JP2015067551A - Dental adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental adhesive composition exhibiting strong and stable adhesiveness to any of enamel and dentine.SOLUTION: A dental adhesive composition is obtained by mixing (A) a dihydrogenphosphate mono(meth)acrylic acid ester group-containing polymerizable monomer represented by the formula (1), (B) a hydrogenphosphate di(meth)acrylic acid ester group-containing polymerizable monomer, and (C) a polyvalent metal compound selected from at least any of polyvalent metal alkoxides, multivalent metal fluorides, polyvalent metal carbonates, polyvalent metal hydrides and alkyl polyvalent metals. [In the formula, R1 represents either of a hydrogen atom or a methyl group, and X represents a hydrocarbon group having a carbon number of 4 or more which may be straight or branched.]

Description

  The present invention relates to a dental adhesive composition used for dental treatment.

  In the case of a tooth cavity damaged by caries or the like, if it is a relatively small cavity in the first mid-term, direct restoration by composite resin is often performed from the viewpoint of aesthetics, simplicity of operation and quickness. . On the other hand, prosthetics made of metal, ceramics, or dental resin are often used for repairing relatively large cavities.

Since these dental restorations such as composite resins and prostheses generally do not have adhesiveness to the tooth substance, a dental adhesive is used for the composite resin in order to adhere this to the tooth substance. A dental cement material is used in combination for the prosthesis. In general, these adhesives and cement materials are composed of a polymerizable monomer composition having a methacrylate polymerizable monomer as a main component.
In addition, these adhesives and cement materials generally do not have sufficient adhesion to the tooth, and in particular, depending on the damage of the tooth, high adhesion is required for each of enamel and dentin. Therefore, prior to the use, the following pretreatment is applied to the tooth surface. That is, (1) An etching material for etching hard teeth (mainly enamel mainly composed of hydroxyapatite) is applied, and (2) a pretreatment as a penetration enhancer called a primer in the teeth The material is being applied.
Here, as the former etching material, an acid aqueous solution for decalcifying the tooth surface is generally used, and an aqueous solution of phosphoric acid, citric acid, maleic acid or the like is used. As the latter primer, it is necessary to infiltrate the adhesive material into the fine enamel surface exposed to the dentin surface after decalcification and the enamel surface deashed with an acid aqueous solution. Therefore, a composition mainly composed of a hydrophilic (meth) acrylate polymerizable monomer having good affinity with a tooth such as hydroxyethyl methacrylate (HEMA) and an organic solvent is used.
In addition, a self-etching primer (hereinafter also referred to as a dental pretreatment material) having the functions (1) and (2) has been proposed. This dental pretreatment agent contains a polymerizable monomer having an acidic group in part, and the action of this acidic group provides a function of decalcifying an aqueous acid solution and a function of promoting the penetration of a primer by a single coating operation. Can be granted. In addition, after the dental pretreatment material is applied, when the restoration is a composite resin, an adhesive is applied thereon and polymerized and cured (for example, refer to Patent Document 1). Dental cement is applied and polymerized and cured, and each is adhered to a tooth (see, for example, Patent Document 2). Since these are processed with the adhesive for composite resin or dental cement according to the restoration after the treatment with the dental pretreatment material, they are two-step type treatments.

  Under these circumstances, a dental one-component adhesive that exhibits high adhesiveness without using a dental pretreatment material in a dental adhesive for the purpose of reducing the operability of the pretreatment material as described above. (Hereinafter, also simply referred to as a dental adhesive) has been proposed. This dental adhesive partially contains a polymerizable monomer having an acidic group, and the action of this acidic group provides a deashing function of an acid aqueous solution and a primer penetration promoting function by a single coating operation. Furthermore, high adhesiveness is expressed by polymerizing and curing. Since this dental adhesive does not require a dental pretreatment material, it can be used as an adhesive excellent in operability (see, for example, Patent Documents 3 to 6).

  Furthermore, recently, for the purpose of reducing the complexity of further operations, a composite resin provided with the functions of the dental pretreatment material and the dental adhesive (hereinafter also simply referred to as a self-adhesive dental composite resin), A dental cement provided with a function of a pretreatment material (hereinafter also simply referred to as a self-adhesive dental cement) has been proposed (see, for example, Patent Documents 7 to 9).

  However, in the self-adhesive dental composite resin and the self-adhesive dental cement, in exchange for the operability, the adhesiveness is still low and stronger adhesiveness is required. Moreover, even when using a two-step type or when using a dental one-pack type adhesive, excellent adhesion can be obtained, but there are advantages and disadvantages in adhesion to enamel and dentin. In any case, satisfactory adhesion is required. Furthermore, these adhesive properties are required to be stable for a long time after the treatment, but are not always sufficient in the oral cavity where water resistance, heat resistance, and impact resistance (chewing resistance) are required. There is also a need for more stable adhesion.

Under these circumstances, as a dental adhesive composition that realizes stronger and more stable adhesiveness, a dental mixture containing a polymerizable monomer containing an acidic group derived from phosphoric acid and a polyvalent metal ion Adhesive compositions have been proposed (see, for example, Patent Documents 10 and 11). According to such a dental adhesive composition, high adhesive strength can be obtained by ionic crosslinking formed by ionic bonding of acidic groups and polyvalent metal ions during polymerization and curing.
However, even such dental adhesive compositions do not satisfy the requirements for adhesiveness required in harsh oral environments, and in particular, satisfactory adhesiveness is still required for both enamel and dentin. This is the current situation.
That is, enamel is mostly composed of hydroxyapatite, which is inorganic, while dentine is composed of a lot of organic collagen fibers and water in addition to hydroxyapatite, and both dentines have different structures. It is said. In dentin, the pretreatment described above facilitates penetration of the polymerizable monomer as an adhesive component, but does not change the configuration itself, and the configurations of both dentines remain different. For this reason, it is necessary to clarify an adhesive composition that exhibits effective adhesion to each of enamel and dentin. However, the current situation is that the examination of such an adhesive composition has not sufficiently progressed.

Japanese Patent Laid-Open No. 7-82115 JP 2003-012430 A Japanese Patent Laid-Open No. 10-236912 JP-A-11-130465 JP 2007-137798 A International Publication No. 2007/139207 JP 2012-171885 A Special table 2008-510038 gazette JP 2008-260753 A JP 2008-201726 A International Publication No. 2010/010901

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a dental adhesive composition that exhibits strong and stable adhesion to both enamel and dentin.

In order to solve the above-mentioned problems, the present inventors diligently studied and obtained the following knowledge.
That is, for a combination of a long-chain dihydrogen phosphate monoester group-containing polymerizable monomer and a short-chain hydrogen phosphate diester group-containing polymerizable monomer, the dihydrogen phosphate monoester as an acidic group is used. When a polyvalent metal compound that binds to an ester group and a hydrogen phosphate diester group is blended, a dental adhesive composition showing strong and stable adhesion to both enamel and dentin can be obtained. I got the knowledge.

The present invention is based on the above knowledge, and means for solving the above problems are as follows. That is,
<1> At least (A) a dihydrogen phosphate monoester group-containing polymerizable monomer represented by the following general formula (1), and (B) a hydrogen phosphate diester represented by the following general formula (2) Group-containing polymerizable monomer and (C) a polyvalent metal compound selected from at least one of a polyvalent metal alkoxide, a polyvalent metal fluoride, a polyvalent metal carbonate, a polyvalent metal hydride, and an alkyl polyvalent metal And a dental adhesive composition characterized by being obtained by mixing.
However, in said general formula (1), R < ¹ > shows either a hydrogen atom and a methyl group, and X shows the C4 or more hydrocarbon group which may be linear or branched.
However, in the general formula (2), R ² and R ³ each independently represent either a hydrogen atom or a methyl group, and Y ¹ and Y ² independently represent an oxygen atom, Any one of —NH—, —NCH ₃ — and —NCH ₂ CH ₃ —, wherein Z ¹ and Z ² are each independently a carbon atom having 2 or 3 carbon atoms which may be linear or branched; Indicates a hydrogen group.
<2> The sum of the number of moles of (A) the dihydrogen phosphate monoester group-containing polymerizable monomer and (B) the hydrogen phosphate diester group-containing polymerizable monomer is (C) in the polyvalent metal compound. The dental adhesive composition according to <1>, wherein the dental adhesive composition is larger than the total valence of the polyvalent metal.
<3> The dental adhesive composition according to any one of <1> to <2>, wherein the (C) polyvalent metal compound is a polyvalent metal alkoxide.
<4> The dental adhesive composition according to any one of <1> to <3>, wherein (C) the polyvalent metal compound is a Group 4 metal compound.
<5> The dental adhesive composition according to any one of <1> to <4>, further including a polymerization initiator.
<6> Further, (C) the above-mentioned containing a fluorine-containing compound such that the molar ratio of fluorine atoms to polyvalent metal atoms of the polyvalent metal compound, and the fluorine atom / polyvalent metal atom is 0.4 to 4.0. The dental adhesive composition according to any one of <1> to <5>.
<7> The dental adhesive composition according to any one of <1> to <6>, which does not substantially contain water.

