JP6995357B2 - Acidic group-containing polymerizable monomer having a functional group with a high dielectric constant - Google Patents

Description

The present invention relates to polymerizable monomers, curable compositions and dental adhesive compositions.

(Meta) acrylate-based polymerizable monomers are used in a wide range of fields such as dental materials such as dental curable compositions or dental adhesives, optical materials, printing plates, photoresist materials, paints, adhesives, inks, and optical molding resins. It is available at. In particular, in dental adhesive compositions, phosphate group-containing polymerizable monomers exemplified in Patent Documents 1 to 3, carboxylic acid group-containing polymerizable monomers exemplified in Patent Documents 4 and 5, and Patent Documents. It is known that the sulfonic acid group-containing polymerizable monomers exemplified in 5 and 6 play an important role in decalcification of the smear layer of the dentin and adhesion to the dentin.

Since the various polymerizable monomers described above have an acidic group, they have low compatibility with a polymerizable monomer having no acidic group, and for example, bisphenol A diglycidyl di (meth) acrylate (Bis-). In order to mix with a polymerizable monomer such as GMA) or triethylene glycol dimethacrylate (TEGDMA), it has a drawback that it is complicated to handle, such as a long-time stirring operation and the need for heating. Further, the salt compound of the calcium ion derived from the dentin and the acidic group-containing polymerizable monomer deposited after decalcifying the smear layer contains an acidic group with respect to the polymerizable monomer having no acidic group. It is more sparingly soluble than the polymerizable monomer itself and has low compatibility. If the compatibility between these salt compounds and other components is low, it is considered to be one of the factors that inhibit adhesion, and sufficient adhesion cannot be obtained.

Japanese Unexamined Patent Publication No. 2014-91692 Japanese Unexamined Patent Publication No. 2010-31048 U.S. Patent Application Publication No. 2016/01/45277 Japanese Unexamined Patent Publication No. 2004-203817 Japanese Unexamined Patent Publication No. 2013-82703 Japanese Unexamined Patent Publication No. 8-310912

The subject of the present invention is a polymerizable monomer having high compatibility with a polymerizable monomer having an acidic group but not having an acidic group, even if it becomes a salt compound. It is an object of the present invention to provide an acidic group-containing polymerizable monomer having high compatibility with a polymerizable monomer having no acidic group.

The present inventor has synthesized various polymerizable monomers in order to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by using an acidic group-containing polymerizable monomer having a functional group having a high dielectric constant introduced as a compatible functional group, and have completed the present invention.

That is, the present invention is an acidic group-containing polymerizable monomer containing a compatibility-enhancing functional group, and is a polymerizable monomer represented by the following general formula (1).

In the general formula (1), A is a divalent hydrocarbon group having 1 to 50 carbon atoms, and may have a branched structure or a cyclic structure, and the carbon atom is an oxygen atom, a sulfur atom, or a sulfur atom. , May be substituted with a nitrogen atom. B is a divalent hydrocarbon group having 1 to 10 carbon atoms, may have a branched structure or a cyclic structure, and the carbon atom may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. .. R ¹ is a hydrogen atom and a methyl group. Y is —O— or ^{—NR2- (R 2 is} a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). n is an integer of 1 to 3. m is an integer from 0 to 4. When n is 2 or 3, A, ^R1 and Y may be the same or different, respectively. X is a functional group having a relative permittivity of 5 or more of the compound XH corresponding to the structure of X, and is any of the functional groups represented by the following X-1 to X-4.

[In X-1, 2 and p is an integer of 0 to 5. In X-4, R ³ and R ⁴ represent hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. ]

Further, the polymerizable monomer of the present invention is preferably represented by the following general formula (2).

[In the general formula (2), A, R ¹ , Y, n and m are synonymous with those in the general formula (1). X'is one of the following X-1 to X-4.

[In X-1, 2 and p is an integer of 0 to 5. In X-4, R ³ and R ⁴ represent hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. ]
l is an integer of 1 to 6. When n is 2 or 3, A, ^R1 and Y may be the same or different, respectively. ]

The polymerizable monomer of the present invention is more preferably represented by the following general formula (3).

[In the general formula (3), ^R1 , X'and n are synonymous with those in the general formula (2). m'is an integer from 0 to 1. l'is an integer of 1 to 3. q is an integer from 1 to 12. When n is 2 or 3, R ¹ and q may be the same or different, respectively. ]

Another invention is a curable composition comprising a polymerizable monomer (I) made of the polymerizable monomer of the present invention and a polymerization initiator.

The curable composition of the present invention preferably further contains an acidic group-free polymerizable monomer in addition to the polymerizable monomer of the present invention.

The curable composition of the present invention can be suitably used for a dental adhesive composition.

The polymerizable monomer of the present invention has high compatibility with a polymerizable monomer having an acidic group but no acidic group, and facilitates the operation at the time of mixing. Can be done. In addition, the polymerizable monomer of the present invention has high compatibility with an inorganic salt in the form of a salt compound. When the polymerizable monomer of the present invention is used as an adhesive composition and a salt compound is produced at the time of adhesion, the salt compound having low compatibility with the surrounding polymerizable monomer is caused by precipitation and deterioration of the polymerizable property. Reduces adhesiveness. It is considered that the salt compound of the polymerizable monomer having low compatibility is likely to precipitate at the interface between the tooth surface and the adhesive (dental adhesive composition), and their polymerizable property is low, so that the adhesiveness is lowered. .. On the other hand, the salt compound formed by the polymerizable monomer of the present invention has high compatibility. Therefore, when the polymerizable monomer of the present invention is used as a dental adhesive composition, the salt compound is used. It is considered that the precipitation at the interface of the compound is suppressed or dispersed on the adhesive side, so that the abundance ratio of the salt compound at the interface can be reduced, and as a result, the adhesiveness can be improved.

