 0.13 parts by mass to 0.50 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer.

<(E) Water>
The water (E) used in the dental adhesive composition of the present invention preferably contains substantially no harmful impurities from the viewpoints of storage stability, biocompatibility and adhesiveness, and is, for example, deionized water. , Distilled water and the like.

From the viewpoint of adhesive strength and dryness at the time of adhesion, the amount of (E) water to be blended in the dental composition shall be 1 part by mass to 50 parts by mass when (A) the polymerizable monomer is 100 parts by mass. Is preferable.

<(F) Organic solvent>
As the (F) organic solvent used in the dental composition of the present embodiment, known organic solvents can be used without limitation, and can be appropriately selected depending on the purpose of the dental composition. (F) Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol and 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 and benzene; Hydrocarbon solvents such as pentane, hexane, heptane and octane; Chlorine solvents such as methylene chloride, chloroform and 1,2-dichloroethane Solvent; Examples thereof include a fluorine-based solvent such as trifluoroethanol.

Among these, acetone, ethanol, isopropyl alcohol and the like are particularly preferable from the viewpoint of solubility, storage stability and the like. (F) The organic solvent may be used alone or in combination of two or more. When two or more kinds of (F) organic solvents are used in combination, the reference amount is the total amount thereof.

The organic solvent may be added only to the first partial composition, may be added only to the second partial composition, and may be added to both the first partial composition and the second partial composition. You may. Further, as the organic solvent added to the first partial composition, 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 partial composition. Further, when an organic solvent is added to each of the first partial composition and the second partial composition, the organic solvent used in the first partial composition and the organic solvent used in the second partial composition are the same. It may be different.

From the viewpoint of controlling the film thickness applied to the adhesive surface, the blending amount of the (F) organic solvent in the dental composition is 50 parts by mass or more when (A) the polymerizable monomer is 100 parts by mass. It is preferable to contain 400 parts by mass.

<Other ingredients>
If necessary, the dental adhesive composition of the present invention may contain components such as various additives other than the above components. Examples of the additive include a filler, a photopolymerization initiator, a colorant, a polymerization inhibitor and the like.

Further, in the above-mentioned dental adhesive composition of the present invention, a reducing agent for (C) an organic peroxide and (D) a transition metal compound is used from the viewpoint of adhesiveness to various restoration materials and storage stability. Although it is preferably not contained, a trace amount of reducing agent may be contained within a range in which no clear significant difference is observed in the adhesive strength and storage stability of the dental adhesive composition of the present invention. Specifically, the amount of the reducing agent in such a case is that the content of the reducing agent is more than 0 and 1/100 or less in terms of molar ratio with respect to (C) an organic peroxide and (D) a transition metal compound. Is preferable.

The filler is added to improve the mechanical strength and operability in the adhesive layer obtained by curing the dental adhesive composition. The filler is not particularly limited, and known inorganic fillers, organic fillers, and inorganic-organic composite fillers can be used.

As the photopolymerization initiator, a known photopolymerization initiator can be used without limitation, and 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 combinations of class and tertiary amines, combinations of α-aminoacetophenones and tertiary amines.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.

<Method for Producing Dental Adhesive Composition of the Present Invention>
The dental adhesive composition of the present invention comprises the above-mentioned (A) polymerizable monomer, (B) borate compound, (C) organic peroxide, (D) transition metal compound, (E) water, and the above-mentioned. (F) Each component of the organic solvent and the above-mentioned other components may be blended and used in a predetermined blending amount, but from the viewpoint that the blending can be performed by a simple operation at the time of dental clinic, and for a long period of time. From the viewpoint of excellent storage stability, it is preferable that the first partial composition is composed of a combination of the first partial composition and the second partial composition in a state where the first partial composition cannot be physically contacted. In this case, each component to be distributed to each partial composition may be appropriately determined, but from the viewpoint of storage stability, it is preferable to use a combination in which each component does not react.

