JP5416456B2 - Phosphate ester compound and polymerizable composition containing the same - Google Patents

Description

  The present invention relates to a novel phosphoric ester compound particularly useful for dental materials, and a polymerizable composition containing the same.

A dental adhesive is usually used when filling or coating a restoration in a tooth defect. As a dental adhesive, one containing a compound having a polymerizable group and a phosphate group is known, and various compounds have been proposed as the compound (for example, see Patent Documents 1 to 3). Among them, 10-methacryloyloxydecyl dihydrogen phosphate (hereinafter referred to as A-2) expresses excellent adhesiveness to the tooth substance and expresses excellent adhesion durability in a moist environment of the oral cavity. It has been reported (see Patent Document 2). In recent years, with the aim of improving adhesion, the following general formula

The compound (henceforth A-3) which has a several polymeric group shown by is proposed (refer patent document 3).

JP-A-57-151607 JP 58-21607 A Special Table 2002-544148

  After being applied to the oral cavity, the dental material is subjected to high bite pressure or frictional force due to a toothbrush. Therefore, high mechanical strength is required for dental materials. According to the study by the present inventors, it was found that there is room for improvement in the mechanical strength of the dental material using Compound A-2 described in Patent Document 2. The dental material using the compound part A-3 described in Patent Document 3 also has a room for improvement although it is expected to improve mechanical strength because it has a plurality of polymerizable groups.

  Therefore, an object of the present invention is to provide a phosphate ester compound that can impart excellent mechanical strength when applied to a dental material. Another object of the present invention is to provide a polymerizable composition suitable for dental materials and capable of giving a cured product having high mechanical strength.

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

(Wherein, R ^1, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, R ⁴ is a good 5 to 20 carbon atoms which may have a substituent Represents an organic group, 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. -, - CONH -, - OCO -, - O -, - S -, - CH 2 O -, - CH 2 S -, - C 6 H 4 O -, - C 6 H 4 CONH -, - C 6 H _{4 NHCO -, - C 6 H} 4 COO -, - C 6 H 4 OCO-, and represents one species selected from the group consisting of -CONHCO-, at least one bond to a secondary carbon of (a) X represents an oxygen atom or a sulfur atom, and m represents an integer of 2 to 6.)

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. (A) is preferably —COO— or —CONH—. It is preferable that m is 2 and R ⁴ is an aliphatic hydrocarbon group having 5 to 20 carbon atoms.

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

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a metal atom, and R ⁷ and R ⁸ are respectively Independently represents a hydrogen atom or a methyl group, R ⁹ represents an aliphatic hydrocarbon having 1 to 16 carbon atoms which may have a substituent, and R ¹⁰ represents 3 to 3 carbon atoms which may have a substituent. 18 represents an aliphatic hydrocarbon group, and the total number of carbon atoms of R ⁹ and R ¹⁰ is 19 or less, and (B) and (C) each independently represent —COO— or —CONH—. , X represents an oxygen atom or a sulfur atom.)

  The present invention is also a polymerizable composition containing the compound (I). The polymerizable composition preferably further contains a polymerizable monomer (II) copolymerizable with the compound (I) other than 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 is suitable for dental use, and can be suitably used as a primer, a bonding material, a composite resin, or a cement.

  According to the present invention, a novel phosphate ester compound (I) is provided, and the polymerizable composition containing the compound (I) is excellent in the mechanical strength (particularly bending strength) of the cured product, and in particular for dental use. Useful for (dental primer, bonding material, composite resin, cement, etc.).

Phosphate ester 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 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may be aliphatic or aromatic, and saturated. Alternatively, it may be unsaturated, and examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylaryl group, an arylalkyl 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) is —COO—, —CONH—, —OCO—, —O—, —S—, —CH ₂ O—, —CH ₂ S—, —C ₆ H ₄ O—, —C ₆ H _{4. CONH -, - C 6 H 4} NHCO -, - C 6 H 4 COO -, - C 6 H 4 OCO-, and represents one species selected from the group consisting of -CONHCO-, bonded to the vinyl group and From the viewpoint of polymerizability, —COO— or CONH— is preferable, and —COO— is more preferable from the viewpoint of ease of production of the compound (I).

