JPH11335222A - Material for crown or material for denture base - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a material for a crown or a material for denture base having low irritation without making a patient feel uneasy about the odor even when used in an oral cavity of the patient, good in operating efficiency when mixed with a polymeric component and further having a sufficient mechanical strength of a cured product. SOLUTION: The material for a crown or the material for a denture base contains an acrylic or a methacrylic ester-based polymerizable monomer represented by the formula (R<1> denotes hydrogen atom or an alkyl group; R<2> and R<3> denote each an alkylene group and R<2> and R<3> may be different; R<4> denotes an alkyl group) such as 2-methacryloxyethyl acetoacetate having an (alkylcarbonyl)alkyl}carbonyloxy group in its molecule and a radical polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a material for a crown or a denture base.

[0002]

2. Description of the Related Art Among dental materials using synthetic polymers, dental materials for crowns or denture bases are generally polymethyl methacrylate (hereinafter abbreviated as PMMA), polyethyl methacrylate (hereinafter abbreviated as PEMA) and A polymer component such as a copolymer of methyl methacrylate and ethyl methacrylate (hereinafter abbreviated as PMMA-PEMA); a two component consisting of a monomer component such as a radical polymerizable compound such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-hydroxyethyl methacrylate; System materials are used.

[0003] Such a two-component material can be prepared by mixing both components and curing the mixture using a radical polymerization initiator. When the monomer component used in the above two-component material is brought into contact with the polymer component, a part of the monomer component dissolves in a short time and penetrates into the polymer component to swell (hereinafter, such an action is simply referred to as polymer swelling). Sex). For this reason, there is an advantage that the viscosity of the mixture of the monomer component and the polymer component can be appropriately adjusted, and the clinical or technical operation can be facilitated.

However, methyl methacrylate, which is the main compound of the above-mentioned monomer component, has problems such as strong odor, strong mucous membranes in the oral cavity and skin, and large heat generation during polymerization.

[0005] The above-mentioned problems are particularly problematic in, for example, dental adhesive filling materials (so-called dental cements) because they rarely come into direct contact with the oral mucous membrane, skin, etc., and even if they do so, the amount used is small. However, it becomes a serious problem when a large amount of the prosthetic material is directly cured on the mucous membrane in the oral cavity of a patient, such as a dental prosthetic material such as a material for a crown or a denture base.

In recent years, various monomers described below have been proposed for the purpose of solving these problems.

That is, Japanese Patent Application Laid-Open No. 62-178502 discloses a (meth) acrylate monomer represented by the following formula (A).

[0008]

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(In the formula, R ¹ represents a hydrogen atom or an alkyl group, R ² represents an alkylene group, and R ³ represents an alkyl group.) This monomer has a high polymer swelling property, but has a slight odor. There is irritation to the oral mucosa and skin.

JP-A-3-74311 discloses a (meth) acrylate monomer represented by the following formula (B).

[0011]

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(Wherein, R ¹ represents a hydrogen atom or an alkyl group, R ² represents an alkylene group, and R ³ represents an alkyl group.) This monomer has a high polymer swelling property, There is irritation on the skin.

JP-A-3-206012 discloses a (meth) acrylate monomer represented by the following formula (C).

[0014]

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(Wherein R ¹ is a hydrogen atom or a C ¹ -C 1)
0 represents an alkyl group, R ² represents an alkylene group having 1 to 15 carbon atoms, R ³ represents an alkylene group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to 15 carbon atoms. This monomer has a high polymer swelling property, but has a slight odor.

JP-A-3-20613 discloses a (meth) acrylate monomer represented by the following formula (D).

[0017]

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(Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
0 represents an alkyl group, R ² represents an alkylene group having 1 to 15 carbon atoms, and R ³ represents an alkyl group having 1 to 15 carbon atoms. This monomer has a high polymer swelling property, but has a slight odor and is irritating to the oral mucosa, skin and the like.

JP-A-6-48912 discloses a (meth) acrylate monomer represented by the following formula (E).

[0020]

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(Wherein, R represents a hydrogen atom or a methyl group, m represents 0 or an integer of 1 or more, n represents an integer of 1 or more, and m + n = 2 or more). Although the polymer has a high swelling property, it irritates the oral mucosa, skin and the like.

