JP2014091692A - Phosphoric acid ester compound and polymerizable composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphoric acid ester compound capable of imparting excellent adhesiveness and high mechanical strength when applied to a dental material, especially a dental adhesive material, and to provide a polymerizable composition capable of imparting a cured product having excellent adhesiveness and high mechanical strength suitable for a dental material.SOLUTION: There is provided a compound (A) represented by the following general formula (1) (wherein, R, Rand Reach independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; Rrepresents an organic group having 2 to 20 carbon atoms which may have a substituent; Rand Reach independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a metal atom; X represents one selected from the group consisting of a specific substituent such as -COO- and -CONH-; Yand Yeach independently represents one selected from the group consisting of -O-, -S- and -NH-; and Z represents an oxygen atom or a sulfur atom.)

Description

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

  A dental adhesive is usually used when filling or coating a restoration in a tooth defect. As a dental adhesive, a compound containing a compound having a polymerizable group and a phosphate group is known, and various compounds have been proposed as the compound. 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. Has been reported (see Patent Document 1).

  Also, in recent years, for the purpose of improving the mechanical strength of the cured product having adhesiveness, the following formula:

The compound (henceforth A-3) which has a several polymeric group shown by is proposed (refer patent document 2).

JP 58-21607 A JP 2010-235554 A

  After being applied to the oral cavity, the dental material is subjected to high bite pressure or frictional force due to a toothbrush. Accordingly, dental adhesive materials are required to have excellent adhesiveness and high mechanical strength. According to the study by the present inventors, it has been found that there is room for improvement in the mechanical strength of the dental adhesive using Compound A-2 described in Patent Document 1. Further, since compound A-3 described in Patent Document 2 has a plurality of polymerizable groups, a dental material using the compound A-3 is expected to improve mechanical strength, while lowering the phosphate group density. There was concern about the decrease in adhesiveness to the tooth due to.

  Therefore, the subject of this invention is providing the phosphate ester compound which can provide the outstanding adhesiveness and high mechanical strength, when it applies to a dental material, especially a dental adhesive material. Another object of the present invention is to provide a polymerizable composition suitable for dental materials, which can give a cured product having excellent adhesiveness and high mechanical strength.

  The present invention relates to a compound (A) 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 2 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, X 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-, ^{Y 1} and ^{Y 2} are each independently, -O -, - 1 represents one selected from the group consisting of S- and -NH-, and Z represents an oxygen atom or a sulfur atom)

In general formula (1), R ¹ and R ² are hydrogen atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is —COO— or —CONH—. Y ¹ and Y ² are each —O— or —S—, R ⁴ is an aliphatic hydrocarbon group having ⁴ to 14 carbon atoms, and R ⁵ and R ⁶ are hydrogen. It is a C1-C6 hydrocarbon group which may have an atom or a substituent.

  In the general formula (1), a more preferable structure is the compound (A) represented by the following formula (2) or (3).

  The present invention also relates to a polymerizable composition containing the compound (A). The polymerizable composition of the present invention preferably further contains a polymerizable monomer (B) copolymerizable with the compound (A) in addition to the compound (A). The polymerizable monomer (B) is preferably a (meth) acrylate compound. The polymerizable composition of the present invention preferably further contains a polymerization initiator (C).

  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.

  ADVANTAGE OF THE INVENTION According to this invention, the novel phosphate ester compound (A) which gives the outstanding adhesiveness and high mechanical strength to a composition is provided. Therefore, the polymerizable composition containing the compound (A) has excellent adhesiveness and high mechanical strength, and is particularly useful for dental use (dental primer, bonding material, composite resin, cement, etc.). is there.

<Compound (A) of the Present Invention>
First, each symbol used in the general formula (1) will be described.

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

  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.

  The number of carbon atoms of the hydrocarbon group is 1 to 20, but the carbon number referred to here is the number of carbon atoms of the entire hydrocarbon group. Preferably, 1-2 is more preferable.

  Moreover, the said hydrocarbon group may have a substituent and if the carbon number of the hydrocarbon group including a substituent is 1-20, the kind and number of a substituent will not be specifically limited. Specific examples of the substituent include an amino group, a hydroxyl group, an alkoxy group, an amide group, an acyl group, an acyloxy group, a halogen atom, a cyano group, and a nitro group.

Among these, R ¹ and R ² are preferably hydrogen atoms from the viewpoint of polymerizability of the bonded vinyl group. R ³ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, from the viewpoint of the polymerizability of the bonded vinyl group. A methyl group is more preferable from the viewpoint of irritation to the living body when the polymerizable site of the compound (A) is eliminated by hydrolysis or the like. From the same viewpoint, R ¹ and R ² are a hydrogen atom, it is preferred that R ³ is a hydrogen atom or a C20 alkyl group having a carbon, R ¹ and R ² are hydrogen atoms, R ³ Is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably R ¹ and R ² are hydrogen atoms and R ³ is a methyl group.

X 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 the one selected from the group consisting of -CONHCO-. Among these, -COO- or CONH- is preferable from the viewpoint of polymerizability of the bonded vinyl group, and -COO- is more preferable from the viewpoint of ease of production of the compound (A).

—CH ₂ CH ₂ NHCO—, which exists as a spacer between X and Y ¹ , is a part that contributes to the characteristics of the compound (A) and plays a role in strengthening the interaction between molecules. It is considered that the polymerization and curing are facilitated by the close proximity of the polymerizable sites.

