JPH07107085B2 - Polymerizable compound and curing agent having acryloyloxyl group and methacryloyloxyl group in one molecule - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a polymerizable compound having both an acryloyloxyl group and a methacryloyloxyl group in one molecule, curability (especially photocurability) containing the compound, The present invention relates to a hardening agent having excellent hardness and strength, and a hardening agent for teeth such as an adhesive for teeth, a composite resin for teeth, and a hard resin for teeth.

[Conventional technology]

Conventionally, as a curable composition for industrial use, a thermosetting, room temperature curing or photocuring composition containing a (meth) acrylic acid ester as a main component has been used. Also, as a curable composition for teeth such as an adhesive for teeth, a composite resin for teeth, a hard resin for teeth, etc., a large number of thermosetting, room temperature curable or photocurable compositions containing (meth) acrylic acid ester as a main component are proposed. Has been done.

However, in the case of a curable composition containing a compound having only an acryloyloxyl group in the molecule as a component, the polymerizability is good, but the water resistance and moisture resistance and heat resistance of the cured product are inferior to the methacrylic ester. On the other hand, in the case of having only a methacryloyloxyl group, the water-moisture resistance and the heat resistance are good, but the polymerizability is inferior to the acrylic ester, and depending on the polymerization conditions, the polymerization rate does not sufficiently increase and the strength of the cured product. There is a problem that the hardness is insufficient. In particular, when it is used in a photocurable composition, which has recently attracted attention as a curable composition for teeth, the polymerization rate on the side far from the light source is low, and the strength and hardness of the cured product are insufficient.

The present inventors compare the properties of the dimethacrylate-derived curable composition, particularly the properties of a room temperature and photopolymerizable curable composition and a heat-polymerizable curable composition, and are advantageous in terms of energy, thermal deformation, working time, etc. At room temperature and photopolymerizable curable composition,
It has been found that a cured product having stable physical properties cannot always be obtained because of the large amount of residual monomers and residual double bonds in a heat-curable curable composition using a radical polymerization initiator such as benzoyl peroxide as a radical polymerization initiator. . As a result of earnest research, 2'-acryloxyethyl-having both an acryloyloxyl group and a methacryloyloxyl group in one molecule.
It has been found that a curable composition containing a polymerizable compound composed of 2-methacryloxyethyl carbamate as a polymerization component does not lower the strength or hardness of the cured product at room temperature or in the case of photopolymerization as compared with the case of heat polymerization. ("Dental Materials and Instruments", Volume 6, No. 2, pp. 131-134, 1987).

[Problems to be solved by the invention]

However, the above-mentioned 2'-acryloxyethyl-2-methacryloxyethyl carbamate is not always satisfactory in strength and hardness of a cured product, and a curing agent having higher strength and hardness is required.

The present invention has good curability at room temperature (particularly photocurability),
The cured product has excellent strength and hardness, sufficiently satisfies the properties required as a tooth curing agent such as a tooth adhesive, a tooth composite resin, and a tooth hard resin, and is suitable for these applications. In addition, it is intended to provide a polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group in one molecule, which can be used for various composite resins for precision machining other than teeth and the like, and a curing agent. .

[Means for solving problems]

 The present invention is the following polymerizable compound and curing agent.

(1) A polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group represented by the following general formula [I] in one molecule.

[In the formula, R ¹ and R ³ are CH ₂ CH ₂ O _n (wherein, n = 0 to 10
Is. ) Is a (poly) ethylene oxide chain, and R ² is an alkylene, arylene or cycloalkylene group. (2) A curing agent containing a polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group represented by the following general formula [I] in one molecule.

[In the formula, R ¹ and R ³ are CH ₂ CH ₂ O _n (wherein, n = 0 to 10
Is. ) Is a (poly) ethylene oxide chain, and R ² is an alkylene, arylene or cycloalkylene group. (3) A hardener for teeth containing a polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group represented by the following general formula [I] in one molecule.

[In the formula, R ¹ and R ³ are CH ₂ CH ₂ O _n (wherein, n = 0 to 10
Is. ) Is a (poly) ethylene oxide chain, and R ² is an alkylene, arylene or cycloalkylene group. The polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group in one molecule according to the present invention is a compound represented by the above general formula [I].

In the general formula [I], the alkylene group represented by R ² is CH _{2 n} (wherein n = 1 to 20), And so on.

Further, as the arylene group represented by R ² , And so on.