R ⁴ represents an organic group having 5 to 20 carbon atoms which may have a substituent, and is an m + 1 valent group. The organic group may be aliphatic or aromatic and may be saturated or unsaturated. Moreover, you may branch. The organic group is not limited to a hydrocarbon, and a carbonyl carbon, an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be inserted into the main chain of the hydrocarbon. Examples include a group obtained by removing m + 1 hydrogen atoms from a saturated aliphatic hydrocarbon, unsaturated aliphatic hydrocarbon, or aromatic hydrocarbon.

The number and type of substituents possessed by the organic group represented by R ⁴ are not particularly limited as long as the purpose of the present invention is not impaired. Examples of the substituents include amino groups, hydroxyl groups, alkoxy groups, amide groups, acyl groups. , Acyloxy group, halogen atom, cyano group, nitro group and the like.

R ⁴ is preferably an aliphatic hydrocarbon group having 5 to 20 carbon atoms, and the aliphatic hydrocarbon group is more preferably a trivalent group.

At least one of (A) is bonded to the secondary carbon of R ⁴ . That is, at least one structure in which one hydrogen atom of the —CH ₂ — group (the bond is bonded to a carbon atom) is substituted with (A) at the R ⁴ site in the general formula (1). There are two. Since at least one of (A) is bonded to the secondary carbon, at least one polymerizable site is bonded to the secondary carbon. Since the polymerizable site bonded to the secondary carbon is more limited in rotation than the polymerizable site bonded to the primary carbon, the polymerizable site and the structure in the vicinity thereof are relatively rigid. Is considered to contribute to improving the mechanical strength of the cured product of the polymerizable composition containing the compound (I).

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. 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 of the cured product of the polymerizable composition containing the compound (I) is increased. m is preferably an integer of 2 to 4, more preferably 2 or 3, and most preferably 2 in terms of ease of production of the compound (I).

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

In the formula, R ⁵ and R ⁶ , and X are as defined above. R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, R ⁹ represents an optionally substituted aliphatic hydrocarbon having 1 to 16 carbon atoms, and R ¹⁰ has a substituent. Represents an aliphatic hydrocarbon group having 3 to 18 carbon atoms, and the total number of carbon atoms of R ⁹ and R ¹⁰ is 19 or less, and (B) and (C) are each independently —COO. -Or -CONH- is represented. The substituent that R ⁹ and R ¹⁰ may have is the same as the substituent that R ⁴ may have. R ⁹ preferably has 1 to 9 carbon atoms, more preferably 1 to 3 carbon atoms. R ¹⁰ preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms. R ⁹ and R ¹⁰ are preferably saturated aliphatic hydrocarbon groups. (B) and (C) are preferably —COO—.

  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 .

The functional group Z ¹ and the functional group Z ² are converted into —COO—, —CONH—, —OCO—, —O—, —S—, —CH ₂ O—, —CH ₂ S—, —C ₆ by these reactions. _{H 4 O -, - C 6} H 4 CONH -, - C 6 H 4 NHCO -, - C 6 H 4 COO -, - C 6 H 4 OCO-, and one selected from the group consisting of -CONHCO- Is selected to produce a bond. 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 a —CONH— bond, —COOH is selected as Z ¹ , —NH ₂ is selected as Z ² , and a dehydration condensation reaction may be performed 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. Further, for example, in the case of forming an —S— bond, ^one of Z ¹ and Z ² may be a halogen atom and the other may be —SH, and a coupling reaction may be performed under alkaline conditions. 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.

Although there is no restriction | limiting in particular in the usage-amount of the ester compound whose Z < ¹ > is -COOR '(In formula, R' is synonymous with the above) in General formula (3), Z < ² > is -OH in General formula (4). 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 0.8 to 3.0 times mol and more preferably 1.0 to 1.5 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 1.8 to 10 moles relative 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 2.0-5 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 polymerizable composition containing the compound (I) is excellent in the mechanical strength (particularly bending strength) of the cured product, and is particularly useful in dental applications. In dental applications, the compound (I) further has an acid etching effect (decalcification action).