Y ¹ and Y ² each independently represent one selected from the group consisting of —O—, —S—, and —NH—. Among these, Y ¹ and Y ² are preferably each independently —O— or —S— from the viewpoint of ease of production of the compound (A), and both Y ¹ and Y ² are oxygen atoms. Is more preferable.

R ⁴ represents an organic group having 2 to 20 carbon atoms which may have a substituent. R ⁴ has a role as a spacer between Y ¹ and Y ² . The phosphate group site (-P (= Z) (OR ⁵ ) (OR ⁶ )) that binds to Y ² interacts with the adhesion target, but the presence of R ⁴ as a spacer makes the polymerizable site the adhesion target. The polymerization at the polymerizable site is facilitated at a more appropriate distance. Moreover, when R ⁴ is present, the concentration of the phosphate group portion per unit weight of the compound (A) is lowered, and the compound (A) is hardly hydrolyzed.

The organic group represented by R ⁴ may be aliphatic or aromatic, and may be saturated or unsaturated, linear or branched. The organic group is not limited to a hydrocarbon group, 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 group. Examples include groups obtained by removing two hydrogen atoms from saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, or aromatic hydrocarbons.

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.

The number of carbon atoms of the organic group represented by R ⁴ is 2 to 20, but the carbon number referred to here is the number of carbon atoms of the whole organic group including the substituent, and is 4 from the viewpoint of adhesiveness and polymerizability. -14 are preferable and 4-12 are more preferable. Adhesiveness is good because the solubility in water of the calcium salt produced by reaction with the tooth substance is low when the carbon number is 2 or more, and the crosslinking density is not too low when the carbon number is 20 or less. Adhesiveness is kept good.

R ⁴ is preferably an aliphatic hydrocarbon group having ^{4 to} 14 carbon atoms, specifically, n-butylene group, isobutylene group, n-pentylene group, isopentylene group, n-hexylene group, isohexylene. Group, n-heptylene group, isoheptylene group, n-octylene group, isooctylene group, n-nonylene group, isononylene group, n-decylene group, isodecylene group, n-undecylene group, isoundecylene group, n-dodecylene group , Isododecylene group, n-tridecylene group, isotridecylene group, n-tetradecylene group, isotetradecylene group, bicyclononanedimethyl group, cyclohexanebutylpropyl group, dimethyldecylene group, diethyldecylene group and the like. Further, from the viewpoint of adhesiveness, an aliphatic hydrocarbon group having 4 to 12 carbon atoms is preferable, and specifically, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene. Group, n-octylene group, n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group and the like.

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 , and the numbers and types of substituents are also the same. 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.

Among these, from the viewpoint of the acidity of the compound (A), R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. It is preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group or a phenyl group. R ⁵ and R ⁶ are preferably both hydrogen atoms.

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

  Specific examples of the compound (A) include compounds having the following structural formulas. In the structural formula, n represents an integer of 2 to 20.

  A more preferable structure of the compound (A) is a structure represented by the following formula (2) or (3).

The compound (A) of the present invention can be produced by combining known methods. As an example, first, a compound represented by the following general formula (4) and a compound represented by the following general formula (5) are reacted to obtain a compound represented by the following general formula (6). The compound (A) can be obtained by introducing a phosphate group into the Y ⁴ group of the compound represented by the general formula (6).

Wherein R ^{1 to} R ⁴ and Y ¹ are as defined above, Y ³ is a functional group capable of reacting with the —NCO group of the compound represented by the general formula (4), and Y ⁴ is phosphorylated. Represents a functional group capable of reacting with the agent)

The functional group Y ³ has one bond selected from Y ¹ , that is, —O—, —S—, and —NH— by reaction with the —NCO group of the compound represented by the general formula (4). Chosen to generate. The functional group Y ³ that generates these bonds and the reaction method are well known to those skilled in the art. For example, when an —O— bond is formed, —OH may be selected as Y ^{3 and} urethanized according to a known method. When forming an —S— bond, Y ³ may be selected from —SH and subjected to a thiourethanization reaction according to a known method. In the case of forming an —NH— bond, it is only necessary to select —NH ₂ as Y ³ and to make a urea reaction according to a known method.

The functional group Y ⁴ is selected such that one type of bond selected from Y ² , ie, —O—, —S—, and —NH—, is formed by reaction with the phosphorylating agent. The functional group Y ⁴ that generates these bonds and the reaction method are well known to those skilled in the art. For example, when an —O— bond is formed, —OH or an aldehyde group may be selected as Y ^{4 and} subjected to a phosphoric esterification reaction according to a known method. When forming an —S— bond, Y ⁴ may be selected from —SH and subjected to a phosphoric acid thioesterification reaction according to a known method. When an —NH— bond is formed, —NH ₂ is selected as Y ⁴ and a thioamidation reaction may be performed according to a known method.

Hereinafter, by the reaction of the functional group Y ³ of the compound represented by the general formula (5) and the —NCO group of the compound represented by the general formula (4), for example, a urethane bond represented by —NHCO—O— is formed. The method (hereinafter referred to as urethanization reaction) to be generated will be described in detail. For the urethanization reaction, reference can be made to the method described in Japanese Patent Publication No. 63-020203.

  Examples of the compounds represented by the general formula (4) include 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

  Examples of the compound represented by the general formula (5) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol 1,5-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4-heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, 1,5-octane Diol, 1,6-octanediol, 1,7-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol , Diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like.

  A catalyst can be used for the reaction between the compound represented by the general formula (4) and the compound represented by the general formula (5). As the catalyst, an organometallic compound and amines can be used.