Further, as the cycloalkylene group represented by R ² , And so on.

The polymerizable compound represented by the general formula [I] is an acrylate methacrylate having an acryloyloxyl group and a methacryloyloxyl group in one molecule. Representative compounds contained in the compound of the general formula [I] include ethylene glycol acrylate methacrylate, propylene glycol acrylate methacrylate, diethylene glycol acrylate methacrylate, triethylene glycol acrylate methacrylate, polyethylene glycol acrylate methacrylate, neopentyl glycol acrylate methacrylate, butylene glycol. Acrylate methacrylate, hexylene glycol acrylate methacrylate, 1-acryloyloxyethoxy-2-methacryloyloxyethoxybenzene, 1
-Acryloyloxyethoxy-3-methacryloyloxyethoxybenzene, 1-acryloyloxyethoxy-4-methacryloyloxyethoxybenzene, 2-
(4'-acryloyloxyethoxyphenyl) -2-
(4'-methacryloyloxyethoxyphenyl) propane, 2- (4 '-(3 "-acryloyloxy-2"
-Hydroxypropoxy) phenyl) -2- (4'-
(3 ″ -methacryloyloxy-2 ″ -hydroxypropoxy) phenyl) propane, 1-acryloyloxymethyl-2-methacryloyloxymethylcyclohexane, 1-acryloyloxymethyl-3-methacryloyloxymethylcyclohexane, 1-acryloyloxymethyl-4 -Methacryloyloxymethylcyclohexane, 2- (4'-acryloyloxyethoxycyclohexyl) -2- (4'-methacryloyloxyethoxycyclohexyl) propane, 2- (4'-acryloyloxycyclohexyl) -2- (4'-methacryloyloxy Cyclohexyl) propane, 2- (4'-
Examples thereof include [3 ″ -acryloyloxy-2 ″ -hydroxypropoxy] cyclohexyl) -2- (4 ′-[3 ″ -methacryloyloxy-2 ″ -hydroxypropoxy] cyclohexyl) propane.

Examples of the method for producing the compound of the general formula [I] include the following methods.

Synthesis from Carboxylic Acid and Alcohol This is the most general method for synthesizing an ester by dehydration reaction of carboxylic acid and alcohol. By using a Lewis acid such as sulfuric acid, hydrochloric acid, dimethylaniline, aromatic sulfonic acid boron fluoride ethylate such as p-toluenesulfonic acid as a catalyst, and refluxing a solvent such as benzene to shift the equilibrium of the following formula to the right. Water is removed from the reaction system.

Synthesis by Acid Halide The ester is synthesized according to the following formula by the reaction of acid halide and alcohol.

R ¹ COX + R ² OH → R ¹ CO ₂ R ² + HX… [III] Actually, by adding a base such as pyridine, triethylamine, tetramethylurea, etc. to the reaction system and removing the generated hydrogen halide from the reaction system. The reaction proceeds to the right.

Synthesis by transesterification reaction An alcohol corresponding to methacrylic acid ester or acrylic acid ester is catalyzed by an acid such as sulfuric acid or p-toluenesulfonic acid or a base such as potassium alkoxide, and the like.
Transesterification is performed according to the following formula.

The reaction proceeds to the right either by using a large excess of alcohol or by distilling off the methanol formed.

Synthesis by reaction of acid anhydride and alcohol Usually, this reaction proceeds only by heating the system, but an acid or base catalyst is often used to accelerate the reaction.

The compound of the general formula [I] has good curability at room temperature (especially photocurability), excellent strength and hardness of the cured product, and can be used as a general curing agent for applications such as precision machining, especially for tooth curing. As an agent, it can be used for applications such as an adhesive for teeth, a composite resin for teeth, and a hard resin for teeth.

The hardener of the second invention and the hardener for teeth of the third invention of the present invention use the compound of the general formula [I] as a general hardener and a hardener for teeth. When the compound of the general formula [I] is used as a hardening agent and a hardening agent for teeth, it is preferable to mix it with a vinyl compound and a radical polymerization initiator and use it as a curable composition.

As the vinyl compound to be blended in such a curable composition, there are usual radical-polymerizable carbon / carbon unsaturated monomers, and more specifically, unsaturated carboxylic acid monomers and ester-based unsaturated monomers. Examples thereof include a monomer, a nitrile unsaturated monomer, and an aromatic vinyl compound. Examples of unsaturated carboxylic acid monomers include acrylic acid and methacrylic acid, and examples of ester unsaturated monomers include (meth) acrylic acid ester monomers, vinyl acetate and allyl acetate. Examples of the lower aliphatic carboxylic acid unsaturated ester monomers are as follows. Examples of the nitrile unsaturated monomer include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and isopropenyltoluene.