Japanese Patent Application Laid-Open No. 6-56619 discloses that
A (meth) acrylate monomer represented by the following formula (F) is disclosed.

[0023]

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(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 2 or more.) This monomer has a high polymer swelling property, but is irritating to the oral mucosa, skin and the like.

With the appearance of the monomers shown above,
Odor, irritation of oral mucosa, skin, etc., and heat generation during polymerization could be reduced to some extent as compared with conventional methyl methacrylate, but they have not been sufficiently satisfactory, and improvement of these has been desired.

Further, when these monomers are used as a material for a crown or a material for a denture base, there is a problem that an unpolymerized layer is formed on the surface of the cured product due to inhibition of polymerization by oxygen in the air.

[0027]

SUMMARY OF THE INVENTION An object of the present invention is to develop a crown material or a denture base material which has low odor, irritation to oral mucous membranes and skin, and low heat generation during polymerization, and has good curability. Was an issue.

[0028]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of a specific (meth) acrylate compound has a strong irritating odor, which is a conventional drawback. The inventors have found that it can eliminate the disadvantages of strong irritation to the oral mucosa, skin, etc., and high heat generation during polymerization, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0030]

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(In the formula, R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ represent an alkylene group, R ² and R ³ may be different, and R ⁴ represents an alkyl group.) Or a denture base material comprising a (meth) acrylate-based polymerizable monomer represented by the formula (1) and a radical polymerization initiator.

Of the above materials for crowns or denture bases,
It further contains a radical polymerizable monomer other than the (meth) acrylate polymerizable monomer represented by the general formula (1), and the radical polymerization initiator is represented by the following general formula (2)

[0033]

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Wherein R ⁵ is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, a pyrimidinetrione derivative, a halogen ion forming compound and a cupric ion or The crown material or denture base material, which is a radical polymerization initiator composed of a ferric ion-forming compound, generates little heat during polymerization and has little polymerization inhibition due to oxygen in the air. It has the feature that the number of polymerized layers is small.

The crown material or the denture base material which further contains a polymer component as a filler in the crown material or the denture base material has a feature that the strength when cured is high.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The material for a crown or denture base of the present invention is a polymerizable (meth) acrylate-based monomer (hereinafter referred to as M) represented by the general formula (1) as a monomer component.
It may be abbreviated as -AE monomer. ) Must be used.

The M-AE monomer has a structural feature of having a {(alkylcarbonyl) alkyl} carbonyloxy group, and has a low odor, low irritation, and polymer swelling when used as a crown material or a denture base material. It has the characteristic of high performance.

R ¹ in the general formula (1) is a hydrogen atom or an alkyl group. Properties required as a material for a crown or a material for a denture base, namely, mechanical strength of a cured product obtained by polymerization, low irritation to oral mucosa or skin, odor, and the above-mentioned two-component crown material or a denture Taking into account the solubility of the polymer when used as a floor material, the R ¹ has 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group.
1 to 2 such as an alkyl group, a methyl group, an ethyl group, etc.
Is preferably an alkyl group.

R ² and R ³ in the general formula (1) are alkylene groups, and R ² and R ³ may be different.
Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylene group, a tetramethylene group, a 1-methyltrimethylene group, a 1,2-dimethylethylene group, and a hexamethylene group for the same reason as described above. Alkylene group having 1 to 6 carbon atoms such as methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, tetramethylene group, 1-methyltrimethylene group, 1,2-dimethylethylene group, etc. 1
It is preferably an alkylene group of from 4 to 4.

R ⁴ in the general formula (1) is an alkyl group. The alkyl group is not particularly limited, but is also preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, as in the alkyl group for R ^1, for the same reason as described above.

As the M-AE monomer that can be suitably used in the present invention, R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently a carbon atom in the general formula (1). 1 to 6 alkylene groups, wherein R ⁴ has 1 carbon atom
6 to 6, particularly preferably R
¹ is an alkyl group having 1 to 2 carbon atoms, R ² and R ³ are each independently an alkylene group having 1 to 4 carbon atoms, R ⁴
Is an alkyl group having 1 to 4 carbon atoms.

M which is particularly preferably used in the present invention
Specific examples of the -AE monomer are as follows.

[0043]

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[0044]

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[0045]

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[0046]

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Many of the above-mentioned M-AE monomers are commercially available, and can be easily produced by the following two methods.