  Therefore, the present invention is also a polymerizable composition containing compound (I). The polymerizable composition may contain a polymerizable monomer (II) copolymerizable with the compound (I) as a polymerizable monomer different from the compound (I). Other components suitable for the polymerizable composition include polymerization initiator (III), polymerization accelerator (IV), filler (V), solvent (VI) and the like.

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 And 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 penetration of the components of the dental adhesive into the tooth, and also permeates into the tooth and adheres to the organic component (collagen) in the tooth.

  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 and handleability 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. The polymerizable monomer (II-b) having no acidic group and having two or more polymerizable groups is not particularly limited, but an aromatic compound-based 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.

  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.

  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 alone or in combination of two or more.

  Photopolymerization initiators include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyls Examples include ether compounds and α-aminoketone 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, benzoyldi -(2,6-dimethylphenyl) phosphonate and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

  The water-soluble acylphosphine oxides used as the photopolymerization initiator preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion, or ammonium ion in the acylphosphine oxide molecule. For example, water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

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

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

  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. 3109 JP, compounds described in JP-A-10-245525 can be cited.

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

  Examples of 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 benzoyl peroxide is particularly preferably used among them.

  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 agent (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 possibility that the adhesive strength is lowered, and more preferably 0.05 part 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 amount 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.

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

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

  Examples of the halogen compound 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 particle diameter in a direction perpendicular to the maximum diameter, in which a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded. Is a filler having an average homogeneity of 0.6 or more divided by its maximum diameter. The average particle diameter of the spherical filler is preferably 0.1 to 5 μm. When the average particle size is less than 0.1 μm, the filling rate of the spherical filler in the composition is lowered, and the mechanical strength may be lowered. On the other hand, when the average particle diameter exceeds 5 μm, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.

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

  The organic-inorganic composite filler used in the present invention is obtained by 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 primer, a bonding material, a composite resin, or a cement. At this time, you may use as a 2 agent type | mold which divided the component of the polymeric composition into two.

Dental primer The adhesive system for dental materials includes a demineralization process where the dentin surface is dissolved with an acidic component, a permeation process where the monomer component penetrates into the collagen layer of the dentin, A curing step of forming a resin impregnated layer). Basically, the product used in the infiltration process is a primer. As a primer, there is also a self-etching primer that performs the deashing step and the permeation step in one step in recent years, and since the compound (I) has a deashing effect, the polymerizable composition of the present invention has a permeation effect. A self-etching primer can be formed by using the polymerizable monomer (II-a).

  The primer can be constituted by replacing a part or all of the polymerizable monomer containing an acidic group with a compound (I) of a known primer containing a polymerizable monomer containing an acidic group. . Examples of the primer composition include 1 to 50 parts by weight of compound (I), 5 to 99 parts by weight of polymerizable monomer (II-a), and polymerization in 100 parts by weight of the total amount of polymerizable monomer components. 0 to 60 parts by weight of the polymerizable monomer (II-b), preferably 1 to 40 parts by weight of the compound (I), 10 to 99 parts by weight of the polymerizable monomer (II-a), and polymerizable 0 to 50 parts by weight of monomer (II-b) is 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 6-3500 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 7-2000 weight part is included. A part of the compound (I) may be a polymerizable monomer (II-c) having an acidic group.