More specifically, the (meth) acrylic acid ester-based monomer is a (meth) acrylic acid ester-based compound formed from acrylic acid or methacrylic acid and a monovalent hydroxyl compound or a polyvalent hydroxyl compound. More specifically, methyl (meth) acrylate, alkyl (meth) acrylate such as ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol. Di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate,
Butylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, 2,2-bis [4
-(Meth) acryloyloxyphenyl] propane, 2,
2-bis [4- (meth) acryloyloxycyclohexyl] propane, 2,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxyphenyl] propane, 1,2-di (meth) acryloyloxyethoxybenzene, 1,3-di (meth) acryloyloxyethoxybenzene, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2,4 (2,4,4 ) -Trimethylhexamethylene diisocyanate (1 mol) and 2-hydroxyethyl (meth) acrylate (2 mol) can be exemplified.

Among these radically polymerizable monomers, a radically polymerizable polyfunctional (meth) acrylate-based monomer having at least two (meth) acryloyloxyl groups in one molecule or a radically polymerizable polyfunctional ( A radically polymerizable monomer mixture containing a (meth) acrylate-based monomer as a main component is particularly preferable. Examples of the radically polymerizable polyfunctional (meth) acrylate-based monomer include (tri) ethylene glycol di (meth) acrylate and 1,3-di (meth)
Acryloyloxyethoxybenzene, 2,2,4 (2,4,4)
-Trimethylhexamethylenediamine diisocyanate 1 mol and 2-hydroxyethyl (meth) acrylate 2
It is preferred to use a mixture of two or more molar adducts.

As the radical polymerization initiator blended in the curable composition, a usual radical polymerization initiator or photopolymerization initiator can be used. Specific examples of such radical polymerization initiators include diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicapryl peroxide, dilauryloyl peroxide, dibenzoyl peroxide, p, p′-dichlorobenzoyl peroxide, p, p′- Dimethoxybenzoyl peroxide,
Examples thereof include organic peroxides such as p, p'-dimethylbenzoyl peroxide and p, p'-dinitrodibenzoyl peroxide. Of these, dibenzoyl peroxide is preferred. When using an organic peroxide, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N-dimethyl-p-tert-butylaniline, N, if necessary. , N-dimethylanisidine, N, N-dimethyl-p-chloroaniline and other aromatic amines can be used in combination, and benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid Aromatic sulfinic acids such as decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid, or salts thereof can also be used together.

When a radical polymerization initiator is used, the composition cures upon completion of the radical polymerization reaction. The time required for this curing varies depending on conditions such as the type of the poly (meth) acrylic acid ester monomer and the polymerization initiator used and the reaction temperature. For example, benzoyl peroxide and N, N-
As for the case of using dimethyl-p-toluidine, a cured composition having a practically sufficient strength can be obtained in a time of several tens of seconds to several minutes.

As the photopolymerization initiator, specifically, diacetyl, 2,3-
Pentanedione, benzyl, dimethoxybenzyl, 4,
Α-such as 4'-dichlorobenzyl and camphorquinone
A diketo carbonyl compound etc. can be illustrated.
When using the α-diketocarbonyl compound as a photopolymerization initiator, triethylamine, trimethylamine, tripropylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N is used as necessary. -Dimethylaniline, N-methyldiphenylamine, 4-dimethylaminobenzaldehyde, 4- (methylhexylamino) benzaldehyde,
4-dimethylaminobenzoic acid, 4-diethylaminobenzoic acid, 4- (methylcyclohexylamino) benzoic acid,
Amine such as methyl 4-dimethylaminobenzoate can also be used in combination. When using a photopolymerization initiator,
A composition containing a photopolymerization initiator is applied to teeth and then irradiated with light. The irradiation light may be xenon lamp light, mercury lamp light, or halogen lamp light. By this light irradiation, the photopolymerization initiator is decomposed into radicals, and radical polymerization is initiated and progressed to cure the composition.
The time required for this curing varies depending on the type and amount of the poly (meth) acrylic acid ester monomer and photopolymerization initiator used, and the amount of the filler, if any, such as camphorquinone and N, As for the case of using N-dimethylaminobenzaldehyde, a cured composition having a practically sufficient strength can be obtained in a time of several seconds to several minutes.

