JP6224481B2 - Organophosphate compound, polymerizable composition containing organophosphate compound, and dental bonding material - Google Patents

Description

  The present invention relates to a novel organophosphate compound, a polymerizable composition containing the organophosphate compound, and a dental bonding material using the polymerizable composition, which are particularly useful for dental materials.

  A dental bonding material is usually used when filling or coating a restoration in a tooth defect. As a dental bonding material, one in which a compound having a polymerizable group and a phosphate group is blended is known, and various compounds have been proposed as the compound (for example, see Patent Documents 1 to 4). Among them, 10-methacryloyloxydecyl dihydrogen phosphate (hereinafter referred to as MDP) expresses excellent adhesiveness to the tooth substance and expresses excellent adhesion durability in the moist environment of the oral cavity. Has been reported (see Patent Document 1). In recent years, the following polymerizable compounds have been proposed for the purpose of improving adhesiveness.

JP 58-21607 A JP 2006-298771 A JP 2010-235553 A JP 2010-235554 A

  A dental bonding material is required to have high mechanical strength because it is applied with a high bite pressure or a toothbrush after being applied to the oral cavity in addition to adhesion and adhesion durability. According to the study by the present inventors, it has been found that the dental material using the compound described in Patent Document 2 has a room for improvement in the adhesion durability and the initial adhesion, although it exhibits a certain degree of adhesion durability. Moreover, although the dental material using the compound of patent document 3 showed the outstanding adhesiveness and adhesion durability, it turned out that there is room for improvement in mechanical strength. Furthermore, although the dental material using the compound described in Patent Document 4 has a plurality of polymerizable groups, a certain degree of improvement in mechanical strength is recognized, but it has been found that there is room for further improvement in mechanical strength. It was.

  Therefore, an object of the present invention is to provide an organophosphate compound that can impart excellent mechanical strength, adhesion, and adhesion durability when applied to a dental material. Another object of the present invention is to provide a polymerizable composition excellent in adhesion and adhesion durability, which can give a cured product having high mechanical strength suitable for a dental material.

  The present invention is a compound (I) represented by the following general formula (1).

(Wherein R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ₄ represents a hydrocarbon group having 5 to 30 carbon atoms, R ₅ And R ₆ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a metal atom, and A represents —COO—, —OCO—, and —O—. X represents an oxygen atom or a sulfur atom, m represents an integer of 2 to 6, and two phosphate groups or phosphate ester groups [—O—P (X) (OR ₅₎ (OR _6)] are each other at a 5 to 30 carbon atoms in R ₄ linked to R _4.)

In the general formula (1), R ₁ and R ₂ are preferably hydrogen atoms, and R ₃ is preferably a hydrogen atom or a methyl group. R ₄ is preferably a hydrocarbon group having 5 to 30 carbon atoms. R ₅ and R ₆ are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. It is preferable that A is —COO— and m is 2.

  The compound (I) of the present invention is preferably a compound represented by the following general formula (2).

(Wherein R ₇ and R ₈ each independently represent a hydrogen atom or a methyl group, R ₉ and R ₁₀ each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and R ₁₁ and R ₁₂ are Each independently represents a hydrocarbon group having 2 to 10 carbon atoms.)

  The present invention is also a polymerizable composition containing the compound (I). The polymerizable composition preferably further contains a polymerizable monomer (II) other than the compound (I) that can be copolymerized with the compound (I). The polymerizable monomer (II) is preferably a (meth) acrylate compound. The polymerizable composition preferably further contains a polymerization initiator (III).

  The polymerizable composition of the present invention can be suitably used as a dental bonding material.

  According to the present invention, a novel organophosphate compound (I) is provided, and the polymerizable composition containing the compound (I) has a mechanical strength (particularly bending strength), adhesiveness, and adhesion of a cured product. It has excellent durability and is particularly useful for dental bonding materials.

Organophosphate compound (I) of the present invention
First, each symbol used in the general formula (1) will be described.

R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may be aliphatic or aromatic, and may be saturated or unsaturated. Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylaryl group, an aryl group. Examples thereof include an alkyl group, an alkylarylalkyl group, and an alkenylaryl group.

  The alkyl group may be linear, branched or cyclic, and examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptanyl group N-octyl group, 2-ethylhexyl group, cyclooctanyl group, n-nonyl group, cyclononanyl group, n-decyl group and the like.

  The alkenyl group may be linear, branched or cyclic, and examples thereof include vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, A cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, etc. are mentioned.

  The alkynyl group may be linear, branched or cyclic, and examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group and 1-methyl-2-propynyl group. 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-ethyl-2-propynyl group, 2-pentynyl group, 3-pentynyl group, 1-methyl-2-butynyl group, 4-pentynyl group, 1 -Methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 2-hexynyl group, 1-ethyl-2-butynyl group, 3-hexynyl group, 1-methyl-2-pentynyl group, Examples include 1-methyl-3-pentynyl group, 4-methyl-1-pentynyl group, 3-methyl-1-pentynyl group, 5-hexynyl group, 1-ethyl-3-butynyl group and the like.

  Examples of the aryl group include phenyl group, naphthyl group, anthryl group, phenanthryl group and the like.

  Examples of the alkylaryl group include an aryl group substituted with a lower alkyl group (particularly an alkyl group having 1 to 6 carbon atoms), specifically, a methylphenyl group, an ethylphenyl group, a butylphenyl group, Examples thereof include a dimethylphenyl group, a dibutylphenyl group, and a methylnaphthyl group.

  Examples of the arylalkyl group include a lower alkyl group (particularly an alkyl group having 1 to 6 carbon atoms) substituted with an aryl group, and specific examples include a benzyl group.

  Examples of the alkylarylalkyl group include a lower alkyl group (particularly an alkyl group having 1 to 6 carbon atoms) having an aryl group substituted with a lower alkyl group (particularly an alkyl group having 1 to 6 carbon atoms) as a substituent. Specifically, a methylbenzyl group and the like can be mentioned.

  Examples of the alkenylaryl group include an aryl group substituted with a lower alkenyl group (particularly an alkenyl group having 1 to 6 carbon atoms), and specific examples include a styryl group and an allylphenyl group.

R ₁ and R ₂ are preferably hydrogen atoms from the viewpoint of the polymerizability of the vinyl group bonded thereto. R ₃ is preferably a hydrogen atom or a methyl group from the viewpoint of the polymerizability of the bonded vinyl group, and is irritating to the living body when the polymerizable site of compound (I) is eliminated by hydrolysis or the like. From the viewpoint, a methyl group is more preferable.

  A represents one selected from the group consisting of —COO—, —OCO—, and —O—. From the viewpoint of the polymerizability of the vinyl group bonded, the viewpoint of the ease of production of the compound (I). Therefore, -COO- is more preferable.

R ₄ represents a hydrocarbon group having 5 to 30 carbon atoms and may be branched. The hydrocarbon group as R ₄ may be either a saturated hydrocarbon or an unsaturated hydrocarbon.

R ₄ is preferably a saturated hydrocarbon group having 5 to 30 carbon atoms.

R ₅ and R ₆ each independently represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a metal atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ₅ and R ₆ are the same as those described for R _{1 to} R ₃ . The number and type of substituents that the hydrocarbon group having 1 to 20 carbon atoms represented by R ₅ and R ₆ may have are not particularly limited as long as the object of the present invention is not impaired. Amino group, hydroxyl group, alkoxy group, amide group, acyl group, acyloxy group, halogen atom, cyano group, nitro group and the like. 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 (I), 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.