  ADVANTAGE OF THE INVENTION According to this invention, the said problems in a prior art can be solved, and the dental adhesive composition which shows strong and stable adhesiveness with respect to both an enamel and dentin is provided. it can.

(Dental adhesive composition)
The dental adhesive composition of the present invention comprises at least (A) a dihydrogen phosphate monoester group-containing polymerizable monomer, (B) a hydrogen phosphate diester group-containing polymerizable monomer, and (C). It is obtained by mixing with a polyvalent metal compound, and contains water, a polymerization initiator, a fluorine-containing compound, and other components as necessary.

<(A) Dihydrogen phosphate monoester group-containing polymerizable monomer>
The (A) dihydrogen phosphate monoester group-containing polymerizable monomer is represented by the following general formula (1).

However, in said general formula (1), R < ¹ > shows either a hydrogen atom or a methyl group, and X shows a C4 or more hydrocarbon group.
The upper limit of the carbon number of the hydrocarbon group is not particularly limited, but is about 15.

The (A) dihydrogen phosphate monoester group-containing polymerizable monomer has a long chain structure depending on the number of carbon atoms of the hydrocarbon group represented by X in the general formula (1). By blending this (A) dihydrogen phosphate monoester group-containing polymerizable monomer, the adhesiveness of the tooth with the dentin can be improved.
In addition, as a specific compound of said (A) dihydrogen phosphate monoester group containing polymerizable monomer, a well-known compound can be utilized without a restriction | limiting in particular. Among them, a compound having a methacrylate group (in the general formula (1), R ¹ is methyl) is particularly useful from the viewpoint of storage stability. As a preferable compound, the compound of the following structure is mentioned, for example.

Especially, in the said Formula (1), the C6-C12 compound of the said hydrocarbon group shown by X is preferable, the compound of 8-12 is more preferable, and the compound of 10 is especially preferable.

  The (A) dihydrogen phosphate monoester group-containing polymerizability in the total polymerizable monomer component including the (B) hydrogen phosphate diester group-containing polymerizable monomer and other polymerizable monomers described later. Although there is no restriction | limiting in particular as content of a monomer, 3 mass%-50 mass% are preferable, and 15 mass%-35 mass% are more preferable. When the content is less than 3% by mass, the adhesive strength to dentin may be reduced, and when it exceeds 50% by mass, the cured body strength may be reduced.

<(B) Hydrogenophosphate diester group-containing polymerizable monomer>
The (B) hydrogen phosphate diester group-containing polymerizable monomer is represented by the following general formula (2).

However, in the general formula (2), R ² and R ³ each independently represent either a hydrogen atom or a methyl group, and Y ¹ and Y ² independently represent an oxygen atom, Any one of —NH—, —N (CH ₃ ) — and —N (CH ₂ CH ₃ ) —, wherein Z ¹ and Z ² are each independently a carbon that may be linear or branched; The hydrocarbon group of number 2 or 3 is shown.

The (B) hydrogen phosphate diester group-containing polymerizable monomer has a short chain structure according to the number of carbon atoms of the hydrocarbon group represented by Z ¹ or Z ² in the formula (2). The (B) hydrogen phosphate diester group-containing polymerizable monomer has higher acidity than the (A) dihydrogen phosphate monoester group-containing polymerizable monomer, and the (C) polyvalent metal compound It is easy to form a salt. This salt is bonded with hydroxyapatite to give strong and stable adhesion to enamel.
In addition, as a specific compound of the said (B) hydrogen-phosphate diester group containing polymerizable monomer, a well-known compound can be utilized without a restriction | limiting in particular. Among them, a symmetric diester compound (in the formula (2), R ² and R ³ , Y ¹ and Y ² , Z ¹ and Z ² are the same) is preferable because of easy availability. Examples of such a compound include compounds having the following structure.

Among them, a methacrylic ester compound (in formula (2), R ² and R ³ are methyl, and Y ¹ and Y ² are oxygen atoms) is preferable, and carbon number 2 is more preferable.

  Although there is no restriction | limiting in particular as content of the said (B) hydrogen phosphate diester group containing polymerizable monomer in the said all polymerizable monomer component, 0.3 mass%-30 mass% are preferable, and 1 mass is preferable. % To 15% by mass is more preferable, and 3% to 10% by mass is particularly preferable. If the content is less than 0.3% by mass, the adhesive strength to enamel may be reduced, and if it exceeds 30% by mass, the adhesive strength to dentin may be reduced.

<(C) Multivalent metal compound>
The (C) polyvalent metal compound is a compound selected from at least one of a polyvalent metal alkoxide, a polyvalent metal fluoride, a polyvalent metal carbonate, a polyvalent metal hydride, and an alkyl polyvalent metal.
The organic group in the polyvalent metal alkoxide is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, octyl, and the like. An alkyl group having 4 or less carbon atoms is preferred.
There is no restriction | limiting in particular as an alkyl group in the said alkyl polyvalent metal, For example, a C1-C20 alkyl group is mentioned.
Among these, the polyvalent metal alkoxide is preferable because of high storage stability and excellent adhesive strength.
In addition, these may be used individually by 1 type and may use 2 or more types together.

In addition, the metal element constituting the polyvalent metal compound is not particularly limited, and examples thereof include metal elements of Group 2 to Group 13 of the periodic table. Metal elements are preferred, with titanium being particularly preferred.
In addition, there is no restriction | limiting in particular as a valence of the said polyvalent metal compound, What is necessary is just bivalent or more.

  Specific examples of the polyvalent metal alkoxide include magnesium diethoxide, calcium diisopropoxide, barium diisopropoxide, aluminum triethoxide, aluminum triisopropoxide, gallium triethoxide, scandium trioxide. Isopropoxide, lanthanum triisopropoxide, ytterbium triisopropoxide, yttrium tetraisopropoxide, cerium tetraisopropoxide, samarium tetraisopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, Titanium tetrabutoxide, zirconium tetraisopropoxide, hafnium tetraisopropoxide, tantalum (V) ethoxide, chromium (III) isop Poxide, molybdenum (V) ethoxide, tungsten (VI) isopropoxide, iron (III) ethoxide, copper (II) ethoxide, zinc (II) ethoxide, and the like. Specific compounds of the polyvalent metal fluorides Examples include magnesium fluoride, calcium fluoride, barium fluoride, strontium fluoride, aluminum fluoride, titanium fluoride, lanthanum fluoride, zirconium fluoride, zinc fluoride, and the like. Specific examples of the compound include calcium carbonate, barium carbonate, aluminum carbonate, lanthanum carbonate, yttrium carbonate, zirconium carbonate, and zinc carbonate. Specific examples of the polyvalent metal hydride include , Calcium hydride, aluminum hydride, zirconium hydride And examples of specific compounds of the alkyl polyvalent metal, for example, diethyl magnesium, trimethyl aluminum, and the like.