The polymerizable monomer of the present invention is characterized by being represented by the following general formula (1).

Here, in the general formula (1), A is a divalent hydrocarbon group having 1 to 50 carbon atoms, and may have a branched structure or a cyclic structure, and the carbon atom is an oxygen atom or a sulfur atom. , Or it may be substituted with a nitrogen atom. B is a divalent hydrocarbon group having 1 to 10 carbon atoms, may have a branched structure or a cyclic structure, and the carbon atom may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. .. R ¹ is a hydrogen atom or a methyl group. X represents a functional group having a relative permittivity of 5 or more for the compound XH corresponding to the structure of X. Y is —O— or ^{—NR2- (R 2 is} a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). n is an integer of 1 to 3. m is an integer from 0 to 4. When n is 2 or 3, A, ^R1 and Y may be the same or different, respectively.

The polymerizable monomer of the present invention has high compatibility with a polymerizable monomer having no acidic group, and can be easily mixed with a polymerizable monomer having no acidic group. Further, the adhesive composition containing the polymerizable monomer of the present invention is a polymerizable monomer having no acidic group of the salt compound of the polymerizable monomer of the present invention generated by the reaction with an inorganic salt or an organic salt. High compatibility with monomers. As a result, high adhesiveness can be exhibited even in an environment where a salt compound is generated. Such an effect is achieved by having the characteristic of having an acidic group and a functional group having a high dielectric constant as a design of the polymerizable monomer. The present inventors presume the reason why such an effect is obtained as follows.

First, it is considered that the reason why the operation at the time of mixing is easy is that a functional group based on the skeleton of the compound having a high dielectric constant is imparted. Generally, amide-based solvents such as dimethylacetamide and dimethylformamide, sulfooxide-based solvents such as dimethyl sulfoxide, cyclic ether-based solvents such as tetrahydrofuran, solvents having a lactam ring such as methylpyrrolidone, carbonate-based solvents and the like. Has a high dielectric constant of 5 or more, and is known to have high compatibility with a compound that is sparingly soluble in a normal organic solvent such as a salt compound. In addition, these solvents are easily compatible with organic solvents such as acetone, which are generally used as solvents. Therefore, by imparting the skeleton of such a compound having a high dielectric constant having a relative permittivity of 5 or more to the polymerizable monomer, compatibility with a polymerizable monomer having a wide range of polarities, a catalyst, or the like is improved. It is thought that it will be done.

Further, the reason why the compatibility of the salt compound is excellent is that, as described above, the polymerizable monomer of the present invention has a functional group based on the skeleton of the compound having a high dielectric constant and does not have an acidic group. This is because it has high compatibility with sex monomers and the like. In addition, even if the polymerizable monomer of the present invention forms a salt compound, the polymerizable monomer of the present invention has a skeleton of the solvent having high solubility of the salt compound, so that the formed salt compound has a skeleton. It is considered that the dispersibility in the polymerizable monomer and the like is improved and the precipitation of the salt compound is suppressed. As a result, for example, when the polymerizable monomer of the present invention is used in a dental adhesive composition, for an adherend such as a dentin in which a salt compound is generated on the adhesive interface with the dental adhesive composition. However, it is considered that the adhesiveness is excellent because the salt compound that inhibits the adhesion is easily dispersed in the dental adhesive composition.

Next, the polymerizable monomer of the present invention will be described in more detail.

First, X in the general formula (1) is a functional group having a relative permittivity of the compound XH corresponding to the structure of X of 5 or more. The compound XH corresponding to the structure of X is a compound in which a hydrogen atom is bonded to the bond of the functional group X. In the present invention, the relative permittivity of XH is preferably in the range of 5 to 50, more preferably in the range of 5 to 30 .

When made into a curable composition, it is highly compatible with other components in the composition, is easy to mix and dissolve, and has excellent adhesiveness even under conditions such as the formation of salt compounds. The group X is specifically one of the following, X-1 which is a cyclic ether, X-2 which is a lactam, X-3 which is a carbonate ring, or X-4 which is an acetamide skeleton. ..

Here, in X-1 and 2, p is an integer of 0 to 5. In X-4, R ³ and R ⁴ represent hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. p is preferably 0 to 2. Further, it is preferable that R ³ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ⁴ is an alkyl group having 1 to 4 carbon atoms.

Among these X-1 to 4, among X-1 or X-4, R ³ is hydrogen or an alkyl group having 1 to 2 carbon atoms, and R ⁴ is an alkyl having 1 to 4 carbon atoms. It is more preferred to be selected from the underlying acetamide.

Preferred structures for X-1 to 4 include a tetrahydrofuran ring and a furan ring as X-1 cyclic ethers, a pyrrolidone ring and a piperidone ring as X-2 lactams, and an ethylene carbonate as X-3 carbonate rings. Examples of the ring, dioxanone ring, and X-4 acetamide skeleton include dimethylacetamide, ethylmethylacetamide, and dimethylpropanamide. As more preferable structures, a tetrahydrofuran ring, a pyrrolidone ring, and dimethylacetamide can be exemplified.