That is, as a first method, the compound can be easily produced by reacting a corresponding hydroxyalkyl (meth) acrylic acid ester with a corresponding carboxylic acid and performing dehydration condensation. According to the method, for example, 1 mol of the corresponding hydroxyalkyl (meth) acrylate and 1 mol of the corresponding carboxylic acid are removed together with an acid catalyst and a polymerization inhibitor in toluene by heating to form water. After reacting for 2 hours, washing with an aqueous sodium carbonate solution and drying over sodium sulfate, the solvent is distilled off under reduced pressure to obtain the desired M-AE monomer.

As another method, the corresponding hydroxyalkyl (meth) acrylate is reacted with diketene {R. J. Clemens, Chemi
cal Review, 86, 241 (1986)}. According to the method, for example, 1 mol of the corresponding hydroxyalkyl (meth) acrylate, 1 g of triethylamine, and 1 g
Of butylhydroxytoluene was dissolved in 500 ml of anhydrous ethyl acetate, and 88 g (1.05 mol) of diketene was added dropwise to the solution within 1 hour with stirring, and the reaction mixture was refluxed. And heat for 2 hours,
After cooling, the mixture is washed with diluted hydrochloric acid and water in that order, dried over sodium sulfate, and then the solvent is distilled off under reduced pressure to obtain the desired M-AE monomer.

In the present invention, the M-AE monomer can be used alone. However, it is preferable to mix and use other components according to the mechanical strength and other physical properties of the cured product obtained by polymerization.

As other components, radical polymerizable monomers other than the M-AE monomer, which are copolymerizable with the M-AE monomer (hereinafter, also referred to as other monomers), and the M-AE monomer
A polymer component which swells in the AE monomer is exemplified.
By blending another monomer, it is possible to improve the mechanical strength of the cured product or reduce the water absorption. Further, the mechanical strength is improved by blending the polymer component.

As the other monomer, any monomer other than the M-AE monomer can be used without any limitation as long as it has low irritation and low odor. In general, (meth) acrylates are preferably used. Is done. The (meth) acrylic esters include n-octadecyl (meth)
Acrylate, n-dodecyl (meth) acrylate, n
-Tridecyl (meth) acrylate, n-hexyl methacrylate, cyclohexyl methacrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth)
Acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1 , 12-stearyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimer diol di (meth) acrylate, bisphenol-
A di (meth) acrylate, 2,2-bis [(meth) acryloyloxypolyethoxyphenyl] propane, trimethylolpropanetri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate Urethane di (meth) acrylate (hydroxyethyl (meth) acrylate and 2,2,4-trimethylhexyl-1,6
-Diisocyanate reaction product).

When using the above other monomers,
The proportion of the M-AE monomer in all monomers is
Although it can be selected from a wide range, it is generally preferable that the M-AE monomer is in the range of 5 to 100% by weight.

The polymer component can be used without any limitation as long as it swells in a monomer component containing an M-AE monomer. In general, PMMA, PEMA, PMMA-PMMA is used in terms of chemical stability and transparency. PEMA, polybutyl methacrylate, polystyrene, polyester or polymers of the above-mentioned other monomers of various (meth) acrylates are preferably used. Above all, PEM
Since A is particularly easily swelled by the M-AE monomer, P
It is preferred to use EMA, PMMA-PEMA, or a mixture of these polymers with other polymers.

The molecular weight of the polymer component is not particularly limited, but is preferably in the range of 50 to 1,000,000 in consideration of the mechanical strength of the obtained cured product, the solubility in the monomer component, the swelling property, and the like. Has an average particle size of 10
It is preferably 100 μm.

When a polymer component is used in combination, the amount of the polymer is 50 to 500 based on 100 parts by weight of the total monomer.
It is preferably used in an amount of 100 parts by weight, preferably 100 to 200 parts by weight. At this time, the ratio of the M-AE monomer to all the monomers is in the range of 10 to 100% by weight, particularly 20 to 100% by weight, based on the total amount of the monomers in consideration of the swelling property of the polymer. It is suitable. The crown material or the denture base material of the present invention contains a radical polymerization initiator for polymerizing and curing the monomer component. As the radical polymerization initiator, known thermal polymerization initiators, room temperature polymerization initiators, and photopolymerization initiators can be used without particular limitation. However, when the crown material or the denture base material of the present invention is used after being polymerized and cured in the oral cavity, it is difficult to heat it. Therefore, as the radical polymerization initiator, a room temperature polymerization initiator and / or It is preferred to use a photopolymerization initiator.