In the above curable composition, when a peroxide is used as a radical polymerization initiator, the ratio of the peroxide used is such that the radical polymerizable monomer mixture (compound of general formula [I] + vinyl compound, The same) Normally 0.01 for 100 parts by weight
To 10 parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably 0.02 to 3 parts by weight. When amines are used in combination with peroxides, the proportion of amines used is radically polymerizable. It is usually in the range of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the monomer mixture.

When a photopolymerization initiator is used as the radical polymerization initiator, the proportion of the α-ketocarbonyl compound used is usually 0.01 with respect to 100 parts by weight of the radically polymerizable monomer mixture.
To 10 parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably 0.02 to 3 parts by weight, and the amount of the amine used is usually 0.01 to 10 parts by weight with respect to 100 parts by weight of the radical-polymerizable monomer mixture. It is in the range of parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably 0.02 to 3 parts by weight.

In the above curable composition, a photocurable composition using a photopolymerization initiator as a polymerization initiator is preferable because it has excellent operability during curing.

The curable composition may further contain other components, if necessary.
For example, a powdered inorganic filler, a composite filler obtained by polymerizing the surface of the inorganic filler with a radical-polymerizable polyfunctional (meth) acrylate-based monomer, an organic polymer, a tackifier, a photosensitizer, and a polymerization agent. A regulator, a polymerization inhibitor, a pigment and the like can be added.

Specific examples of the powdery inorganic filler include kaolin, talc, clay, calcium carbonate, silica, silica-alumina, alumina, titanium oxide, calcium phosphate, glass powder and quartz powder. As the organic polymer, wax, ethylene / vinyl acetate copolymer,
Examples thereof include polymethyl acrylate, polymethyl methacrylate and copolymers thereof. The mixing ratio of these components is appropriate.

The photocurable composition using the photopolymerization initiator is polymerized and cured by irradiation with light. The light beam may be a natural light beam or an artificial light beam, and a light beam from the ultraviolet region to the visible region can be adopted. As the artificial light ray, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a halogen lamp, a tungsten lamp or the like can be used. The temperature during photocuring is usually 0 to 80
C., preferably in the range of 5 to 50.degree. C., and the light irradiation time is usually 1 second to 5 minutes.

〔Example〕

Examples of the present invention will be described below. % Of each example
Is based on weight.

Example 1 112.0 parts of 2-hydroxyethyl acrylate, 105.9 parts of methacrylic acid chloride, 0.1 part of hydroquinone monomethyl ether, and 500 parts of diethyl ether were placed in a flask, and 80.2 parts of pyridine and 200 parts of ethyl ether were added with stirring at 25 ° C. The mixture was added dropwise over 1 hour. After reacting for 8 hours as it was, 300 parts of water was added to stop the reaction. The ether layer in this reaction solution was washed 3 times with 500 ml of a 2% aqueous sodium bicarbonate solution, 3 times with 500 parts of 5% hydrochloric acid and 500 times with water.
Part, washed 3 times, dried over magnesium sulfate, distilled off diethyl ether under reduced pressure, and then distilled under reduced pressure to 68 ° C.
125.0 parts of the target ester A was obtained as a colorless transparent liquid which was distilled off at ˜70 ° C./1 mmHg. The IR chart is as shown in FIG. When ¹ H-NMR was measured, it was 1.9 ppm
3H (t), 4.4ppm to 4H (s), 5.5 to 6.4ppm to 5H
The peak of (m) was observed. The ester A was ethylene glycol acrylate methacrylate represented by the following formula.

Example 2 50.0 parts of diethylene glycol monomethacrylate (PE-90 manufactured by NOF CORPORATION), 30.0 parts of acrylic acid chloride,
Hydroquinone monomethyl ether (0.05 parts) and diethyl ether (500 parts) were placed in a flask, cooled to -10 ° C using an ice salt bath, and stirred with triethylamine 3 parts.
A mixture of 0.0 parts and 200 parts of ethyl ether was added dropwise over 2 hours. After stirring as it was for 30 minutes, 300 parts of water was added to stop the reaction. 2 ether layers of this reaction
% Sodium bicarbonate aqueous solution 3 times with 500 ml, 5% hydrochloric acid 500 parts 3 times
The extract was washed 3 times with 500 parts of water and dried over magnesium sulfate, and then diethyl ether was distilled off under reduced pressure to obtain 26.5 parts of the target ester B as a colorless transparent liquid. The IR chart is as shown in FIG. When ¹ H-NMR was measured, 3H (t) was observed at 1.9 ppm and 8H was observed at 3.7-4.4 ppm.
A peak of 5H (m) was observed at (m) and 5.5 to 6.4 ppm. This ester B was diethylene glycol acrylate methacrylate represented by the following formula.