Y represents —O— or ^{—NR2- (R 2 is} a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). It is preferably —O— or —NR ^21— (R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and more preferably —O— or —NR ^{22— (R 22 is} , An alkyl group having 1 to 3 carbon atoms).

A is a divalent hydrocarbon group having 1 to 50 carbon atoms, which may have a branched structure or a cyclic structure, and the carbon atom may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. good.

Specific examples of A include the following A-1 to A-11.

In A-1 to A-11, a represents an integer of 0 to 49, b represents an integer of 1 to 16, c represents an integer of 1 to 11, and d represents an integer of 1 to 9. .. The values a to d are preferably selected in the range of structural formulas A-1 to A-6 in the range where the number of atoms in the main chain is 25 or less, and are preferably selected in the range of 12 or less. More preferred. Further, R ⁵ and R ⁶ are alkyl groups having 1 to 24 carbon atoms, and R ⁷ and R ⁸ are alkyl groups having 1 to 23 carbon atoms. R ⁵ and R ⁶ are preferably 1 to 12 alkyl groups, more preferably 1 to 6 alkyl groups, from the viewpoint of improving compatibility and adhesiveness. R ⁷ and R ⁸ are preferably 1 to 10 alkyl groups, more preferably 1 to 4 alkyl groups, from the viewpoint of improving compatibility and adhesiveness. e is an integer of 0 to 5, and is preferably selected in the range of 0 to 3. Further, the two bonds A-9 to A-11 can be bonded to any carbon of the cyclic hydrocarbon, may be bonded to different carbon atoms, or may be bonded to the same carbon atom. good.

As the structure of A, A-1, A-3, A-5, A-7, and A-8 are preferable, and A-1, A-3, and A-8 are more preferable.

B represents a divalent hydrocarbon group having 1 to 10 carbon atoms. It may have a branched structure or a cyclic structure, and the carbon atom may be replaced with an oxygen atom, a sulfur atom, or a nitrogen atom. Specific examples of B include the following B-1 to B-13.

In B-1 to B-9, x represents an integer of 0 to 9, y represents an integer of 1 to 8, z represents an integer of 1 to 3, and w represents an integer of 1 to 2. The values of x to w are preferably selected in the range of structural formulas B-1 to B-9 in the range where the number of atoms in the main chain is 6 or less, and are preferably selected in the range of 3 or less. More preferred. Further, R ⁹ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. v is an integer of 0 to 5, and is preferably selected in the range of 1 to 3. Further, the two bonds of B-10 to B-11 can be bonded to any carbon of the cyclic hydrocarbon group, may be bonded to different carbon atoms, or are bonded to the same carbon atom. May be good. Further, R ¹⁰ and R ¹¹ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and may be the same or different from each other.

As the structure of B, B-1, B-10, and B-12 are preferable, and B-1 is preferable because it is not easily hydrolyzed, can move flexibly, and can impart appropriate hydrophobicity. Is more preferable.

R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably selected based on its copolymerizability with other polymerizable monomers. For example, when methyl methacrylate is selected as the other polymerizable monomer, R ¹ is preferably a methyl group.

n represents an integer of 1 to 3. n can be selected depending on the mechanical strength required for the cured product of the curable composition and the like. For example, when a curable composition for obtaining a rigid cured product is obtained, it is preferable that n is large. On the other hand, when a curable composition for obtaining a flexible cured product is obtained, it is preferable that n is small.

m represents an integer from 0 to 4. From the viewpoint of ease of manufacture, it is preferably selected from the range of 0 to 1, and more preferably 0.

The polymerizable monomer of the present invention represented by the general formula (1) is preferably represented by the following general formula (2).

[In the general formula (2), A, R ¹ , Y, n and m are synonymous with those in the general formula (1). X'is one of the following X-1 to X-4.

[In X-1, 2 and p is an integer of 0 to 5. In X-4, R ³ and R ⁴ represent hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. ]
l is an integer of 1 to 6. When n is 2 or 3, A, ^R1 and Y may be the same or different, respectively. ]

In the general formula (2), A, R ¹ , Y, n and m are the same as those described in the general formula (1). Further, X-1, X-2, X-3 and X-4 in X'are those in X-1, X-2, X-3 and X-4 described in X of the above general formula (1). Is synonymous with.

l is an integer of 1 to 6, preferably 1 to 3.

Further, the polymerizable monomer of the present invention represented by the general formula (2) is particularly preferably represented by the following general formula (3). The general formula (3) shows the structure in the general formula (2) when A is the above-mentioned A-1.

[In the general formula (3), ^R1 , X'and n are synonymous with those in the general formula (2). m'is an integer from 0 to 1. l'is an integer of 1 to 3. q is an integer from 1 to 12. When n is 2 or 3, R ¹ and q may be the same or different, respectively. ]

In the general formula (3), R ¹ , X'and n are the same as those described in the general formula (2).

The polymerizable monomer of the present invention can be synthesized by appropriately combining a known starting material and a known synthesis method, and the production method thereof is not particularly limited. For example, when synthesizing the polymerizable monomer of the present invention represented by the general formula (1), the compound represented by the following general formula (4) is reacted with the compound represented by the general formula (5) and phosphorus oxychloride. A manufacturing method including at least a step may be used.

Here, A, ^R1 , Y, m and n in the general formula (4) are synonymous with those in the general formula (1).

Here, B and X in the general formula (5) are synonymous with those in the general formula (1).