There is no restriction | limiting in particular as content in the said dental adhesive composition of the said (C) polyvalent metal compound, Although it can select suitably according to the objective, Deashing effect is high and stable adhesive strength. Therefore, the sum of the number of moles of the (A) dihydrogen phosphate monoester group-containing polymerizable monomer and the (B) hydrogen phosphate diester group-containing polymerizable monomer is the above (C). A range that is larger than the total valence of the polyvalent metal in the polyvalent metal compound is preferable.
Here, the “total valence of the polyvalent metal in the polyvalent metal compound” means the number of moles of the total amount of the polyvalent metal compound contained in the dental adhesive composition, and the value of the polyvalent metal compound. It is a product of numbers.
Within the above range, the ratio between the number of moles of the (B) hydrogen phosphate diester group-containing polymerizable monomer and the total valence of the polyvalent metal (hydrogen phosphate diester group-containing polymerizable monomer) Body / total number of polyvalent metals) is preferably 0.3 to 2.5, more preferably 0.75 to 2.0, and 1.0 to 1.75. Particularly preferred.

In the dental adhesive composition, the (C) polyvalent metal compound is preferentially bonded to the (B) hydrogen phosphate diester group-containing polymerizable monomer as described above, and a salt is formed. Most of the polyvalent metals in the added polyvalent metal compound act as active ingredients. The type and content of the polyvalent metal, such as when the unreacted (C) polyvalent metal compound is removed, can be measured using an inductively coupled plasma (ICP) emission spectrometer.
Similarly, in the dental adhesive composition, the (A) dihydrogen phosphate monoester group-containing polymerizable monomer and the (B) hydrogen phosphate diester group-containing polymerizable monomer. And the content of (A) the dihydrogen phosphate monoester group-containing polymerizable monomer and (B) the hydrogen phosphate diester group contained in the dental adhesive composition by preparative high performance liquid chromatography. The polymerizable monomer can be isolated and the content can be measured, and the structure can be measured by mass spectrometry and nuclear magnetic resonance spectroscopy (NMR) of the isolated phosphate monomer. In particular, by measuring NMR of ³¹ P, from the chemical shift value, the (A) dihydrogen phosphate monoester group-containing polymerizable monomer and the (B) hydrogen phosphate diester group-containing polymerizable monomer The type of body can be identified.

<Water>
Generally, the polymerizable monomer having an acidic group imparts high adhesiveness to a dental adhesive composition by coexisting with water. This is considered to be because the demineralization action of the tooth by the acidic group is strengthened by the presence of water, and the penetration action of the adhesive component into the tooth is promoted.
However, if the dental adhesive composition contains sufficient water to give a high decalcification action, the acidic group is hydrolyzed, leading to a decrease in adhesiveness and an increase in viscosity, and storage. May be inferior in stability.
In the said dental adhesive composition which concerns on this invention, sufficient adhesiveness is shown only with the water | moisture content contained in an oral cavity, It can preserve | save in the aspect which does not contain water substantially. Further, since it is not necessary to mix the dental adhesive composition with water during dental treatment, excellent operability is imparted.
The “substantially free of water” means that water is not added to the dental adhesive composition, and a minute amount of moisture contained in the composition from the beginning, or the dental It does not exclude the slight moisture content that may be generated by the reaction of the compositions in the adhesive composition.
In the dental adhesive composition according to the present invention, an embodiment which does not substantially contain water is taken as one embodiment.

However, according to the use of the dental adhesive composition, from the viewpoint of promoting the decalcification action of the tooth due to the acidic group and obtaining more reliable adhesiveness, other aspects of the dental adhesive composition Then, it is good also as including the said water.
In this case, the water is preferably substantially free of impurities that reduce biocompatibility and adhesiveness, and deionized water, distilled water, or the like is preferably used.
Although it does not restrict | limit especially as a compounding quantity of water, 5 mass parts-50 mass parts are preferable with respect to 100 mass parts of all the polymerizable monomers, and 10 mass parts-30 mass parts are more preferable.

<Polymerization initiator>
The polymerization initiator is not particularly limited, and any of a photopolymerization type, a chemical polymerization type, and a heat polymerization type can be used, but a photopolymerization initiator is preferable because it can be polymerized and cured at an arbitrary timing. . The polymerization initiator can be used in combination with a polymerization accelerator.
The photopolymerization initiator is not particularly limited, and examples thereof include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and the like. Α-diketones, thioxanthones such as 2,4-diethylthioxanthone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morphol Linophenyl) -butanone-1,2-benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2 -Benzyl-dimethylamino-1- (4-morpholinophenyl) -pen Α-aminoacetophenones such as Tanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide and other acyl phosphine oxide derivatives.

The polymerization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 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 -Dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxy Tyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N -Dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, Tertiary amines such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, 5-butylbarbituric acid, 1-benzyl-5 Such as phenyl barbituric acid Examples include mercapto compounds such as rubituric acids, dodecyl mercaptan, pentaerythritol tetrakis (thioglycolate) and the like.
Further, in addition to the polymerization initiator and the polymerization accelerator, an electron acceptor such as an iodonium salt, a trihalomethyl-substituted S-triazine, or a phenanthylsulfonium salt compound may be added.

You may mix | blend a chemical polymerization initiator with the said dental adhesive composition. The chemical polymerization initiator is composed of a plurality of components and generates a polymerization initiating species (radical) when these components are brought into contact with each other. Specifically, a system comprising an arylborate compound and an acidic compound; a system comprising a sulfinic acid (or sulfinate) and an acidic compound; a system comprising an organic peroxide and an amine compound; a azo compound and an organic peroxide Examples include chemical polymerization initiators composed of systems such as systems composed of pyrimidinetrione derivatives, halogen ion forming compounds, and metal ion forming compounds.
Among them, a chemical polymerization initiator composed of a system consisting of the aryl borate compound and an acidic compound, a system consisting of the sulfinic acid (or sulfinate) and an acidic compound, and a system consisting of the organic peroxide and an amine compound, It is preferable because of its high polymerization activity and excellent safety to living bodies.
Furthermore, because of the high polymerization activity of the composition containing the acidic group-containing polymerizable monomer, the system comprising the aryl borate compound and the acidic compound, the system comprising the sulfinic acid (or sulfinate) and the acidic compound. The constituted chemical polymerization initiator is preferred.
Further, in the system consisting of the aryl borate compound and the acidic compound, as a polymerization accelerator, a + II, + III, + IV, and + V valent metal compound, preferably a + IV valence, which is a decomposition accelerator for organic peroxides. And / or + V valent vanadium compounds and / or organic peroxides that are oxidizing agents are preferably used in combination. The metal compound that can be added as the decomposition accelerator is distinguished from the above-described (C) polyvalent metal compound.
As the organic peroxide, known hydroperoxides, peroxyketals, ketone peroxides, alkylsilyl peroxides, diacyl peroxides, peroxyesters and the like can be used.
More specifically, the hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2, 5-Dihydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like can be mentioned.
Examples of the peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t -Butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis (t- Butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like.
Examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
Examples of the alkylsilyl peroxides include t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyltrimethylsilyl peroxide, and t-hexyltrimethylsilyl peroxide.
Examples of the diacyl peroxides include benzoyl peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide and the like.
Examples of the peroxyesters include t-butyl peroxyneodecanoate and cumyl peroxyneodecanoate.
As said aryl borate compound, a well-known thing can be mix | blended without a restriction | limiting. Examples of particularly suitable ones include tetraphenylboric acid, tetra (p-fluorophenyl) boric acid, tetra (p-chlorophenyl) boric acid, trialkyl (p-fluorophenyl) boric acid, trialkyl (3, And tertiary ammonium salts such as 5-bistrifluoromethyl) phenyl boric acid and dialkyldiphenyl boric acid, quaternary ammonium salts, sodium salts and the like.
As said sulfinic acid (or sulfinate), a well-known thing can be mix | blended without a restriction | limiting. Examples of particularly suitable ones include benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid. As aromatic sulfinic acid or salts thereof, sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate, p-fluorobenzene Examples thereof include sodium sulfinate.

  Although there is no restriction | limiting in particular as a compounding quantity of the said polymerization initiator, 0.01 mass part-10 mass parts are preferable with respect to 100 mass parts of said all polymerizable monomer components, 0.1 mass part-5 Part by mass is more preferable.

<Fluorine-containing compound>
The fluorine-containing compound is used from the viewpoint of improving the storage stability and adhesive strength of the dental adhesive composition.
There is no restriction | limiting in particular as said fluorine-containing compound, For example, hydrofluoric acid, monovalent | monohydric metal fluoride, ammonium fluoride, etc. are mentioned. When the polyvalent metal fluoride is used as the polyvalent metal compound, these compounds also act as the fluorine-containing compound.
In addition, these may be used individually by 1 type and may use 2 or more types together.