Example 3 63.2 parts of triethylene glycol monomethacrylate (PE-130 manufactured by NOF CORPORATION), acrylic acid chloride 31.5
Parts, 0.05 parts of hydroquinone monomethyl ether, and 500 parts of diethyl ether were charged into a flask, cooled to -10 ° C using an ice salt bath, and a mixture of 33.0 parts of triethylamine and 200 parts of ethyl ether was stirred for 2 hours. Was dropped. After stirring as it was for 30 minutes, 300 parts of water was added to stop the reaction. The ether layer in this reaction solution was washed 3 times with 500 ml of 2% aqueous sodium bicarbonate solution, 3 times with 5 parts of 5% hydrochloric acid and 3 times with 500 parts of water, dried over magnesium sulfate, and then distilled under reduced pressure to remove diethyl ether. Then, 31.5 parts of the target ester C was obtained as a colorless transparent liquid. That IR
The chart is as shown in FIG. Moreover, when ¹ H-NMR was measured, 3 H (t) was observed at 1.9 ppm and 12 H was observed at 3.7 to 4.4 ppm.
A peak of 5H (m) was observed at (m) and 5.5 to 6.4 ppm. The ester C was triethylene glycol acrylate methacrylate represented by the following formula.

Example 4 100 parts by weight of 1,3-bis (2'-hydroxyethoxy) benzene, 52 parts by weight of methacrylic acid, 2 parts by weight of p-toluenesulfonic acid monohydrate, and 0.1 part by weight of hydroquinone monomethyl ether were added to 1,500 parts by weight of benzene. Dissolved in 1 part and dehydrated under heating and refluxing for 24 hours. After cooling the reaction solution to room temperature and filtering the insoluble matter, the filtrate was shaken with 500 parts by weight of a 0.5N aqueous sodium hydroxide solution until neutral, washed with 500 parts by weight of water, and washed with sodium sulfate and sulfuric acid. It was dried with magnesium. Benzene was distilled off under reduced pressure, and the residue was vacuum dried to give 1- (2'-methacryloxyethoxy) -3-.
86.5 parts by weight of (2'-hydroxyethoxy) benzene were obtained. Subsequently, 86.5 parts by weight of the obtained compound and 35.0 parts by weight of acrylic acid chloride were dissolved in 700 parts by weight of diethyl ether, and a mixture of 50 parts by weight of triethylamine and 450 parts by weight of diethyl ether was stirred for 1 hour while stirring at 0 ° C. Was dropped. After reacting for 6 hours as it was, 5 parts by weight of water was added to stop the reaction. The reaction solution is filtered and the filtrate is
The mixture was shaken with 500 parts by weight of an aqueous sodium hydroxide solution until it became neutral, washed with 500 parts by weight of water, and dried with sodium sulfate and magnesium sulfate. The ether was distilled off under reduced pressure, and the residue was vacuum dried to obtain 41.8 parts by weight of the target ester D. The IR spectrum is shown in FIG. ¹ H-NMR
When measured, 3H at 1.5ppm, 8H at 4.0-4.7ppm, 5.4
Peaks of 5H were observed at ~ 6.3ppm and 4H at 6.3-7.3ppm. This ester D was 1-acryloyloxyethoxy-3-methacryloyloxyethoxybenzene represented by the following structural formula.

Example 5 A 1: 1 (weight ratio) mixture of the ester A of Example 1 and UDMA [dimethacryloyloxyethyl (trimethylhexamethylene diurethane) represented by the following formula [X]] was mixed with camphorquinone as a photopolymerization initiator. 0.1% and p-dimethylaminobenzaldehyde 0.1% were added and mixed uniformly, and then poured into a mold made of polytetrafluoroethylene. Put this in the xenon lamp XS for Denta color (made by Kurza-Corporation), irradiate it with light and cure it to a thickness.
A cured product of 3 mm was obtained, and the compression strength and Brinell hardness (light-irradiated surface and 3 mm below the irradiated surface) were measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold. The compressive strength and Brinell hardness test methods were as described in Yoshio Nakabayashi, Kozo Tomoda, Mitsuo Arakane, “Dental Materials and Instruments”, 5, 422, (1986).