The compound represented by the general formula (4) is reacted with phosphorus oxychloride (POCl ₃ ), further reacted with the compound represented by the general formula (5), and finally hydrolyzed to obtain the general formula (1). The method for obtaining the represented polymerizable monomer of the present invention will be described.

The amount of POCl ₃ used is not particularly limited, but is preferably 1.0 to 1.5 times mol, more preferably 1.0 to 1.2 times mol, with respect to the compound represented by the general formula (4).

In the reaction between the compound represented by the general formula (4) and POCl ₃ , a basic compound can be used if necessary. Examples of the basic compound include nitrogen-containing compounds such as triethylamine, tri-n-butylamine and pyridine. The amount of the basic compound used is not particularly limited, but is preferably 1.0 to 2.0 times the molar amount of POCl ₃ .

The reaction between the compound represented by the general formula (4) and POCl ₃ can be carried out in the presence or absence of a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the reaction, and for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl. Ethers such as ethers, diethylene glycol dimethyl ethers and tetrahydrofurans; chlorine-containing compounds such as dichloromethane, chloroform and carbon tetrachloride; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, pyridines, triethylamine and the like. Examples of the nitrogen-containing compounds of. These may be used alone or in combination of two or more. When a solvent is used, the amount used is not limited, but it is preferably selected from the range of 2 to 500 times by weight with respect to the compound represented by the general formula (4), and 5 to 100 times by weight. It is more preferable to be selected from the range of.

The reaction temperature in the reaction between the compound represented by the general formula (4) and POCl ₃ is usually preferably in the range of −100 ° C. to 100 ° C., more preferably in the range of −50 ° C. to 20 ° C. ..

After completion of the above reaction, the following reaction is carried out by adding the compound represented by the general formula (5) to the reaction solution.

The amount of the compound represented by the general formula (5) to be used is not particularly limited, but 0.8 to 1.5 times the molar amount is preferable with respect to the compound represented by the general formula (4), and 0.9 to 1.2 times. Double moles are more preferred.

In the reaction with the compound represented by the general formula (5), a basic compound can be additionally used as needed. Examples of the basic compound include nitrogen-containing compounds such as triethylamine, tri-n-butylamine and pyridine. The amount of the basic compound used is not particularly limited, but is preferably 1.0 to 2.0 times the molar amount of POCl ₃ added previously. At this time, it does not have to be the same as the basic compound added earlier.

When the compound represented by the general formula (5) is added, it may be added together with a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the reaction, and for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl. Ethers such as ethers, diethylene glycol dimethyl ethers and tetrahydrofurans; chlorine-containing compounds such as dichloromethane, chloroform and carbon tetrachloride; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, pyridines, triethylamine and the like. Examples of the nitrogen-containing compounds of. These may be used alone or in combination of two or more. When a solvent is used, the amount used is not limited, but it is preferably selected from the range of 2 to 100 times the weight of the compound represented by the general formula (5), and 2 to 10 times the weight is preferable. It is more preferable to be selected from the range of.

The reaction temperature in the reaction with the compound represented by the general formula (5) is usually preferably in the range of −100 ° C. to 100 ° C., and more preferably in the range of −50 ° C. to 20 ° C.

After completion of the above reaction, water is added to the reaction solution to hydrolyze the reaction solution to obtain the polymerizable monomer of the present invention represented by the general formula (1). The amount of water used is not particularly limited, but is preferably 1.1 to 10 times mol, more preferably 1.1 to 5.0 times mol, with respect to the compound represented by the general formula (4).

In the hydrolysis reaction, a basic compound can be added and used as needed. Examples of the basic compound include nitrogen-containing compounds such as triethylamine, tri-n-butylamine and pyridine. The amount of the basic compound used is not particularly limited, but is preferably 1.0 to 2.0 times the molar amount of POCl ₃ added previously. At this time, it does not have to be the same as the basic compound added earlier.

When adding water, it may be added together with a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the reaction, and for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl. Ethers such as ethers, diethylene glycol dimethyl ethers and tetrahydrofurans; chlorine-containing compounds such as dichloromethane, chloroform and carbon tetrachloride; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, pyridines, triethylamine and the like. Examples of the nitrogen-containing compounds of. These may be used alone or in combination of two or more. When a solvent is used, the amount used is not limited, but it is preferably selected from the range of 1 to 100 times the weight of the compound represented by the general formula (5), and 2 to 10 times the weight is preferable. It is more preferable to be selected from the range of.

The reaction temperature in the hydrolysis reaction is usually preferably in the range of −100 ° C. to 100 ° C., more preferably in the range of −50 ° C. to 20 ° C.

The polymerizable monomer of the present invention represented by the general formula (1) can be obtained as a salt addition salt by a hydrolysis reaction. After completion of the reaction, the target polymerizable monomer of the present invention represented by the general formula (1) is released from the salt-added salt by acid treatment, extracted with an organic solvent, and the obtained solution is concentrated. Therefore, the polymerizable monomer of the present invention represented by the general formula (1) can be obtained.

The polymerizable monomer of the present invention is a curable composition containing the polymerizable monomer of the present invention and other components from the viewpoint of being used in various applications (hereinafter, the polymerizable monomer of the present invention is used. It is also preferable to use it as a composition containing).