Dental bonding material The product used in the above curing process is a bonding material. The bonding material is constituted by replacing a part or all of the polymerizable monomer containing an acidic group with a compound (I) of a known bonding material containing a polymerizable monomer containing an acidic group. Can do. Examples of the composition of the bonding material include 1 to 40 parts by weight of the compound (I), 0 to 60 parts by weight of the polymerizable monomer (II-a), and 100 parts by weight of the total amount of the polymerizable monomer components. 5 to 99 parts by weight of the polymerizable monomer (II-b) is blended, preferably 1 to 30 parts by weight of the compound (I), 0 to 50 parts by weight of the polymerizable monomer (II-a), and polymerization 20 to 99 parts by weight of the polymerizable monomer (II-b) is 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 bonding material has been developed in which an infiltration process, a decalcification process, and a curing process are performed in one step. The bonding material is 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 compound (I) has a decalcification action and a hardening action, a one-step one-component 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 bonding material, 1 to 40 parts by weight of the compound (I), the polymerizable monomer (II-a) in 100 parts by weight of the total amount of the polymerizable monomer component 0 to 80 parts by weight and 5 to 99 parts by weight of the polymerizable monomer (II-b) are blended, and preferably 3 to 30 parts by weight of the compound (I) and the polymerizable monomer (II-a) 10 -60 parts by weight and 10-60 parts by weight of the polymerizable monomer (II-b) are 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, 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.

Dental composite resin A composite resin is a dental material that is usually used in a form in which a cavity is formed after cutting a carious site and forming a cavity. The composite resin is required to have high mechanical strength. However, since the compound (I) has a plurality of polymerizable groups, the composite resin using the polymerizable composition of the present invention should have high mechanical strength. Can do. Further, since the compound (I) has a decalcifying action and a curing action, a self-adhesive composite resin can be constituted by the polymerizable composition of the present invention.

  The composite resin is constituted by replacing a part or all of the polymerizable monomer containing an acidic group of the known composite resin containing a polymerizable monomer containing an acidic group with the compound (I). Can do. Examples of the composition of the composite resin include 1 to 40 parts by weight of the compound (I), 0 to 80 parts by weight of the polymerizable monomer (II-a), and 100 parts by weight of the total amount of the polymerizable monomer components. 10 to 99 parts by weight of polymerizable monomer (II-b) is blended, preferably 3 to 30 parts by weight of compound (I), 10 to 70 parts by weight of polymerizable monomer (II-a), and polymerization 20 to 87 parts by weight of the polymerizable monomer (II-b) is 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 to contain 50-3000 weight part of filler (V) with respect to 100 weight part of whole quantity of a polymerizable monomer component, and it is more preferable to contain 80-2000 weight part. 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.

Dental cement Dental cement is a dental material that is usually used as a bonding material for fixing a dental restoration material made of metal or ceramic called an inlay or crown to a tooth. Although high mechanical strength is required for cement, since compound (I) has a plurality of polymerizable groups, high mechanical strength can be imparted to cement using the polymerizable composition of the present invention. . Further, since the compound (I) has a decalcifying action and a hardening action, a self-adhesive cement can be constituted by the polymerizable composition of the present invention. Examples of the cement include a resin cement and a resin reinforced glass ionomer cement.

The cement can be constituted by replacing a part or all of the polymerizable monomer containing an acidic group with a compound (I) of a known cement containing a polymerizable monomer containing an acidic group. . As an example of the composition of the resin cement, 2 to 50 parts by weight of the compound (I), 0 to 60 parts by weight of the polymerizable monomer (II-a), and 100 parts by weight of the total amount of the polymerizable monomer component, and 10 to 98 parts by weight of polymerizable monomer (II-b) is blended, preferably 2 to 40 parts by weight of compound (I), 0 to 50 parts by weight of polymerizable monomer (II-a), and polymerization 20 to 98 parts by weight of the polymerizable monomer (II-b) is 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 50-2000 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 80-1000 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 the resin cement, it is preferable to use a chemical polymerization initiator as the polymerization initiator (III), and it is preferable to use amines and / or sulfinic acid and salts thereof as the polymerization accelerator (IV). In the resin cement, from the viewpoint of storage stability, it is preferable that the compound (I), the polymerization initiator (III), and the polymerization accelerator (IV) are of a two-part type in which they are stored in separate containers.