  As the organometallic compound, an organometallic compound having catalytic activity for the urethanization reaction can be used. Specific examples include organic cobalt compounds such as cobalt naphthenate, and organic tin compounds such as tetra-n-butyltin, trimethyltin hydroxide, dimethyltin dichloride, di-n-butyltin dilaurate, and octoate tin. . Examples of amines include triethylamine, tributylamine, trioctylamine and the like.

  The amount of the catalyst used is usually preferably about 0.000001 to 1 mol, more preferably 0.00001 to 0.01 mol, per 1 mol of the compound represented by the general formula (5) as the raw material. preferable. When the usage-amount of a catalyst is less than 0.000001 mol, there exists a possibility that the efficiency of a catalyst may fall and reaction time may become long. On the other hand, if it exceeds 1 mol, the effect due to the increase in the amount used cannot be obtained.

  Further, this reaction 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-butyl hydroquinone; 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.

  The reaction may be carried out in a solvent-free system or using a solvent. Examples of the solvent that can be used include a solvent in which the solubility of the compound represented by the general formula (5) is preferably 0.5% by mass or more, more preferably 10% by mass or more. Specific examples include hexane, heptane, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethyl acetate, diethyl ether, tetrahydrofuran, diisopropyl ether, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Diethyl ether and diisopropyl ether are preferred because of easy removal of the solvent during purification. A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

  The reaction temperature between the compound represented by the general formula (4) and the compound represented by the general formula (5) is usually preferably about 0 to 150 ° C, more preferably 10 to 100 ° C. If the temperature is too low, the reaction rate decreases and the reaction time becomes longer. Moreover, when reaction temperature is high, side reactions, such as superposition | polymerization, will advance easily and the purity of a product will fall significantly.

  The pressure during the reaction is preferably about 0.01 to 10 MPa in absolute pressure, more preferably normal pressure (101.3 kPa) to 1 MPa, and most preferably normal pressure. If the pressure is too high, there is a safety problem and a special device is required, which is not industrially useful. When the pressure is 10 MPa or less, safety is ensured, so that no special device is required, which is industrially useful.

  Thus, the compound represented by the general formula (6) is obtained. In the present invention, after completion of the above reaction, the target product may be purified by washing, distillation, crystallization, column separation or the like. The purification method can be selected depending on the properties of the product and the type of impurities.

Subsequently, the compound (A) can be obtained by reacting the Y ⁴ group of the compound represented by the general formula (6) with a phosphorylating agent of POCl ₃ or PSCl ₃ and further performing hydrolysis or alcoholysis. it can. When R ⁵ and R ⁶ in the general formula (1) are, for example, metal atoms, the compound represented by the general formula (1) in which R ⁵ and R ⁶ are hydrogen atoms is converted into a metal salt. Good.

Hereinafter, a method of obtaining the compound (A) by reacting the compound represented by the general formula (6) with POCl ₃ and further hydrolyzing it will be described. For the phosphorylation reaction, the method described in Patent Document 2 can be referred to.

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 (6). .

In the reaction of the compound represented by the general formula (6) 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, 0.8 to 5.0 moles preferably against POCl _3.

The reaction of the compound represented by the general formula (6) 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 (6). 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 (6) and POCl ₃ is usually preferably in the range of −50 to 50 ° C., and more preferably in the range of −40 to 20 ° C.

  After completion of the above reaction, the compound (A) can be obtained by hydrolysis by adding water to the reaction solution.

The amount of water used is not particularly limited, but it is usually preferably in the range of 2 to 10 times the molar amount of the reaction product of the compound represented by the general formula (6) and POCl ₃ .

In the hydrolysis reaction, a basic compound can be used as necessary. The basic compound is not particularly limited, and examples thereof include nitrogen-containing compounds such as triethylamine, tri-n-butylamine, and pyridine. The amount of basic compound is preferably in the range of from 2.0 to 5 mols per mol of the reaction product of a compound and POCl ₃ represented by the general formula (6).

  The reaction temperature in the hydrolysis reaction is usually preferably in the range of −40 to 50 ° C., more preferably in the range of −30 to 10 ° C.

  After completion of the reaction, the amine hydrochloride which is a by-product is removed by washing with water, and the compound (A) can be obtained by extracting the compound (A) with an organic solvent and concentrating the resulting solution. .

  Furthermore, in the present invention, the compound (A) obtained as described above may be purified by washing, distillation, crystallization, column separation or the like. The purification method can be selected depending on the properties of the product and the type of impurities.

  The compound (A) thus obtained is excellent in mechanical strength due to polymerization and curing of the polymerizable site containing a vinyl group, while the site having a phosphate group is a prosthesis made of teeth, zirconia, metal or the like. It exhibits good adhesion.

  Since the polymerizable composition containing the compound (A) has excellent adhesiveness and can increase the mechanical strength of the cured product, it is particularly useful in dental applications.

  Therefore, the present invention also provides a polymerizable composition containing the compound (A). The polymerizable composition may contain a polymerizable monomer (B) copolymerizable with the compound (A) as a polymerizable monomer different from the compound (A). Examples of other components suitable for the polymerizable composition include a polymerization initiator (C), a polymerization accelerator (D), a filler (E), and a solvent (F).

Polymerizable monomer (B)
The polymerizable monomer (B) copolymerizable with the compound (A) includes a polymerizable monomer (Ba) having no acidic group and having one polymerizable group, and acidic. Examples thereof include a polymerizable monomer (Bb) having no group and having two or more polymerizable groups. As the polymerizable monomer (B), 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 present specification, “(meth) acrylate compound” means a methacrylate compound and an acrylate compound, and “(meth) acrylamide compound” means a methacrylamide compound and an acrylamide compound.