  X represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable from the viewpoint of ease of production of the compound (I).

  m is an integer of 2-6. When the compound (I) has m, that is, a plurality of polymerizable groups, the mechanical strength and adhesiveness of the cured product of the polymerizable composition containing the compound (I) are increased. m is preferably an integer of 2 to 4, more preferably 2 or 3, and most preferably 2 from the viewpoint of ease of production of the compound (I).

Two phosphoric acid group or phosphoric acid ester group linked to R ₄ [-O-P (X) (OR 5) (OR 6) ] are each, 5 to 30 carbon atoms in R ₄ It is bonded to R ₄ at a distance. According to the knowledge of the present inventors, the number of carbon atoms in R ₄ between two phosphate groups or phosphate ester groups is 1 to 4 or 31 or more, compared with an organic phosphate compound. An organophosphate compound having 5 to 30 carbon atoms can exhibit more excellent mechanical strength, adhesive strength, and adhesion durability. From the viewpoint of further improving mechanical strength, adhesive strength, and adhesion durability, the number of carbon atoms in R ₄ between two phosphate groups or phosphate ester groups is more preferably 9-21, 21 is more preferable.

  Compound (I) preferably has a structure represented by the following general formula (2).

In the formula, R ₇ and R ₈ each independently represent a hydrogen atom or a methyl group, R ₉ and R ₁₀ each independently represent a hydrocarbon group having 1 to 4 carbon atoms, R ₁₁ and R ₁₂ each independently represents a hydrocarbon group having 2 to 10 carbon atoms. R ₉ and R ₁₀ preferably have 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. R ₁₁ and R ₁₂ preferably have 4 to 10 carbon atoms, more preferably 6 to 10 carbon atoms. From the viewpoint of molecular alignment, the carbon number of R _{11 and} the carbon number of R ₁₂ are preferably approximated. It is considered that the bonding efficiency of the dental bonding material using the polymerizable composition containing the compound (I) represented by the general formula (2) can be improved by aligning the molecules. The difference between the carbon number of R _{11 and} the carbon number of R ₁₂ is preferably 1 to 5, and more preferably the carbon number of R _{11 and} the carbon number of R ₁₂ are the same.

  Compound (I) of the present invention can be produced by combining known methods. As an example, first, a compound represented by the following general formula (3) and a compound represented by the following general formula (4) are reacted to obtain a compound represented by the following general formula (5).

In the formula, R _{1 to} R ₄ , A, and m are as defined above, Z ¹ is a functional group capable of reacting with Z ² , and Z ² is a functional group capable of reacting with Z ¹ . Further, the two hydroxyl groups attached to R _4, corresponding to two phosphate groups or phosphate ester groups of the compounds of the present invention (I), together, 5 to 30 carbons in R ₄ Bonded to R ₄ with atoms separated.

The functional group Z ¹ and the functional group Z ² are selected so that one kind of bond selected from the group consisting of —COO—, —OCO—, and —O— is generated by these reactions. The functional groups Z ¹ and Z ² that generate these bonds and their reaction methods are well known to those skilled in the art. For example, in the case of forming a —COO— bond, as Z ¹ , —COOH, —COOR ′ (R ′ represents an aliphatic hydrocarbon group) or —COCl is selected, and —OH is selected as Z ^2. Then, the esterification reaction may be carried out according to a known method. For example, in the case of forming an —O— bond, an etherification reaction (Williamson synthesis) may be performed with ^one of Z ¹ and Z ² as a halogen atom and the other as —ONa. The hydroxyl group of the compound represented by the general formula (4) is protected with a protecting group, if necessary, then reacted with the compound represented by the general formula (3), and deprotected to give a compound of the general formula (5) You can also get

Subsequently, the compound represented by the general formula (1) can be obtained by reacting the compound represented by the general formula (5) with POCl ₃ or PSCl ₃ , followed by hydrolysis or alcoholysis. . When R ₅ and R ₆ are metal atoms, the compound represented by the general formula (1) in which R ₅ and R ₆ are hydrogen atoms may be converted into a metal salt.

Hereinafter, the reaction for generating a —COO— bond will be described in detail. As the reaction for forming a —COO— bond, a carboxylic acid compound in which Z ¹ is —COOH in the general formula (3) and Z ^{2 in the} general formula (4) in the presence of an esterification catalyst, if necessary, is —OH. In the presence of a catalyst, Z ¹ is —COOR ′ (wherein R ′ has the same meaning as described above). The ester compound of general formula (4) and a hydroxyl group-containing compound in which Z ² is —OH (hereinafter referred to as esterification method (b)), and optionally a base. In the presence of a reactive compound, a method of reacting an acid chloride compound in which Z ¹ is —COCl in general formula (3) and a hydroxyl group-containing compound in which Z ² is —OH in general formula (4) (hereinafter referred to as esterification method) (Referred to as (c)).

Hereinafter, the esterification method (a) will be described in detail. In the compound of the general formula (4) used as a raw material and Z ² is —OH, it is desirable that the other hydroxyl group of Z ² is protected by a protecting group. The protecting group is not particularly limited as long as it can withstand the esterification reaction conditions, and examples thereof include an allyl group and a benzyl group. Although Z ¹ in the general formula (3) is not particularly limited to the use of as the raw material carboxylic acid compound is -COOH, Z ² of the formula (4) Z ² are included in the hydroxyl group-containing compound is -OH Usually, it is preferably in the range of 0.8 to 30 times mol with respect to the group, and more preferably in the range of 1 to 20 times mol from the viewpoint of reaction rate and volumetric efficiency. However, this is not the case when a carboxylic acid compound in which Z ¹ is —COOH in the general formula (3) is used as a solvent.

The esterification process (a) can be carried out in the presence or absence of a solvent. Such a solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether And ethers such as diethylene glycol dimethyl ether and tetrahydrofuran. These may be used individually by 1 type, and may use 2 or more types together. When a solvent is used, the amount used is not particularly limited, but is usually in the range of 0.5 to 20 times the weight of the hydroxyl group-containing compound in which Z ² is —OH in the general formula (4) of the raw material. It is preferable to be in the range of 1 to 5 times weight from the viewpoint of volume efficiency.

  In the esterification method (a), water is by-produced as the reaction proceeds, and the reaction reaches an equilibrium state. Therefore, from the viewpoint of improving the yield of the target ester compound, it is preferable to carry out the reaction while removing such water from the reaction system. The method for removing water from the reaction system is not particularly limited. For example, a method of coexisting a solvent azeotropic with water and azeotropically with the solvent to remove water from the reaction system is preferable. Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane. Further, by-product water may be removed by allowing a dehydrating agent that does not adversely influence the reaction such as molecular sieve to coexist in the reaction system.

Examples of acids used in the esterification method (a) include mineral acids such as sulfuric acid and hydrochloric acid; organic acids such as p-toluenesulfonic acid and methanesulfonic acid; aluminum triisopropoxide, titanium acetylacetonate, and vanadium acetylacetate. Lewis acids such as nate; heteropolyacids such as silicomolybdic acid and phosphotungstic acid; solid acids such as silica, silica-alumina, activated clay, and acidic ion exchange resin. Among these, it is preferable to use an organic acid or a mineral acid from the viewpoint of allowing the reaction to proceed smoothly. There is no particular limitation on the amount of acid used, relative to the hydroxyl group-containing compound Z ² is -OH with a raw material of the general formula (4), usually in the range of 0.0001 wt%, preferably From the viewpoint of reaction rate, side reaction, and suppression of product coloring, it is more preferably in the range of 0.001 to 20% by weight.