(In the formula, one of R ⁴ and R ⁵ is a hydrogen atom and the other is a methyl group.) Example 6 A 1: 1 (weight ratio) mixture of the ester A of Example 1 and the UDMA of Example 5 was exposed to light. Camphorquinone as a polymerization initiator 0.
After 1% and p-dimethylaminobenzaldehyde 0.1% were added and mixed uniformly, 1.8 parts of filler was added to 1 part of this mixture to form a uniform paste. The filler mixed at this time has the following composition. That is, fused silica Aerosil RM-50 (product name, manufactured by Nippon Aerosil Co., Ltd.)
To 1 part, TMPT composite filler [100 parts of trimethylolpropane trimethacrylate, 100 parts of fused silica Aerosil R-972 (manufactured by Nippon Aerosil Co., Ltd.) and 1 part of benzoyl peroxide were added and mixed uniformly, and then 2
Polymerize by heating for 0 minutes, crush this and average particle size 20μm
Powdered. ] 1 part is mixed. Pour this paste into a mold made of polytetrafluoroethylene and then use the xenon lamp XS for Denta Color.
(Made by Kurzer Co., Ltd.) and irradiated with light to be cured to obtain a cured product with a thickness of 3 mm, and compression strength and Brinell hardness (irradiated surface and 3 mm below irradiated surface) were measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

Example 7 In a 1: 1 (weight ratio) mixture of the ester C of Example 3 and UDMA of Example 5, camphorquinone as a photopolymerization initiator was added.
1% and 0.1% of p-dimethylaminobenzaldehyde were added and mixed uniformly, and then poured into a mold made of polytetrafluoroethylene. Put this in the xenon lamp XS for Denta color (made by Kurzer Co., Ltd.) to perform light irradiation,
After curing, a cured product having a thickness of 3 mm was obtained, and the compressive strength and Brinell hardness (light-irradiated surface and 3 mm below the irradiated surface) were measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both surfaces of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

Example 8 In a 1: 1 (weight ratio) mixture of the ester C of Example 3 and UDMA of Example 5, camphorquinone as a photoinitiator was added.
After 1% and p-dimethylaminobenzaldehyde 0.1% were added and mixed uniformly, 1.8 parts of filler was added to 1 part of this mixture to form a uniform paste. The filler mixed at this time has the following composition. That is, 1 part of TMPT composite filler of Example 6 was mixed with 1 part of fused silica Aerosil RM-50 (manufactured by Nippon Aerosil Co., Ltd.). After pouring this paste into a mold made of polytetrafluoroethylene, put it in a xenon lamp XS for Denta Color (made by Kurzer Co., Ltd.) and irradiate it with light to obtain a cured product with a thickness of 3 mm. The Brinell hardness (light irradiation surface and 3 mm below the irradiation surface) was measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

Comparative Example 1 Ethylene glycol dimethacrylate and UDMA of Example 5
0.1% by weight of camphorquinone and 0.1% of p-dimethylaminobenzaldehyde as a photopolymerization initiator were added to the 1: 1 (weight ratio) mixture and mixed uniformly, and then poured into a mold made of polytetrafluoroethylene. This was put in a xenon lamp XS for Denta Color (manufactured by Kurzer Co., Ltd.) and irradiated with light to be cured to obtain a cured product with a thickness of 3 mm. Compressive strength and Brinell hardness (irradiated surface and 3 m below irradiated surface)
m) was measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

Comparative Example 2 Ethylene glycol dimethacrylate and UDMA of Example 5
0.1% camphorquinone and 0.1% p-dimethylaminobenzaldehyde as a photopolymerization initiator were added to the 1: 1 (weight ratio) mixture, and mixed uniformly, and then 1.8 parts of filler was added to 1 part of this mixture. As a uniform paste. The filler mixed at this time has the following composition. That is, 1 part of fused silica Aerosil RM-50 (manufactured by Nippon Aerosil Co., Ltd.) to 1 part of TMPT composite filler of Example 6
It is a mixture of parts. After pouring this paste into a mold made of polytetrafluoroethylene, put it in a xenon lamp XS for Denta color (made by Kurzer Co., Ltd.) and irradiate it with light to obtain a cured product with a thickness of 3 mm.
Compressive strength and Brinell hardness (light irradiation surface and under irradiation surface
3 mm) was measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