The compounding amount of the fluorine-containing compound is not particularly limited, but the molar ratio of fluorine atoms in the fluorine-containing compound to the polyvalent metal atoms in the (C) polyvalent metal compound, fluorine atom / polyvalent metal atom However, the quantity which becomes 0.4-4.0 is preferable. When the polyvalent metal fluoride is selected as the polyvalent metal compound (C), the amount of all fluorine atoms including fluorine atoms contained in the polyvalent metal fluoride is preferably in the range of the molar ratio described above.
Normally, most of the blended fluorine-containing compound is present in the dental adhesive composition as an active ingredient, and as a fluorine atom content such as when the unreacted fluorine-containing compound is removed, It can be measured by anion chromatography.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, said (A) dihydrogen phosphate monoester group containing polymerizable monomer and said (B) hydrogen phosphate Other polymerizable monomers other than the diester group-containing polymerizable monomer, inorganic fillers, volatile organic solvents and the like can be mentioned.

-Other polymerizable monomers-
The other polymerizable monomer refers to a compound that contains at least one polymerizable unsaturated group in a molecule and can form a polymer by a polymerization reaction. Examples of the polymerizable unsaturated group include: Examples include acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl groups, allyl groups, ethynyl groups, and styryl groups. Among them, acrylate group, methacrylate group, acrylamide group, methacrylamide group and the like are preferable, and acrylate group and methacrylate group are particularly preferable because of the high curing rate.

-Other acidic group-containing polymerizable monomer-
Examples of the other polymerizable monomer include other acidic group-containing polymerizable monomers. The other acidic group-containing polymerizable monomer has at least one acidic group in the molecule, and the acidic group has a pKa (25 ° C.) lower than 5 and a functional capable of dissociating active protons. Preferred examples include a dihydrogen phosphate monoester group, a hydrogen phosphate diester group, a pyrophosphate group, a phosphonic acid group, a carboxyl group, and a sulfonic acid group. Specifically, 2- (meth) acryloyloxyethyl dihydrogen as a dihydrogen phosphate monoester group-containing polymerizable monomer other than the (A) dihydrogen phosphate monoester group-containing polymerizable monomer. Phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 3- (meth) acryloyloxypropan-2-yl dihydrogen phosphate, 1,3-di (meth) acryloyloxypropan-2-yl dihydro And (B) hydrogen phosphate diester group-containing polymerizable monomers other than the (B) hydrogen phosphate diester group-containing polymerizable monomer include 2- (meth) acryloyloxyethylphenyl hydrogen. Phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen Phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate Examples of the phosphonic acid group-containing polymerizable monomer include 6- (meth) acryloyloxyhexylphosphonic acid, 8- (meth) acryloyloxyoctylphosphonic acid, and 10- (meth) acryloyloxydecylphosphonic acid. , 6- (meth) acryloyloxyhexylphosphonoacetate, 6- (meth) acryloyloxyhexylphosphonopropionate, and the like. As the carboxyl group-containing polymerizable monomer, (meth) acrylic acid, 4- (Meta) acryloil And citric trimellitic acid, 2- [10- (meth) acryloyloxydecyl] malonic acid, and the like. Examples of the sulfonic acid group-containing polymerizable monomer include 2-methyl-2- (meth) acrylamidepropanesulfonic acid. Etc.

  The blending amount of the other acidic group-containing polymerizable monomer is not particularly limited. However, if blended in a large amount, the adhesive strength may decrease. The amount is preferably at most 10 parts by mass, more preferably at most 10 parts by mass.

  Moreover, as said other polymerizable monomer, the non-acidic group containing polymerizable monomer which does not have the said acidic group can be used. The non-acidic group-containing polymerizable monomer refers to a compound having no acidic group among the other polymerizable monomers having at least one polymerizable unsaturated group, and is appropriately selected from known compounds. It can be selected and used. Among these, the polyfunctional polymerizable monomer having a plurality of the polymerizable unsaturated groups is preferably used from the viewpoint of improving the curing speed, the mechanical properties of the cured body, the water resistance, the color resistance, and the like. A (meth) acrylate polymerizable monomer is preferably used. Representative examples of the polyfunctional (meth) acrylate polymerizable monomer include bifunctional polymerizable monomers, trifunctional polymerizable monomers, and four compounds shown in the following (1) to (3). A functional polymerizable monomer is mentioned.

(1) Bifunctional polymerizable monomer Examples of the bifunctional polymerizable monomer include aromatic compound-based polymerizable monomers and aliphatic compound-based polymerizable monomers.
Examples of the aromatic compound-based polymerizable monomer include 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 2,2′-bis [ 4- (meth) acryloyloxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxydiethoxyphenyl] propane 2,2′-bis [4- (meth) acryloyloxytetraethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxypentaethoxyphenyl] propane, 2,2′-bis [4- (Meth) acryloyloxydipropoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxypheny ] Propane, 2- [4- (meth) acryloyloxydiethoxyphenyl] -2- [4- (meth) acryloyloxytriethoxyphenyl] propane, 2- [4- (meth) acryloyloxydipropoxyphenyl]- Addition of 2- [4- (meth) acryloyloxytriethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxypropoxyphenyl] propane; and an OH group-containing vinyl monomer and an aliphatic diisocyanate compound And diaducts obtained from the above.
Examples of the OH group-containing vinyl monomer include methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate, and acrylates corresponding to these methacrylates. Examples of the diisocyanate include diisocyanate methylbenzene and 4,4′-diphenylmethane diisocyanate.

Examples of the aliphatic compound-based polymerizable monomer include 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetra Ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates, 1,8- Methacrylates such as octanediol dimethacrylate, 1,10-decanediol dimethacrylate, ethylene glycol diglycidyl ether dimethacrylate, etc. Corresponding acrylate or the like; diadduct and the like obtained from the addition of the well OH group-containing vinyl monomer and aliphatic diisocyanate compounds.
Examples of the OH group-containing vinyl monomer include those exemplified above, and examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, Examples include forone diisocyanate and methylenebis (4-cyclohexylisocyanate).

(2) Trifunctional polymerizable monomer Examples of the trifunctional polymerizable monomer include, for example, methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate; Examples thereof include acrylates corresponding to these methacrylates.

(3) Tetrafunctional polymerizable monomer Examples of the tetrafunctional polymerizable monomer include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate; and a diadduct obtained from an adduct of a diisocyanate compound and glycidol dimethacrylate. Can be mentioned.
Examples of the diisocyanate compound include diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 4,4-diphenylmethane diisocyanate, and tolylene-2. 4-diisocyanate etc. can be mentioned.
In addition, these polyfunctional (meth) acrylate type | system | group polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

Furthermore, you may use a monofunctional (meth) acrylate type | system | group polymerizable monomer as needed.
Examples of the monofunctional (meth) acrylate polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth). Examples include acrylate and glycidyl (meth) acrylate.

Moreover, you may use polymerizable monomers other than the said (meth) acrylate type | system | group polymerizable monomer.
Examples of such polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; styrenes such as styrene, divinylbenzene, α-methylstyrene, and α-methylstyrene dimer. Compounds; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate;
When the dental adhesive composition does not contain water and an organic solvent, an aromatic bifunctional compound such as 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane is used. In addition, it is preferable that a polymerizable monomer containing an OH group is contained, but on the other hand, when such a polymerizable monomer is contained in a large amount, the viscosity increases and the penetration into the tooth is inhibited. 50 mass parts or less are preferable in 100 mass parts of the said all polymerizable monomers, and 20 mass parts or less are more preferable.

In the case where water is contained in the dental adhesive composition, an amphiphilic polymerizable monomer should be used in combination when the polymerizable monomer contains a lot of highly hydrophobic monomers. Is preferred.
Examples of the amphiphilic polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate (polyethylene glycol polymerization degree 9 to 50), 1 2,3,4-butanetetraol-1,4-di (meth) acrylate and the like. By blending such an amphiphilic polymerizable monomer, the uniformity of the composition can be ensured and the permeability to dentin is further improved. As a result, high adhesive strength can be obtained stably.