The other components used together with the polymerizable monomer of the present invention are not particularly limited and may be appropriately selected depending on the intended use of the composition containing the polymerizable monomer of the present invention. Specific examples of other components include, for example, other polymerizable monomers other than the polymerizable monomer of the present invention (hereinafter, also simply referred to as other polymerizable monomers), and low molecules having no reactivity. Examples thereof include organic compounds, resins, fillers, organic-inorganic composite materials, polymerization initiators, various additives other than polymerization initiators, solvents and the like, and two or more of these components can be used in combination.

By combining with other polymerizable monomers as other components used in combination with the polymerizable monomer of the present invention, the physical properties of the mixture of the polymerizable monomers and the cured product thereof can be adjusted. As the other polymerizable monomer, a known polymerizable monomer can be used without limitation. However, from the viewpoint of high copolymerizability with the polymerizable monomer of the present invention, the (meth) acrylate-based polymerizable monomer is preferable.

As the (meth) acrylate-based polymerizable monomer, a polyalkylene glycol di (meth) acrylate such as triethylene glycol dimethacrylate (3G) (more specifically, the degree of polymerization of the alkylene glycol unit is 1 or more and 14 or less). Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having a degree of polymerization of 1 or more and 7 or less in units of alkylene glycol, polymethylene glycol di (meth) acrylate having 2 to 10 carbon atoms, etc.), neopentyl glycol di (meth) ) Acrylate, tricyclodecanedimethanol di (meth) acrylate, alkandi (meth) acrylate such as 1,9-nonanediol dimethacrylate (more specifically, alkandi (meth) acrylate having 2 or more and 20 or less hydrocarbons, etc. ), Bisphenol A dimethacrylate (BisGMA), methyl (meth) acrylate, ethyl (meth) acrylate, tetrahydrofurfuryl methacrylate and other acidic group-free polymerizable monomers; methacrylyloxyethyl phosphate (P1M), dimethacrylate Acidic group-containing polymerizables other than the polymerizable monomer of the present invention, such as leuroxyethyl phosphate (P2M), methacrylooxydecanephosphate (MDP), 4- (meth) acryloyloxyethyl trimellitic anhydride, etc. Monomers can be mentioned.

The composition containing the polymerizable monomer of the present invention contains a polymerization initiator as other components and has curability. As the polymerization initiator used in the composition containing the polymerizable monomer, a known polymerization initiator can be used, and a radical photopolymerization initiator, an azo-based or peroxide-based thermal polymerization initiator, and the like. Various polymerization initiators such as redox polymerization initiators can be appropriately used. For example, in the case of polymerization and curing by light irradiation, a photopolymerization initiator such as camphorquinone or ethyl pn, N-dimethylaminobenzoate can be used. When polymerizing and curing by heat polymerization, an organic peroxide such as benzoyl peroxide and an azo compound such as azoisobutyronitrile can be used. When polymerizing and curing by chemical polymerization, organic peroxides such as benzoyl peroxide and amine compounds such as N, N-dimethylparatoluidine, p-N, N-dimethylaminobenzoate ethyl and p-tolyldiethanolamine are used. Can be used. Two or more kinds of these polymerization initiators can be used in combination.

Further, other additives such as known polymerization inhibitors and sensitizers can be used in combination with the polymerization initiator. For example, as the polymerization inhibitor, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, nitrobenzene and the like can be used. Other additives include, as UV absorbers, for example, benzophenone compounds such as (2-hydroxy-4-methoxybenzophenone and (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole. Triazole-based compounds and the like can be used.

It is also suitable to add a filler to the composition containing the polymerizable monomer of the present invention. The filler can improve the mechanical strength, the wear resistance, the coefficient of thermal expansion, the operability, the water absorption, the solubility, and the like. As the inorganic filler, for example, an inorganic filler composed of particles of an inorganic oxide such as amorphous silica, silica-titania, silica-zirconia, silica-titania-barium oxide, quartz, and alumina can be used. , Organic fillers and organic-inorganic composite fillers can also be used. The particle size and shape of the filler are not particularly limited, but for example, particles having a spherical shape or an indefinite shape and an average particle diameter of about 0.01 μm to 100 μm can be appropriately used depending on the intended purpose. In addition, these fillers have good compatibility with other materials such as the polymerizable monomer of the present invention and other polymerizable monomers used in combination as necessary, and have improved mechanical strength and water resistance. From the viewpoint of improvement, it may be treated with a surface treatment agent typified by a silane coupling agent.

The polymerizable monomer of the present invention has a high dielectric constant and an acidic group, and has high compatibility with any compound having a high dielectric constant or a low dielectric constant. Therefore, it is preferable and advantageous to use it in an application in which a low dielectric constant component and a high dielectric constant component need to be mixed. For example, it is preferable for applications such as dental materials such as dental curable compositions or dental adhesives, and coating materials such as metal coatings, glass coatings, and inorganic coatings. For example, when the polymerizable monomer of the present invention is used as an adhesive. Contains a polymerizable monomer (such as Bis-GMA) that imparts strength and an adhesive polymerizable monomer (an acidic group-containing polymerizable monomer or a sulfur atom other than the polymerizable monomer of the present invention). By mixing with the polymerizable monomer), the effect of the polymerizable monomer of the present invention can be exhibited.