  In the polymerizable monomer (Ba) 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 (Ba) promotes the penetration of the components of the dental adhesive into the tooth, and also penetrates the tooth itself and adheres to the organic component (collagen) in the tooth.

  The polymerizable monomer (Ba) having no acidic group and having one polymerizable group may be used alone or in combination of two or more. Examples of the polymerizable monomer (Ba) 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 and the like. Among these, from the viewpoint of improving the permeability of dentin into the collagen layer, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) Acrylate and N-acryloylmorpholine are preferable, and 2-hydroxyethyl methacrylate is more preferable.

  The polymerizable monomer (Bb) having no acidic group and having two or more polymerizable groups improves the mechanical strength, handleability, and the like of the polymerizable composition. In addition, the acidic group in a polymerizable monomer (Bb) is synonymous with the acidic group in a polymerizable monomer (Ba).

  The polymerizable monomer (Bb) having no acidic group and having two or more polymerizable groups can be used alone or in combination of two or more. Although it does not specifically limit as a polymerizable monomer (Bb) which does not have an acidic group and has 2 or more polymeric groups, Aromatic compound type bifunctional polymerizable monomer, fat Group compound-based bifunctional polymerizable monomers, trifunctional or higher functional polymerizable monomers, and the like.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “BisGMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane), 2,2-bis (4- (Meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaeth Cyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) ) Propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2 -(4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) Propane, 1,4-bis (2- (meth) acryloyl Kishiechiru) pyromellitate and the like.

  Examples of aliphatic compound-based bifunctional polymerizable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3-methacryloyloxy) 2-hydroxypropoxy) ethane and 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), and the like.

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

  The compound (A) has a phosphoric acid group and thus has an acid etching effect. In addition to the polymerizable monomer, the compound (A) has an acidic group or a polymerizable monomer (Bc) having an acid anhydride. You may use together. As the polymerizable monomer (Bc) having an acidic group, an acidic group or an acid anhydride group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, or a sulfonic acid group is used. Examples thereof include a polymerizable monomer having at least one and having at least one polymerizable group such as acryloyl group, methacryloyl group, vinyl group, and styrene group.

  Specific examples of the polymerizable monomer (Bc) having an acid group or an acid anhydride group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen. Phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2 -(Meth) acrylamidoethyl dihydrogen phosphate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (10- (meth) acryloyloxydecyl) hydrogen phosphate, bis {2- (meta Acryloyloxy- (1-hydroxymethyl) ethyl} hydrogen phosphate, 11-methacryloyloxy-1,1-undecanedicarboxylic acid, 4-methacryloyloxyethyl trimellitic acid, N-methacryloyl-5-aminosalicylic acid, 2-methyl Examples include compounds described in Japanese Patent No. 4611028 and Japanese Patent Application Laid-Open No. 2010-235465, such as 2- (meth) acrylamidepropanesulfonic acid and 4-methacryloyloxyethyl trimellitic anhydride.

  The compounding amount of the compound (A) is preferably 1 to 80 parts by weight, more preferably 3 to 50 parts by weight, and further preferably 5 to 30 parts by weight in 100 parts by weight of the total amount of the polymerizable monomer components. When the compounding amount of the compound (A) is 1 part by weight or more, a sufficient effect of improving adhesiveness is exhibited, and when the compounding amount of the compound (A) is 80 parts by weight or less, it sufficiently penetrates into the tooth. Therefore, the effect of improving adhesiveness is also good.

  The blending amount of the polymerizable monomer (Ba) is preferably 0 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomer components. The compounding amount of the polymerizable monomer (Bb) is preferably 5 to 98 parts by weight and more preferably 10 to 50 parts by weight in 100 parts by weight of the total amount of the polymerizable monomer components. The compounding amount of the polymerizable monomer (Bc) is preferably 1 to 40 parts by weight and more preferably 2 to 20 parts by weight in 100 parts by weight of the total amount of the polymerizable monomer components.

  In addition, the weight ratio [A / Ba] of the compound (A) and the polymerizable monomer (Ba) is preferably 1/10 to 10/1 from the viewpoint of tooth permeability, and 1/5. ~ 1/1 is more preferable. The weight ratio [A / Bb] of the compound (A) to the polymerizable monomer (Bb) is preferably 1/10 to 10/1, and preferably 1/5 to 1/1 from the viewpoint of polymerization curability. 1 is more preferable. The weight ratio [A / Bc] between the compound (A) and the polymerizable monomer (Bc) is preferably 1/1 to 10/1, preferably 2/1 to 5 / from the viewpoint of polymerization curability. 1 is more preferable.

  In the present invention, the total amount of the polymerizable monomer component means the compound (A), the polymerizable monomer (Ba), the polymerizable monomer (Bb), and the polymerizable monomer (B -C) and the total amount of other polymerizable monomers copolymerizable therewith.

Polymerization initiator (C)
The polymerization initiator (C) 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.

  Examples of the photopolymerization initiator include (bis) acylphosphine oxides, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, and the like.

  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, and bis- (2,6-dichloro). Benzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2 Such as 5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

  Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Is more preferable.

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

  Examples of the ketone peroxide 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, and among these, benzoyl peroxide is more preferably used from the comprehensive balance of safety, storage stability, and radical generating ability.