Hereinafter, for each radical polymerization initiator, a polymerization initiator that can be suitably used, a suitable amount to be used, and a method of use (a method of curing the material for crown or denture base of the present invention)
Will be described.

First, the case where the radical polymerization initiator is a thermal polymerization initiator will be described. As the thermal polymerization initiator,
Any material that generates a radical by heating can be used without any limitation, and peroxides, azo compounds, and the like are preferably used. Known peroxides and azo compounds are used without any limitation. Specific examples of peroxides that can be suitably used include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dilauroyl peroxide and the like. Specific examples of azo compounds that can be preferably used include 2,2′-azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), and 2,2′-azobis (2,4 -Dimethylvaleronitrile) and the like.

The preferred amount of the above-mentioned heat polymerization initiator varies depending on the kind of the heat polymerization initiator to be used, the composition of the monomer components, and the like, and cannot be unconditionally limited. In general, the amount is 0.1 to 100 parts by weight of all the monomer components. It is preferably used in the range of 0.5 to 5 parts by weight, more preferably 0.1 to 2 parts by weight.
In the case of curing using the above heat polymerization initiator, the material for a crown or the material for a denture base of the present invention containing the above heat polymerization initiator is generally used at 40 to 150 ° C, preferably 50 to 130 ° C. Heating may be performed within the range described above.

When the radical polymerization initiator is a room temperature polymerization initiator, examples of the room temperature polymerization initiator include a combination of a peroxide and a curing accelerator represented by an amine or a salt thereof, a pyrimidinetrione derivative, A polymerization initiator in combination with an ion-forming compound and a cupric or ferric ion-forming compound is preferably used.

As the peroxide, amine or salt thereof, known compounds are used without any particular limitation. For example,
As the organic peroxide, the compounds described above are used. As the amine, a secondary or tertiary amine having an amine bonded to an aryl group is preferably used from the viewpoint of acceleration of curing. For example, N, N′-dimethylaniline, N, N′-dimethyl-p-toluidine, N-methyl-N′-β-hydroxyethylaniline, p-tolyldiethanolamine and the like can be mentioned as preferable examples. These amines may form salts with hydrochloric acid, acetic acid, phosphoric acid, organic acids and the like.

Preferable examples of these combinations include benzoyl peroxide / N,
N'-dimethyl-p-toluidine, a combination of benzoyl peroxide / p-tolyldiethanolamine, and the like.

In these room temperature polymerization initiators, the amount of peroxide and amine used is 0.05 to 5 parts by weight, and 0.1 to 2 parts by weight, based on 100 parts by weight of all monomer components.
It is preferably in parts by weight. The method of curing using the room temperature polymerization initiator is not particularly limited, but generally, a unit containing benzoyl peroxide and a unit containing amine are mixed in an appropriate ratio at the time of use and put into a predetermined mold, Alternatively, it is preferable to prepare the shape and use it after polymerization at normal temperature.

When the room-temperature polymerization initiator is a combination of a pyrimidinetrione derivative, a halogen ion-forming compound and a cupric or ferric ion-forming compound, known compounds are particularly limited for each compound used in the combination. Be used. Among them, a pyrimidine trione derivative represented by the following general formula (2)

[0065]

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(In the formula, R ⁵ is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms.) In the case of using a pyrimidinetrione derivative represented by the formula: It is particularly preferable to use the pyrimidion derivative because of its good properties.

In the above general formula (2), R ⁵ is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms. Among the groups, methyl group, ethyl group, propyl group, sec
-Butyl, tert-butyl, cyclopentyl and cyclohexyl are preferred. That is, examples of the pyrimidion derivative represented by the above general formula (2) that can be suitably used include those in which R ^{5 in} the formula is the above preferable group.