Considering the above-mentioned characteristics of the polymerizable monomer of the present invention, the polymerizable monomer of the present invention can be widely used as a component of a dental curable composition. The polymerizable monomer of the present invention is a polymerizable monomer constituting a dental material, particularly a dental adhesive composition such as a dental adhesive used for adhering to a tooth surface or a dental adhesive resin cement. It is preferable to use it as a

Examples and comparative examples relating to the present invention are shown below, but the present invention is not limited to these examples. The abbreviations / abbreviations of the substances used in the preparation of the samples of each example and the comparative example, their structural formulas or substance names, the preparation methods of various samples, and various evaluation methods will be described below.

(material)
(Abbreviations / abbreviations and their structural formulas or substance names)
[Polymeric monomer containing phosphoric acid diester skeleton (polymerizable monomer represented by the general formula (1))]
MEPP: Methalyloxyethylpyrrolidone ethyl phosphate

MDPT: Methacryloxydecanetetrahydrofurfuryl phosphate

MEGPC: Methacryloxydiethylene glycol glycerin carbonate phosphate

MEPET: Methacryloxyethyl Tetrahydrofurfuryl Diethylene Glycol Phosphoric Acid

MEPET is obtained as a mixture with methacryloyloxyethyl phosphate (P1M) and its molar ratio is MEPET: P1M = 80:20.

DMGPT: Dimethacryloyloxyglycerol tetrahydrofurfuryl phosphate

DMGPA: Dimethacryloyloxyglycerol methylacetamide phosphate

TAPPT: Pentaerythritol Triacryloyloxytetrahydrofurfuryl Phosphate

TAPPT is obtained as a mixture with pentaerythritol triacryloyloxymonophosphate (TAPP) and its molar ratio is TAPPT: TAPP = 85: 15.

[Polymeric monomer containing phosphoric acid diester skeleton (polymerizable monomer having a molecular structure other than the general formula (1))]
P2M: Dimethacryloyloxyethyl phosphoric acid PhP: Methacryloyloxyethylphenylphosphate What is a polymerizable monomer containing a phosphoric acid diester skeleton (a polymerizable monomer having a molecular structure other than the general formula (1))? It is a polymerizable monomer containing a phosphoric acid diester skeleton in which the specific dielectric constant of the compound XH corresponding to the structure of X is less than 5.

[Polymeric monomer containing no phosphoric acid diester skeleton (polymerizable monomer having a molecular structure other than the general formula (1))]
Bis-GMA: Bisphenol A diglycidyl dimethacrylate Bis-EMA: Bisphenol A polyethoxydimethacrylate TEGDMA: Triethylene glycol dimethacrylate HEMA: 2-Hydroxyethyl methacrylate MDP: 10-methacryloxydecanephosphate P1M: Methacryloxyethyl Phosphate TAPP: Pentaerythritoltriacrylloyoxymonophosphate

[Photopolymerization initiator]
CQ: Camphorquinone DMBE: p-N, N-dimethylaminoethyl benzoate

[Polymerization inhibitor]
BHT: 2,6-di-tert-butyl-p-cresol

(Evaluation method and evaluation criteria)
The adhesive tests for the dental adhesive compositions of Examples and Comparative Examples described later are as follows.

1. 1. Adhesion test First, the anterior teeth of cows removed within 24 hours after slaughter were polished with water-resistant abrasive paper P600 under water injection, and the enamel or dentin surface was carved out so as to be parallel and flat on the lip surface. .. Next, compressed air was blown onto the machined flat surface for about 5 seconds to dry it. Then, a double-sided tape having a hole with a diameter of 3 mm is attached to this flat surface, and further, paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm is applied to the center of the hole of the double-sided tape attached earlier. A simulated cavity was formed by aligning and fixing the centers of the wax holes. The dental adhesive composition is applied to this simulated cavity, left for 20 seconds, and then irradiated with visible light for 20 seconds using a visible light irradiator (LCT, manufactured by Cabo Dental Systems Japan) to cure the dental adhesive composition. I let you. Further, a composite resin (Esterite Sigma Quick manufactured by Tokuyama Dental Co., Ltd.) was filled therein, pressure-welded with a polyester sheet, and after filling, it was irradiated with visible light for 10 seconds to cure.

Resin cement (Bistite II manufactured by Tokuyama Dental Co., Ltd.) was applied to the upper surface of the composite resin cured product of the adhesion test piece, and a cylindrical SUS attachment having a diameter of 8 mm and a length of 25 mm was further adhered. After the resin cement was cured at 23 degrees for 30 minutes, the adhesion test piece was immersed in water at 37 degrees for 24 hours to obtain an adhesion test piece with an attachment.

Using a universal testing machine (Autograph, manufactured by Shimadzu Corporation), the adhesive test piece with attachment was pulled at a crosshead speed of 2 mm / min, and the tensile adhesive strength between the tooth and the composite resin cured product was measured. The tensile adhesive strength was measured for each of the eight test pieces prepared for each Example or each Comparative Example. Then, the average value of the tensile adhesive strength of 8 times was taken as the adhesive strength of each Example or Comparative Example.

Among the polymerizable monomers used in the preparation of the dental adhesive composition, those corresponding to the polymerizable monomer represented by the general formula (1) were synthesized by the following procedure.

<Example 1 Synthesis of MEPP>
First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of tetrahydrofuran (THF) were added and cooled to −20 ° C. Subsequently, 20.0 g of hydroxyethyl methacrylate (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 19.4 g of N-hydroxyethylpyrrolidone (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained solution, and the mixture was reacted at −20 ° C. for 1 hour. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain MEPP (yield 42.0 g, yield 87%, HPLC purity 97%). The data of the obtained ¹ H NMR spectrum of MEPP were as follows.