Comparative Example 3 Triethylene glycol dimethacrylate and Example 5
To a 1: 1 (weight ratio) mixture of UDMA, 0.1% camphorquinone and 0.1% p-dimethylaminobenzaldehyde as a photopolymerization initiator were added and mixed uniformly, and then poured into a mold made of polytetrafluoroethylene. This is put in a xenon lamp XS for Denta Color (made by Kurzer), irradiated with light, and cured to obtain a cured product having a thickness of 3 mm.
Compressive strength and Brinell hardness (light irradiation surface and under irradiation surface
3 mm) was measured. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

Comparative Example 4 of triethylene glycol dimethacrylate and Example 5
To a 1: 1 (weight ratio) mixture of UDMA, 0.1 wt% of camphorquinone and 0.1 wt% of p-dimethylaminobenzaldehyde as a photopolymerization initiator were added and mixed uniformly, and then 1.8 parts of filler was added to 1 part of this mixture. Was added to form a uniform paste. The filler mixed at this time has the following composition. That is, 1 part of TMPT composite filler of Example 6 was mixed with 1 part of fused silica Aerosil RM-50 (manufactured by Nippon Aerosil Co., Ltd.). After pouring this paste into a polytetrafluoroethylene mold,
Put it in a xenon lamp XS (made by Kurzer Co., Ltd.) for Denta color, irradiate it with light, and cure it to obtain a cured product with a thickness of 3 mm, and measure the compressive strength and Brinell hardness (irradiated surface and 3 mm below the irradiated surface). went. At this time, in the case of the test piece for compressive strength, light was irradiated for 2 minutes from both sides of the mold, and in the case of the test piece for Brinell hardness, light was irradiated for 2 minutes from one surface of the mold.

The above results are summarized in Table 1.

In Table 1, Examples 5, 6, 7, 8 and Comparative Examples 1, 2,
Comparing Nos. 3 and 4, with respect to compressive strength, the value obtained when a polymerizable compound containing an acryloyloxyl group and a methacryloyloxyl group was higher than that obtained when a compound containing only a methacryloyloxyl group was used. ing. Of particular note here is the comparison of Brinell hardness between the light-irradiated surface and 3 mm below the irradiated surface. In the case of only methacryloyloxyl groups, the hardness on the light-irradiated surface is lower than when using a polymerizable compound containing an acryloyloxyl group and a methacryloyloxyl group, and the decrease in Brinell hardness at 3 mm below the light-irradiated surface is also large. ing. From these results, it is clear that when using a polymerizable compound containing an acryloyloxyl group and a methacryloyloxyl group, the photopolymerizability is higher than when using a compound containing only a methacryloyloxyl group,
The utility of a polymerizable compound containing an acryloyloxyl group and a methacryloyloxyl group in the case of radical polymerization with a photopolymerization initiator is clear.

〔The invention's effect〕

As described above, according to the present invention, a polymerizable compound having a novel and useful acryloyloxyl group and methacryloyloxyl group in one molecule is obtained, and a curing agent and a tooth curing agent containing the same are curable at room temperature, In particular, the photocurability is good, and the strength and hardness of the cured product are excellent.

[Brief description of drawings]

1 to 4 are diagrams showing the IR charts of Examples 1 to 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08F 299/00 MRR C09J 4/02 JBL

Claims (3)

[Claims] 1. A polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group represented by the following general formula [I] in one molecule. [In the formula, R ¹ and R ³ are CH ₂ CH ₂ O _n (wherein, n = 0 to 10
Is. ) Is a (poly) ethylene oxide chain, and R ² is an alkylene, arylene or cycloalkylene group. ] 2. A curing agent containing a polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group represented by the following general formula [I] in one molecule. [In the formula, R ¹ and R ³ are CH ₂ CH ₂ O _n (wherein, n = 0 to 10
Is. ) Is a (poly) ethylene oxide chain, and R ² is an alkylene, arylene or cycloalkylene group. ] 3. A hardener for teeth containing a polymerizable compound having an acryloyloxyl group and a methacryloyloxyl group represented by the following general formula [I] in one molecule. [In the formula, R ¹ and R ³ are CH ₂ CH ₂ O _n (wherein, n = 0 to 10
Is. ) Is a (poly) ethylene oxide chain, and R ² is an alkylene, arylene or cycloalkylene group. ]