  The esterification method (a) is preferably carried out in the presence of a polymerization inhibitor. Examples of such polymerization inhibitors include hydroquinones such as hydroquinone, hydroquinone monomethyl ether and 2,5-di-t-butylhydroquinone; quinones such as p-benzoquinone; naphthols such as α-naphthol and β-naphthol; And catechols such as 3,5-di-t-butylcatechol; pyrogallols such as pyrogallol and phenylethyl pyrogallol; and anisole such as 2,6-di-t-butylanisole. These may be used individually by 1 type, and may use 2 or more types together.

  In the esterification method (a), the reaction temperature is usually preferably in the range of 20 to 300 ° C, more preferably in the range of 60 to 200 ° C. The esterification method (a) can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen or argon. Furthermore, the esterification method (a) may be carried out under atmospheric pressure or under reduced pressure.

  After completion of the reaction, depending on the acid used, the reaction mixture is appropriately washed with an aqueous solution of a basic substance such as an aqueous sodium hydroxide solution or an aqueous sodium hydrogen carbonate solution to remove the acid, or solid by filtration, decantation, etc. After removing the acid, it is concentrated and purified by ordinary purification means such as recrystallization, distillation, column chromatography, etc. to separate and obtain the target ester compound in which A is —COO— in the general formula (5). can do. When a protecting group is introduced into the compound represented by the general formula (4) and subjected to an esterification reaction, after the deprotection under known conditions, the above operation is performed, whereby A is represented by the general formula (5). The ester compound which is —COO— can be separated and obtained.

Next, the esterification method (b) will be described. In the ester compound in which Z ¹ is —COOR ′ (wherein R ′ is as defined above) in the general formula (3) used in the esterification method (b), examples of R ′ include a methyl group, Examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like. Among these, a methyl group or an ethyl group is preferable.

In the compound of the general formula (4) used in the esterification method (b) and Z ² is —OH, it is desirable that the other hydroxyl group of Z ² is protected with a protecting group. The protecting group is not particularly limited as long as it can withstand the esterification reaction conditions, and examples thereof include an allyl group and a benzyl group.

Formula (3) Z ¹ is -COOR '(wherein, R' has the same meaning as defined above) is not particularly limited on the amount of the ester compound is, in general formula (4) Z ² is -OH In general, it is preferably in the range of 0.8 to 40 times mol with respect to the Z ² group contained in the hydroxyl group-containing compound, and from the viewpoint of reaction rate, it is more preferably in the range of 1 to 30 times mol. preferable.

The esterification method (b) can be carried out in the presence or absence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether And ethers such as diethylene glycol dimethyl ether and tetrahydrofuran. These may be used individually by 1 type, and may use 2 or more types together. When a solvent is used, the amount used is not particularly limited, but it is usually preferably 0.5 to 20 times the weight with respect to the hydroxyl group-containing compound in which Z ² is —OH in the general formula (4). From the viewpoint of volumetric efficiency, the weight is more preferably 1 to 5 times.

In the esterification method (b), as the reaction proceeds, the R ′ moiety of the ester compound in which Z ¹ is —COOR ′ (wherein R ′ is as defined above) in the general formula (3) used When, for example, R ′ is a methyl group, methanol is by-produced and the reaction is in an equilibrium state. Therefore, from the viewpoint of improving the yield of the target ester compound, it is preferable to carry out the reaction while removing the alcohol from the reaction system. Examples of the method for removing alcohol from the reaction system include a method of using a solvent azeotropic with the by-produced alcohol and performing the reaction while distilling the alcohol out of the reaction system by azeotropic distillation.

  Examples of the catalyst used in the esterification method (b) include mineral acids such as sulfuric acid and hydrochloric acid; salts of mineral acids such as sodium hydrogen sulfate, sodium monohydrogen phosphate and potassium dihydrogen phosphate; methanesulfonic acid, p- Organic acids such as toluenesulfonic acid; salts of organic acids such as pyridinium p-toluenesulfonate; organotin compounds such as dibutyltin oxide, dibutyltin dilaurate, dibutyltin dioctylate, dibutyltin di (2-ethylhexanoate), dibutyltin oxide; Lewis acids such as aluminum triisopropoxide, titanium acetylacetonate, vanadium acetylacetonate; heteropolyacids such as silicomolybdic acid and phosphotungstic acid; solid acids such as silica, silica-alumina, activated clay, and acidic ion exchange resin ;sodium Alkali metal alkoxides such as toxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide; alkali metal or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, calcium hydroxide; sodium carbonate, carbonic acid Examples thereof include alkali metal carbonates or hydrogen carbonates such as sodium hydrogen; alkali metal acetates such as sodium acetate and potassium acetate. Among these, it is preferable to use a mineral acid, an organic acid, or an organic tin compound from the viewpoint of reaction rate and suppression of side reactions.

The amount of the catalyst used is usually preferably in the range of 0.0001 to 40% by weight with respect to the hydroxyl group-containing compound in which Z ² is —OH in the general formula (4), and the reaction rate and side reaction are suppressed. And from a viewpoint of coloring suppression of a product, it is more preferable that it is the range of 0.001 to 20 weight%.

  The esterification method (b) is preferably carried out in the presence of a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone, hydroquinone monomethyl ether and 2,5-di-t-butylhydroquinone; quinones such as p-benzoquinone; naphthols such as α-naphthol and β-naphthol; Catechols such as 3,5-di-t-butylcatechol; pyrogallols such as pyrogallol and phenylethylpyrogalol; anisole such as 2,6-di-t-butylanisole; p-hydroxydiphenylamine, phenothiazine, diethylhydroxylamine And the like; N-oxyls such as 2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl . These may be used individually by 1 type, and may use 2 or more types together. However, when an acid is used as a catalyst, it is preferable to use a polymerization inhibitor other than amines and N-oxyls.

  In the esterification method (b), the reaction temperature is usually preferably in the range of 20 to 300 ° C, more preferably in the range of 60 to 200 ° C. The esterification method (b) can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen or argon. Furthermore, the esterification method (b) may be carried out under atmospheric pressure or under reduced pressure.

  After completion of the reaction, depending on the catalyst used, it is washed with an aqueous solution of a basic substance such as an aqueous sodium hydroxide solution or an aqueous sodium hydrogen carbonate solution or an aqueous solution of an acidic substance such as sulfuric acid or hydrochloric acid, or by filtration or decantation. After removing the components, it is concentrated, and purified by ordinary purification means such as recrystallization, distillation, column chromatography, etc., thereby separating and obtaining the target ester compound of the general formula (5) where A is —COO—. can do. When a protecting group is introduced into the compound represented by the general formula (4) and subjected to an esterification reaction, after the deprotection under known conditions, the above operation is performed, whereby A is represented by the general formula (5). The ester compound which is —COO— can be separated and obtained.

Next, the esterification method (c) will be described. In the compound of the general formula (4) used in the esterification method (b) and Z ² is —OH, it is desirable that the other hydroxyl group of Z ² is protected with a protecting group. The protecting group is not particularly limited as long as it can withstand the esterification reaction conditions, and examples thereof include an allyl group, a benzyl group, a methoxymethyl group, a t-butyldimethylsilyl group, and a tetrahydropyranyl group.

Although Z ¹ in the general formula (3) is not particularly limited on the amount of acid chloride compound is -COCl, Z ² group to which the general formula (4) Z ² are included in the hydroxyl group-containing compound is -OH In general, it is preferably in the range of 0.8 to 20 times mol, and more preferably in the range of 1 to 10 times mol from the viewpoint of yield and volume efficiency.

The esterification process (c) can be carried out in the presence or absence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether , Ethers such as diethylene glycol dimethyl ether and tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, pyridine, 4-dimethylaminopyridine, quinoline, triethylamine, trimethylamine, etc. Nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane. These may be used individually by 1 type, and may use 2 or more types together. When a solvent is used, the amount used is not particularly limited, but it is usually preferably 0.5 to 200 times the weight with respect to the hydroxyl group-containing compound in which Z ² is —OH in the general formula (4). From the viewpoint of volumetric efficiency, the weight is more preferably 1 to 100 times.

