JP4866201B2 - NOVEL COMPOUND AND COMPOSITION CONTAINING THE SAME - Google Patents

Description

  The present invention relates to a compound having a polymerizable group, a carboxyl group and a phosphate group, and a (co) polymer obtained by polymerizing the compound.

  A dental adhesive is usually used when filling or coating a restoration in a tooth defect. As dental adhesives, those containing a compound having a polymerizable group and an acidic group are known.

  For example, in Dental Materials and Instruments Vol.17 No.2 120-125 (1998) (Non-Patent Document 1), N-methacryloyl-ω, which is an amino acid derivative having a methacryloyl group in the molecule and a different methylene chain length, is disclosed. -Described for amino acids (hereinafter sometimes abbreviated as "NMωA"). When this NMωA is used as a primer to act on dentin collagen, as the methylene chain length of NMωA increases, the interaction between NMωA and dentin collagen increases and the bond strength between the dentin and the composite resin is improved. Has been. However, further material improvements have been desired with respect to adhesive strength.

  Here, when such a dental adhesive is allowed to act on the dentin, a decalcification action that dissolves the dentin surface with an acidic component, a penetration action that the monomer component penetrates into the collagen layer of the dentin, and It is important that the infiltrated monomer component is hardened and has a curing action to form a hybrid layer with collagen (hereinafter sometimes referred to as “resin-impregnated layer”).

  From the three-liquid three-step type in which the decalcification action, the permeation action, and the curing action are applied in order up to the present, the two-liquid two-step type that unifies the decalcification action and the permeation action, and further the decalcification action, Studies are being made to simplify the use of dental adhesives into a one-pack, one-step type that integrates all of the penetrating action and the hardening action. In any use mode, a compound that can be used as a dental adhesive excellent in adhesiveness is required.

Dental Materials and Instruments Vol.17 No.2 120-125 (1998)

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a novel compound (A) having a polymerizable group, a carboxyl group and a phosphoric acid group suitable for a dental composition. is there. Another object of the present invention is to provide a (co) polymer obtained by polymerizing the novel compound (A).

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して水素原子、シアノ基又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^４は、水素原子、又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^５及びＲ^６は、それぞれ独立して水素原子、置換基を有してもよい炭素数１〜２０の炭化水素基、又は金属原子である。］ The said subject is solved by providing the compound (A) shown by the following general formula (1).

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁴ represents a hydrogen atom. Or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁵ and R ⁶ each independently represent a hydrogen atom and a substituent having 1 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group or a metal atom. ]

At this time, R ¹ and R ² are preferably a hydrogen atom, R ³ is preferably a hydrogen atom or a methyl group, and R ⁴ is preferably a hydrogen atom or a methyl group. Moreover, it is a suitable embodiment that it is a composition containing a compound (A). It is preferable that the polymerizable monomer (B) copolymerizable with the compound (A) other than the compound (A) and the compound (A) is included, and the polymerizable monomer (B) includes A (meth) acrylate compound is preferred. It is preferable that the polymerization initiator (C) is included, and it is preferable that the polymerization accelerator (D) is included. It is preferable that a filler (E) is included, it is preferable that a solvent (F) is included, and it is preferable that the solvent (F) includes water (G).

  A preferred embodiment of the composition containing such a compound (A) is a dental composition, and particularly suitable as a primer, a bonding material, a cement, a composite resin or a caries treatment agent.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、前記式（１）と同じであり、ｎ＝１の場合にはＸは水酸基又はハロゲン原子であり、ｎ＝２の場合にはＸは酸素原子である。］

［式中、Ｒ^４、Ｒ^５及びＲ^６は、前記式（１）と同じである。］ As a method for producing the compound (A), at least one compound (a1) selected from the group consisting of carboxylic acid, acid halide and acid anhydride represented by the following general formula (2), and the following general formula: A method of subjecting the amine (b1) represented by (3) to a condensation reaction is preferably provided.

[Wherein R ¹ , R ² and R ³ are the same as those in the formula (1), X is a hydroxyl group or a halogen atom when n = 1, and X is oxygen when n = 2. Is an atom. ]

[Wherein, R ⁴ , R ⁵ and R ⁶ are the same as those in the formula (1). ]

  At this time, it is preferable to extract the compound (a1) using an organic solvent after the condensation reaction, and it is preferable to remove the inorganic salt using a cation exchange resin after the condensation reaction. In addition, it is preferable to remove the inorganic salt using an electrodialyzer after the condensation reaction.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して水素原子、シアノ基又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^４は、水素原子、又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^５及びＲ^６は、それぞれ独立して水素原子、置換基を有してもよい炭素数１〜２０の炭化水素基、又は金属原子である。］ Moreover, the said subject is also solved by providing the (co) polymer containing the structural unit shown by following General formula (4).

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁴ represents a hydrogen atom. Or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁵ and R ⁶ each independently represent a hydrogen atom and a substituent having 1 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group or a metal atom. ]

  At this time, it is preferable that the content of the structural unit represented by the general formula (4) is 0.1 to 100 mol%. A preferred embodiment comprising such a (co) polymer is a dental composition, particularly suitable as a cement or caries treatment agent.

  The novel compound (A) of the present invention has a polymerizable group, a carboxyl group and a phosphate group. When the composition containing the compound (A) of the present invention is used for dental use, it exhibits good adhesive strength. Therefore, it is suitable as a dental composition, and particularly suitable as a primer, bonding material, cement, composite resin, and caries treatment agent. A composition containing a (co) polymer obtained by polymerizing the novel compound (A) is also suitable as a dental composition, particularly as a cement and a caries treatment agent.

  The compound (A) of the present invention has a polymerizable group, a carboxyl group, and a phosphoric acid group, and a composition containing it is useful as a dental composition.

  The compound (A) of the present invention is represented by the following general formula (1) and has a polymerizable group. By having a polymerizable group, radical polymerization is possible and copolymerization with other monomers is possible. Examples of the polymerizable group include (meth) acryl group, (meth) acrylamide group, vinyl (thio) ether group, allyl (thio) ether group, vinyl ester group, styryl group and the like. Among these, a (meth) acryl group or a (meth) acrylamide group is preferable from the viewpoint of easy radical polymerization. The compound (A) of the present invention is preferably used as a component of a dental composition. However, since the oral cavity is a moist environment, there is a possibility that a polymerizable group may be eliminated by hydrolysis or the like. When considering the resistance to hydrolysis, it is more preferable to use a (meth) acrylamide group as the polymerizable group. Furthermore, when the irritation to the living body of the detached polymerizable group is considered, it is particularly preferable to use a methacryl group or a methacrylamide group.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して水素原子、シアノ基又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^４は、それぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^５及びＲ^６は、それぞれ独立して水素原子、置換基を有してもよい炭素数１〜２０の炭化水素基、又は金属原子である。］

[Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁴ is each independently And a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, and R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 20 hydrocarbon groups or metal atoms. ]

In the said General formula (1), R < ¹ >, R < ² > and R < ³ > are respectively independently a C1-C20 hydrocarbon group which may have a hydrogen atom, a cyano group, or a substituent. Examples of the hydrocarbon group having 1 to 20 carbon atoms that may have a substituent include an alkyl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkenyl group which may have a substituent, an arylalkynyl which may have a substituent Group, a cycloalkyl group which may have a substituent, and the like.

  Here, in the present invention, the alkyl group which may have a substituent is a linear or branched alkyl group which may have a substituent. As the alkyl group, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group Group, isohexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

  In the present invention, the alkenyl group which may have a substituent is a linear or branched alkenyl group which may have a substituent. Examples of the alkenyl group include a vinyl group and an allyl group. Group, methyl vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like.

  In the present invention, the alkynyl group which may have a substituent is a linear or branched alkynyl group which may have a substituent. Examples of the alkynyl group include ethynyl, 1- Propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 1-methyl- 2-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2- Examples include pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, 1-ethyl-3-butynyl and the like. It is.

  In the present invention, the aryl group that may have a substituent is an aromatic hydrocarbon group that may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Group, phenanthryl group and the like.

  In the present invention, the arylalkyl group which may have a substituent is a group in which a linear or branched alkyl group substituted by an aryl group may have a substituent. Are, for example, benzyl, phenethyl, 3-phenylpropyl, trityl, 1-naphthylmethyl, 2- (1-naphthyl) ethyl, 2- (2-naphthyl) ethyl, 3- (2- And a naphthyl) propyl group.

  In the present invention, the arylalkenyl group which may have a substituent is a group in which a linear or branched alkenyl group substituted by an aryl group may have a substituent. Examples include styryl group.

  In the present invention, the arylalkynyl group which may have a substituent is a group in which a linear or branched alkynyl group substituted by an aryl group may have a substituent. Examples thereof include a phenylethynyl group.

  In the present invention, the cycloalkyl group which may have a substituent is a cyclic alkyl group which may have a substituent. Examples of the cycloalkyl group include a cyclopropyl group and a cyclobutyl group. , Cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, cyclononanyl group, cyclodecanyl group, cycloundecanyl group, cyclododecanyl group and the like.

In the general formula (1), it is preferable that R ¹ and R ² are hydrogen atom, is advantageous in that excellent polymerizable by this. In the general formula (1), it is preferred that R ³ is a hydrogen atom or a methyl group, an advantage of excellent polymerizable by this. In particular, when R ¹ and R ² are hydrogen atoms and R ³ is a methyl group, as described above, when the compound of the present invention undergoes an action such as hydrolysis and the polymerizable group is eliminated. Also has the advantage of low irritation to the living body.

Here, the number and kind of substituents which the hydrocarbon group of R ¹ , R ² and R ³ has is not particularly limited, and there is substitution between R ¹ , R ² and R ³ and the double bond carbon. The case of having a group is also included. In R ³ , such a substituent is preferably an ester bond. Examples of R ³ include those shown below.