  In addition, as said non-acidic group containing polymerizable monomer, a suitable quantity can be mix | blended in the range which does not impair the effect of this invention.

-Filler-
The dental adhesive composition can be used by appropriately blending a filler (filler) depending on the application, and is not particularly limited and can be appropriately selected from known compounds.
Examples of the filler include inorganic fillers, organic-inorganic fillers, and organic fillers.
Examples of the inorganic filler include silica, zirconia, titania, silica-zirconia, silica-titania, barium glass, strontium glass, lanthanum glass, and fluoroaluminosilicate glass.

The inorganic filler is made hydrophobic with a surface treatment agent typified by a silane coupling agent, so that it can be used well with a polymerizable monomer, and mechanical strength and water resistance can be improved.
There is no restriction | limiting in particular as the method of the said hydrophobization, A well-known method is mentioned. That is, as the silane coupling agent, for example, 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) ethyltrimethoxysila , N- phenyl--γ- aminopropyltrimethoxysilane, hydrophobic and the like with hexamethyldisilazane.
In addition, as the organic-inorganic composite filler, a granular material obtained by adding a polymerizable monomer to the inorganic filler in advance and polymerizing and pulverizing the inorganic filler, or the inorganic filler, A granular material obtained by impregnating aggregated particles with the polymerizable monomer is used.
Further, as the organic filler, a granular material obtained by polymerizing the polymerizable monomer is used.
There is no restriction | limiting in particular as an average particle diameter of these fillers, Although 0.01 micrometer-100 micrometers of the magnitude | size currently generally used as a dental material may be sufficient, 0.01 micrometer-5 micrometers are preferable. Moreover, there is no restriction | limiting in particular also as the refractive index of the said filler, It may be 1.4-1.7 which a general dental filler has. In addition, as said filler, you may use individually by 1 type, but you may use together and use several fillers from which a particle size range, an average particle diameter, a refractive index, and a material differ.
The shape of these fillers is not particularly limited, and may be any of an indefinite shape, a spherical shape, and a substantially spherical shape. Among them, the use of a spherical inorganic filler increases the surface smoothness of the resulting cured product. Since it can be an excellent dental filling / restoring material, a spherical shape is preferable.

  The blending amount of the filler is not particularly limited, and may be appropriately determined in consideration of the viscosity (operability) and the mechanical properties of the cured body depending on the use of the composition. When used as a composite resin or a self-adhesive dental cement, it is preferably 30 parts by weight to 1,500 parts by weight, and 50 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the total polymerizable monomer. More preferred. Moreover, when using as a dental adhesive for composite resins and a primer, 0.5 mass part-100 mass parts are preferable with respect to 100 mass parts of said all polymerizable monomer components, and 5 mass parts-50 mass parts. Is more preferable.

-Volatile organic solvent-
In addition, as the dental adhesive composition, the volatile organic solvent may be blended from the viewpoint of allowing components effective for adhesion to penetrate into the tooth structure and vaporizing itself after the penetration so that the components can be removed. Good.
As the volatile organic solvent, those which are volatile at room temperature and exhibit water solubility can be used. Here, the “volatile” means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. The “water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 mL or more, and it is preferably compatible with water at 20 ° C. in an arbitrary ratio.
There is no restriction | limiting in particular as such a volatile water-soluble organic solvent, For example, methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, etc. are mentioned. Of these, ethanol, isopropyl alcohol, and acetone are preferable in view of toxicity to the living body. In addition, these may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said volatile organic solvent, 2 mass parts-400 mass parts are preferable with respect to 100 mass parts of said all polymerizable monomers, and 5 mass parts-100 mass parts are more preferable.

  These volatile organic solvents are used after being removed by air blowing after the dental adhesive composition is applied to the tooth surface and before the dental adhesive composition is polymerized and cured.

  Furthermore, an organic thickener such as a polymer compound such as polyvinyl pyrrolidone, carboxymethyl cellulose, or polyvinyl alcohol can be added to the dental adhesive composition as long as the effects of the present invention are not impaired. Various additives such as ultraviolet absorbers, dyes, antistatic agents, pigments, and fragrances can be selected and used as necessary.

The method for preparing the dental adhesive composition is not particularly limited except when the water is blended, and each component may be weighed and mixed, but the (A) dihydrogen phosphate monoester group may be used. Until the content of the containing polymerizable monomer, the (B) hydrogen phosphate diester group-containing polymerizable monomer, the (C) polyvalent metal compound, and, in some cases, the fluorine-containing material are uniform. A method of stirring and mixing and then adding components other than these is preferable, and the (B) hydrogen phosphate diester group-containing polymerizable monomer, the (C) polyvalent metal compound, and optionally the fluorine-containing More preferably, the product is first stirred and mixed until uniform, and then components other than these are added.
On the other hand, when adding the said water, the method of mixing components other than the said water previously with said preparation method, and adding the said water at the end is preferable.
And (A) a dihydrogen phosphate monoester group-containing polymerizable monomer, or (B) a phosphate group-containing polymerizable monomer such as a hydrogen phosphate diester group-containing polymerizable monomer, When the (C) polyvalent metal compound is mixed, volatile components such as alcohols may be produced, but these volatile components do not affect the adhesive property at all. On the other hand, when the dental adhesive composition is applied to a composite resin or the like, these volatile components gradually volatilize, and the fluidity of the composite resin and the like may change over time. Alternatively, it may be removed by heating, vacuum pump, rotary evaporator, or the like.

<Application>
The dental adhesive composition is used for the purpose of adhering a dental restoration such as a dental pretreatment material, a composite resin or a prosthesis used for the purpose of improving the permeability of an adhesive component to a tooth. Useful as a dental adhesive used, a self-adhesive dental composite resin that combines the functions of a dental adhesive and a composite resin, and a self-adhesive dental cement that combines the functions of a dental pretreatment material and a dental cement Can be used. In particular, since it shows high adhesive strength without containing water, it is suitable as a dental adhesive, self-adhesive dental composite resin, or self-adhesive dental cement that does not require an air blow and has a simplified operation. Among them, it can be most suitably used as a self-adhesive dental composite resin.

  In addition, the dental adhesive composition can preferentially strongly bond the (B) hydrogen phosphate diester group-containing polymerizable monomer to the polyvalent metal compound in a mixed state. Can be used.

Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the technical idea of the present invention is not limited by these.
In addition, about each component used for manufacture of an Example and a comparative example, those abbreviations, and abbreviations, it is as follows.

(Each component and their abbreviations and abbreviations)
<(A) Dihydrogen phosphate monoester group-containing polymerizable monomer>

<(B) Polymerizable monomer having hydrogen phosphate diester group>

<Other polymerizable monomers>
D-2.6E: 2,2-bis [(4-methacryloyloxypolyethoxy) phenyl] propane Bis-GMA: 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane 3G : Triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate

<(C) Multivalent metal compound>
CaH ₂ : Calcium hydride CaCO ₃ : Calcium carbonate Ca (Oi-Pr) ₂ : Calcium diisopropoxide Ba (Oi-Pr) ₂ : Barium diisopropoxide Al (Me) ₃ : Trimethylaluminum Al (Oi-Pr) ₃ : Aluminum triisopropoxide Sc (Oi-Pr) ₃ : Scandium triisopropoxide La (Oi-Pr) ₃ : Lanthanum triisopropoxide Yb (Oi- Pr) ₃ : Ytterbium triisopropoxide Ti (OMe) ₄ : Titanium tetramethoxide Ti (OEt) ₄ : Titanium tetraethoxide Ti (Oi-Pr) ₄ : Titanium tetraisopropoxide Ti (OBu) ₄ : titanium tetrabutoxide _{Zr (O-i-Pr)} 4: zirconium Toraiso propoxide _{Hf (O-i-Pr)} 4: hafnium tetraisopropoxide AlF _3: aluminum fluoride TiF _4: titanium fluoride

<Fluorine-containing compound>
NaF: Sodium fluoride TMAF: Tetramethylammonium fluoride