The esterification method (c) can be carried out in the presence or absence of a basic compound. Basic compounds include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-dimethylaminopyridine, 2,6- Dimethylpyridine, 2,4,6-trimethylpyridine, quinoline, isoquinoline, 1,8-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, lithium carbonate Sodium carbonate, potassium carbonate, sodium hydrogen carbonate sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc., among these, triethylamine, pyridine, - dimethylaminopyridine are preferred. No particular limitation is imposed on the amount of the basic compound but with respect to Z ² groups in the general formula (4) Z ² are included in the hydroxyl group-containing compound is -OH, it is 0.8 to 20 times mole Preferably, it is 1-10 times mole. These basic compounds may be used alone or in admixture of two or more. Moreover, you may use these basic compounds as a solvent.

  The esterification method (c) is preferably carried out in the presence of a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone, hydroquinone monomethyl ether and 2,5-di-t-butylhydroquinone; quinones such as p-benzoquinone; naphthols such as α-naphthol and β-naphthol; Catechols such as 3,5-di-t-butylcatechol; pyrogallols such as pyrogallol and phenylethylpyrogalol; anisole such as 2,6-di-t-butylanisole; p-hydroxydiphenylamine, phenothiazine, diethylhydroxylamine And the like; N-oxyls such as 2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl . These may be used individually by 1 type, and may use 2 or more types together.

  In the esterification method (c), the reaction temperature is usually preferably in the range of −40 to 100 ° C., more preferably in the range of −20 to 60 ° C.

  After completion of the reaction, the ester compound in which A is —COO— in the general formula (5) is liberated from the base addition salt of the ester compound in which A is —COO— in the general formula (5) by acid treatment, and organic After extracting with a solvent and concentrating the resulting solution, the solution is purified by ordinary purification means such as recrystallization, distillation, column chromatography, etc., whereby A is -COO- in the general formula (5). An ester compound can be obtained separately. When a protecting group is introduced into the compound represented by the general formula (4) and subjected to an esterification reaction, after the deprotection under known conditions, the above operation is performed, whereby A is represented by the general formula (5). The ester compound which is —COO— can be separated and obtained.

Next, a method for obtaining the compound represented by the general formula (1) by reacting the compound represented by the general formula (5) with POCl ₃ and further hydrolyzing it will be described.

The amount of POCl ₃ used is not particularly limited, but is preferably 1.6 to 6.0 times mol and more preferably 2.0 to 3.0 times mol for the compound represented by the general formula (5). .

In the reaction between the compound represented by the general formula (5) and POCl ₃ , a basic compound can be used as necessary. Examples of the basic compound include nitrogen-containing compounds such as triethylamine, tri-n-butylamine, and pyridine. The amount of basic compound is not particularly limited, 1.0 to 5.0 moles preferably against POCl _3.

The reaction of the compound represented by the general formula (5) and POCl ₃ can be carried out in the presence or absence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether , Ethers such as diethylene glycol dimethyl ether and tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, pyridine, 4-dimethylaminopyridine, quinoline, triethylamine, trimethylamine, etc. Nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane. These may be used individually by 1 type, and may use 2 or more types together. When using a solvent, the amount used is not particularly limited, but it is usually preferably in the range of 0.5 to 200 times the weight of the compound represented by the general formula (5). From the viewpoint, it is more preferably in the range of 0.5 to 100 times weight.

The reaction temperature in the reaction between the compound represented by the general formula (5) and POCl ₃ is usually preferably in the range of −50 to 50 ° C., more preferably in the range of −40 to 20 ° C.

  After completion of the reaction, hydrolysis can be performed by adding water to the reaction solution to obtain the compound represented by the general formula (1).

  Although the amount of water used is not particularly limited, it is usually preferably in the range of 3.6 to 20 moles compared to the compound represented by the general formula (5).

  In the hydrolysis reaction, a basic compound can be used as necessary. Although a basic compound is not specifically limited, Nitrogen-containing compounds, such as a triethylamine, a tri n-butylamine, and a pyridine, are mentioned. It is preferable that the usage-amount of a basic compound is the range of 4.0-10 times mole with respect to the compound represented by General formula (5).

  In general, the reaction temperature in the hydrolysis reaction is preferably in the range of −40 to 100 ° C., and more preferably in the range of −30 to 50 ° C.

  After completion of the reaction, the target phosphoric acid ester compound represented by general formula (1) is liberated from the base addition salt of the phosphoric acid ester compound represented by general formula (1) by acid treatment and extracted with an organic solvent. And the compound represented by General formula (1) can be obtained by concentrating the obtained solution.

  The present invention is also a polymerizable composition containing compound (I). The polymerizable composition containing the compound (I) is excellent in the mechanical strength (particularly bending strength), adhesiveness and adhesion durability of the cured product, and is particularly useful in dental applications. In dental use, the compound (I) has an acid etching effect (decalcification action), and the polymerizable composition containing the compound (I) has excellent adhesion to the tooth.

  The polymerizable composition containing the compound (I) includes a polymerizable monomer (II) copolymerizable with the compound (I) as a polymerizable monomer different from the compound (I), and a polymerization initiator (III). , Polymerization accelerator (IV), filler (V), solvent (VI) and the like may be included.

  The compounding amount of the compound (I) is preferably 1 to 80 parts by weight and more preferably 3 to 50 parts by weight in 100 parts by weight of the total amount of the polymerizable monomer components. When the compounding amount of compound (I) is less than 1 part by weight, there is a possibility that the effect of improving adhesiveness and adhesion durability cannot be obtained sufficiently. On the other hand, when the compounding amount of compound (I) is more than 80 parts by weight, the permeability is lowered, and there is a possibility that the effect of improving adhesiveness cannot be obtained sufficiently.

Polymerizable monomer (II)
The polymerizable monomer (II) copolymerizable with the compound (I) includes a polymerizable monomer (II-a) having no acidic group and having one polymerizable group, and acidic Examples thereof include a polymerizable monomer (II-b) having no group and having two or more polymerizable groups. As the polymerizable monomer (II), a (meth) acrylate compound and a (meth) acrylamide compound are preferable and a (meth) acrylate compound is more preferable from the viewpoint of reactivity and safety to living bodies.

  In the polymerizable monomer (II-a) having no acidic group and having one polymerizable group, the acidic group is a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group. It means an acid group, a sulfonic acid group and the like. The polymerizable monomer (II-a) promotes the penetration of the components of the dental bonding material into the tooth, and also penetrates the tooth itself and contributes to the improvement of the adhesiveness.

  The polymerizable monomer (II-a) having no acidic group and having one polymerizable group can be used alone or in combination of two or more. Examples of the polymerizable monomer (II-a) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N , N- (dihydroxyethyl) (meth) acrylamide, N-acryloylmorpholine, etc., among these, 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of improving the penetration of dentin into the collagen layer. 3-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N- acryloyl morpholine is preferable, particularly preferably 2-hydroxyethyl methacrylate.

  The polymerizable monomer (II-b) having no acidic group and having two or more polymerizable groups improves the mechanical strength, handleability and the like of the dental composition. In the polymerizable monomer (II-b), the acidic group has the same meaning as described above.

  The polymerizable monomer (II-b) having no acidic group and having two or more polymerizable groups can be used alone or in combination of two or more. Although it does not specifically limit as a polymerizable monomer (II-b) which does not have an acidic group and has two or more polymerizable groups, An aromatic compound type bifunctional polymerizable monomer, fat Group compound-based bifunctional polymerizable monomers, trifunctional or higher functional polymerizable monomers, and the like.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “BisGMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane), 2,2-bis (4- (Meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaeth Cyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) ) Propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) 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) acryloyl Kishiechiru) pyromellitate and the like.