［式中、Ｒ^７は置換基を有してもよいアルキル基であり、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して水素原子、又は置換基を有してもよいアルキル基である。］

[Wherein, R ⁷ is an alkyl group which may have a substituent, and R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group which may have a substituent. . ]

In the hydrocarbon group having an ester bond, R ⁷ may employ the alkyl group exemplified in the description of R ¹ , R ² and R ³ . When R ⁷ is an alkyl group, it is preferably an alkyl group having 4 or less carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoint of polymerizability of the compound. R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group which may have a substituent. Examples of the alkyl group which may have a substituent include R ¹ , R it can be employed those exemplified in the description of the ² and R ^3. When R ⁸ , R ⁹ and R ¹⁰ are alkyl groups, they are preferably alkyl groups having 4 or less carbon atoms from the viewpoint of polymerizability of the compound, and are methyl groups, ethyl groups or tert-butyl groups. Is more preferable.

In the said General formula (1), R < ⁴ > is respectively independently a hydrogen atom or a C1-C20 hydrocarbon group which may have a substituent. As the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, the substituents exemplified in the description of R ¹ , R ² and R ³ can be employed. In the general formula (1), R ⁴ is preferably a hydrogen atom or a methyl group. When R ⁴ is a hydrogen atom or a methyl group, the arrangement of the carboxyl group and the phosphate group in the molecule becomes a state suitable for interaction with calcium ions, which contributes to an improvement in adhesion. From this viewpoint, R ⁴ is more preferably a hydrogen atom. R ⁴ is also preferably produced by using the phosphoric acid ester of an amino acid such as phosphoserine or phosphothreonine as the raw material of the compound (A) of the present invention. When phosphoserine is used, R 4 ⁴ is a hydrogen atom, and when phosphothreonine is used, R ⁴ is a methyl group.

In the said General formula (1), R < ⁵ > and R < ⁶ > are respectively independently a hydrogen atom, the C1-C20 hydrocarbon group which may have a substituent, or a metal atom. As the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, the substituents exemplified in the description of R ¹ , R ² and R ³ can be employed. Further, the metal atom is preferably a metal atom of Group 1 or Group 2 of the periodic table, and specific examples include sodium, potassium, calcium, magnesium and the like. From the viewpoint of the acidity of the compound (A), R ⁵ and R ⁶ are preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. It is more preferably a group, an ethyl group or a phenyl group, and further preferably a hydrogen atom.

  The production method of the compound (A) of the present invention is not particularly limited. Preferably, at least one compound selected from the group consisting of carboxylic acid, acid halide and acid anhydride represented by the following general formula (2) ( It can be obtained by subjecting a1) and an amine (b1) represented by the following general formula (3) to a condensation reaction.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、前記式（１）と同じであり、ｎ＝１の場合にはＸは水酸基又はハロゲン原子であり、ｎ＝２の場合にはＸは酸素原子である。］

［式中、Ｒ^４、Ｒ^５及びＲ^６は、前記式（１）と同じである。］

[Wherein R ¹ , R ² and R ³ are the same as those in the formula (1), X is a hydroxyl group or a halogen atom when n = 1, and X is oxygen when n = 2. Is an atom. ]

[Wherein, R ⁴ , R ⁵ and R ⁶ are the same as those in the formula (1). ]

  In the general formula (2), when n = 1, X is a hydroxyl group or a halogen atom. When X is a hydroxyl group, the compound (a1) is a carboxylic acid, and when X is a halogen atom, the compound (a1 ) Becomes an acid halide. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. From the viewpoint of the stability of the acid halide and the ease of preparation, chlorine is preferably employed. When n = 2, X is an oxygen atom, and at this time, the compound (a1) is an acid anhydride. When an acid anhydride is used, there is an advantage that it is not necessary to trap halide ions generated when an acid halide described later is used with alkali metal ions such as sodium ions. Examples of such acid anhydrides include (meth) acrylic anhydride.

  The compound (a1) represented by the general formula (2) contains a polymerizable group. The polymerizable group is not particularly limited and includes (meth) acryl group, (meth) acrylamide group, vinyl (thio) ether group, allyl (thio) ether group, vinyl ester group, styryl group, etc. Among these, a (meth) acryl group or a (meth) acrylamide group is preferable from the viewpoint of easy radical polymerization. The compound (A) of the present invention is preferably used as a component of a dental composition. However, since the oral cavity is a moist environment, there is a possibility that a polymerizable group may be eliminated by hydrolysis or the like. When considering the resistance to hydrolysis, it is more preferable to use a (meth) acrylamide group as the polymerizable group. Furthermore, when the irritation to the living body of the detached polymerizable group is considered, it is particularly preferable to use a methacryl group or a methacrylamide group.

  The amine (b1) represented by the general formula (3) is preferably an amino acid phosphate ester. An amino acid phosphate ester is a compound in which a phosphate group is bonded to a hydroxy group of an amino acid having a hydroxy group. When the amine (b1) is a phosphate ester of an amino acid, the amino group of the amine (b1) and the compound (a1) undergo a condensation reaction, and the resulting compound (A) of the present invention has a carboxyl group. And having a phosphate group.

The amine (b1) used in the method for producing the compound (A) of the present invention is preferably selected from phosphoserine or phosphothreonine. Amino acids are widely present in the living body, and amino acids having a hydroxy group are often phosphorylated in the living body and often exist in the form of phosphoric acid esters of amino acids. For this reason, even when the compound (A) of the present invention is applied to the living body for a long period of time and a decomposition product is produced by an action such as hydrolysis, the amino acid as described above is used as the amine (b1). By using the phosphate ester, the substance originally contained in the living body is released by the decomposition. Therefore, there is a great merit from the viewpoint of safety. In the general formula (3), R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, and in the general formula (3), R ⁴ is a methyl group, and R ⁵ and R ⁶ are hydrogen. When it is an atom, it is a phosphothreonine.

  The method for reacting the compound (a1) represented by the general formula (2) with the amine (b1) represented by the general formula (3) is not particularly limited. When the compound (a1) is an acid halide, a Schotten-Baumann reaction in which the reaction is performed in the presence of an alkali can be employed. In this method, sodium hydroxide or the like is added to the reaction system in which amine (b1) is uniformly dissolved to make the pH alkaline, and acid halide is added dropwise thereto. A precipitate is generated by acidifying the reaction solution after the dropping, and the compound (A) of the present invention can be obtained by purifying the precipitate. By reacting in this manner, the compound (A) of the present invention can be obtained under mild conditions.

  Although the usage-amount of the said acid halide and the said amine (b1) is not specifically limited, It is preferable to use 0.5-3 mol of acid halides with respect to 1 mol of amine (b1), and to use 0.6-2 mol. More preferred. The amount of use described above also depends on the availability of the acid halide and the amine (b1). That is, if the acid halide is more difficult to obtain than the amine (b1), the amount of the acid halide used is 1 mol or less of the amine (b1), and all the acid halides are reacted. Is economically advantageous. When the amine (b1) is more difficult to obtain, the reverse is true.

  The reaction temperature for reacting the acid halide with the amine (b1) is not particularly limited. Preferably, a production method is adopted in which the acid halide is gradually added dropwise while stirring the solution containing the amine (b1). The acid halide may be added dropwise neat, or may be added dropwise after diluting with a solvent. Although the temperature at the time of dripping is not specifically limited, Preferably it is -10-10 degreeC, More preferably, it is -5-5 degreeC. After completion of the dropwise addition, stirring is performed until the reaction is completed. The reaction temperature at that time is usually 10 to 60 ° C., preferably 15 to 45 ° C.

  The reaction time when the acid halide and the amine (b1) are reacted is not particularly limited, and is usually 1 to 6 hours, and preferably 2 to 4 hours. In this reaction, it is important to maintain the pH of the reaction system. Under acidic conditions, the reactivity of the amino group of the amine (b1) decreases, and thus the reaction may not proceed. On the other hand, when the basicity of the reaction system is too strong, the amide bond in the resulting compound (A) of the present invention may be hydrolyzed. For this reason, when implementing this reaction, it is preferable that pH of a reaction system is 8-9. As the acid halide is dropped and the reaction proceeds, the pH in the system decreases and shifts to the acidic side. It is preferable to adjust the pH of the reaction system as appropriate. Although it does not specifically limit as a basic solution, The solution of sodium hydroxide or potassium hydroxide is used suitably.

  In the method for producing the compound (A) of the present invention, the compound (a1) is preferably extracted using an organic solvent after the condensation reaction between the compound (a1) and the amine (b1). When the compound (a1) is an acid halide, a Schotten-Baumann reaction in which the reaction is performed in the presence of an alkali as described above can be employed. It is preferable because excess acid halide can be removed while being present. The organic solvent used is not particularly limited. Preferred organic solvents include hydrocarbon solvents such as hexane, heptane, octane, benzene, and toluene; ether solvents such as diethyl ether, diisopropyl ether, and methyl t-butyl ether; ester solvents such as ethyl acetate; chloroform, dichloromethane, and the like And halogen-containing solvents. Among these, it is more preferable to use a hydrocarbon solvent in view of selectivity for selectively removing only excess acid halide, and it is more preferable to use hexane in consideration of safety and the like.

  In the production method of the compound (A) of the present invention, it is preferable to remove the inorganic salt using a cation exchange resin after the condensation reaction between the compound (a1) and the amine (b1). As described above, when the compound (a1) is an acid halide and the Schotten-Baumann reaction is employed, a halide ion generated from the acid halide as the reaction proceeds is, for example, an alkali metal ion such as a sodium ion. After the reaction is completed, an equimolar amount of inorganic salt with the reaction product is generated. In particular, when the compound (A) obtained by the condensation reaction has high hydrophilicity, it is difficult to separate the compound (A) from the inorganic salt, and therefore, the significance of using a cation exchange resin is great.