  Although the compounding quantity of the polymerization initiator (C) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, a polymerization start is with respect to 100 weight part of whole quantity of a polymerizable monomer component. It is preferable to contain 0.001-30 weight part of agents (C). When the blending amount of the polymerization initiator (C) 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 blending amount of the polymerization initiator (C) 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. Since it may cause precipitation, the amount is more preferably 20 parts by weight or less.

Polymerization accelerator (D)
The composition of the present invention preferably contains a polymerization accelerator (D). Examples of the polymerization accelerator (D) used in the present invention include amines, sulfinic acids and salts thereof, triazine compounds, copper compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, bisulfites, and thioureas. Compound etc. are mentioned.

  The amines used as the polymerization accelerator (D) 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 salts thereof used as the polymerization accelerator (D) 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, and sodium 2,4,6-triisopropylbenzenesulfinate are more preferable. .

  Examples of the triazine compound used as the polymerization accelerator (D) 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- 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 , 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 preferable in terms of polymerization activity, and 2-phenyl-4 in terms 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 (D), for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  The vanadium compound used as the polymerization accelerator (D) 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 (D) 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 (D) 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 (D) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

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

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

  Examples of the thiourea compound used as the polymerization accelerator (D) include 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.

  Although the compounding quantity of the polymerization accelerator (D) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, superposition | polymerization acceleration | stimulation is carried out with respect to 100 weight part of whole quantity of a polymerizable monomer component. It is preferable to contain 0.001-30 weight part of agents (D). When the blending amount of the polymerization accelerator (D) 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 blending amount of the polymerization accelerator (D) 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 (E)
Depending on the embodiment, it is preferable to further add a filler (E) 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. 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. In the present specification, the average particle diameter of the filler can be measured by any method known to those skilled in the art, and can be easily measured by, for example, a laser diffraction type particle size distribution measuring apparatus.

  The compounding quantity of the filler (E) used for this invention is not specifically limited, 1-2000 weight part of filler (E) is preferable with respect to 100 weight part of whole quantity of a polymerizable monomer component. Since the suitable compounding amount of the filler (E) 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 E) will be shown.

Solvent (F)
The polymerizable composition of the present invention preferably contains a solvent (F) 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 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 content of water exceeds 2000 parts by weight, the polymerizability of the monomer is lowered, the adhesive strength is lowered, and the mechanical strength 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 (F) 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 solvent content 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 has high adhesiveness and can be used, for example, as an adhesive material for biological hard tissues, metal materials, organic polymer materials, ceramics and the like. The polymerizable composition of the present invention is particularly preferably 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 (A) has a decalcification effect, the polymerizable composition of the present invention has a permeation effect. A self-etching primer can be formed by using the polymerizable monomer (Ba).

  The primer can be constituted by replacing part or all of the polymerizable monomer containing an acidic group with a compound (A) 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 the compound (A), 5 to 99 parts by weight of the polymerizable monomer (Ba), and polymerization in 100 parts by weight of the polymerizable monomer component. 0 to 60 parts by weight of the polymerizable monomer (Bb), preferably 1 to 40 parts by weight of the compound (A), 10 to 99 parts by weight of the polymerizable monomer (Ba), and polymerizable A monomer (Bb) 0-50 weight part is mix | blended. And it is preferable that a polymerization initiator (C) 0.001-30 weight part and a polymerization accelerator (D) 0.001-30 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and polymerization is carried out. More preferably, it contains 0.05 to 20 parts by weight of the initiator (C) and 0.05 to 20 parts by weight of the polymerization accelerator (D). Moreover, it is preferable that 6-3500 weight part of solvent (F) 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. In addition, it is good also considering the polymerizable monomer (Bc) which has a part of compound (A) as 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 (A) 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 (A), 0 to 60 parts by weight of the polymerizable monomer (Ba), and 100 parts by weight of the total amount of the polymerizable monomer components. 5 to 99 parts by weight of the polymerizable monomer (Bb) is blended, preferably 1 to 30 parts by weight of the compound (A), 0 to 50 parts by weight of the polymerizable monomer (Ba), and polymerization 20 to 99 parts by weight of the polymerizable monomer (Bb) is blended. And it is preferable that a polymerization initiator (C) 0.001-30 weight part and a polymerization accelerator (D) 0.001-30 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and polymerization is carried out. More preferably, it contains 0.05 to 20 parts by weight of the initiator (C) and 0.05 to 20 parts by weight of the polymerization accelerator (D). Moreover, it is preferable that 0-30 weight part of filler (E) 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 a solvent (F) may be used, it is more preferable not to contain substantially. In addition, it is good also considering the polymerizable monomer (Bc) which has a part of compound (A) as 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 the compound (A) has a deashing 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 (A) and the polymerizable monomer (Ba) 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 (Bb) are blended, preferably 3 to 30 parts by weight of the compound (A), 10 of the polymerizable monomer (Ba). -60 weight part and 10-60 weight part of polymerizable monomers (Bb) are mix | blended. And it is preferable that a polymerization initiator (C) 0.001-30 weight part and a polymerization accelerator (D) 0.001-30 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and polymerization is carried out. More preferably, it contains 0.05 to 20 parts by weight of the initiator (C) and 0.05 to 20 parts by weight of the polymerization accelerator (D). Moreover, it is preferable that 0-30 weight part of filler (E) 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 (F) 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. In addition, it is good also considering the polymerizable monomer (Bc) which has a part of compound (A) as 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. Since the compound (A) has a decalcifying action and a high curing action, a self-adhesive composite resin can be constituted by the polymerizable composition of the present invention.