  Examples of aliphatic compound-based bifunctional polymerizable 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, glycerin di (meth) acrylate, pentaerythritol 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 and 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), and the like.

  Examples of trifunctional or higher polymerizable monomers include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) Examples include bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate and 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

  Compound (I) has an acid etching effect, but may be used in combination with a polymerizable monomer (II-c) having an acidic group other than compound (I). The polymerizable monomer having an acidic group (II-c) has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, and a sulfonic acid group, In addition, a polymerizable monomer having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, and a styrene group can be used.

  Specific examples of (II-c) include the following.

  Examples of the polymerizable monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, and 20- (meth) acryloyloxyeicosyl. Dihydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl phosphate, 2- (meth) acryloyloxyethyl 2′-bromoethyl phosphorus Acids, (meth) acryloyloxyethyl phenylphosphonates, and acid chlorides thereof.

  Examples of the polymerizable monomer having a pyrophosphate group include di (2- (meth) acryloyloxyethyl) pyrophosphate and acid chlorides thereof. Examples of the polymerizable monomer having a thiophosphate group include 2- (meth) acryloyloxyethyl dihydrogen dithiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate, and acid chlorides thereof. .

  Examples of the polymerizable monomer having a carboxylic acid group include 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic anhydride, and 5- (meth) acryloylaminopentylcarboxylic acid. Acids, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, and acid chlorides thereof.

  Examples of the polymerizable monomer having a sulfonic acid group include compounds containing a sulfonic acid group such as 2- (meth) acrylamide-2-methylpropanesulfonic acid and styrenesulfonic acid.

  In the present invention, the total amount of the polymerizable monomer component means compound (I), polymerizable monomer (II-a), polymerizable monomer (II-b), polymerizable monomer (II -C) and the total amount of other polymerizable monomers copolymerizable therewith.

Polymerization initiator (III)
The polymerization initiator (III) used in the present invention can be selected from polymerization initiators used in the general industry, and among them, polymerization initiators used for dental applications are preferably used. In particular, polymerization initiators for photopolymerization and chemical polymerization are used singly or in appropriate combination of two or more.

  Photopolymerization initiators include (bis) acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α- Examples include amino ketone compounds.

  Among the (bis) acylphosphine oxides used as the photopolymerization initiator, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2 , 6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine 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, and bis (2,6-dichloro). Benzoyl) -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) phenylphosphine oxide, ( And 5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

  Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Particularly preferred are phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide sodium salt.

  Examples of thioxanthones or quaternary ammonium salts of thioxanthones used as the photopolymerization initiator 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-trime Ru-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 厶 salt of thioxanthones is 2 -Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of ketals used as the photopolymerization initiator include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the α-diketone used as the photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′- Examples thereof include oxybenzyl and acenaphthenequinone. 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 used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 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′-carbonylbiscuc Marine, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl Nzo [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-nitrobe) Zoyl) 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-methoxy) Coumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3 -(2-Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethi Ruamino) 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. Compounds described in 3109 JP or Hei 10-245525 discloses the like.

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

  Examples of the anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1 -Hydroxyanthraquinone and the like.

  Examples of benzoin alkyl ethers used as the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of α-aminoketones used as the photopolymerization initiator 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, a polymerizable composition having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

  Of the polymerization initiator (III) 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 used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

  Examples of the hydroperoxide used as the chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1, 1,3,3-tetramethylbutyl hydroperoxide and the like.

  Examples of the diacyl peroxide used as the chemical polymerization initiator include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 2,4-dichlorobenzoyl. Examples thereof include peroxide and lauroyl peroxide.

  Examples of the dialkyl peroxide used as the chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like.

  Examples of the peroxyketal used as the chemical polymerization initiator 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, etc. Can be mentioned.

  Peroxyesters used as the chemical polymerization initiator include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentyl. Peroxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Examples include butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. It is done.

  Examples of the peroxydicarbonate used as the chemical polymerization initiator include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples include peroxydicarbonate, di-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 among them, benzoyl peroxide is particularly preferably used.

  The blending amount of the polymerization initiator (III) used in the present invention is not particularly limited, but from the viewpoint of the curability of the resulting composition, the polymerization is initiated with respect to 100 parts by weight of the total amount of the polymerizable monomer components. It is preferable to contain 0.001-30 weight part of agents (III). When the blending amount of the polymerization initiator (III) is less than 0.001 part by weight, the polymerization does not proceed sufficiently and there is a risk of causing a decrease in adhesive strength, and the blending amount of the polymerization initiator (III) is more preferably Is 0.05 parts by weight or more. On the other hand, when the amount of the polymerization initiator (III) exceeds 30 parts by weight, if the polymerization performance of the polymerization initiator itself is low, there is a risk that sufficient adhesive strength may not be obtained. Since it may cause precipitation, the blending amount of the polymerization initiator (III) is more preferably 20 parts by weight or less.

Polymerization accelerator (IV)
The composition of the present invention preferably contains a polymerization accelerator (IV). The polymerization accelerator (IV) used in the present invention includes amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiols. Compound, sulfite, bisulfite, thiourea compound and the like can be mentioned.

  The amines used as the polymerization accelerator (IV) 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-methylethanolamine; 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 Amine and the like. 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 its salt used as the polymerization accelerator (IV) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluenesulfine. Acid calcium, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, Potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylben Sulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid Lithium, calcium 2,4,6-triisopropylbenzenesulfinate, and the like. Sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable. .

  The borate compound used as the polymerization accelerator (IV) 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.

  Further, as borate compounds having two aryl groups in one molecule, dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron Dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitrophenyl) ) 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. .

  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 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 used as the polymerization accelerator (IV) include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, and 5-butyl. Barbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric 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-cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl -1-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, 5-methyl barbituric acid, 5-propyl barbituric acid, 1,5-diethyl barbituric acid, 1-ethyl-5-methylbarbi Tool 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 (Especially alkali metals or alkaline earth metals are preferred) Examples of the salt of barbituric acid include sodium 5-butyl barbiturate, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate.

  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 used as the polymerization accelerator (IV) 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 (trichloromethyl) ) -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-to Lyazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) 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} ethoxy] -4 3,6-Bis (trichloromethyl) -s-triazine, 2- [2- {N, N- diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

  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 the copper compound used as the polymerization accelerator (IV), for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound used as the polymerization accelerator (IV) include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. It is done. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compounds used as the polymerization accelerator (IV) are preferably IV and / or V valent vanadium compounds. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium oxide 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 used as the polymerization accelerator (IV) include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like. Are preferably used.

  Examples of aldehydes used as the polymerization accelerator (IV) 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 used as the polymerization accelerator (IV) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Examples of the sulfite used as the polymerization accelerator (IV) include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite.

  Examples of the bisulfite used as the polymerization accelerator (IV) include sodium bisulfite and potassium bisulfite.

  As the thiourea compound used as the polymerization accelerator (IV), 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′— Diethylthiourea, N, N′-di-n-propylthiourea, N, N′-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthio Examples include urea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like.