  Moreover, in the manufacturing method of the compound (A) of this invention, it is preferable to remove an inorganic salt using an electrodialyzer after the condensation reaction of a compound (a1) and an amine (b1). As a result, not only cations derived from inorganic salts but also anions can be removed.

  Here, when the inorganic salt is removed using only the cation exchange resin, it is difficult to remove the anion in the reaction system. As a result, the anion remaining in the reaction system may reduce the cation removal efficiency. When removing an inorganic salt using only an electrodialyzer, the electrodialysis membrane used is often weak against alkalis, which is not preferable when the pH of a solution containing an inorganic salt is high. Furthermore, when only an electrodialyzer is used, it is possible to remove ions in a dissociated state, but it is not possible to remove non-ionized salts, and the phosphate becomes a free phosphate group. May be difficult. From this point of view, it is more preferable to perform a two-step process of removing inorganic salts using an electrodialyzer after removing inorganic salts using a cation exchange resin. More preferably, after removing the salt, a two-step treatment of removing the inorganic salt using a cation exchange resin is performed. In particular, if the inorganic salt is removed first using a cation exchange resin, the cation derived from the inorganic salt is exchanged for hydrogen ion, the solution containing the inorganic salt becomes acidic, and the inorganic salt is removed using a later electrodialyzer. This is preferable because the electrodialysis membrane is not easily damaged. From the viewpoint of sufficiently removing inorganic salt-derived cations and anions, the above two-step process of removing inorganic salts using an electrodialyzer after removing inorganic salts using a cation exchange resin. In addition, it is preferable to further perform a three-step process for removing inorganic salts using a cation exchange resin. By such three-step treatment, the inorganic salt can be sufficiently removed, and the compound (A) of the present invention can be obtained in a state where the phosphate group is free.

  Moreover, in this invention, the (co) polymer which consists of a structural unit shown by following General formula (4) can be obtained by carrying out the polymerization reaction of the said compound (A). This (co) polymer is also novel.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して水素原子、シアノ基又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^４は、それぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜２０の炭化水素基であり、Ｒ^５及びＲ^６は、それぞれ独立して水素原子、置換基を有してもよい炭素数１〜２０の炭化水素基、又は金属原子である。］

[Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁴ is each independently And a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, and R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 20 hydrocarbon groups or metal atoms. ]

In the (co) polymer comprising the structural unit represented by the general formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as the general formula (1), The same as described in the general formula (1) is adopted.

  The (co) polymer has a carboxyl group and a phosphate group. By having both a carboxyl group and a phosphoric acid group, the acidity becomes high, and when this (co) polymer is used for dental use, it is possible to decalcify the tooth quality well. .

  The (co) polymer may be a homopolymer or a copolymer, and may be appropriately prepared depending on the purpose of use. When it is a copolymer, it is preferably a copolymer of the compound (A) of the present invention and the polymerizable monomer (B). The (co) polymer preferably has a content of the structural unit represented by the general formula (4) of 0.1 to 100 mol%. The lower limit of the content of the structural unit is more preferably 1 mol% or more, further preferably 3 mol% or more, and particularly preferably 5 mol% or more. On the other hand, the upper limit of the content of the structural unit is not particularly limited, and a polymer having only 100 mol%, that is, a polymer composed only of the structural unit represented by the general formula (4) is also preferably used. When a hydrophobic group or a crosslinkable group is introduced into the (co) polymer to impart water resistance or mechanical strength, the upper limit of the content of the structural unit is more preferably 98 mol% or less. More preferably 95 mol% or less, and particularly preferably 90 mol% or less. The weight average molecular weight of the (co) polymer is not particularly limited, but it is usually preferably from 1,000 to 40,000.

  The compound (A) and the (co) polymer of the present invention obtained by the method as described above can be used alone, or the compound (A) of the present invention and the (co) polymer are mixed. However, it is preferable to mix other components and use them as a composition. When used as a composition, it preferably contains a polymerizable monomer (B) other than the compound (A). Although it does not specifically limit as such a polymerizable monomer (B), When mixing and using the compound (A) of this invention, it is preferable that it is copolymerizable with a compound (A). Among these, a (meth) acrylate compound is preferable. Specific examples of the (meth) acrylate compound are shown below.

  Examples of monofunctional monomers having no acidic group are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) Acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (Meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxy Sil (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 2,4-dihydroxybutyl (meth) acrylate, 2-hydroxymethyl-3-hydroxy Propyl (meth) acrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) Acrylamide, N, N-(dihydroxyethyl) (meth) acrylamide, 3-methacryloxypropyltrimethoxysilane such as acryloyloxy propyl trimethoxy silane.

  Examples of monofunctional monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, and N- (meth) acryloyl asparagine. Acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate , 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl -P-aminobenzoic acid, N- (me ) Acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) Examples include acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, and the like, and acid anhydrides or acid halides of the above radical polymerizable monomers.

  Examples of monofunctional monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane- 1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl-3 ′ -Methacryloyloxy-2 '-(3,4-dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, 4- (2- (meth) acryloyloxyethyl) ) Trimellitate, 4- (meth) acryloyloxyethyl trimellitate, 4 (Meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 6- (meta ) Acrylyloxyethylnaphthalene-1,2,6-tricarboxylic acid anhydride, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid anhydride, 4- (meth) acryloyloxyethylcarbonylpropionoyl -1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic anhydride, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 13- (meth) Acryloyloxytridecane-1,1-dicarboxylic acid, 1 - (meth) acrylamide undecanoic 1,1-dicarboxylic acid.

  Examples of monofunctional monomers having a phosphinicooxy group or phosphonooxy group in the molecule (sometimes referred to as monofunctional radical polymerizable acidic phosphate ester) include, for example, 2- (meth) acryloyloxy Ethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 2 -(Meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2- (meth) acrylamidoethyl dihydrogen phosphate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (1 - (meth) acryloyloxydecyl) hydrogen phosphate, bis {2- (meth) acryloyloxy - (1-hydroxymethyl) ethyl} hydrogen phosphate, and the like.

  Other monofunctional monomers having an acidic group, such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, 10-sulfodecyl (meth) acrylate, and other monofunctional monomers having a sulfo group in the molecule Etc.

  Bifunctional monomers are roughly divided into two types, aromatic compounds and aliphatic compounds. Examples of aromatic bifunctional monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2. -Hydroxypropoxyphenyl] propane (commonly called "Bis-GMA"), 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- (meta ) Acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) Lopan, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyditriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyethyl) pyromellitate, etc. Can be mentioned.

  Examples of aliphatic compound-based bifunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylenebis ( 2-ka Ba carbamoyloxy ethyl) dimethacrylate (commonly known as "UDMA") and bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, and the like.

  Examples of trifunctional or higher monomers include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2 , 4-Trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxy Chill-4-oxy-heptane, and the like.

  The said (meth) acrylate compound may be used individually by 1 type, and may be used in combination of multiple types. In addition to (meth) acrylate compounds, α-cyanoacrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, esters of unsaturated organic acids such as sorbic acid, maleic acid, itaconic acid, vinyl esters, Vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like may be used in combination as necessary.

  The compounding quantity ratio of the said compound (A) and the said polymerizable monomer (B) is not specifically limited. In a preferred embodiment, when the total of (A) and (B) is 100 parts by weight, the blending ratio is 1 to 99 parts by weight of (A) and 1 to 99 parts by weight of (B). . The blending ratio is more preferably 2 to 90 parts by weight of (A) and 10 to 98 parts by weight of (B), 3 to 80 parts by weight of (A) and 20 to 97 parts by weight of (B). More preferably, it is a part. Further, the blending ratio of the (co) polymer obtained by polymerizing the compound (A) and the polymerizable monomer (B) is not particularly limited. In a preferred embodiment, when the total of the (co) polymer and the (B) is 100 parts by weight, the blending ratio is 1 to 99 parts by weight of the (co) polymer and the (B) 1 to 99. Parts by weight. The blending ratio is more preferably 2 to 90 parts by weight of the (co) polymer and 10 to 98 parts by weight of the (B), and 3 to 80 parts by weight of the (co) polymer and the (B). More preferably, it is 20 to 97 parts by weight.

  As a polymerization initiator (C) used for this invention, it can select and use from the polymerization initiator currently used in the general industry, Among these, the polymerization initiator used for a dental use is used preferably. In particular, polymerization initiators for photopolymerization and chemical polymerization are used alone or in combination of two or more.

  Among the polymerization initiator (C) used in the present invention, as the photopolymerization initiator, (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, Examples include α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, and the like.

  Among the (bis) acylphosphine oxides contained in the photopolymerization initiator used in the present invention, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine. Oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenyl Examples thereof include phosphine oxide and benzoyl di- (2,6-dimethylphenyl) phosphonate. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

  The water-soluble acyl phosphine oxides contained in the photopolymerization initiator used in the present invention preferably have alkali metal ions, alkaline earth metal ions, pyridinium ions, or ammonium ions in the acyl phosphine oxide molecules. For example, water-soluble acylphosphine oxides are disclosed in European Patent No. It can be synthesized by the method disclosed in Japanese Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

  Specific examples of the water-soluble acyl phosphine oxides include monomethyl acetyl phosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethyl benzoyl phosphonate / sodium, monomethyl (1-oxobutyl) phosphine. Phosphonate sodium, monomethyl (2-methyl-1-oxopropyl) phosphonate sodium, acetyl phosphonate sodium, monomethyl acetyl phosphonate sodium, acetyl methyl phosphonate sodium, methyl 4- (hydroxy Methoxyphosphinyl) -4-oxobutanoate sodium salt, methyl-4-oxophosphonobutanoate mononatrium salt, acetyl phenyl phosphinate Sodium salt, (1-oxopropyl) pentylphosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphite Nate sodium, methyl (1,1-dimethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium Methyl-4- (hydroxymethylphosphinyl) -4-oxobutanoate lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl- 1,3-dioxolan-2-yl) Phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phosphonite sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium Salt, acetyl phosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1,1-diethoxyethyl) methyl phosphonite sodium salt, methyl (2-methyloxathio) Lan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phos Finate sodium salt, (1-methoxyvinyl) methyl phosphinate sodium salt, (1-ethylthiovinyl) methyl phosphinate sodium salt, methyl (2-methylperhydro-1,3-diazin-2-yl) phosphonate sodium salt, methyl (2-methylperhydro-1, 3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidine- 2-yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetyl methyl phosphinate oxime natrium salt, acetyl methyl phosphinate-O-benzyl Oxime sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate na Lithium salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenyl hydrazone ethyl) phosphinate sodium salt, [-(2,4-dinitrophenylhydrazono) ethyl] methyl phosphine Finate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formyl Methyl phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate・ Dodeci Guanidine salt, (1,1-dimethoxypropyl) methylphosphinate-isopropylamine salt, acetylmethylphosphinate thiosemicarbazone sodium salt, 1,3,5-tributyl-4-methylamino-1,2, 4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4-triazolium (1,1-dimethoxyethyl)- Methyl phosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide ammonium salt Etc. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is also mentioned.

  Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) acylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  Examples of thioxanthones or quaternary ammonium salts of thioxanthones contained in the photopolymerization initiator used in the present invention include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9- Oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy)- N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy -3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N Trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy -3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride and the like can be used.

  Among these thioxanthones or quaternary ammonium salts of thioxanthones, a particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and a particularly preferred quaternary ammonium salt of thioxanthones is 2 -Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of ketals contained in the photopolymerization initiator used in the present invention include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the α-diketone contained in the photopolymerization initiator used in the present invention include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4 , 4′-oxybenzyl, acenaphthenequinone and the like. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  Examples of the coumarin compound contained in the photopolymerization initiator used in the present invention include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, 3 -Benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p -Nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3 '-Carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, Zoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7 -Methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- (4 -Methoxybenzoyl) coumarin, 3- (4- Trobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3- [(3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6- Methoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzoimidazoloyl) -7- (Diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3-carbonylbis (7-dibutylaminocoumarin), 3 , 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3 6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2 , 3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, etc. Rights 9-3109, JP-compounds described in JP-A-10-245525 can be cited.

  Among the above-mentioned coumarin compounds, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

  Examples of anthraquinones contained in the photopolymerization initiator used in the present invention include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2- Examples include ethyl anthraquinone and 1-hydroxyanthraquinone.

  Examples of benzoin alkyl ethers contained in the photopolymerization initiator used in the present invention include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of α-aminoketones contained in the photopolymerization initiator used in the present invention include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds. As a result, it has excellent photocurability in the visible and near-ultraviolet region, and has an adhesive property including a compound (A) that exhibits sufficient photocurability even when using any light source of a halogen lamp, a light emitting diode (LED), or a xenon lamp. A composition is obtained.

  Of the polymerization initiator (C) used in the present invention, an organic peroxide is preferably used as the chemical polymerization initiator. The organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

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

  Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

  Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. Is mentioned. Dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Examples thereof include bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne.

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

  Examples of the peroxyester include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexa Noate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate , T-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxymaleic acid.

  Examples of the peroxydicarbonate include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di- Examples include n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

  Among these organic peroxides, diacyl peroxide is preferably used from the overall balance of safety, storage stability and radical generating ability, and benzoyl peroxide is particularly preferably used among them.

  The compounding quantity of the said polymerization initiator (C) is not specifically limited. From the viewpoint of curability and the like of the resulting composition, the compound (A) or the (co) polymer obtained by polymerizing the compound (A) and the polymerizable monomer (B) in total 100 parts by weight On the other hand, the polymerization initiator (C) is preferably blended in an amount of 0.01 to 15 parts by weight, and more preferably 0.03 to 10 parts by weight.

  In a preferred embodiment, the above-mentioned polymerization initiator (C) is used together with a polymerization accelerator (D). Examples of the polymerization accelerator (D) used in the present invention include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, and thiols. Compound etc. are mentioned.

  The amines contained in the polymerization accelerator (D) used in the present invention are classified into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methyldiethanolamine; N -Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, Tertiary fats such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Such as family amines. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among them, N-methyldiethanolamine and triethanolamine are more preferably used.

  Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N , N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4- Examples include butyl dimethylaminobenzoate. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- from the viewpoint of imparting excellent curability to the composition. At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.

  Examples of the sulfinic acid and salts thereof included in the polymerization accelerator (D) used in the present invention include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, and lithium p-toluenesulfinate. P-toluenesulfinate calcium, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethyl Sodium benzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-to Ethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Calcium, 2,4,6-isopropylbenzenesulfinic acid, sodium 2,4,6-isopropylbenzenesulfinate, potassium 2,4,6-isopropylbenzenesulfinate, lithium 2,4,6-isopropylbenzenesulfinate, 2 1,4,6-isopropylbenzenesulfinate calcium and the like, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-isopropylbenzenesulfinate are particularly preferable.

  The borate compound contained in the polymerization accelerator (D) used in the present invention is preferably an aryl borate compound. Specific examples of suitably used aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule. Phenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl ] Boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxy) Phenyl) boron, trialkyl (m-butyloxyphenyl) boron, Alkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) A) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinori Examples thereof include a nium salt and a butyl quinolinium salt.

  Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenyl. Boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and di Sodium salt, lithium salt, potassium salt of rualkyldi (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) Magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. It is done.

  Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) phenyl boron, 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, monoal Rutri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl, n-octyl, n-dodecyl, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, A butyl quinolinium salt etc. are mentioned.

  Further, borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, 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-octyloxyphenyl) boron , Tetrakis (m-octyloxyf Nyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, ( p-Butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetra Examples thereof include methylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

  Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. These aryl borate compounds may be used alone or in combination of two or more.

  Examples of the barbituric acid derivative contained in the polymerization accelerator (D) used in the present invention include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid. 5-butyl barbituric acid, 5-ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbi Tool acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, Rohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methyl Barbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and These salts (especially preferred are alkali metals or alkaline earth metals). It is, as the salts of these barbituric acids include sodium 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

  Particularly preferred barbituric acid derivatives include 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, And sodium salts of these barbituric acids.

  Examples of the triazine compound contained in the polymerization accelerator (D) used in the present invention include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl)- s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (Trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (O-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-tri Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ester Toxi] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine and the like are exemplified. The

  Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable from the viewpoint of polymerization activity, and 2-phenyl-4 is preferable from the viewpoint of storage stability. , 6-Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis ( Trichloromethyl) -s-triazine. You may use the said triazine compound 1 type or in mixture of 2 or more types.

  As a copper compound contained in the polymerization accelerator (D) used in the present invention, for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound contained in the polymerization accelerator (D) used in the present invention include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyl. Examples thereof include tin dilaurate. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compound contained in the polymerization accelerator (D) used in the present invention is preferably IV-valent and / or V-valent vanadium compounds. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No. 2003, such as phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V) The compound described in -96122 is mentioned.

  Examples of the halogen compound contained in the polymerization accelerator (D) used in the present invention include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, di Lauryldimethylammonium bromide or the like is preferably used.

  Examples of aldehydes contained in the polymerization accelerator (D) used in the present invention include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde, and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

  Examples of the thiol compound contained in the polymerization accelerator (D) used in the present invention include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  The compounding quantity of the said polymerization accelerator (D) is not specifically limited. From the viewpoint of curability and the like of the resulting composition, the compound (A) or the (co) polymer obtained by polymerizing the compound (A) and the polymerizable monomer (B) in total 100 parts by weight In contrast, 0.01 to 15 parts by weight of the polymerization accelerator (D) is preferably blended.

  Depending on the embodiment, the composition containing the compound (A) of the present invention or the (co) polymer obtained by polymerizing the compound (A) may further contain a filler (E). Such fillers are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, and chloroprene. Examples include rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like, either alone or as a mixture of two or more. Can be used. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle diameter of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Inorganic fillers include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, alumino Examples thereof include silicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. These can also be used individually or in mixture of 2 or more types. The shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle size of the inorganic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Examples of the shape of the inorganic filler include an amorphous filler and a spherical filler. From the viewpoint of improving the mechanical strength of the composition, it is preferable to use a spherical filler as the inorganic filler. Furthermore, when the spherical filler is used, there is an advantage that a composite resin excellent in surface lubricity can be obtained when a composition containing the compound (A) of the present invention is used as a dental composite resin. Here, the spherical filler is a particle diameter in a direction perpendicular to the maximum diameter, in which a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded. Is a filler having an average homogeneity of 0.6 or more divided by its maximum diameter. The average particle diameter of the spherical filler is preferably 0.1 to 5 μm. When the average particle size is less than 0.1 μm, the filling rate of the spherical filler in the composition is lowered, and the mechanical strength may be lowered. On the other hand, when the average particle diameter exceeds 5 μm, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.

  In order to adjust the fluidity | liquidity of a composition, you may use the said inorganic filler, after surface-treating beforehand with well-known surface treatment agents, such as a silane coupling agent, as needed. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The organic-inorganic composite filler used in the present invention is obtained by previously adding a polymerizable monomer to the above-described inorganic filler, forming a paste, polymerizing, and pulverizing. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) can be used. The shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  The compounding quantity of the said filler (E) is not specifically limited. In a preferred embodiment, the polymerization accelerator is used with respect to a total of 100 parts by weight of the compound (A) or a (co) polymer obtained by polymerizing the compound (A) and the polymerizable monomer (B). (D) is blended in an amount of 0.1 to 2000 parts by weight. Since the suitable compounding amount of the filler (E) varies greatly depending on the embodiment to be used, a filler (corresponding to each embodiment is described together with the description of the specific embodiment of the compound (A) of the present invention described later). A suitable blending amount of E) will be shown.