  The glass ionomer cement is typically one in which an inorganic filler such as fluoroaluminosilicate glass and a polyalkenoic acid such as polyacrylic acid react and harden by an acid-base reaction. And it is thought that an adhesive function expresses when the said polyalkenoic acid and calcium in the hydroxyapatite which comprises a tooth | gear interact. Examples of the composition of the glass ionomer cement include 2 to 50 parts by weight of the compound (I), 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 10 to 98 parts by weight of the polymerizable monomer (II-b), preferably 2 to 40 parts by weight of the compound (I), 0 to 50 parts by weight of the polymerizable monomer (II-a), and 20 to 98 parts by weight of the polymerizable monomer (II-b) is 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 10-200 weight part of polyalkenoic acid and 50-500 weight part of fluoro aluminosilicate glass are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, 10-100 weight part of polyalkenoic acid, and fluoro More preferably, it contains 80 to 400 parts by weight of aluminosilicate glass. Moreover, 0 to 2000 parts by weight, preferably 10 to 1000 parts by weight of filler (V) other than fluoroaluminosilicate glass may be added. Moreover, it is preferable that 1-500 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 10-50 weight part is included. A part of the compound (I) may be a polymerizable monomer (II-c) having an acidic group.

  In the glass ionomer cement, from the viewpoint of storage stability, it is preferable that the polyalkenoic acid and the fluoroaluminosilicate glass are of a two-part type in which they are stored in separate containers. Moreover, it is preferable to store the polymerization initiator (III) and the polymerization accelerator (IV) in separate containers.

  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: 10-methacryloyloxydecyl dihydrogen phosphate A-3:

[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 [photoinitiator]
TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [inorganic filler]
Inorganic filler 1: Nippon Aerosil "R972"

[Synthesis of Compound (I)]
<Example 1 (synthesis of A-1)>
[Synthesis of 1-methoxymethyl-10-undecenyl ether]
In a three-necked flask, 10.0 g (58.7 mmol) of 10-undecen-1-ol, 100 ml of methylene chloride, and 37.9 g (293.6 mmol) of diisopropylethylamine were substituted with nitrogen. While stirring at 0 ° C., 23.6 g (293.6 mmol) of chloromethyl methyl ether was added dropwise over 10 minutes. After completion of dropping, stirring was continued for 6 hours. After completion of the reaction, 50 ml of distilled water was added and extracted with methylene chloride. The obtained organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain an oily substance. The obtained oily substance was purified by silica gel column chromatography (developing solution; n-hexane / ethyl acetate = 10/1), and 11.2 g of 1-methoxymethyl-10-undecenyl ether (HPLC purity 99) as an oily substance. 2%, 51.8 mmol, 88% yield).

[Synthesis of 11-methoxymethylundecane-1,2-diol]
To a three-necked flask, 11.2 g of 1-methoxymethyl-10-undecenyl ether obtained above, 200 ml of acetone, 2.4 g of tetraethylammonium acetate, and 8.3 g of 90% by weight of t-butyl hydroperoxide were added. And stirred at room temperature for 30 minutes. Subsequently, a solution prepared by dissolving 0.03 g of osmium tetroxide in 6 ml of t-butanol was added while stirring at 0 ° C., and the mixture was stirred at 0 ° C. for 2 hours and at room temperature for 12 hours. After adding 300 ml of diethyl ether, a 10% aqueous sodium hydrogen sulfite solution was added while stirring at 0 ° C. until no peroxide was detected. Sodium chloride was added to the resulting solution to separate it into two liquids, and the aqueous phase was extracted with diethyl ether. The organic layers were combined and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a highly viscous oily substance. The obtained oily substance was purified by silica gel column chromatography (developing solution; n-hexane / ethyl acetate = 3/1), and 9.9 g of 11-methoxymethylundecane-1,2-diol as a waxy substance ( HPLC purity 97.0%, 38.8 mmol, yield 75%) was obtained.

[Synthesis of 10,11-dimethacryloyloxyundecan-1-ol]
In a three-necked flask, 5.0 g (19.5 mmol) of 11-methoxymethylundecane-1,2-diol, 9.9 g (97.6 mmol) of triethylamine, 20 mg of N, N-dimethyl-4-aminopyridine, hydroquinone monomethyl ether 5 mg and 50 ml of dimethylformamide were taken and purged with nitrogen. While stirring at 0 ° C., 6.1 g (58.6 mmol) of methacrylic acid chloride was added dropwise over 30 minutes. After completion of the dropwise addition, stirring was continued for 6 hours at room temperature, then adjusted to pH 1 with 6N hydrochloric acid, and stirring was continued for 2 hours at room temperature. The obtained reaction solution was extracted with diethyl ether, the organic layer was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain an oily substance. The obtained oily substance was purified by silica gel column chromatography (developing solution: n-hexane / ethyl acetate = 5/1) to give 4.2 g of 10,11-dimethacryloyloxyundecan-1-ol as an oily substance ( 12.3 mmol, HPLC purity 98.8%, yield 63%).