Here, the "physically inaccessible state" means a state in which one composition and the other composition are separated by an inhibitory member that inhibits molecular diffusion between the two. As the inhibitory member, a solid member such as a resin, glass, metal, or ceramics, which is generally used as a material for a container or a bag, is used, but a molecule between one composition and another composition is used. A liquid or a gas may be used as long as the diffusion can be inhibited. A typical example of the "physically inaccessible state" is a state in which one type of composition is stored in a sealed state in a container that blocks outside air and light.

As each component to be blended in each of the first partial composition and the second partial composition, from the viewpoint of storage stability, the first partial composition contains at least the (a1) acidic group-containing polymerization. It is preferable to contain the sex monomer and the (D) transition metal compound, and the second partial composition preferably contains at least the (B) borate compound and the (C) organic peroxide.

The dental adhesive composition of the present embodiment is in a state where the first partial composition and the second partial composition are physically inaccessible to each other in the state before use (at the time of storage). Although not particularly limited, from the practical viewpoint such as handleability, each of the first partial composition and the second partial composition is placed in various containers such as syringes, bags, and bottles (that is, sachets). It is preferable to store it. In other words, a suitable storage method for the dental adhesive composition of the present embodiment is preferably stored in a state of being packaged in the first partial composition and the second partial composition. Then, at the time of use, the first partial composition and the second partial composition are mixed. In the state before use (during storage), of course, the dental adhesive composition of the present embodiment can be distributed as a product on the market.

Regarding the mixing ratio of the first partial composition and the second partial composition (first partial composition / second partial composition) when the dental adhesive composition of the present embodiment is used, adhesion is performed. It can be appropriately selected as long as the operability and operability are not significantly impaired, but from the practical viewpoints such as handleability and ease of product packaging, the mixing ratio (first partial composition / second partial composition). The product) is preferably in the range of 1/5 to 5/1 in terms of volume ratio, more preferably in the range of 1/3 to 3/1, or in the range of 1/5 to 5/1 in terms of mass ratio. It is preferably in the range of 1/3 to 3/1, more preferably. In addition, the user of the dental adhesive composition of the present embodiment usually has a mixing ratio determined by the developer, manufacturer or seller of the dental adhesive composition of the present embodiment (hereinafter, "designated mixing ratio"). The first agent and the second agent are mixed according to (referred to as). 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 (rate) can be displayed on the mixing ratio (rate) information display medium. The mixing ratio (rate) information display medium includes, for example, i) a product package consisting of a paper box or the like, ii) a paper medium and / or a product instruction manual provided as electronic data, iii) a first agent and a second agent. Containers (bottles, syringes, packaging bags, etc.) for storing each agent in a sealed state, iv) Product catalog provided as paper media and / or electronic data, v) Product use by e-mail, mail, etc. separately from the product You can use the correspondence sent to the person. Further, the designated mixing ratio may be provided to the product user in a manner that can be recognized by the product user by means other than those shown in i) to v) above.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. The components used in the examples are as follows.
<(A) Polymerizable monomer>
(A1) Acidic group-containing polymerizable monomer (acid monomer)
MDP: 10-methacryloxydecyldihydrogen phosphate PM2: bis (2-methacryloxyethyl) acid phosphate- (a2) Acid group-free polymerizable monomer (non-acid monomer)
BisGMA: 2.2'-bis [4- (2-hydroxy-3-methacrylicoxypropoxy) phenyl] propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate <(B) borate compound>
PhB-Na: Sodium salt of tetraphenylboron PhB-TEOA: Triethanolamine salt of tetraphenylboron <(C) Organic peroxide>
Perocta H: 1,1,3,3-tetramethylbutylhydroperoxide <(D) transition metal compound>
BMOV: Oxovanadium (IV) bis (maltrat)
<Other ingredients>
BHT: Dibutylhydroxytoluene AANA: Sodium ascorbate <Examples 1 to 14, Comparative Examples 1 to 14>
(Preparation of Dental Adhesive Composition)
By mixing each component as shown in Tables 1 and 2, a dental adhesive composition consisting of a first partial composition and a second partial composition was prepared.