  The self-adhesive composite resin is a known composite resin containing a polymerizable monomer containing an acidic group, by replacing part or all of the polymerizable monomer containing an acidic group with the compound (A), Can be configured. Examples of the composition of the self-adhesive composite resin include 1 to 40 parts by weight of the compound (A) and 0 to 80 parts by weight of the polymerizable monomer (Ba) in 100 parts by weight of the total amount of the polymerizable monomer components. And 10 to 99 parts by weight of the polymerizable monomer (Bb), preferably 3 to 30 parts by weight of the compound (A), and 10 to 70 parts by weight of the polymerizable monomer (Ba). , And 20 to 87 parts by weight of the polymerizable monomer (Bb). And it is preferable that a polymerization initiator (C) 0.001-30 weight part and a polymerization accelerator (D) 0.001-30 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and polymerization is carried out. More preferably, it contains 0.05 to 20 parts by weight of the initiator (C) and 0.05 to 20 parts by weight of the polymerization accelerator (D). Moreover, it is preferable that 50-3000 weight part of filler (E) is included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and it is more preferable that 80-2000 weight part is included. Moreover, although a solvent (F) may be used, it is more preferable not to contain substantially. In addition, it is good also considering the polymerizable monomer (Bc) which has a part of compound (A) as 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. Since the compound (A) has a decalcifying action and a hardening action, it is also possible to constitute a self-adhesive cement with 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 of a known cement containing a polymerizable monomer containing an acidic group with the compound (A). . As an example of the composition of the resin cement, 2 to 50 parts by weight of the compound (A), 0 to 60 parts by weight of the polymerizable monomer (Ba), and 100 parts by weight of the total amount of the polymerizable monomer component, and 10 to 98 parts by weight of the polymerizable monomer (Bb) is blended, preferably 2 to 40 parts by weight of the compound (A), 0 to 50 parts by weight of the polymerizable monomer (Ba), and polymerization 20 to 98 parts by weight of the polymerizable monomer (Bb) is blended. And it is preferable that a polymerization initiator (C) 0.001-30 weight part and a polymerization accelerator (D) 0.001-30 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and polymerization is carried out. More preferably, it contains 0.05 to 20 parts by weight of the initiator (C) and 0.05 to 20 parts by weight of the polymerization accelerator (D). Moreover, it is preferable that 50-2000 weight part of filler (E) 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 a solvent (F) may be used, it is more preferable not to contain substantially. In addition, it is good also considering the polymerizable monomer (Bc) which has a part of compound (A) as an acidic group.

  In the resin cement, it is preferable to use a chemical polymerization initiator as the polymerization initiator (C), and it is preferable to use amines and / or sulfinic acid and salts thereof as the polymerization accelerator (D). In the resin cement, from the viewpoint of storage stability, it is preferable that the compound (A), the polymerization initiator (C), and the polymerization accelerator (D) 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 (A), 0 to 60 parts by weight of the polymerizable monomer (Ba), 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 (Bb), preferably 2 to 40 parts by weight of the compound (A), 0 to 50 parts by weight of the polymerizable monomer (Ba), and 20-98 weight part of polymeric monomers (Bb) are mix | blended. And it is preferable that a polymerization initiator (C) 0.001-30 weight part and a polymerization accelerator (D) 0.001-30 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component, and polymerization is carried out. More preferably, it contains 0.05 to 20 parts by weight of the initiator (C) and 0.05 to 20 parts by weight of the polymerization accelerator (D). 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. Further, 0 to 2000 parts by weight, preferably 10 to 1000 parts by weight of filler (E) other than fluoroaluminosilicate glass may be added. Moreover, it is preferable that 1-500 weight part of solvent (F) 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. In addition, it is good also considering the polymerizable monomer (Bc) which has a part of compound (A) as 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. When dividing into two agents, compound (A) is blended on the polyalkenoic acid side. Moreover, it is preferable to store the polymerization initiator (C) and the polymerization accelerator (D) 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. First, it describes about each component of the polymeric composition produced in the Example and the comparative example.

[Phosphate compound]
A-1:

A-2: 10-methacryloyloxydecyl dihydrogen phosphate A-3:

[Polymerizable monomer having no acidic group and having one polymerizable group (Ba)]
HEMA: 2-hydroxyethyl methacrylate [polymerizable monomer (Bb) having no acidic group and having two or more polymerizable groups]
BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane TEGDMA: triethylene glycol dimethacrylate [polymerizable monomer having acidic group (Bc)]
PME: 2-methacryloyloxyethyl dihydrogen phosphate [photopolymerization initiator]
TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [chemical polymerization initiator]
BPO: Benzoyl peroxide [polymerization accelerator]
AMN: N, N-di (2-hydroxyethyl) -p-toluidine [inorganic filler]
Inorganic filler (1): Nippon Aerosil "R972"
Inorganic filler (2): Barium glass “GM27884NF180” manufactured by SCHOTT, γ-methacryloyloxypropyltrimethoxysilane 13% surface-treated product

Example 1 (Synthesis of A-1): Synthesis of Compound (A)
[Synthesis of pentanediol and monourethane methacrylate]
A three-necked flask was charged with 10.4 g (0.1 mol) of 1,5-pentanediol, and 2.6 mg of dibutyltin dilaurate and 22.6 mg of hydroquinone monomethyl ether were dissolved. While stirring at 20 ° C., 15.5 g (0.1 mol) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz MOI) was added dropwise. After completion of the dropwise addition, the mixture was aged at 50 ° C., and the reaction was terminated after confirming disappearance of the peak derived from the isocyanate group by IR.