  The composition containing the compound (A) of the present invention or the (co) polymer obtained by polymerizing the compound (A) preferably contains a solvent (F) depending on its specific embodiment. Examples of the solvent (F) include water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, hexane, toluene, chloroform, ethyl acetate, butyl acetate and the like. Among these, at least one selected from the group consisting of water, ethanol and acetone is preferably used in consideration of both safety to the living body and ease of removal based on volatility. Especially, it is preferable that the composition containing the compound (A) or the (co) polymer of the present invention further contains water (G). By containing water (G), when the composition containing the compound (A) of the present invention or the (co) polymer is used as a dental composition, the decalcification action of the tooth can be promoted. There are advantages such as being able to. As water (G), it is preferable not to contain the impurity which has a bad influence, and distilled water or ion-exchange water is preferable. The water (G) may be used alone or as a mixed solvent of water (G) and a solvent (F) other than water (G). The compounding quantity of the said solvent (F) is not specifically limited, Depending on embodiment, there exists a thing which does not require the mixing | blending of the said solvent (F). In the embodiment using the solvent (F), the solvent (F) is 1 with respect to 100 parts by weight of the total of the compound (A) or the (co) polymer and the polymerizable monomer (B). ˜5000 parts by weight are blended. Since the suitable compounding amount of the solvent (F) varies greatly depending on the embodiment to be used, in conjunction with the description of specific embodiments of the compound (A) of the present invention described later, the above-mentioned according to each embodiment A suitable blending amount of the solvent (F) will be shown.

  In addition, the composition containing the compound (A) of the present invention is blended with a polymerization inhibitor, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired. Also good.

  A composition containing the compound (A) of the present invention and a composition containing a (co) polymer obtained by polymerizing the compound (A) are suitably used as a dental composition. The dental composition containing the compound (A) of the present invention comprises a primer, a bonding material, a composite resin, a cement (resin cement, glass ionomer cement, resin reinforced glass ionomer cement), a caries treatment agent, and a crevice fissure filling The dental composition containing the compound (A) of the present invention can be suitably used as a primer, bonding material, composite resin, cement, or caries treatment agent. . Moreover, the composition containing the said (co) polymer is used suitably as a cement or a caries treatment agent. Hereinafter, each embodiment will be described in detail.

  As described above, a dental adhesive is usually used when filling or covering a restoration on a tooth defect. Typically, the dental adhesive is acted on the dentin. Here, when such a dental adhesive is allowed to act on the dentin, a decalcification action that dissolves the dentin surface with an acidic component, a penetration action that the monomer component penetrates into the collagen layer of the dentin, and It is important that the infiltrated monomer component is hardened and has a curing action to form a hybrid layer with collagen (hereinafter sometimes referred to as “resin-impregnated layer”). An adhesion system that performs these three steps of “demineralization”, “penetration”, and “curing” separately is usually called a “three-step adhesion system”. Basically, the product used in the infiltration process is a primer, and the product used in the curing process is a bonding material.

  In recent years, in order to simplify the work process, a product that combines the decalcification process and the infiltration process in one step has been developed and put into practical use, and the product is called a “self-etching primer”. . An adhesion system using a self-etching primer and a bonding material is usually called a “two-step adhesion system”. Since the compound (A) of the present invention has a phosphate group, it exhibits high acidity and has excellent decalcification ability. Moreover, since it has a phosphate group and a carboxyl group in the molecule, it shows high permeability to the dentin collagen layer. For this reason, the composition containing the compound (A) of the present invention is preferably used as a dental primer, and is preferably used as a dental self-etching primer. Actually, as is clear from the comparison between Examples 1 and 2 in Examples described later and Comparative Example 1, by using the compound (A) of the present invention, the adhesive force is remarkably improved, and self It is clear that it exhibits excellent performance as an etching primer.

  The primer containing the compound (A) of the present invention is a composition containing the compound (A), a polymerizable monomer (B), a polymerization initiator (C), a polymerization accelerator (D) and a solvent (F). It is preferable. The blending amount of each component is preferably (A) 10 to 50 parts by weight and (B) 50 to 90 parts by weight when the total of (A) and (B) is 100 parts by weight. (A) 15 to 45 parts by weight and (B) 55 to 85 parts by weight are more preferable, and (A) 20 to 45 parts by weight and (B) 55 to 80 parts by weight are more preferable. Moreover, it contains (C) 0.1-5 weight part, (D) 1-30 weight part, and (F) 20-300 weight part with respect to a total of 100 weight part of said (A) and said (B). (C) 0.2 to 4 parts by weight, (D) 2 to 25 parts by weight and (F) 30 to 250 parts by weight are more preferable, (C) 0.3 to 3 parts by weight, (D 3) to 20 parts by weight and (F) 40 to 200 parts by weight are more preferable.

  From the viewpoint of enhancing the hydrophilicity of the composition and improving the permeability of the dentin into the collagen layer, the polymerizable monomer (B) used is more preferably one having a hydroxyl group in the molecule. Similarly, amines are preferable as the polymerization accelerator (D), and the solvent (F) preferably contains water (G). The content of water (G) in the solvent (F) is more preferably 50% by weight or more, further preferably 70% by weight or more, and particularly preferably 90% by weight or more. Most preferably (F) consists essentially of water (G).

  Since the compound (A) of the present invention has a phosphate group and a carboxyl group in the molecule, it strongly interacts with calcium in hydroxyapatite constituting the tooth. For this reason, the composition containing the compound (A) of the present invention is preferably used as a bonding material. The bonding material in the “two-step bonding system” is preferably a composition containing the above-mentioned (A), (B), (C), (D) and (E). The amount of each component is preferably (A) 1 to 30 parts by weight and (B) 70 to 99 parts by weight when the total of (A) and (B) is 100 parts by weight. (A) 2 to 20 parts by weight and (B) 80 to 98 parts by weight are more preferable, and (A) 3 to 15 parts by weight and (B) 85 to 97 parts by weight are more preferable. From the viewpoint of increasing the mechanical strength of the cured product, the (B) used is more preferably a polymerizable monomer containing two or more polymerizable groups. Moreover, (C) 0.1-10 weight part, (D) 0.1-20 weight part, and (E) 1-30 weight part with respect to a total of 100 weight part of said (A) and said (B). (C) 0.2 to 8 parts by weight, (D) 0.5 to 15 parts by weight, and (E) 3 to 20 parts by weight, more preferably (C) 0.3 to 6 parts by weight More preferably, it contains 1 to 10 parts by weight of (D) and 4 to 15 parts by weight of (E).

  In recent years, there has been a demand for further simplification of work, so products that implement the three steps of "decalcification", "penetration" and "curing" in one step have been developed. It is called “adhesion system”. As a bonding material used in such a one-step bonding system, a so-called “1” which is provided in the form of a bonding material used by mixing two liquids divided into A liquid and B liquid immediately before use, and one liquid from the beginning. Two types of bonding materials for liquid type one-step bonding systems are typical products. Among these, the one-pack type has a greater merit in use because the process is more simplified. When the composition containing the compound (A) of the present invention is used as a bonding material for the one-component one-step adhesive system, the composition is (A), (B), (C), (D), (E). And a composition containing (F). The amount of each component is preferably (A) 1 to 30 parts by weight and (B) 70 to 99 parts by weight when the total of (A) and (B) is 100 parts by weight. (A) 5 to 25 parts by weight and (B) 75 to 95 parts by weight are more preferable, and (A) 7 to 20 parts by weight and (B) 80 to 93 parts by weight are more preferable. In the one-component one-step adhesive system, since “penetration” and “curing” are performed at a time, the (B) used includes two polymerizable monomers containing a hydroxyl group and two polymerizable groups. It is more preferable that it is a mixture with the polymerizable monomer contained above. Moreover, (C) 0.5 to 20 parts by weight, (D) 0.1 to 20 parts by weight, and (E) 1 to 40 parts by weight with respect to a total of 100 parts by weight of (A) and (B). And (F) 5 to 70 parts by weight, preferably (C) 1 to 17 parts by weight, (D) 0.5 to 15 parts by weight, (E) 3 to 30 parts by weight, and (F) 10 to 65 parts by weight. More preferably, (C) 3-15 parts by weight, (D) 1-10 parts by weight, (E) 5-25 parts by weight, and (F) 20-60 parts by weight are further included.

  Since the compound (A) of the present invention has a phosphate group and a carboxyl group in the molecule, it strongly interacts with calcium in hydroxyapatite constituting the tooth. For this reason, the composition containing the compound (A) of the present invention is preferably used as a composite resin. When the composition containing the compound (A) of the present invention is used as a composite resin, the composition is preferably a composition containing (A), (B), (C), (D) and (E). . The composite resin is usually used in such a form that it is filled in the cavity after cutting the carious site and forming the cavity. Thereafter, the filled composite resin is usually cured by photopolymerization. For this reason, as said (C), it is preferable to use a photoinitiator. In addition, since the composite resin filled and cured as described above receives an occlusal pressure in the oral cavity, excellent mechanical strength is required. For this reason, it is preferable that the said composition contains 200-2000 weight part of fillers (E) with respect to a total of 100 weight part of said (A) and said (B), and contains 250-1500 weight part more. Preferably, it contains 300 to 1200 parts by weight. When content of a filler (E) is less than 200 weight part, there exists a possibility that the mechanical strength of hardened | cured material may become inadequate. On the other hand, when the content of the filler (E) exceeds 2000 parts by weight, it becomes difficult to uniformly disperse the filler (E) in the (A) and (B). Insufficient composition may result.