  The blending amount of the polymerization accelerator (IV) used in the present invention is not particularly limited, but from the viewpoint of curability of the resulting composition, polymerization is accelerated with respect to 100 parts by weight of the total amount of the polymerizable monomer components. It is preferable to contain 0.001-30 weight part of agent (IV). When the blending amount of the polymerization accelerator (IV) is less than 0.001 part by weight, the polymerization does not proceed sufficiently and there is a possibility that the adhesive strength is lowered, and more preferably 0.05 part by weight or more. On the other hand, if the blending amount of the polymerization accelerator (IV) exceeds 30 parts by weight, if the polymerization performance of the polymerization initiator itself is low, there is a possibility that sufficient adhesive strength cannot be obtained, and further from the composition. Since it may cause precipitation, the amount is more preferably 20 parts by weight or less.

Filler (V)
Depending on the embodiment, it is preferable to further add a filler (V) to the polymerizable composition of the present invention. Such fillers are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene. Chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. These may be used alone or in combination of two or more. Can be used as a mixture. 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 size of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and glass ceramic. , Aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. . 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 having excellent surface lubricity can be obtained when the polymerizable composition of the present invention is used as a dental composite resin. Here, the spherical filler is a photo of the filler taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded, in a direction perpendicular to the maximum diameter. A filler having an average uniformity obtained by dividing the particle diameter by the maximum diameter is 0.6 or more. 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 adding a monomer compound to the above-mentioned inorganic filler in advance, 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 property 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 filler (V) used for this invention is not specifically limited, 1-2000 weight part of filler (V) is preferable with respect to 100 weight part of whole quantity of a polymerizable monomer component. Since the suitable compounding amount of the filler (V) varies greatly depending on the embodiment to be used, in addition to the description of specific embodiments of the polymerizable composition of the present invention described later, the filler ( A suitable blending amount of V) will be shown.

Solvent (VI)
The polymerizable composition of the present invention preferably contains a solvent (VI) depending on its specific embodiment. Examples of the solvent include water, organic solvents, and mixed solvents thereof.

  When the polymerizable composition of the present invention contains water, it exhibits excellent adhesive strength as well as excellent adhesive strength. As content of water, 6-2000 weight part is preferable with respect to 100 weight part of whole quantity of a polymerizable monomer component. When the water content is less than 6 parts by weight, demineralization of the tooth surface becomes insufficient and the adhesive strength is lowered. On the other hand, when the water content exceeds 2000 parts by weight, the polymerizability of the monomer is lowered, the adhesive strength is lowered and the adhesion durability is lowered. The water content is more preferably 7 parts by weight or more, and still more preferably 10 parts by weight or more. The water content is more preferably 1500 parts by weight or less. It is preferable that the water does not contain impurities that have an adverse effect, and distilled water or ion exchange water is preferable.

  Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, diisopropyl ether, hexane, toluene, chloroform, ethyl acetate, Examples include butyl acetate. Among these, the organic solvent is preferably a water-soluble organic solvent in consideration of both safety to the living body and ease of removal based on volatility. Specifically, ethanol, 2-propanol, 2 -Methyl-2-propanol, acetone, and tetrahydrofuran are preferably used. The content of the organic solvent is not particularly limited, and some embodiments do not require blending of the organic solvent. In the embodiment using the organic solvent, it is preferable to contain 1 to 2000 parts by weight of the organic solvent with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Since the suitable compounding amount of the solvent (VI) varies greatly depending on the embodiment to be used, in addition to the description of the specific embodiments of the polymerizable composition of the present invention described later, the solvent according to each embodiment A suitable blending amount will be shown.

  In addition, the polymerizable composition of the present invention is blended with a pH adjuster, 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.

  The polymerizable composition of the present invention is suitably used as a dental composition. The dental composition can be used for dental materials such as primers, bonding materials, composite resins, cements (resin cements, resin reinforced glass ionomer cements), pit fissure filling materials, denture base resins, and the like. Among them, it can be suitably used as a dental bonding material. At this time, you may use as a 2 agent type | mold which divided the component of the polymeric composition into two.

  The dental material adhesion system consists of a decalcification process in which the dentin surface is dissolved with an acidic component, a permeation process in which the monomer component penetrates into the dentin collagen layer, and a hybrid layer (resin impregnated layer) in which the penetrated monomer component is solidified ) To form a curing step.

Dental bonding material The product used in the above curing process is a dental bonding material. A dental bonding material is obtained by replacing a part or all of a polymerizable monomer containing an acidic group with a compound (I) of a known dental bonding material containing a polymerizable monomer containing an acidic group. Can be configured. Examples of the composition of the dental bonding material include 1 to 40 parts by weight of the compound (I) and 0 to 60 parts by weight of the polymerizable monomer (II-a) in 100 parts by weight of the total amount of the polymerizable monomer components. , And 5 to 99 parts by weight of the polymerizable monomer (II-b), preferably 1 to 30 parts by weight of the compound (I), 0 to 50 parts by weight of the polymerizable monomer (II-a), And 20-99 weight part of polymerizable monomers (II-b) are mix | blended. And it is preferable to contain 0.001-30 weight part of polymerization initiator (III) and 0.001-30 weight part of polymerization accelerators (IV) with respect to 100 weight part of whole quantity of a polymerizable monomer component, More preferably, it contains 0.05 to 20 parts by weight of initiator (III) and 0.05 to 20 parts by weight of polymerization accelerator (IV). Moreover, it is preferable that 0-30 weight part of filler (V) is included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and it is more preferable that 0-15 weight part is included. Moreover, although solvent (VI) may be used, it is more preferable not to contain substantially. A part of the compound (I) may be a polymerizable monomer (II-c) having an acidic group.

  In recent years, a one-step type dental bonding material in which an infiltration process, a decalcification process, and a curing process are performed in one step has been developed. Further, dental bonding materials are divided into a two-component type in which two components are mixed immediately before use, and a one-component type in which one component can be used as it is, but at present one-component type is the mainstream. Since the compound (I) has a decalcifying action and a hardening action, a one-step one-pack type dental bonding material can be constituted by the polymerizable composition of the present invention.

  As an example of the composition of the one-step one-component dental bonding material, 1 to 40 parts by weight of the compound (I), polymerizable monomer (II- a) 0 to 80 parts by weight and 5 to 99 parts by weight of the polymerizable monomer (II-b) are blended, preferably 3 to 30 parts by weight of the compound (I), the polymerizable monomer (II-a 10-60 parts by weight and 10-60 parts by weight of the polymerizable monomer (II-b). And it is preferable to contain 0.001-30 weight part of polymerization initiator (III) and 0.001-30 weight part of polymerization accelerators (IV) with respect to 100 weight part of whole quantity of a polymerizable monomer component, More preferably, it contains 0.05 to 20 parts by weight of initiator (III) and 0.05 to 20 parts by weight of polymerization accelerator (IV). Moreover, it is preferable that 0-30 weight part of filler (V) is included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and it is more preferable that 0-15 weight part is included. Moreover, it is preferable that 6-2000 weight part of solvent (VI) is included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and it is more preferable that 7-1000 weight part is included. A part of the compound (I) may be a polymerizable monomer (II-c) having an acidic group.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. Abbreviations used below are as follows.

[Acid monomer]
A-1:

  A-2:

A-3: 10-methacryloyloxydecyl dihydrogen phosphate A-4:

  A-5:

[Polymerizable monomer having no acidic group and having one polymerizable group]
HEMA: 2-hydroxyethyl methacrylate [polymerizable monomer having no acidic group and having two or more polymerizable groups]
BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane [photopolymerization initiator]
BAPO: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide CQ: d1-camphorquinone [polymerization accelerator]
JA: ethyl N, N-dimethylaminobenzoate DEPT: diethanol-p-toluidine [inorganic filler]
Inorganic filler 1: Nippon Aerosil Co., Ltd. “R972”
[Polymerization inhibitor]
BHT: Dibutylhydroxytoluene

[Synthesis of Compound (I)]
<Example 1 (synthesis of A-1)>
[Synthesis of 9,9-bis (methacryloyloxymethyl) -1,17 heptadecanediol]
After dissolving 5.11 g (24.4 mmol) of 8-bromo-1-octanol in 125 ml of dichloromethane under a nitrogen atmosphere, 2.00 g (29.4 mmol) of imidazole and tert-butyldimethylsilyl chloride (TBSCl) 4 at room temperature. .05 g (26.9 mmol) was added and stirred for 2 hours, and the disappearance of the raw materials was confirmed by thin film chromatography (TLC). After the reaction system was cooled to 0 ° C., water was added to stop the reaction. Next, the organic layer obtained by extraction with dichloromethane was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Next, after sodium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 7.57 g (23.4 mmol) of intermediate compound A in a yield of 96%.