As for Comparative Example 14, since the second partial composition was not uniformly miscible and could not be prepared, the subsequent evaluation of the adhesive strength and the storage stability was omitted.

Next, the obtained dental adhesive composition was evaluated according to the "adhesive strength evaluation" and "appearance evaluation after long-term storage" shown below.

(Evaluation of adhesive strength to tooth substance)
The following two types of adherends were prepared.

(1) Tooth substance / No chemical treatment The anterior teeth of cows removed within 24 hours after slaughter were polished with water-resistant abrasive paper P600 under water injection, and the dentin plane was carved out so as to be parallel and flat to the lip surface. Adhesive body.

(2) Tooth substance / with chemical treatment The anterior teeth of cows removed within 24 hours after slaughter were polished with water-resistant polishing paper P600 under water injection, and the dentin plane was carved out so as to be parallel and flat to the lip surface. Later, the adherend was coated with neo-cleaner "Sekine" (manufactured by Neo Pharmaceutical Co., Ltd.), left to stand for 30 seconds, and washed with water for 15 seconds.

Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the polished surface of each of these two types of adherends. Subsequently, the dental adhesive compositions of Examples and Comparative Examples shown in Tables 1 and 2 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.

As for the dental adhesive composition, the first partial composition and the second partial composition were mixed on a mixing dish and applied to the adhesive surface. The mixing ratio of the first partial composition and the second partial composition was set so that the mixing ratio of each component shown in Tables 1 and 2 was maintained as it was. For example, in Example 2, the first partial composition: 205.35 parts by mass was mixed with 175 parts by mass of the second partial composition.

Subsequently, a SUS304-made circle to which a dental adhesive resin cement (Esthesem II, manufactured by Tokuyama Dental) was previously polished and a dental adhesive composition was applied to the adhesive surface to which the dental adhesive composition was applied. A rod (diameter 8 mm, height 18 mm) was glued. The excess resin cement protruding 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 tensile adhesive strength of these samples was measured using an autograph manufactured by Shimadzu Corporation (crosshead speed 2 mm / min). 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 adhesive strength measurement from the water.

Table 3 below shows 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. It was judged that the tensile strength was good if it was 10 MPa or more.

(Evaluation of adhesive durability strength between metal oxide ceramics and resin cement)
Zirconia ceramics "TZ-3Y-E sintered body" (manufactured by Tosoh Corporation, length 10 mm x width 10 mm x thickness 3 mm) is polished with # 1500 water-resistant abrasive paper and then sandblasted with a metal oxide (zirconia ceramics). I prepared my body.

Next, 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 adhesive compositions of Examples and Comparative Examples shown in Tables 1 and 2 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.

As for the dental adhesive composition, the first partial composition and the second partial composition were mixed on a mixing dish and applied to the adhesive surface. The mixing ratio of the first partial composition and the second partial composition was set so that the mixing ratio of each component shown in Tables 1 and 2 was maintained as it was. For example, in Example 2, the first partial composition: 205.35 parts by mass was mixed with 175 parts by mass of the second partial composition.

Subsequently, a SUS304-made circle to which a dental adhesive resin cement (Esthesem II, manufactured by Tokuyama Dental) was previously polished and a dental adhesive composition was applied to the adhesive surface to which the dental adhesive composition was applied. A rod (diameter 8 mm, height 18 mm) was glued. The excess resin cement protruding 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 tensile adhesive strength of these samples was measured using an autograph manufactured by Shimadzu Corporation (model: AG5000D, crosshead speed 2 mm / min). 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 adhesive strength measurement from the water.

Immersion treatment in which 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. 1 is set as one set, and the measurement results of the adhesive strength (adhesive strength after the durability test) after repeating this 7000 times are shown in Table 3. It was judged that the tensile strength was good if it was 20 MPa or more.