  It is also one preferred embodiment that the compound (A) of the present invention is used as a dental cement by taking advantage of its strong interaction with the tooth substance. Preferred examples of the cement include resin cement, glass ionomer cement, and resin reinforced glass ionomer cement. When the composition containing the compound (A) of the present invention is used as a resin cement, the composition is preferably a composition containing (A), (B), (C), (D) and (E). . For example, dental cement is preferably used as a bonding material for fixing a dental restoration material made of metal or ceramic called an inlay or crown to a tooth. Therefore, excellent mechanical strength is required to withstand occlusal pressure and the like. From this viewpoint, the (B) is more preferably a polymerizable monomer containing two or more polymerizable groups. Moreover, in the case of the above usage forms, since most of the restoration materials for crowns are light-impermeable, it is not easy to cure the cement by photopolymerization. For this reason, it is preferable to use a chemical polymerization initiator as said (C). In order to increase the reactivity when the compound (A) is polymerized using a chemical polymerization initiator, it is preferable to use amines and / or sulfinic acid and salts thereof as the (D). More preferably, the sulfinic acid and its salt are used simultaneously. Moreover, it does not specifically limit as a filler (E) used. When it is desired to give the cement a sustained release of fluorine, the filler (E) is selected from fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. It is preferable to use at least one selected from the group consisting of, and more preferably, fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass. On the other hand, when it is desired to give the X-ray contrast property to the cement, the filler (E) includes barium glass, strontium glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, strontium fluoroaluminosilicate glass, and barium fluoroaluminosilicate. It is preferable to use at least one selected from the group consisting of glasses, and it is more preferable to use barium glass and / or barium fluoroaluminosilicate glass.

  Moreover, when using a chemical polymerization initiator, it is preferable to store said (C) and said (D) in a respectively separate container from a viewpoint of storage stability. That is, in a preferred embodiment, the resin cement is used in a two-part form. Moreover, in a suitable actual aspect, when mix | blending a filler (E), the composition (liquid state) and the filler (E) (powder) containing the compound (A) of this invention are knead | mixed, and it is made into a paste. For this reason, in a more preferred embodiment, the resin cement is used in a two-paste type. It is preferable to store each paste in a state where the pastes are separated from each other, knead the two pastes immediately before use, and advance the chemical polymerization to cure. In addition, since the compound (A) of the present invention has a phosphoric acid group in the molecule and exhibits strong acidity, when amines and / or sulfinic acid and salts thereof are used as the (D), storage stability is obtained. In view of the above, it is preferable to store the (A) and the (D) in separate containers. When the above two pastes are referred to as A paste and B paste, respectively, the A paste includes (A), (B), (C), and (E), and the B paste includes (B) and (D). And embodiments comprising (E) are particularly preferably used.

  When the composition containing the compound (A) of the present invention is used as a dental cement, the amount of each component is not particularly limited, but when the total of (A) and (B) is 100 parts by weight, (A) 0.1 to 30 parts by weight and (B) 70 to 99.9 parts by weight are preferred, (A) 0.3 to 20 parts by weight and (B) 80 to 99.7 parts by weight. More preferably, (A) 0.5 to 10 parts by weight and (B) 90 to 99.5 parts by weight are more preferable. Moreover, as a compounding quantity of said (C) and said (E), when considering that suitable hardening time is obtained, with respect to a total of 100 weight part of said (A) and said (B), (C ) 0.1-10 parts by weight and (D) 0.1-10 parts by weight, preferably (C) 0.3-8 parts by weight and (D) 0.3-8 parts by weight. More preferably, it contains (C) 0.5-6 parts by weight and (D) 0.5-6 parts by weight.

  Furthermore, it is preferable that the filler (E) is contained in an amount of 20 to 1000 parts by weight, more preferably 40 to 600 parts by weight, and more preferably 70 to 400 parts by weight with respect to a total of 100 parts by weight of the (A) and (B). It is more preferable to include a part. When content of a filler (E) is less than 20 weight part, there exists a possibility that the mechanical strength of hardened | cured material may become inadequate. On the other hand, when the content of the filler (E) exceeds 1000 parts by weight, the fluidity of the paste is insufficient when the resin cement is used as a two-paste type cement which is a preferred embodiment thereof. Since it becomes difficult to perform proper mixing, the strength of the cured product may be reduced.

  The composition containing the compound (A) of the present invention is preferably used as a glass ionomer cement, and more preferably used as a resin reinforced glass ionomer cement. Glass ionomer cements typically react and cure an inorganic filler such as fluoroaluminosilicate glass and a polyalkenoic acid such as polyacrylic acid by an acid-base reaction. It is considered that the adhesion function is expressed by interaction with calcium in the hydroxyapatite to be formed. Here, since the compound (A) of the present invention exhibits a very strong interaction with calcium as described above, it is considered that the compound (A) is suitable for use in a glass ionomer. When the composition containing the compound (A) of the present invention is used as a glass ionomer cement, particularly preferably a resin-reinforced glass ionomer cement, the composition is (A), (B), (C), (D), A composition containing (E), (F) and polyalkenoic acid is preferred.

  The polyalkenoic acid is a polymer of unsaturated monocarboxylic acid or unsaturated dicarboxylic acid. Specific examples of the polyalkenoic acid include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 2-cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, A homopolymer such as uraconic acid or a copolymer with a monomer copolymerizable with these unsaturated carboxylic acids can be mentioned. In the case of a copolymer, the proportion of unsaturated carboxylic acid units is preferably 50 mol% or more based on the total structural units. The copolymerizable monomer is preferably an ethylenically unsaturated polymerizable monomer such as styrene, acrylamide, acrylonitrile, methyl methacrylate, acrylates, vinyl chloride, allyl chloride, vinyl acetate, 1,1,6. -A trimethyl hexamethylene dimethacrylate ester etc. can be mentioned. Among these polyalkenoic acids, homopolymers or copolymers of acrylic acid or maleic acid are preferred. When these polyalkenoic acids have a weight average molecular weight of less than 5,000, the strength of the cured product of the dental cement composition is lowered, and the durability may be inferior. On the other hand, when the weight average molecular weight exceeds 40,000, the consistency of the dental cement composition at the time of kneading becomes hard and the operability may be lowered. Accordingly, the preferred polyalkenoic acid has a weight average molecular weight of 5,000 to 40,000.

  The filler (E) used is fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass from the viewpoints of curability in acid-base reaction and sustained release of fluorine in the composition. And at least one selected from the group consisting of strontium calcium fluoroaluminosilicate glass, and more preferably fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass.

  Moreover, as a solvent (F) used, it is preferable that the said solvent (F) contains water (G) from a viewpoint of making an acid-base reaction advance smoothly. The content of water (G) in the solvent (F) is more preferably 50% by weight or more, further preferably 70% by weight or more, particularly preferably 90% by weight or more, Most preferably, the solvent (F) consists essentially of water (G).

  The amount of each component when the composition containing the compound (A) of the present invention is used as a glass ionomer cement, particularly preferably a resin-reinforced glass ionomer cement, is not particularly limited, but the above (A) and (B) When the total is 100 parts by weight, it is preferably (A) 1 to 99 parts by weight and (B) 1 to 99 parts by weight, (A) 3 to 90 parts by weight and (B) 10 to 97 parts by weight. It is more preferable that Moreover, as a compounding quantity of said (C) and said (E), when considering that suitable hardening time is obtained, with respect to a total of 100 weight part of said (A) and said (B), (C ) 0.1-10 parts by weight and (D) 0.1-10 parts by weight, preferably (C) 0.3-8 parts by weight and (D) 0.3-8 parts by weight. More preferably, it contains (C) 0.5-6 parts by weight and (D) 0.5-6 parts by weight. Furthermore, the filler (E) is preferably contained in an amount of 10 to 1000 parts by weight, more preferably 20 to 600 parts by weight, more preferably 25 to 400 parts by weight, based on 100 parts by weight of the total of (A) and (B). It is more preferable to include a part. When content of a filler (E) is less than 10 weight part, there exists a possibility that the mechanical strength of hardened | cured material may become inadequate. On the other hand, when the content of the filler (E) exceeds 1000 parts by weight, the fluidity of the composition paste decreases and it becomes difficult to perform sufficient mixing, so that the acid-base reaction does not proceed smoothly. There is a case. As a result, the strength of the cured product may be reduced.

  Moreover, it is preferable that 10-300 weight part of solvent (F) is included with respect to a total of 100 weight part of said (A) and said (B), It is more preferable that 20-250 weight part is included, 30-200 weight It is more preferable to include a part. By containing the solvent (F) in such a range, the acid-base reaction can proceed smoothly, and the resulting cured product has good mechanical strength and adhesion to the tooth.

  The polyalkenoic acid is preferably contained in an amount of 10 to 300 parts by weight, more preferably 20 to 250 parts by weight, and more preferably 30 to 200 parts by weight with respect to 100 parts by weight of the total of (A) and (B). Is more preferable. By containing the polyalkenoic acid in such a range, curing due to the acid-base reaction proceeds smoothly, and disintegration due to hydrolysis in the oral cavity of the obtained cured product can be reduced.

  As described above, since the glass ionomer cement is cured by the progress of the acid-base reaction, from the viewpoint of storage stability, the filler (E) and the polyalkenoic acid are packaged in separate containers and mixed immediately before use. It is preferable to be used. As a product form, a so-called powder-liquid type product form is also preferably used, but from the viewpoint of improving handling properties, it is more preferable to take the form of a so-called two-paste glass ionomer cement containing two types of paste. In the case of a two-paste type product form, when the above two pastes are referred to as A paste and B paste, respectively, the A paste is (A), (B), (D), (E), (F) And polyalkenoic acid, and the B paste contains (B), (C) and (E). Further, the A paste includes (A), (B), (C), (E), (F) and polyalkenoic acid, and the B paste includes (B), (D) and (E). Are also preferably used. In any embodiment, since the polyalkenoic acid is contained on the A paste side, as the filler (E) contained in the B paste, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoro It is preferable to use at least one selected from the group consisting of aluminosilicate glass and strontium calcium fluoroaluminosilicate glass, and it is more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass. On the other hand, as the filler (E) contained in the A paste, it is preferable to use a filler that does not react with polyalkenoic acid, and quartz is particularly preferably used.