  This synthetic solution was repeatedly washed with water to remove unreacted pentanediol, thereby obtaining 20.0 g of a mixture of pentanediol / monourethane methacrylate and pentanediol / diurethane methacrylate. When analyzed by gas chromatography, the area ratio of unreacted pentanediol / pentanediol monourethane methacrylate / pentanediol diurethane methacrylate was 1.2 / 71.0 / 22.1.

[Synthesis of A-1]
A three-necked flask purged with nitrogen was charged with 50 g of diethyl ether and 2.74 g (0.018 mol) of phosphorus oxychloride, and cooled to −40 ° C. In a separate container, 5 g of the mixture of pentanediol / monourethane methacrylate and pentanediol / diurethane methacrylate obtained above and 1.66 g (0.016 mol) of triethylamine were dissolved in 25 g of diethyl ether and added dropwise. did. After completion of dropping, the mixture was aged at -20 ° C for 1 hour. Subsequently, 3.64 g (0.036 mol) of triethylamine, 1.45 g (0.082 mol) of water, and 25 g of diethyl ether mixed solution were added dropwise so as not to exceed 0 ° C., and the mixture was kept at 0 to 5 ° C. for 1 hour. Aged. The obtained synthesis solution was repeatedly washed with water to remove the generated triethylamine hydrochloride. The obtained organic layer was dried over magnesium sulfate, and then diethyl ether was distilled off under reduced pressure. By repeatedly washing with cyclohexane, the pentanediol diurethane methacrylate as an impurity was removed to obtain 4.0 g of the desired product.

The ¹ H-NMR data of the obtained compound is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.33 to 1.41 (m, 2H), 1.45 to 1.65 (m, 4H), 1.86 (s, 3H), 3 .31 to 3.43 (m, 2H), 3.80 to 4.02 (m, 4H), 4.08 to 4.15 (m, 2H), 5.49 (s, 1H), 6.00 (S, 1H), 8.50-8.75 (m, 2H).

Production Example 1 (Synthesis of A-3)
[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%).

[Synthesis of 11-methoxymethylundecane-1,2-diol]
To the 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 wt% 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 bisulfite 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%) 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 replaced 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 ( HPLC purity 98.8%) was obtained.

[Synthesis of A-3]
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 10,11-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. Then, 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. The ¹ H-NMR data of the obtained compound A-3 are shown below.

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 1.27-1.33 (m, 14H), 1.62-1.66 (m, 4H), 1.93 (s, 6H), 3 .99-4.06 (m, 2H), 4.15-4.20 (m, 1H), 4.29-4.32 (m, 1H), 5.17-5.23 (m, 1H) 5.57 (s, 2H), 6.10 (s, 2H).

Examples 2-7 and Comparative Examples 1-2 (Preparation of dental adhesive composition)
With the compounding amounts (parts by weight) shown in Table 1, the phosphate ester compound, the polymerizable monomer (Ba), the polymerizable monomer (BB) and the polymerizable monomer (Bc) To 100 parts by weight of the polymerizable monomer composition obtained by mixing 22 parts by weight of ethanol, 22 parts by weight of water, 4 parts by weight of TMDPO, and 14 parts by weight of inorganic filler (1) were mixed at room temperature to obtain a dental composition. A certain dental adhesive composition was prepared, and the adhesive strength with bovine enamel and bovine dentin and the Vickers hardness were measured according to the following methods. The results are summarized in Table 1.

[Method for evaluating adhesion of dental composition to bovine enamel and bovine dentin]
The lip surface of bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to expose the enamel flat surface and the dentin flat surface. Get a sample. Each of the obtained samples is further polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After the polishing is completed, the surface water is dried by air blowing. An adhesive tape having a thickness of about 150 μm having a round hole with a diameter of 3 mm is attached to the smooth surface after drying to regulate the adhesion area.

  The prepared dental composition is applied in the above-mentioned round hole with a brush and left for 20 seconds. If the composition contains a solvent such as ethanol or water, the surface of the dental composition is applied by air blowing. Dry until the composition is no longer fluid. Next, the applied dental composition is cured by light irradiation for 10 seconds with a dental visible light irradiator “Pen Cure 2000” (manufactured by Morita Co., Ltd.).

  A composite resin for dental filling (trade name “Clearfill AP-X” (registered trademark) manufactured by Kuraray Noritake Dental Co., Ltd.) was applied to the surface of the cured product of the obtained dental composition, and a release film (polyester) Cover with. Next, a glass slide is placed on the release film and pressed to smooth the application surface of the composite resin. Subsequently, the composite resin is irradiated with light using the irradiator “Pencure 2000” (manufactured by Morita Co., Ltd.) for 20 seconds through the release film to cure the composite resin.

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

  The tensile bond strength of the five adhesion test samples is measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min, and the average value is taken as the tensile bond strength.

[Evaluation method of Vickers hardness of dental composition]
1 g of the dental composition is applied onto a glass plate, and the surface is air blown to dry until the applied dental composition has no fluidity. After filling the dried dental composition into a stainless steel mold (dimensions 4 mmφ × 4 mm), the top and bottom are pressed with a slide glass, and a dental visible light irradiator “Pencure 2000” (Morita Co., Ltd.) is used. It is cured by light irradiation for 10 seconds on one side. After taking out the cured product from the mold, the Vickers hardness of the light-irradiated surface and the back surface is measured using a Vickers hardness tester (manufactured by Shimadzu Corporation) under the condition of a load HV0.2.