  Sodium hydride (545 mg, 60% in oil, 13.6 mmol) was suspended in DMF (30 ml) at room temperature under a nitrogen atmosphere. After the reaction system was cooled to 0 ° C., 500 mg (0.530 ml, 3.12 mmol) of diethyl malonate was added dropwise and stirred until no hydrogen was generated. Thus, Solution A was obtained. In a separate flask, 4.00 g (12.4 mmol) of intermediate compound A was weighed and dissolved in 30 ml of DMF to obtain solution B. The obtained solution B was added dropwise to the flask containing the solution A at room temperature, and the mixture was stirred for 3 hours while maintaining the temperature at 60 ° C. to 80 ° C., and the completion of the reaction was confirmed by TLC. After the reaction system was cooled to room temperature, water was added to stop the reaction, and extraction with diethyl ether was performed. The organic layer obtained by this extraction was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. Next, after sodium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 3.79 g (5.88 mmol) of intermediate compound B in a yield of 95%.

  A suspension of 1.37 g (36.1 mmol) of lithium aluminum hydride in tetrahydrofuran (100 ml) under a nitrogen atmosphere and a solution of 1.81 g (2.80 mmol) of the intermediate compound B in 50 ml of tetrahydrofuran at room temperature. It was dripped at the liquid. Then, the mixture was stirred for 2 hours, and disappearance of raw materials was confirmed by TLC. After the reaction system was cooled to 0 ° C., 1.37 ml of water, 1.37 ml of a 15% aqueous sodium hydroxide solution and 4.11 ml of water were added in this order to stop the reaction. The resulting solid powder was removed by celite filtration and washed with ethyl acetate. In this case, it was confirmed that no product was detected from the washing solution. The solid powder thus obtained was washed with saturated saline and then dried over anhydrous sodium sulfate. Next, after sodium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.39 g (2.35 mmol) of intermediate compound C in a yield of 84%.

  Intermediate compound C 1.30 g (2.21 mmol) was dissolved in 160 ml of dichloromethane under a nitrogen atmosphere and cooled to 0 ° C., then 1.15 g (1.58 ml, 11.4 mmol) of triethylamine, DMAP (N, N-dimethyl-4 -Aminopyridine) (amount of catalyst: about 10 mg) and 0.98 g (0.92 ml, 9.4 mmol) of methacryl chloride were added and stirred for 1 hour, and disappearance of the raw materials was confirmed by TLC. Next, water was added to stop the reaction, and extraction with dichloromethane was performed. The organic layer obtained by this extraction was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. Next, after sodium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.42 g (1.96 mmol) of intermediate compound D in a yield of 85%.

  Intermediate compound D (1.13 g, 1.56 mmol) was dissolved in tetrahydrofuran (8 ml) at room temperature under a nitrogen atmosphere, and then TBAF (tetra-n-butylammonium fluoride) (1.0 M solution in THF (tetrahydrofuran)) 1 .80 ml (1.80 mmol) was added dropwise and the mixture was stirred for 4 hours. After confirming the disappearance of the raw material by TLC, water was added to stop the reaction. Next, the organic layer obtained by extraction with diethyl ether was washed with water and saturated brine, and dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.720 g (1.46 mmol) of 9,9-bis (methacryloyloxymethyl) -1,17 heptadecanediol in a yield of 94%.

  After 299 mg (0.60 mmol) of 9,9-bis (methacryloyloxymethyl) -1,17heptadecanediol obtained as described above was dissolved in 5 ml of diethyl ether at room temperature under a nitrogen atmosphere, 260 mg of triethylamine was obtained. (2.57 mmol) was added. In this way, Solution C was prepared. Separately, 240 mg (1.57 mmol) of phosphorus oxychloride placed in a three-necked flask was dissolved in diethyl ether under a nitrogen atmosphere, and then the temperature inside the three-necked flask was cooled to −5 ° C. Solution C was dropped into the three-necked flask with a syringe and washed with 5 ml of diethyl ether once. At that time, the temperature inside the three-necked flask was not allowed to exceed 0 ° C. Stirring was continued for 3 hours while raising the temperature of the reaction solution to room temperature, and disappearance of the raw material was confirmed by TLC. At this time, a large amount of ammonium salt was produced.

The reaction solution was cooled again to 0 ° C., and further 5 ml of acetone cooled to 0 ° C. was added to stir the contents, and then stirring was stopped to precipitate an ammonium salt. In this way, Solution D was prepared. In another flask, 10 ml of water and 10 ml of acetone were placed and cooled to 0 ° C., and then the supernatant of solution D was added dropwise with a syringe. At that time, the next drop was added after the reaction solution became homogeneous, and the ammonium salt was not transferred. Washing was performed three times with acetone (5 ml) cooled to 0 ° C. Also in this case, it was dripped as described above. After confirming the disappearance of the components in the solution D by TLC, the reaction solution was transferred to a separatory funnel and washed three times with 30 ml of hexane. Extraction was performed 4 times with a mixture of hexane and ethyl acetate (volume ratio of hexane and ethyl acetate is 1: 4), and then the organic layer collected by extraction was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the solvent was distilled off under reduced pressure to obtain A-1 (HPLC (high performance liquid chromatography) purity 99%, yield 86%). The ¹ H-NMR data of A-1 obtained are shown below.

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 1.269-1.334 (m, 14H), 1.615-1.62 (m, 4H), 1.933 (s, 6H), 3 994-4.064 (m, 2H), 4.151-4.198 (m, 1H), 4.286-4.324 (m, 1H), 5.170-5.228 (m, 1H) 5,567 (s, 2H), 6.096 (s, 2H).

<Example 2 (synthesis of A-2)>
A-2 (HPLC purity 99%, yield 55%) was obtained by carrying out the reaction and purification in the same manner as in Example 1 except that 8-bromo-1-octanol was replaced with 2-bromo-1-ethanol. . The ¹ H-NMR data of A-2 obtained are shown below.

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 1.269-1.334 (m, 14H), 1.615-1.62 (m, 4H), 1.933 (s, 6H), 3 994-4.064 (m, 2H), 4.151-4.198 (m, 1H), 4.286-4.324 (m, 1H), 5.170-5.228 (m, 1H) 5,567 (s, 2H), 6.096 (s, 2H).

[Preparation of one-part dental composition]
<Example 3>
The following components were mixed at room temperature to prepare a one-part dental bonding material composition that is a one-part dental composition, and the three-point bending strength of the cured product was measured. The obtained results are shown in Table 1.
One-part dental bonding material composition:
A-1 10 parts by weight BisGMA 30 parts by weight HEMA 30 parts by weight CQ 2 parts by weight JJA 1 part by weight BAPO 1 part by weight DEPT 1 part by weight BHT 0.05 part by weight Inorganic filler 6 parts by weight

[Bending strength evaluation method]
After the paste is filled into a stainless steel mold (dimensions 2 mm x 2 mm x 25 mm), the top and bottom are pressed with a slide glass, and 2 each from both sides with a dental irradiator (Morita Manufacturing Co., Ltd., Alpha Light II). It was cured by irradiating light for 1 minute. About each Example and the comparative example, 5 hardened | cured material was produced for every one, and after taking out from the metal mold | die, the hardened | cured material was stored in 37 degreeC distilled water for 24 hours. Moreover, evaluation after storing hardened | cured material in 70 degreeC for 10 days was also implemented as a durability test.