  The compound (A) of the present invention is suitably used as a component of a dental composition as described above, but a (co) polymer obtained by polymerizing the compound (A) is used as a component of a dental composition. When used, it is suitably used as cement. Among the cements, it is preferably used as a glass ionomer cement, and more preferably used as a resin reinforced glass ionomer cement. As described above, the glass ionomer cement can be obtained by curing the fluoroaluminosilicate glass and polyalkenoic acid by causing an acid-base reaction in the presence of water. The glass ionomer cement thus obtained is The acidic component is only a carboxyl group derived from polyalkenoic acid. Therefore, the present inventors have confirmed that the decalcification of the tooth surface and the removal of the smear layer necessary for adhesion are not necessarily sufficient, and the interaction with calcium in the tooth is not sufficient. Has been. The (co) polymer obtained by polymerizing the compound (A) of the present invention has both a carboxyl group and a phosphoric acid group, and thus has a high acidity. This (co) polymer is used in place of polyalkenoic acid. The glass ionomer cement obtained by using for is expected to have a good decalcification action and a good interaction with calcium. It is also one preferred embodiment to use the (co) polymer and the polyalkenoic acid in combination.

  Moreover, the compound (A) of this invention or the (co) polymer obtained by superposing | polymerizing this compound (A) can be used suitably as a remineralization promoter of a tooth. As a remineralization promoter for teeth, one containing a peptide containing phosphoserine or the like is known, and by incorporating such a peptide having a phosphate group, calcium ions and phosphorus in the oral cavity are mixed. The abundance ratio of acid ions (Ca / P ratio) is increased, and remineralization of the tooth is promoted. Since the compound (A) of the present invention or the (co) polymer obtained by polymerizing the compound (A) has not only a phosphate group but also a carboxyl group, it is expected to have a better calcium carrying ability. Specifically, when an aqueous solution containing the compound (A) or the (co) polymer having such a calcium supporting ability is applied to a site where initial demineralization occurs, the compound (A) or the (co-polymer) is applied. ) The polymer is adsorbed on the tooth, and the Ca / P ratio is increased in the oral cavity to promote remineralization of the decalcified tooth. Therefore, the compound (A) of the present invention or the (co) polymer obtained by polymerizing the compound (A) can be suitably used as a caries treatment agent, particularly as an initial caries treatment agent.

  In addition, as a preferred usage mode of the (co) polymer obtained by polymerizing the compound (A) of the present invention, there is a calcium sustained-release source that slowly releases calcium at a site where calcium is present in a small amount. Is a calcium source that provides a reaction field with a high calcium ratio by administering to a site where the Ca / P ratio is small, and the (co) polymer loaded with calcium is introduced into the living body to the site where calcium is required. Examples include calcium carriers that transport calcium.

  The composition containing the compound (A) of the present invention and the (co) polymer obtained by polymerizing the compound are used for dental, such as bone cement, building adhesive, ceramic adhesive, sealing material, coating material, etc. It is also useful for applications other than applications.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Synthesis of N-methacryloyl-β-alanine]
100 mL of water was added to a 500 mL reaction vessel, and then 44.3 g of sodium hydroxide and 44.5 g of β-alanine (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred to prepare a completely dissolved solution. Subsequently, the internal temperature of the reaction system was cooled to −5 ° C. using an ice-salt bath. After the cooling treatment, 57 g of methacryloyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 30 minutes using a dropping funnel while stirring the reaction system. Upon dropping, the reaction system was cooled so that the internal temperature of the reaction system did not exceed 0 ° C. After completion of the dropwise addition, the reaction system was further stirred for 1 hour. After stirring for 1 hour, an aqueous hydrochloric acid solution having a concentration of 6 mol / L was added to make the pH of the reaction solution 3 or less. With the addition of the aqueous hydrochloric acid, a white precipitate was formed in the reaction system. The solution was extracted 3 times with 1000 mL of ethyl acetate. The obtained ethyl acetate solution was washed with 700 mL of water, and then magnesium sulfate was added to the ethyl acetate layer for dehydration. After dehydration, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a light brown oily substance. The obtained oily substance was used for recrystallization from diethyl ether to obtain 31.4 g of white crystals (melting point: 76 ° C.). The chemical reaction formula is shown below.

[Synthesis of phosphoserine methacrylate]
(Synthesis Example 1)
Phosphoserine (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.0 g) and sodium hydroxide (2.0 g) were charged into a 100 mL beaker serving as a reaction vessel. 10 mL of water was added and stirred at room temperature. The phosphoserine and sodium hydroxide were completely dissolved to obtain a colorless and transparent solution. A pH meter (“pH meter F-55” manufactured by Horiba, Ltd.) was set, and a 6 mol / L sodium hydroxide aqueous solution was added dropwise with stirring until the pH reached 9. The reaction system was cooled by setting an ice bath. Thereafter, the reaction system was kept at about 1 to 4 ° C. While maintaining the pH of the reaction system to be 8 to 9, 3.5 mL of methacryloyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and a 6 mol / L sodium hydroxide aqueous solution are each little by little using a Pasteur pipette. It was dripped alternately. After completion of the dropwise addition, the reaction system was stirred for 2 hours while being cooled in an ice bath. Since the reaction system becomes acidic as the reaction proceeds, a 6 mol / L aqueous sodium hydroxide solution was added dropwise to maintain the pH at 8-9 (in about 1 hour 30 minutes from the start of the reaction, pH movement decreases rapidly). After confirming the disappearance of the raw materials and the formation of the target product by TLC, the reaction system was transferred to a 300 mL separatory funnel using 50 mL of water and washed with 20 mL of hexane to remove excess methacryloyl chloride. The obtained aqueous layer was neutralized by adding a cation exchange resin (“Amberlite IR120” manufactured by Aldrich) to obtain a solution containing the product. When the pH of the solution reached 1.2, the pH did not change even when more cation exchange resin was added, so the neutralization reaction was terminated at that stage. The cation exchange resin was filtered off from the solution. After adding water to the resulting solution to a total volume of 150 mL, a tabletop electrodialyzer ("MICRO ACILYZER S1" manufactured by Astom Co., Ltd.) and an electrodialysis membrane ("AC-110-10" manufactured by Astom Co., Ltd.) were used. The inorganic salt was removed from the solution. Three hours after the start of the operation for removing the inorganic salt, the electric conductivity of the solution no longer decreased, so the operation was stopped. By performing the removal operation, the electrical conductivity of the solution, which was 60 μS before the operation, decreased to 10 μS at the end. The pH of the solution after removing the inorganic salt was 2.0. The solution was neutralized again by adding a cation exchange resin. When the pH of the solution reached 1.1, the pH did not change even when more cation exchange resin was added, so the neutralization reaction was terminated at that stage. 500 μL of the solution was sampled, concentrated under reduced pressure using an evaporator (bath temperature: 28 ° C.), ¹ H-NMR measurement was performed using heavy water as a solvent, and the desired phosphoserine methacrylate as the compound (A) of the present invention was obtained. It was confirmed that it was obtained. The chemical reaction formula is shown below.

The chemical shift δ (ppm, TMS) of the ¹ H-NMR spectrum (400 MHz, D ₂ O) of the phosphoserine methacrylate obtained by the above method was as follows.
δ = 1.83 (s; 3H), 4.08 (ddd; 1H), 4.18 (ddd; 1H), 4.54 (t; 1H), 5.40 (s; 1H), 5.67 (S; 1H)

Further, when the ¹³ C-NMR spectrum (100 MHz, D ₂ O (internal standard: CD ₃ OD)) of phosphoserine methacrylate obtained by the above method was measured, the chemical shift δ (ppm) was as follows. It was.
δ = 18.5, 54.5, 65.6, 122.7, 139.3, 172.6, 173.3

Subsequently, the yield of phosphoserine methacrylate was measured according to the following method.
[Preparation of internal standard solution]
1.000 g of methyl-α-glucopyranoside (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in heavy water, and the total volume was made 10 mL using a volumetric flask (hereinafter, the obtained solution is described as “internal standard solution”). There). Since the molecular weight of methyl-α-glucopyranoside is 194.18, the concentration of the solution is 5.15 × 10 ⁻¹ mol / L.

[Measurement of yield of phosphoserine methacrylate]
Using a volumetric flask, the volume of the solution containing phosphoserine methacrylate was 200 mL. When the yield of this reaction is 100%, 27.0 mmol of phosphoserine methacrylate is contained in the solution. 5.0 mL of the solution (theoretically containing 6.75 × 10 ⁻¹ mmol of phosphoserine methacrylate) was sampled, transferred to an eggplant flask weighed in advance, and concentrated under reduced pressure using an evaporator ( (Bath temperature: 28 ° C.). Concentration was interrupted when the concentration progressed to some extent, and the weight of the concentrated solution was weighed together with the eggplant flask. As a result, the weight of the concentrated solution was 309 mg. The solution was colorless and transparent, no precipitates were observed, and the whole was uniform. Next, 30.6 mg of the solution was weighed in a 3 mL sample tube (theoretically containing 6.68 × 10 ⁻² mmol of phosphoserine methacrylate). To this sample tube, 100 μL of the above-mentioned “internal standard solution” was further added using a micropipette (“Eppendorf Reference 4910” manufactured by Eppendorf Co., Ltd.) (by this operation, 6 phosphoserine methacrylate was added in the sample tube). .68 × 10 ⁻² mmol and 5.15 × 10 ⁻² mmol of methyl-α-glucopyranoside are included in the same amount). Using the resulting mixed solution, a sample for NMR using heavy water as a solvent was prepared, and ¹ H-NMR was measured. The average value of the integrated intensity of the signal (δ 5.40, 5.67 ppm) derived from phosphoserine methacrylate and the signal derived from the internal standard (methyl-α-glucopyranoside) (δ 3.60, 3.70 ppm) in the obtained spectrum chart. The average values of the integrated intensities were compared. The integrated intensity of the signal derived from the above-mentioned phosphoserine methacrylate and the signal derived from the internal standard (methyl-α-glucopyranoside) is 5.15 × 10 ⁻² mmol of methyl-α-glucopyranoside contained in the mixed solution. From this ratio, it was revealed that the mixed solution contained 5.61 × 10 ⁻² mmol of phosphoserine methacrylate. Therefore, the yield was 5.74 g and the yield was 84%. The concentration of the solution containing phosphoserine methacrylate after concentration was 47% by weight.