  From the result of Table 1, the dental adhesive composition (Example 2 to Example 7) containing A-1 which is the compound (A) of the present invention is an adhesive containing the compound A-2 that has been widely used conventionally. Compared to the material composition (Comparative Example 1) or the adhesive composition containing Compound A-3 (Comparative Example 2), both the enamel adhesive strength and the dentin adhesive strength were high, indicating excellent adhesion. Similarly, it was found that the Vickers hardness is high and the mechanical strength is increased.

Examples 8 to 10 and Comparative Examples 3 to 4 (Preparation of dental self-adhesive composite resin composition)
A polymerizable monomer composition obtained by mixing the phosphate ester compound, the polymerizable monomer (Ba), and the polymerizable monomer (BB) in the blending amounts (parts by weight) shown in Table 2. 4 parts by weight of TMDPO are mixed and dissolved in 100 parts by weight of the product, and the inorganic filler (1) and the inorganic filler (2) are mixed and kneaded at room temperature with the blending amount (parts by weight) shown in Table 2. A dental self-adhesive composite resin composition was prepared, and the adhesive strength with bovine enamel and bovine dentin was measured in the same manner as the dental adhesive composition of Example 2, and the bending strength was Measured according to the method. The results are summarized in Table 2.

[Method for measuring bending strength of dental composition]
A dental composition is filled in a mold (2 mm × 2 mm × 25 mm), and using a dental visible light irradiator “Pencure 2000” (manufactured by Morita Co., Ltd.), light irradiation (10 seconds × 5 times for each side) After performing and hardening, it is immersed in 37 degreeC water for 24 hours, and a test piece is produced. Using a universal testing machine (Instron), the bending strength of the test piece is measured by a three-point bending test method at a crosshead speed of 1 mm / min.

  From the results shown in Table 2, the dental self-adhesive composite resin compositions (Examples 8 to 10) containing A-1 which is the compound (A) of the present invention are compound A-2 which has been widely used conventionally. Compared to a dental self-adhesive composite resin composition (Comparative Example 3) or a dental self-adhesive composite resin composition (Comparative Example 4) containing Compound A-3, both enamel adhesive strength and dentin adhesive strength It was found to be high and exhibit excellent adhesion. Similarly, it was found that the bending strength was high and the mechanical strength was increased.

Examples 11-13 and Comparative Examples 5-6 (Preparation of dental cement composition)
A polymerizable monomer composition obtained by mixing the phosphate ester compound, the polymerizable monomer (Ba), and the polymerizable monomer (BB) in the blending amounts (parts by weight) shown in Table 3. 3 parts by weight of BPO was mixed and dissolved in 100 parts by weight of the product, and the inorganic filler (1) and inorganic filler (2) were mixed and kneaded at room temperature with the blending amounts (parts by weight) shown in Table 3 to prepare paste A. . Similarly, 1 part by weight of AMN is mixed and dissolved in 100 parts by weight of the polymerizable monomer composition obtained by mixing the polymerizable monomer (Ba) and the polymerizable monomer (BB). Then, inorganic filler (1) and inorganic filler (2) were mixed and kneaded at room temperature to prepare paste B. Paste A and paste B were mixed and kneaded at a weight ratio of 1: 1 to prepare a dental cement composition, which is a dental composition, and the adhesive strength between bovine enamel and bovine dentin was determined in Example 2. The bending strength was measured in the same manner as in the dental self-adhesive composite resin composition of Example 8. The results are summarized in Table 3.

  From the results of Table 3, the dental cement composition (Example 11 to Example 13) containing A-1 which is the compound (A) of the present invention is a cement composition containing compound A-2 which has been widely used conventionally. It was found that both the enamel bond strength and the dentin bond strength were higher than those of the product (Comparative Example 5) or the cement composition containing Compound A-3 (Comparative Example 6), and showed excellent adhesiveness. Similarly, it was found that the bending strength was high and the mechanical strength was increased.

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

Claims (16)

Compound (A) 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 2 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, X 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-, ^{Y 1} and ^{Y 2} are each independently, -O -, - 1 represents one selected from the group consisting of S- and -NH-, and Z represents an oxygen atom or a sulfur atom) The compound (A) according to claim 1, wherein R ¹ and R ² are hydrogen atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.   The compound (A) according to claim 1 or 2, wherein X is -COO- or -CONH-. Y < ¹ > and Y < ² > are respectively independently -O- or -S-, The compound (A) in any one of Claims 1-3. R ⁴ is A compound according to claim 1 is an aliphatic hydrocarbon group having 4 to 14 carbon atoms (A). R ⁵ and R ⁶ is a hydrogen atom or a compound according to any one of claims 1 to 5 is a hydrocarbon group having carbon atoms of 1-6 that may have a substituent group (A). The compound (A) in any one of Claims 1-6 represented by following formula (2) or (3).

  Polymeric composition containing the compound (A) in any one of Claims 1-7.   The polymerizable composition according to claim 8, further comprising a polymerizable monomer (B) copolymerizable with the compound (A) in addition to the compound (A).   The polymerizable composition according to claim 9, wherein the polymerizable monomer (B) is a (meth) acrylate compound.   The polymerizable composition according to any one of claims 8 to 10, further comprising a polymerization initiator (C).   The polymerizable composition according to any one of claims 8 to 11, which is for dental use.   A primer using the polymerizable composition according to claim 12.   A bonding material using the polymerizable composition according to claim 12.   A composite resin using the polymerizable composition according to claim 12.   A cement using the polymerizable composition according to claim 12.