^{1 1} H NMR δ δ 1.93 (s, 3H), 2.04 (m, 2H), 2.35 (m, 2H) 3.48 (m, 2H), 3.56 (m, 2H), 4 .24-4.43 (m, 6H), 5.59 (s, 1H), 6.10 (s, 1H).

<Example 2 Synthesis of MDPT>
To 260 g (1.5 mol) of methacrylic acid, 65 g (0.8 mol) of decanediol and 7 g (0.08 mol) of p-toluenesulfonic acid monohydrate were added, and the generated water was added at 90 ° C. for 4 hours. It was reacted while being removed. 250 mL of hexane was added to the obtained solution, the resulting solid was filtered off, the filtrate was washed twice with a 5% aqueous potassium carbonate solution and twice with a saturated aqueous sodium chloride solution, and magnesium sulfate was added to the recovered hexane layer. , The contained water was removed. Then, magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator. The concentrate was purified by silica gel column chromatography to obtain hydroxydecane methacrylate (yield 115 g, yield 63%, HPLC purity 95%).

First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of THF were added and cooled to −20 ° C. Subsequently, 36.3 g of hydroxydecane methacrylate (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 15.0 g of tetrahydrofurfuryl alcohol (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained solution, and the mixture was reacted at −20 ° C. for 1 hour. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain MDPT (yield 55.9 g, yield 92%, HPLC purity 93%). The data of the obtained ¹ H NMR spectrum of MDPT were as follows.

^{1 1} H NMR δ δ 1.20-1.45 (m, 12H), 1.60-2.10 (m, 11H) 3.75-4.25 (m, 9H), 5.55 (s, 1H) ), 6.10 (s, 1H).

<Example 3 Synthesis of MEGPC>
First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of THF were added and cooled to −20 ° C. Subsequently, 26.1 g of ethylene glycol monomethacrylate (0.15 mol, manufactured by Kyoeisha Chemical Co., Ltd.), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 17.7 g of glycerin carbonate (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained solution, and the mixture was reacted at −20 ° C. for 1 hour. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain MEGPC (yield 46.7 g, yield 88%, HPLC purity 94%). The data of the obtained ¹ H NMR spectrum of MEGPC were as follows.

^{1 1} H NMR δ δ 1.95 (s, 3H) 3.75-3.77 (m, 4H) 4.35-4.64 (m, 6H) 4.83-5.14 (m, 1H), 5.67 (s, 1H), 6.15 (s, 1H).

<Example 4 Synthesis of MEPET>
First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of THF were added and cooled to −20 ° C. Subsequently, 19.5 g of hydroxyethyl methacrylate (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 30.0 g of poly (ethylene glycol) tetrahydrofurfuryl ether (average repeating unit n = 2, 0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained liquid, and -20 was added. The reaction was carried out for 1 hour. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain a mixture of MEPET and P1M (yield 45.8 g, yield 80%, HPLC purity 93%). The ¹ H NMR spectrum data of the obtained mixture of MEPET and P1M was as follows.

^{1 1} H NMR δ δ 1.64-2.12 (m, 7H), 3.74-4.32 (m, 15H), 4.44 (t, 2H), 5.58 (s, 1H), 6 .08 (s, 1H).

<Example 5 Synthesis of DMGPT>
First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of THF were added and cooled to −20 ° C. Subsequently, 34.2 g of glycerin dimethacrylate (0.15 mol, manufactured by Kyoeisha Chemical Co., Ltd.), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 15.0 g of tetrahydrofurfuryl alcohol (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained solution, and the mixture was reacted at −20 ° C. for 1 hour. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain DMGPT (yield 53.0 g, yield 90%, HPLC purity 96%). The data of the obtained ¹ H NMR spectrum of DMGPT were as follows.

^{1 1} H NMR δ δ 1.60-2.10 (m, 10H) 3.70-4.35 (m, 7H) 4.37 (d, 4H) 4.83-5.34 (m, 1H), 5.60 (s, 2H), 6.16 (s, 2H).

<Example 6 Synthesis of DMGPA>
N-Methyl-N-acetylaminoethanol was synthesized according to Non-Patent Document 1 (Journal of Organic Chemistry, 2004, 69, 577).

First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of THF were added and cooled to −20 ° C. Subsequently, 34.2 g of glycerin dimethacrylate (0.15 mol, manufactured by Kyoeisha Chemical Co., Ltd.), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 17.6 g of N-methyl-N-acetylaminoethanol (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained solution, and the mixture was reacted at -20 ° C for 1 hour. rice field. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain DMGPA (yield 51.9 g, yield 85%, HPLC purity 91%). The data of the obtained ¹ H NMR spectrum of DMGPA were as follows.

^{1 1} H NMR δ δ 2.10 (s, 6H), 2.15 (s, 3H), 2.95, 3.10 (s, 3H), 3.54, 3.76 (t, 2H), 4 .30-4.38 (m, 6H), 4.83-5.34 (m, 1H), 5.60 (s, 2H), 6.16 (s, 2H).

<Example 7 Synthesis of TAPPT>
First, pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was purified by silica gel column chromatography (yield 47%, HPLC purity 93%).