(Appearance evaluation after long-term storage)
After preparing the dental adhesive compositions of Examples and Comparative Examples shown in Tables 1 and 2, they were sealed in a container and further stored in a constant temperature bath at 50 ° C. for 1 week. Subsequently, the appearance of each of the container in which the first partial composition was sealed and the container in which the second partial composition was sealed taken out from the constant temperature bath was visually observed, and the first part before and after storage was observed. Table 3 shows the results of evaluation of the presence or absence of changes in the composition and the second partial composition and denaturation such as gelation.

(About the evaluation results shown in Table 3)
Examples 1 to 15 shown in Table 3 use adhesive compositions formulated so as to satisfy the constitution of the present invention. In all cases, the adhesion test results were good. In addition, no significant change was confirmed in the appearance change after storage.

On the other hand, in Comparative Example 1, since the value of the borate compound by mass / 100 parts by mass was low, it is considered that the adhesiveness to the dentin treated with the oxidizing agent was low.

In Comparative Example 2, since sodium ascorbate that reacts with the (D) transition metal compound is contained in the first partial composition, the adhesiveness to the dentin treated with an oxidant-based agent is low, and the gel is gelled after storage. It is probable that the conversion has occurred.

In Comparative Example 3, since the second partial composition contained (C) sodium ascorbate that reacts with the organic peroxide, the adhesiveness to the dentin treated with the oxidant-based agent was low. However, since the second composition did not contain the (A) polymerizable monomer, there was no change in the appearance after storage.

It is probable that in Comparative Examples 4 to 6, since the acidic group-containing polymerizable monomer / borate compound was low, the acidic group-containing polymerizable monomer was insufficient and the adhesive durability to the metal oxide-based ceramics was low.

It is considered that Comparative Example 7 had a high content of the acidic group-containing polymerizable monomer in the composition and a high amount of the acidic group-containing polymerizable monomer / borate compound, so that the adhesive durability to the metal oxide-based ceramics was low. Be done.

Since Comparative Examples 8 and 9 did not contain or contained (a1) an acidic group-containing polymerizable monomer, it is considered that the adhesiveness to the dentin and the adhesive durability to the metal oxide-based ceramics were low.

Since Comparative Examples 10 to 13 do not contain (B) borate compound, (D) transition metal compound, and (E) water, respectively, it is considered that sufficient adhesive strength to the dentin was not obtained.

Since Comparative Example 14 does not contain (F) an organic solvent, it is considered that the (C) organic peroxide of the second partial composition was not miscible with (E) water, and a uniform composition could not be obtained.

Claims (5)

A dental adhesive composition for dentin treated with an oxidant-based agent.
(A1) Polymerizable monomer containing an acidic group-containing polymerizable monomer , (B) borate compound, (C) organic peroxide, (D) transition metal compound, (E) water, and ( F) Contains an organic solvent ,
The content of the (B) borate compound with respect to 100 parts by mass of the total amount of the dental adhesive composition is 0.9 to 4.0 parts by mass.
The content of the (a1) acidic group- containing monomer with respect to 100 parts by mass of the (A) polymerizable monomer is 3 to 30 parts by mass, and
The content of the (a1) acidic group-containing monomer with respect to 1 mol of the (B) borate compound is 2.5 to 8.0 mol .
The dental adhesive composition. The dental adhesive composition according to claim 1, wherein each mol of the (B) borate compound contains 0.5 to 1.5 mol of the (C) organic peroxide. The invention according to claim 1 or 2, wherein the transition metal compound (D) is contained in an amount of 0.13 parts by mass to 0.50 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer. Dental adhesive composition. The dental adhesive composition according to any one of claims 1 to 3, which does not contain a reducing agent for (C) an organic peroxide and (D) a transition metal compound. A combination for preparing the dental adhesive composition according to any one of claims 1 to 4.
The combination is composed of a combination of a first partial composition and a second partial composition that is physically inaccessible to the first partial composition.
The dental adhesive composition comprises a mixture of the first partial composition and the second partial composition.
The first partial composition contains at least the (a1) acidic group-containing polymerizable monomer and the (D) transition metal compound.
The combination , wherein the second partial composition comprises at least the (B) borate compound and the (C) organic peroxide.