[Synthesis of phosphothreonine methacrylate]
(Synthesis Example 2)
In Synthesis Example 1, phosphothreonine methacrylate was synthesized in the same manner as in Synthesis Example 1 except that phosphothreonine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of phosphoserine. ¹ H-NMR measurement was performed using heavy water as a solvent, and it was confirmed that phosphothreonine methacrylate, which is the target compound (A) of the present invention, was obtained. The chemical reaction formula is shown below.

The chemical shift δ (ppm, TMS) of the ¹ H-NMR spectrum (400 MHz, D ₂ O) of the phosphothreonine methacrylate obtained by the above method was as follows.
δ = 1.23 (s; 3H), 1.83 (s; 3H), 4.53 (d; 1H), 4.73 (m; 1H), 5.40 (s; 1H), 5.65 (S; 1H)

Further, when the ¹³ C-NMR spectrum (100 MHz, D ₂ O (internal standard: CD ₃ OD)) of phosphothreonine methacrylate obtained by the above method was measured, the chemical shift δ (ppm) was as follows. It was.
δ = 19.3, 19.5, 58.7, 75.6, 123.2, 140.2, 173.6, 173.7

  Subsequently, in order to evaluate a dental composition containing the compound (A) described later, a high concentration aqueous solution containing the compound (A) was prepared according to the method shown below.

[Preparation of high concentration aqueous solution]
100 mL was sampled from the 200 mL aqueous solution containing the phosphoserine methacrylate created above. The solution was concentrated under reduced pressure using an evaporator (bath temperature: 28 ° C.). At this time, the concentration was stopped when the white powder was deposited on the bottom of the container. From the concentrated solution, only the liquid portion was extracted using a Pasteur pipette so as not to contain the white powder deposited on the bottom, and transferred to a sample tube. Using the concentrated colorless and transparent solution thus obtained, the concentration of phosphoserine methacrylate contained in the solution was quantified by a quantification method using the above-mentioned internal standard solution. As a result, the concentration of the solution was 52% by weight. Using the high-concentration aqueous solution thus obtained, a composition containing phosphoserine methacrylate was prepared and evaluated as a dental composition. In addition, a high concentration aqueous solution of phosphothreonine methacrylate (concentration: 47% by weight) was prepared using the same technique. A composition containing phosphothreonine methacrylate was prepared using a high-concentration aqueous solution of the phosphothreonine methacrylate and evaluated as a dental composition.

  Abbreviations used below are as follows.

[Acid monomer]
A-1: Phosphoserine methacrylate A-2: Phosphothreonine methacrylate A-3: N-methacryloyl-β-alanine

[Polymerizable monomer having water solubility]
HEMA: 2-hydroxyethyl methacrylate

[Polymerizable monomer having crosslinkability]
BisGMA: bisphenol A diglycidyl methacrylate # 801: 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane NPG: neopentyl glycol dimethacrylate

[Photopolymerization initiator]
TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[Inorganic filler]
Inorganic filler 1: Nippon Aerosil "R972"
Inorganic filler 2: Nippon Aerosil "Ar380"

[Preparation of two-component dental composition]
Example 1
The following components were mixed at room temperature to prepare a primer composition and a bonding material composition, and the adhesive strength with bovine enamel was measured.
Primer composition:
A-1 10 parts by weight HEMA 40 parts by weight Water 40 parts by weight # 801 15 parts by weight Ethanol 8 parts by weight TMDPO 0.5 part by weight

Bonding material composition:
BisGMA 40 parts by weight HEMA 40 parts by weight NPG 20 parts by weight TMDPO 3 parts by weight Inorganic filler 1 5.5 parts by weight Inorganic filler 2 1.5 parts by weight

[Adhesion evaluation method with bovine enamel]

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

  The prepared primer composition was applied in the round hole using a brush, left for 20 seconds, and then air blown on the surface to dry the applied primer composition until the fluidity of the primer composition disappeared. Subsequently, the above-mentioned bonding material composition was applied repeatedly on the tooth surface to which the primer was applied and dried. Subsequently, the applied primer composition and the bonding material composition were cured by irradiating with a dental visible light irradiator “JET Light 3000” (manufactured by J. Morita USA) for 20 seconds.

  A composite resin for dental filling (Kuraray Medical Co., Ltd., trade name “Clearfill AP-X” (registered trademark)) is applied to the surface of the cured product of the obtained bonding material composition, and a release film (polyester) is used. Covered. Subsequently, a glass slide was placed on the release film and pressed to smooth the coated surface of the composite resin. Subsequently, the composite resin was irradiated with light using the irradiator “JET Light 3000” for 20 seconds through the release film to cure the composite resin.

  A stainless steel cylindrical rod (diameter 7 mm, length) using a commercially available dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.) on the surface of the cured product of the obtained dental filling composite resin. One end face (circular cross section) of 2.5 cm) was bonded. After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. The sample immersed in the distilled water was allowed to stand for 24 hours in a thermostat maintained at 37 ° C., thereby preparing a sample for adhesion test. A total of five samples for adhesion test were prepared.

[Measurement of adhesive strength]
Tensile bond strength of the above five adhesion test samples was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min, and the average value was taken as the tensile bond strength. . The adhesive strength with bovine enamel was 9.7 MPa. The obtained results are summarized in Table 1.

(Example 2)
In Example 1, instead of using 10 parts by weight of the acidic monomer “A-1”, the primer composition and the bonding material composition were the same as in Example 1 except that 10 parts by weight of “A-2” was used. Was prepared and the adhesive strength with bovine enamel was measured. The obtained results are summarized in Table 1.

(Comparative Example 1)
In Example 1, instead of using 10 parts by weight of the acidic monomer “A-1”, the primer composition and the bonding material composition were the same as in Example 1 except that 10 parts by weight of “A-3” was used. Was prepared and the adhesive strength with bovine enamel was measured. The obtained results are summarized in Table 1.

  From Table 1, in Example 1 using phosphoserine methacrylate which is “A-1” as an acidic monomer, the adhesive strength between the composite resin and the enamel is 9.7 MPa, and phosphothreonine which is “A-2”. In Example 2 using methacrylate as an acidic monomer, the adhesive strength between the composite resin and the enamel is 9.2 MPa, and the adhesiveness is good, which is useful as a two-pack type dental composition. On the other hand, in the comparative example 1 which used "A-3" which does not have a phosphate group as an acidic monomer, the adhesive strength of a composite resin and enamel was inferior greatly.

Claims (26)

Compound (A) represented by the following general formula (1).

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁴ represents a hydrogen atom. Or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁵ and R ⁶ each independently represent a hydrogen atom and a substituent having 1 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group or a metal atom. ] The compound (A) according to claim 1, wherein R ¹ and R ² are hydrogen atoms, and R ³ is a hydrogen atom or a methyl group. The compound (A) according to claim 1 or 2, wherein R ⁴ is a hydrogen atom or a methyl group.   The composition containing the compound (A) in any one of Claims 1-3.   The composition of Claim 4 containing the polymerizable monomer (B) copolymerizable with the said compound (A) other than the said compound (A) and the compound (A) in any one of Claims 1-3. object.   The composition according to claim 5, wherein the polymerizable monomer (B) is a (meth) acrylate compound.   The composition according to any one of claims 4 to 6, comprising a polymerization initiator (C).   The composition according to any one of claims 4 to 7, comprising a polymerization accelerator (D).   The composition according to any one of claims 4 to 8, comprising a filler (E).   The composition according to any one of claims 4 to 9, comprising a solvent (F).   The composition according to claim 10, wherein the solvent (F) comprises water (G).   A dental composition comprising the composition according to claim 4.   A primer comprising the dental composition according to claim 12.   A bonding material comprising the dental composition according to claim 12.   A cement comprising the dental composition according to claim 12.   A composite resin comprising the dental composition according to claim 12.   A caries treatment agent comprising the dental composition according to claim 12. At least one compound (a1) selected from the group consisting of a carboxylic acid, an acid halide and an acid anhydride represented by the following general formula (2), and an amine (b1) represented by the following general formula (3): The method for producing the compound (A) according to claim 1, wherein the condensation reaction is performed.

[Wherein R ¹ , R ² and R ³ are the same as those in the formula (1), X is a hydroxyl group or a halogen atom when n = 1, and X is oxygen when n = 2. Is an atom. ]

[Wherein, R ⁴ , R ⁵ and R ⁶ are the same as those in the formula (1). ]   The method for producing the compound (A) according to claim 18, wherein the compound (a1) is extracted using an organic solvent after the condensation reaction.   The method for producing a compound (A) according to claim 18 or 19, wherein the inorganic salt is removed using a cation exchange resin after the condensation reaction.   The manufacturing method of the compound (A) in any one of Claims 18-20 which removes an inorganic salt using an electrodialyzer after the said condensation reaction. A (co) polymer containing a structural unit represented by the following general formula (4).

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁴ represents a hydrogen atom. Or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁵ and R ⁶ each independently represent a hydrogen atom and a substituent having 1 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group or a metal atom. ]   The (co) polymer according to claim 22, wherein the content of the structural unit represented by the general formula (4) is 0.1 to 100 mol%.   A dental composition comprising the (co) polymer according to claim 22 or 23.   A cement comprising the dental composition according to claim 24.   A caries treatment agent comprising the dental composition according to claim 24.