First, 2.5 mL of phosphorus oxychloride (0.16 mol) and 150 mL of THF were added and cooled to −20 ° C. Subsequently, 44.7 g of pentaerythritol triacrylate (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at −20 ° C. for 1 hour. Then, 15.0 g of tetrahydrofurfuryl alcohol (0.15 mol), 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added to the obtained solution, and the mixture was reacted at −20 ° C. for 1 hour. Then, 10 mL of distilled water, 20 mL of triethylamine (0.15 mol) and 30 mL of THF were added, and the mixture was reacted at 0 ° C. for 2 hours. After adding potassium carbonate, the mixture was transferred to a separating funnel, washed with toluene, and then dilute hydrochloric acid was added dropwise to the recovered aqueous phase to adjust the pH to about 1 and extraction with methylene chloride was performed. The recovered methylene chloride phase was washed with distilled water three times, and then silica gel was added to remove the contained water. Then, the silica gel was filtered off, and the filtrate was concentrated on a rotary evaporator. Further, the concentrate was vacuum dried to obtain a mixture of TAPPT and TAPP (yield 61.6 g, yield 89%, HPLC purity 94%). The ¹ H NMR spectrum data of the obtained mixture of TAPPT and TAPP was as follows.

^{1 1} H NMR δ δ 1.60-2.10 (m, 4H) 3.70-4.35 (m, 7H) 4.39 (s, 6H) 5.62-6.19 (m, 9H).

<Preparation of Examples 8 to 14, Comparative Examples 1 and 2 Dental Adhesive Compositions>
A polymerizable monomer containing a phosphoric acid diester skeleton and a polymerizable monomer not containing a phosphoric acid diester skeleton were mixed at a predetermined mass ratio shown in Table 1 and added to 100 parts by mass of a mixture of these polymerizable monomers. On the other hand, after adding 0.5 part by mass of CQ, 1.0 part by mass of DMBE, and 0.1 part by mass of BHT, the mixture was stirred in a dark place until uniform. This gave a dental adhesive composition.

Table 1 shows the composition of the dental adhesive composition prepared by using the polymerizable monomer containing the phosphoric acid diester skeleton, and the results of the adhesive test.

From the comparison between Examples 8 to 14 and Comparative Examples 1 and 2, the compound of the present invention has a higher adhesive strength than the known P2M and PhP having no skeleton X of the compound having a relative permittivity of 5 or more. It turns out that it is expensive. This is because the polymerizable monomer of the present invention has high compatibility with a polymerizable monomer having no acidic group, and even if the polymerizable monomer of the present invention becomes a salt compound, it has an acidic group. Due to its high compatibility with non-polymerizable monomers, salt compounds produced by dentin-derived calcium ions generated by decalcification and acidic group-containing polymerizable monomers form an adhesive composition with the tooth surface during bonding. It is considered that this is because it did not precipitate at the interface with and was dispersed in the adhesive composition. From the comparison between Examples 8 to 10 and Example 11, it can be seen that the effect of improving the adhesiveness is greater when B in the general formula (1) is an alkyl chain than when it is ethylene glycol. From the comparison between Examples 8 and 9 and Example 10, it can be seen that the pyrrolidone skeleton or the tetrahydrofuran skeleton has a greater effect of improving the adhesiveness than the ethylene carbonate skeleton in which X in the general formula (1) is used. From this, it can be seen that the effect of improving the adhesiveness is greater when the relative permittivity of the compound corresponding to the introduced skeleton is 50 or less.

Claims (8)

A polymerizable monomer represented by the following general formula (1).

[In general formula (1),
A is a divalent hydrocarbon group having 1 to 50 carbon atoms, which may have a branched structure or a cyclic structure, and may have a carbon atom substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. Often,
B is a divalent hydrocarbon group having 1 to 10 carbon atoms, may have a branched structure or a cyclic structure, and the carbon atom may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. ,
R ¹ is a hydrogen atom or a methyl group.
X is a functional group having a relative permittivity of 5 or more of the compound XH corresponding to the structure of X, and is described below as X-1 to X-4.

{However, p in X-1 and X-2 represents an integer of 0 to 5, and R ³ and R ⁴ in X-4 represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, respectively. It may be the same or different. }
Represents any of the functional groups indicated by
Y is —O— or ^{—NR2- (R 2 is} a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). n is an integer of 1 to 3 and
m is an integer from 0 to 4 and
When n is 2 or 3, A, ^R1 and Y may be the same or different, respectively. ] The polymerizable monomer according to claim 1, which is represented by the following general formula (2).

[In the general formula (2), A, R ¹ , Y, n and m are synonymous with those in the general formula (1), X'is synonymous with X in the general formula (1), and l is. It is an integer of 1 to 6 . ] The polymerizable monomer according to claim 2, which is represented by the following general formula (3).

[In the general formula (3), R ¹ , X'and n are synonymous with those in the general formula (2), m'is an integer of 0 to 1, and l'is an integer of 1 to 3. , Q is an integer of 1 to 12, and when n is 2 or 3, R ¹ and q may be the same or different, respectively. ] A curable composition comprising the polymerizable monomer (I) composed of the polymerizable monomer according to any one of claims 1 to 3 and a polymerization initiator. The curable composition according to claim 4, further comprising an acidic group-free polymerizable monomer. A dental adhesive composition comprising the curable composition according to claim 4 or 5. The dental adhesive composition comprising the curable composition according to claim 6, further comprising an acidic group-containing polymerizable monomer (II) other than the polymerizable monomer (I). The dental adhesive composition containing the curable composition according to claim 7, wherein the acidic group-containing polymerizable monomer (II) is a phosphoric acid group-containing polymerizable monomer.