[Synthesis of A-1]
In a three-necked flask purged with nitrogen, 1.62 g (10.6 mmol) of phosphorus oxychloride and 5 ml of diethyl ether were taken. While stirring at −40 ° C., 3.0 g (8.8 mmol) of 1,2-dimethacryloyloxyundecan-1-ol prepared in a separate container in advance, 5 ml of diethyl ether, 1.09 g (10.6 mmol) of triethylamine The mixture was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at −40 ° C. for 30 minutes, −20 ° C. for 1 hour, 0 ° C. for 4 hours, and room temperature for 3 hours. After completion of stirring, the mixture was cooled to 0 ° C., and 0.5 g of water was added dropwise over 3 minutes. Next, a mixed solution of 1.78 g (17.6 mmol) of triethylamine prepared in a separate container in advance, 3 mg of hydroquinone monomethyl ether and 5 ml of diethyl ether was added dropwise over 10 minutes. After completion of dropping, the mixture was stirred at 0 ° C. for 12 hours. After completion of the stirring, the pH was adjusted to 1 with 1N hydrochloric acid and extracted with diethyl ether. The organic layer was washed with 50 ml of distilled water. The solvent was distilled off from the organic layer under reduced pressure to obtain 3.8 g of an oily substance (HPLC purity 95.6%, 8.6 mmol, yield 98%). The ¹ H-NMR data of the obtained compound A-1 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 2>
The following components were mixed at room temperature to prepare a one-component bonding material composition, which is a one-component dental composition, and the three-point bending strength of the cured product was measured. The obtained results are shown in Table 1.
One-component bonding material composition:
A-1 10 parts by weight BisGMA 30 parts by weight HEMA 30 parts by weight TMDPO 3 parts by weight Inorganic filler 1 5 parts by weight

[Bending strength evaluation method]
After filling the paste into a stainless steel mold (dimensions 2 mm x 2 mm x 25 mm), press the top and bottom with glass slides, and light for 2 minutes each from both sides with a dental laboratory light irradiator (Morita, Alpha Light II) Was cured by irradiation. 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. As a durability test, evaluation after storage in distilled water at 50 ° C. for 2 weeks was also conducted.

  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.

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

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

  From the results of Example 2 and Comparative Example 1, it can be seen that the compound of the present invention is superior in mechanical strength as compared with Compound A-2 which has been widely used conventionally. From the results of Example 2 and Comparative Example 2, it can be seen that the compound of the present invention is superior in mechanical strength as compared with Compound A-3 having a plurality of known polymerizable groups.

  The polymerizable composition containing the novel phosphate ester compound of the present invention can be used for various applications that require mechanical strength, and is particularly useful for dental applications.

Claims (6)

Compound (I) represented by the following general formula (2).

(In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁹ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms. , R ¹⁰ represents an aliphatic hydrocarbon group having 3 to 12 carbon atoms, (B) and (C) represent —COO—, and X represents an oxygen atom.) The R ⁷ and R ⁸ are methyl groups, R ⁹ is a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ¹⁰ is a saturated aliphatic hydrocarbon group having 9 carbon atoms. Compound (I).   A polymerizable composition comprising the compound (I) according to claim 1 or 2.   The polymerizable composition according to claim 3, further comprising a polymerizable monomer (II) copolymerizable with the compound (I) other than the compound (I).   The polymerizable composition according to claim 4, wherein the polymerizable monomer (II) is a (meth) acrylate compound.   The polymerizable composition according to any one of claims 3 to 5, further comprising a polymerization initiator (III).