<Volatile water-soluble organic solvent>
IPA: isopropyl alcohol

<Polymerization initiator (photopolymerization initiator)>
CQ: camphorquinone DMBE: ethyl pN, N-dimethylaminobenzoate BTPO: bis (2,6-dimethylbenzoyl) phenylphosphine oxide TAZ: 2,4,6-tetrakistrichloromethyl-s-triazine DMPT: dimethyl Amino-p-toluidine

<Polymerization inhibitor>
BHT: 2,6-di-t-butyl-p-cresol HQME: hydroquinone monomethyl ether

<Filler>
FS1: fumed silica (average particle size 0.018 μm, specific surface area 220 m ² / g, surface silanol group amount 5.0 / nm ² )
FS2: fumed silica (average particle size 0.007 μm, specific surface area 230 m ² / g, surface silanol group content 1.2 / nm ² , treated with dimethyldichlorosilane)
F1: Quartz (average particle size 3 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane F2: Amorphous silica zirconia (average particle size 3 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane F3: 25 parts by mass of 0.5 parts by mass of azobisisobutyronitrile previously dissolved as a polymerization initiator in 100 parts by mass of a mixture of 60 parts by mass of Bis-GMA and 40 parts by weight of 3G 75 parts by mass of F5 was mixed in an agate mortar to form a paste, which was heated and cured for 1 hour at 95 ° C. in a nitrogen atmosphere, and then pulverized using a vibration ball mill (average particle size: 12 μm )
F4: Spherical silica (average particle size 0.13 μm)
F5: Spherical silica-zirconia (average particle size 0.2 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane

  Among the above components, DMPP, DMIPP, DMBP, DMHP, DMDP, DAEP, DMAEP, and DEAEP were synthesized as follows without using commercially available products.

<Synthesis of DMPP>
30.7 g (0.2 mol) of phosphoryl chloride was dissolved in 100 ml of dehydrated tetrahydrofuran, and 57.7 g (0.4 mol) of 3-methacryloyloxypropanol and 40.5 g ( 0.4 mol) of triethylamine was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours, and 3.6 g (0.2 mol) of water and 20.3 g (0.2 mol) of triethylamine were added dropwise and stirred for 1 hour. After the stirring was completed, 100 ml of 0.5N hydrochloric acid was added, and the mixture was extracted 3 times with 50 ml of diethyl ether. Further, the diethyl ether layer was washed once with 50 ml of 0.5N hydrochloric acid and twice with distilled water, and dried with granular silica gel. After drying, diethyl ether was distilled off with a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain DMPP (49.7 g, yield 71%). The data of ¹ H NMR spectrum of the obtained DMPP was as follows.
¹ H NMR δ 1.76 (m, 4H), 1.93 (s, 6H), 3.53 (t, 4H), 4.15 (t, 4H), 5.58 (s, 2H), 6 .15 (s, 2H)

<Synthesis of DMIPP>
Similarly to the synthesis of DMPP, 57.7 g (0.4 mol) of 3-methacryloyloxypropan-2-ol was reacted and purified by silica gel column chromatography to obtain DMIPP (35.0 g, yield 50%). . The data of ¹ H NMR spectrum of the obtained DMIPP was as follows.
¹ H NMR δ 1.21 (d, 6H), 1.92 (s, 6H), 3.99 (m, 2H), 4.30 (d, 4H), 5.58 (s, 2H), 6 .15 (s, 2H)

<Synthesis of DMBP>
Similarly to the synthesis of DMPP, 63.3 g (0.4 mol) of 4-methacryloyloxybutanol was reacted and purified by silica gel column chromatography to obtain DMBP (65.2 g, yield 65%). The data of ¹ H NMR spectrum of the obtained DMBP was as follows.
¹ H NMR δ 1.48-1.57 (m, 8H), 1.93 (s, 6H), 3.53 (d, 4H), 4.15 (d, 4H), 5.58 (s, 2H), 6.15 (s, 2H)

<Synthesis of DMHP>
Similarly to the synthesis of DMPP, 74.5 g (0.4 mol) of 6-methacryloyloxyhexanol was reacted and purified by silica gel column chromatography to obtain DMHP (62.6 g, yield 72%). The data of ¹ H NMR spectrum of the obtained DMHP was as follows.
¹ H NMR δ 1.29-1.58 (m, 16H), 1.93 (s, 6H), 3.52 (d, 4H), 4.14 (d, 4H), 5.58 (s, 2H), 6.15 (s, 2H)

<Synthesis of DMDP>
Similarly to the synthesis of DMPP, 96.9 g (0.4 mol) of 10-methacryloyloxydecanol was reacted and purified by silica gel column chromatography to obtain DMDP (84.2 g, yield 77%). The data of ¹ H NMR spectrum of the obtained DMDP was as follows.
¹ H NMR δ 1.22-1.59 (m, 32H), 1.93 (s, 6H), 3.53 (d, 4H), 4.14 (d, 4H), 5.58 (s, 2H), 6.15 (s, 2H)

<Synthesis of DAEP>
30.7 g (0.2 mol) of phosphoryl chloride was dissolved in 100 ml of dehydrated tetrahydrofuran, and 46.1 g (0.4 mol) of aminoethanol-N-acrylamide and 40.5 g were added to the solution while cooling in an ice bath. (0.4 mol) of triethylamine was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours, and 3.6 g (0.2 mol) of water and 20.3 g (0.2 mol) of triethylamine were added dropwise and stirred for 1 hour. After completion of stirring, 0.5 ml of concentrated hydrochloric acid was added and dried with granular silica gel. After drying, tetrahydrofuran was distilled off by a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain DAEP (17.5 g, yield 30%). The data of ¹ H NMR spectrum of the obtained DAEP was as follows.
¹ H NMR δ 3.15 (d, 4H), 3.80 (d, 4H), 5.71 (d, 2H), 6.17 (d, 2H), 6.48 (m, 2H), 8 .0 (t, 2H)

<Synthesis of DMAEP>
Similarly to the synthesis of DAEP, 51.7 g (0.4 mol) of N-methylaminoethanol-N-acrylamide was reacted and purified by silica gel column chromatography to obtain DMAEP (26.9 g, yield 42%). . The data of ¹ H NMR spectrum of the obtained DMAEP was as follows.
¹ H NMR δ 2.90 (s, 6H), 3.15 (d, 4H), 3.79 (d, 4H), 5.55 (d, 2H), 6.12 (d, 2H), 6 .62 (m, 2H)

<Synthesis of DMEEP>
Similarly to the synthesis of DAEP, 57.3 g (0.4 mol) of N-ethylaminoethanol-N-acrylamide was reacted and purified by silica gel column chromatography to obtain DMEEP (30.0 g, 43% yield). . The data of ¹ H NMR spectrum of the obtained DMEEP was as follows.
¹ H NMR δ 1.20 (m, 6H), 3.00 (t, 6H), 3.12 (d, 4H), 3.78 (d, 4H), 5.55 (d, 2H), 6 .12 (d, 2H), 6.62 (m, 2H)

(Dental adhesive not containing water / Examples 1 to 66 and Comparative Examples 1 to 11)
<Example 1>
5 g DMEP and 0.82 g calcium diisopropoxide were mixed with stirring at room temperature for 24 hours. Thereafter, the pressure was reduced with a vacuum pump to remove volatile components. Thereafter, 25 g of MDP, 30 g of D-2.6E, 20 g of Bis-GMA, 20 g of 3G, 0.4 g of CQ, and 1.0 g of DMBE were added and stirred at room temperature until uniform. A dental adhesive composition according to No. 1 was produced. This dental adhesive composition is manufactured as a composition for use in a dental adhesive, and is substantially free of water.

<Examples 2-66 and Comparative Examples 1-11>
Each dental adhesive according to Examples 2 to 66 and Comparative Examples 1 to 11 is the same as Example 1 except that it is manufactured based on the composition described in Tables 1-1 to 1-4. A sex composition was produced.