  Using a universal testing machine (manufactured by Shimadzu Corporation), the bending strength was measured under the conditions of span: 20 mm, crosshead speed: 1 mm / min, and the average value of the measured values of each test piece was calculated. It was.

<Example 4>
In Example 3, instead of using 10 parts by weight of the acidic monomer “A-1”, a polymerizable composition was prepared in the same manner as in Example 3 except that 10 parts by weight of “A-2” was used. Three-point bending strength was measured. The obtained results are shown in Table 1.

<Comparative Example 1>
In Example 3, instead of using 10 parts by weight of the acidic monomer “A-1”, a polymerizable composition was prepared in the same manner as in Example 2 except that 10 parts by weight of “A-3” was used. Three-point bending strength was measured. The obtained results are shown in Table 1.

<Comparative example 2>
In Example 3, instead of using 10 parts by weight of the acidic monomer “A-1”, a polymerizable composition was prepared in the same manner as in Example 2 except that 10 parts by weight of “A-4” was used. Three-point bending strength was measured. The obtained results are shown in Table 1.

<Comparative Example 3>
In Example 3, instead of using 10 parts by weight of the acidic monomer “A-1”, a polymerizable composition was prepared in the same manner as in Example 2 except that 10 parts by weight of “A-5” was used. Three-point bending strength was measured. The obtained results are shown in Table 1.

  From the results of Examples 3 and 4 and Comparative Example 1, the compound of the present invention has an effect of increasing the mechanical strength of the cured product of the polymerizable composition as compared with Compound A-3 which has been widely used conventionally. You can see that it is bigger. From the results of Examples 3 and 4 and Comparative Examples 2 and 3, the compound of the present invention was compared with the compound A-4 or A-5 having a plurality of known polymerizable groups. It can be seen that the effect of increasing the mechanical strength is greater.

[Preparation of one-part dental composition]
<Example 5>
The following components were mixed at room temperature to prepare a one-component dental bonding material composition which is a one-component dental composition, and the adhesive strength and adhesion durability with bovine dentin were evaluated.
One-part dental bonding material composition:
A-1 5 parts by weight BisGMA 30 parts by weight HEMA 30 parts by weight CQ 2 parts by weight JJA 1 part by weight BAPO 1 part by weight DEPT 1 part by weight BHT 0.05 part by weight Inorganic filler 1 6 parts by weight Water 15 parts by weight Ethanol 15 parts by weight

[Adhesion with bovine enamel and durability evaluation method]
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. Each of the obtained samples 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 one-part dental bonding material composition was applied to the round hole using a brush, left for 10 seconds, and then air-blowed on the surface to apply the applied one-part dental bonding material composition. Dry until free of fluidity. Next, the applied one-part dental bonding material composition was cured by irradiating light for 10 seconds with a dental visible light irradiator “Pencure 2000” (Morita Manufacturing Co., Ltd.).

  A composite resin for dental filling (trade name “Clearfill AP-X” (registered trademark) manufactured by Kuraray Medical Co., Ltd.) is applied to the surface of the cured product of the obtained one-component dental bonding material composition, and then released. Covered with a film (polyester). 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 for 20 seconds using the irradiator “Pencure 2000” 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 (manufactured by Kuraray Medical Co., Ltd., trade name “Panavia 21”) 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. In addition to the above operation, an adhesion durability test sample was prepared by applying a thermal cycle load of immersing 4000 times alternately in a water bath at 4 ° C. and a water bath at 60 ° C. for 1 minute each.

[Measurement of adhesive strength]
Tensile bond strengths of the above five adhesion test samples and adhesion durability test samples were measured with a universal testing machine (manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm / min, and averaged. The value was taken as the tensile bond strength. The obtained results are summarized in Table 2.

<Example 6>
In Example 5, instead of using 5 parts by weight of the acidic monomer “A-1”, a one-part dental bonding material composition as in Example 5 except that 5 parts by weight of “A-2” was used. Articles were prepared and evaluated for adhesion strength and adhesion durability with bovine enamel. The obtained results are summarized in Table 2.

<Comparative Example 4>
In Example 5, instead of using 5 parts by weight of “A-1” which is an acidic monomer, the same composition as in Example 5 except that 10 parts by weight of “A-3” was used. Articles were prepared and evaluated for adhesion strength and adhesion durability with bovine enamel. The obtained results are summarized in Table 2.

<Comparative Example 5>
In Example 5, instead of using 5 parts by weight of "A-1" which is an acidic monomer, the same composition as in Example 5 except that 10 parts by weight of "A-4" was used. Articles were prepared and evaluated for adhesion strength and adhesion durability with bovine enamel. The obtained results are summarized in Table 2.

<Comparative Example 6>
In Example 5, instead of using 5 parts by weight of the acidic monomer “A-1”, the same composition as in Example 5 except that 10 parts by weight of “A-5” was used. Articles were prepared and evaluated for adhesion strength and adhesion durability with bovine enamel. The obtained results are summarized in Table 2.

  From the results of Examples 5 and 6 and Comparative Example 4, the compound of the present invention was compared with the conventionally used compound A-3. It can be seen that the effect of increasing the adhesion and adhesion durability is greater. From the results of Examples 5 and 6 and Comparative Examples 5 and 6, the compound of the present invention is a cured product of the polymerizable composition as compared with Compound A-4 or Compound A-5 having a plurality of known polymerizable groups. It can be seen that the effect of increasing the adhesion and adhesion durability is greater.

  The polymerizable composition containing the novel organophosphate compound of the present invention can be used for various applications requiring high mechanical strength and strong adhesiveness, and is particularly useful for dental applications.

Claims (8)

Compound (I) represented by the following general formula (1)

(Wherein R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ₄ represents a hydrocarbon group having 5 to 30 carbon atoms, R ₅ And R ₆ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a metal atom, and A represents —COO—, —OCO—, and —O—. X represents an oxygen atom or a sulfur atom, m represents an integer of 2 to 6, and two phosphate groups or phosphate ester groups [—O—P (X) (OR ₅₎ (OR _6)] are each other at a 5 to 30 carbon atoms in R ₄ linked to R _4.) R ₁ and R ₂ are hydrogen atoms, R ₃ is a hydrogen atom or a methyl group, R ₄ is a hydrocarbon group having 5 to 30 carbon atoms, and R ₅ and R ₆ are each independently a hydrogen atom. Or it is a C1-C6 hydrocarbon group, A is -COO-, m is 2, The compound (I) of Claim 1. The compound (I) according to claim 1 represented by the following general formula (2).

(Wherein R ₇ and R ₈ each independently represent a hydrogen atom or a methyl group, R ₉ and R ₁₀ each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and R ₁₁ and R ₁₂ are Each represents a hydrocarbon group having 2 to 10 carbon atoms.)   The polymeric composition containing the compound (I) of any one of Claims 1-3.   The polymerizable composition according to claim 4, further comprising a polymerizable monomer (II) other than the compound (I), which is copolymerizable with the compound (I).   The polymerizable composition according to claim 5, wherein the polymerizable monomer (II) is a (meth) acrylate compound.   The polymerizable composition according to any one of claims 4 to 6, further comprising a polymerization initiator (III).   A dental bonding material using the polymerizable composition according to any one of claims 4 to 7.