(Adhesion test / dental adhesive without water)
The adhesion test based on preparation of the adhesion test piece I demonstrated below was implemented with respect to each dental adhesive composition (dental adhesive material) of Examples 1-66 and Comparative Examples 1-11.
First, the front teeth of the cow were removed within 24 hours after slaughter, and the enamel and dentin planes were cut out under water injection so as to be parallel to the lip surface with # 600 emery paper.
Next, compressed air was blown onto these planes for about 10 seconds to dry them, and then a double-sided tape with a 3 mm diameter circular hole was fixed to either the enamel or dentin plane.
Next, a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm was fixed on the circular hole so as to have the same center, thereby forming a simulated cavity.
Next, each dental adhesive composition according to Examples 1 to 66 and Comparative Examples 1 to 11 was applied to each simulated cavity and left for 20 seconds, and then a dental visible light irradiator (Toxo Power Light, For 10 seconds. Furthermore, a dental composite resin (Esthelite, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon and irradiated with light for 30 seconds with a visible light irradiator.
Thereby, the adhesion test piece I used for an adhesion test was produced.

After the adhesion test piece I was immersed in water at 37 ° C. for 24 hours, a metal jig was attached and pulled using a tensile tester (Autograph AG5000, manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm / min. The tensile bond strength between the quality, dentin and the dental composite resin was measured.
In addition, the measurement of this adhesive strength was performed by producing eight adhesion test pieces I for each dental adhesive composition, and the average value was taken as the value of the adhesive strength.
The test results of the above adhesion test are shown in Tables 1-1 to 1-4 below. In addition, “number of moles of phosphate ester / (number of moles of polyvalent metal × valence)” shown in these tables is the above (A) dihydrogen phosphate monoester group-containing polymerizable monomer and (B) The sum of the number of moles of the hydrogen phosphate diester group-containing polymerizable monomer, or (B) the number of moles of the hydrogen phosphate diester group-containing polymerizable monomer, the number of moles of the polyvalent metal compound, The value obtained by dividing the valence of the valent metal compound by the total valence of the polyvalent metal is shown, and “diester / polyvalent metal × valence” represents the (B) hydrogen phosphate diester group-containing polymerization. The value obtained by dividing the number of moles of the functional monomer by the total number of moles of the polyvalent metal compound multiplied by the total number of the polyvalent metal compound obtained by multiplying the number of moles of the polyvalent metal compound by the valence of the polyvalent metal compound. Ester + diester) / (polyvalent metal x total valence) "means (A) dihydrogen phosphate monoester group The sum of the number of moles of the polymerizable monomer and the (B) hydrogen phosphate diester group-containing polymerizable monomer is multiplied by the total number of moles of the polyvalent metal compound and the valence of the polyvalent metal compound. The value divided by the total valence of the combined polyvalent metals is shown.

  As shown in the above-mentioned Table 1-1 to Table 1-4, the dental adhesive composition according to Comparative Example 1 that does not contain the (C) polyvalent metal compound, and the (B) hydrogen phosphate diester group-containing polymerization. A dental adhesive composition according to Comparative Example 2 that does not contain a polymerizable monomer and (C) the polyvalent metal compound, (A) a dihydrogen phosphate monoester group-containing polymerizable monomer, and (C) Dental adhesive composition according to Comparative Example 3 containing no polyvalent metal compound, Dental adhesive composition according to Comparative Example 4 containing no (A) dihydrogen phosphate monoester group-containing polymerizable monomer Each of (A) dihydrogen phosphate monoester group-containing polymerizable monomer, (B) hydrogen phosphate diester group-containing polymerizable monomer, and (C) the polyvalent metal compound. In each of the dental adhesive compositions according to Examples 1 to 66, including enamel and elephant In each of quality, and it can exhibit higher adhesive strength.

As shown in Table 1-1 and Table 1-4, the short chain dihydrogen phosphate monoester group, which is a comparative component of the polymerizable monomer containing (A) dihydrogen phosphate monoester group, is included. For each dental adhesive composition according to Comparative Examples 5 and 7 using a polymerizable monomer (MEP, MPP), the long-chain (A) dihydrogen phosphate monoester group-containing polymerizable monomer In the dental adhesive composition according to Example 12 using the body (MDP), each of enamel and dentin can exhibit higher adhesive strength. In addition, this result is the same also in the dental adhesive composition which concerns on Example 62 and the dental adhesive composition which concerns on the comparative example 6 containing a filler (refer above-mentioned Table 1-3 and Table 1-4). ).
Moreover, as shown in the above-mentioned Table 1-1, Table 1-2, and Table 1-4, the long-chain hydrogen phosphate which is a comparative component of the (B) hydrogen phosphate diester group-containing polymerizable monomer For each dental adhesive composition according to Comparative Examples 8 to 10 using a diester group-containing polymerizable monomer (DMBP, DMHP, DMDP), the short-chain (B) hydrogen phosphate diester group-containing polymerization is performed. In each of the dental adhesive compositions according to Examples 12 and 20 to 34 using the adhesive monomer (DMEP, DMPP, DMIPP, DAEP, DMAEP, DMEEP), higher adhesion is obtained in each of the enamel and the dentin. The strength can be shown.
Further, each of the (A) dihydrogen phosphate monoester group-containing polymerizable monomer and the (B) hydrogen phosphate diester group-containing polymerizable monomer was compared using comparative components (MEP, DMDP). In contrast to the dental adhesive composition according to Example 11, each of the dental adhesive compositions according to Examples 12 and 20 to 34 can exhibit higher adhesive strength in each of enamel and dentin. ing.

As shown in Table 1-1, the dental adhesive composition according to Example 1 using the polyvalent metal alkoxide (calcium diisopropoxide) as the polyvalent metal compound (C) is Than each dental adhesive composition according to Examples 2 and 3 using a polyvalent metal hydride (calcium hydride) and the polyvalent metal carbonate (calcium carbonate), in each of enamel and dentin, High adhesive strength is shown.
Similarly, the dental adhesive composition according to Example 6 using the polyvalent metal alkoxide (aluminum triisopropoxide) as the polyvalent metal compound (C) is the same as the alkyl polyvalent metal (trimethyl). Each of the enamel and the dentin shows higher adhesive strength than the dental adhesive composition according to Example 5 using aluminum.
Further, as shown in Table 1-1 above, as the (C) polyvalent metal compound, the group 4 polyvalent metal alkoxide (titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium) Each dental adhesive composition according to Examples 10 to 14 using tetrabutoxide, zirconium tetraisopropoxide) is the above polyvalent metal alkoxide other than Group 4 (barium diisopropoxide, aluminum triisopropoxide). In addition to the dental adhesive compositions according to Examples 4 and 6 to 9 using scandium triisopropoxide, lanthanum triisopropoxide, ytterbium triisopropoxide), each of enamel and dentin, High adhesive strength is shown. The dental adhesive composition according to Example 12 using titanium tetraisopropoxide as the group 4 polyvalent metal alkoxide is an example using zirconium tetraisopropoxide or hafnium tetraisopropoxide. Compared with the dental adhesive compositions according to Nos. 14 and 15, the enamel and the dentin each show a high adhesive strength.

As shown in the above-mentioned Tables 1-1 and 1-2, the moles of (A) the dihydrogen phosphate monoester group-containing polymerizable monomer and (B) the hydrogen phosphate diester group-containing polymerizable monomer. In each dental adhesive composition according to Examples 12, 25 to 33, in which the sum of the numbers is larger than the total valence of the polyvalent metal in the (C) polyvalent metal compound, Compared with Example 34 which is smaller than the total valence of the polyvalent metal in the (C) polyvalent metal compound, each of the enamel and the dentin shows high adhesive strength. The “total valence of the polyvalent metal in the polyvalent metal compound” means the number of moles of the total amount of the polyvalent metal compound contained in the dental adhesive composition and the valence of the polyvalent metal compound. Multiply.
Further, the ratio of the number of moles of the (B) hydrogen phosphate diester group-containing polymerizable monomer to the total valence of the polyvalent metal (hydrogen phosphate diester group-containing polymerizable monomer / polyvalent metal In each of the dental adhesive compositions according to Examples 12 and 26 to 32 in which the total valence) is 0.3 to 2.5, the ratio falls outside the range of 0.3 to 2.5. Compared to the dental adhesive compositions according to 33 and 34, the adhesive strength of the dental adhesive composition according to Example 33 to the dentin is similar to that of the dental adhesive composition according to Example 26 to the dentin. Except for being equivalent to strength, each of enamel and dentin shows high adhesive strength.

  As shown in Table 1-1 and Table 1-3, the molar ratio of the fluorine atom to the polyvalent metal atom of the polyvalent metal compound, the fluorine atom / polyvalent metal atom is 0.4 to 4. In the dental adhesive compositions according to Examples 52 and 53 containing the fluorine-containing compound (sodium fluoride, tetramethylammonium fluoride) so as to be 0, the dental adhesive according to Example 12 not including this Each of the enamel and the dentin exhibits higher adhesive strength than the sex composition. In addition, the polyvalent metal fluoride as the polyvalent metal compound (C) that is also the fluorine-containing compound is used, and the fluorine-containing compound is included so that the molar ratio is 0.4 to 4.0. In the dental adhesive composition according to Examples 54 to 59, compared with the dental adhesive composition according to Example 60 in which the molar ratio deviates from 0.4 to 4.0, each of the enamel and the dentin. , Showing high adhesive strength.

(Dental adhesive composite resin containing no water / Examples 67 to 70 and Comparative Examples 12 to 16)
<Example 67>
33 g of the dental adhesive composition according to Example 12 and 40 g of F1 and 27 g of F4 were mixed in an agate mortar and defoamed under vacuum to remove the dental adhesive composition according to Example 67. Manufactured. This dental adhesive composition is produced as a composition for use in a dental adhesive composite resin, and is substantially free of water.

<Examples 68 to 70, Comparative Examples 12 to 16>
Each dental adhesive composition according to Examples 68 to 70 and Comparative Examples 12 to 16 was produced in the same manner as Example 67 except that it was produced based on the composition described in Table 2 below.

(Adhesion test / Dental adhesive composite resin)
The adhesion test based on preparation of the adhesion test piece II demonstrated below was implemented with respect to each dental adhesive composition (dental adhesive composite resin) which concerns on Examples 67-70 and Comparative Examples 12-16.
That is, each of the dental adhesive compositions according to Examples 67 to 70 and Comparative Examples 12 to 16 was filled in a simulated cavity formed by the same method as the method for manufacturing the adhesive test piece I, and left for 20 seconds. The sample was irradiated with light for 10 seconds using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) to produce an adhesion test piece II.
An adhesion test similar to the adhesion test for the adhesion test piece I was performed on the adhesion test piece II, and the adhesion strength was measured.
The test results of the adhesion test are shown in Table 2 below.

  As shown in Table 2 above, each dental adhesive composition according to Examples 67 to 70 configured for use in a dental adhesive composite resin using the dental adhesive composition according to Example 12, Compared to each dental adhesive composition according to Comparative Examples 12 to 16 configured for use in a dental adhesive composite resin by using each dental adhesive composition according to Comparative Examples 1 to 5, enamel and dentin Each of these can exhibit high adhesive strength.

(Dental adhesive composition containing water / Examples 71 and 72 and Comparative Examples 17 to 21)
<Example 71>
5 g of DMEP and 0.88 g of titanium tetraisopropoxide were mixed with stirring at room temperature for 24 hours. Thereafter, 25 g of MDP, 20 g of HEMA, 30 g of Bis-GMA, 20 g of 3G, 1.3 g of CQ, 1.3 g DMBE, 10 g of FS2 were added and mixed with stirring at room temperature until uniform. Thereafter, 85 g of IPA and 19 g of water were added, and the mixture was stirred and mixed at room temperature until uniform, whereby a dental adhesive composition according to Example 71 was produced. This dental adhesive composition is produced as a composition for use in a dental adhesive and contains water.

<Example 72, Comparative Examples 17-21>
Each dental adhesive composition according to Example 72 and Comparative Examples 17 to 21 was manufactured in the same manner as Example 71 except that it was manufactured based on the composition described in Table 3 below.

(Adhesion test / Dental adhesive containing water)
For each of the dental adhesive compositions (dental adhesive composite resin) according to Examples 71 and 72 and Comparative Examples 17 to 21, an adhesion test based on the production of an adhesion test piece III described below was performed.
That is, each dental adhesive composition according to Examples 71 and 72 and Comparative Examples 17 to 21 was applied in a simulated cavity formed by the same method as the method of manufacturing the adhesive test piece I, and compressed air was applied for about 10 seconds. After spraying and drying, it was left for 20 seconds, and then irradiated with light for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Furthermore, a dental composite resin (Esthelite, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon and irradiated with light for 30 seconds with a visible light irradiator.
Thereby, the adhesion test piece III used for an adhesion test was produced.
This adhesion test piece III is put in a thermal shock tester, immersed in a 4 ° C. water bath for 1 minute, then transferred to a 60 ° C. water bath, immersed for 1 minute, and returned to the 4 ° C. water bath again 5,000 times. Thereafter, an adhesion test similar to the adhesion test for the adhesion test piece I was conducted except that the tensile strength was measured, and the adhesion strength was measured.
The test results of the adhesion test are shown in Table 3 below.

As shown in Table 3 above, (C) the dental adhesive composition according to Comparative Example 17 containing no polyvalent metal compound, (B) the hydrogen phosphate diester group-containing polymerizable monomer and ( C) Dental adhesive composition according to Comparative Example 18 containing no polyvalent metal compound, (A) the dihydrogen phosphate monoester group-containing polymerizable monomer, and (C) the polyvalent metal compound not included. For each of the dental adhesive composition according to Comparative Example 19 and the dental adhesive composition according to Comparative Example 20 that does not contain the (A) dihydrogen phosphate monoester group-containing polymerizable monomer, A) Examples 71 and 72 including all of the dihydrogen phosphate monoester group-containing polymerizable monomer, the (B) hydrogen phosphate diester group-containing polymerizable monomer, and the (C) polyvalent metal compound. In each dental adhesive composition, enamel and dentin Rezorede, and it can exhibit higher adhesive strength.
Similarly, the short-chain dihydrogen phosphate monoester group-containing polymerizable monomer (MEP), which is a comparative component of the (A) dihydrogen phosphate monoester group-containing polymerizable monomer, was used. Each dental according to Examples 71 and 72 using the long-chain (A) dihydrogen phosphate monoester group-containing polymerizable monomer (MDP) for the dental adhesive composition according to Comparative Example 21 In the adhesive composition for use, enamel and dentin can each exhibit higher adhesive strength.

Claims (7)

At least (A) a dihydrogen phosphate monoester group-containing polymerizable monomer represented by the following general formula (1), and (B) a hydrogen phosphate diester group-containing polymerization represented by the following general formula (2) And a polyvalent metal compound selected from at least one of (C) a polyvalent metal alkoxide, a polyvalent metal fluoride, a polyvalent metal carbonate, a polyvalent metal hydride, and an alkyl polyvalent metal. A dental adhesive composition obtained by mixing.
However, in said general formula (1), R < ¹ > shows either a hydrogen atom and a methyl group, and X shows the C4 or more hydrocarbon group which may be linear or branched.
However, in the general formula (2), R ² and R ³ each independently represent either a hydrogen atom or a methyl group, and Y ¹ and Y ² independently represent an oxygen atom, Any one of —NH—, —NCH ₃ — and —NCH ₂ CH ₃ —, wherein Z ¹ and Z ² are each independently a carbon atom having 2 or 3 carbon atoms which may be linear or branched; Indicates a hydrogen group.   The sum of the number of moles of (A) a dihydrogen phosphate monoester group-containing polymerizable monomer and (B) a hydrogen phosphate diester group-containing polymerizable monomer is (C) a polyvalent metal in a polyvalent metal compound. The dental adhesive composition according to claim 1, wherein the dental adhesive composition is larger than   The dental adhesive composition according to claim 1, wherein (C) the polyvalent metal compound is a polyvalent metal alkoxide.   The dental adhesive composition according to any one of claims 1 to 3, wherein (C) the polyvalent metal compound is a Group 4 metal compound.   Furthermore, the dental adhesive composition in any one of Claim 1 to 4 containing a polymerization initiator.   Further, (C) the fluorine-containing compound is contained so that the molar ratio of fluorine atom to polyvalent metal atom of the polyvalent metal compound, and the fluorine atom / polyvalent metal atom is 0.4 to 4.0. The dental adhesive composition according to any one of 5.   The dental adhesive composition according to any one of claims 1 to 6, which contains substantially no water.