The halogen ion-forming compound is not particularly limited as long as it forms a halide ion in a solution, and a known compound can be used. Suitable halogen ion-forming compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, diisobutylamine hydrochloride, tetra-n-butylammonium chloride, triethylamine hydrochloride, trimethylamine hydrochloride, dimethylamine hydrochloride. Chloride, diethylamine hydrochloride, methylamine hydrochloride, ethylamine hydrochloride, isobutylamine hydrochloride, triethanolamine hydrochloride, β-phenylethylamine hydrochloride, acetylcholine chloride, 2-chlorotrimethylamine hydrochloride, (2-chloroethyl Triethylammonium chloride, tetra-decyldimethylbenzylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, dilauryldimethylammonium bromide, tetrabutylammonium bromide, Examples thereof include benzyltriethylammonium bromide, and these may be used alone or in combination of two or more.

The compound forming a cupric or ferric ion is not particularly limited as long as it forms a divalent copper ion or a trivalent iron ion in a solution. Suitable cupric or ferric ion forming compounds include copper acetylacetone, cupric acetate, copper oleate, iron acetylacetone and the like, and these may be used alone or in combination of two or more. Further, the halide ion-forming compound and the cupric or ferric ion-forming compound do not necessarily have to be different compounds, and the halide ion and the divalent copper ion or 2
It may be a compound that forms both of the valence iron ions at the same time. As such a compound, for example, cupric halide or ferric halide can be used, and specific examples thereof include halogenated cupric chloride and cupric bromide. Examples thereof include ferric halides such as cupric, ferric chloride, and ferric bromide.

Preferred examples of these combinations include 1-cyclohexyl-5-methylpyrimidinetrione / dilauryldimethylammonium chloride / copper acetylacetone and 5-butyl-1-cyclohexylpyrimidinetrione / lauryldimethyl. Benzyl ammonium chloride / cupric acetate, 5-sec
-Butyl-1-cyclohexylpyrimidinetrione / dilauryldimethylammonium chloride / copper acetylacetone and a combination of 1,5-dicyclohexylpyrimidinetrione / dilauryldimethylammonium chloride / copper acetylacetone.

In the room temperature polymerization initiator comprising the pyrimidinetrione derivative, the halogen ion-forming compound and the cupric or ferric ion-forming compound, the mixing ratio of each component is as follows. The range of 0.001 to 0.5 part by weight and 0.0001 to 0.05 part by weight of the cupric or ferric ion forming compound is preferable.

When a room temperature polymerization initiator comprising a combination of the above pyrimidine trione derivative, a halogen ion-forming compound and a cupric or ferric ion-forming compound is used as the radical polymerization initiator, Since the formation of an unpolymerized layer due to oxygen is suppressed, it is suitable for use as a material for a crown or a material for a denture base. At this time, it is particularly preferable to use the pyrimidine trione derivative represented by the general formula (2) as the pyrimidine trione derivative from the viewpoint of aesthetics.

The amount of the room-temperature polymerization initiator comprising the combination of the pyrimidinetrione derivative, the halogen ion-forming compound and the cupric or ferric ion-forming compound is 0.05 to 15 parts by weight based on 100 parts by weight of all the monomer components. It may be used in the range of parts by weight, preferably in the range of 0.1 to 10 parts by weight. When the addition amount of each component is in the range of 0.1 to 10 parts by weight, a cured product having a high curing rate and no coloring derived from metal ions contained in the cupric or ferric ion forming compound can be obtained.

The method of curing using a room temperature polymerization initiator comprising a combination of the above pyrimidine trione derivative, a halogen ion forming compound and a cupric or ferric ion forming compound is not particularly limited. At the time of use, a unit containing a compound forming a cupric or ferric ion and a unit containing a compound forming a halogen ion are mixed at an appropriate ratio and put into a predetermined mold, or are used after being shaped and polymerized at room temperature. It is preferred to do so.

When the radical polymerization initiator is a photopolymerization initiator, a known photosensitizer can be used as the photopolymerization initiator. Suitable photopolymerization initiators (that is, photosensitizers) include diacetyl, acetylbenzoyl,
Α-diketones such as benzyl, camphorquinone, 9,10-phenanthrenequinone and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; 2,4-diethylthioxanthone and methylthio Thioxanthone compounds such as xanthone; benzophenone, p, p'-dimethylaminobenzophenone, p, p '
-Benzophenone-based compounds such as dimethoxyaminobenzophenone.

When a photopolymerization initiator is used as the radical polymerization initiator, it can be used together with a curing accelerator. Dimethyl paratoluidine as a curing accelerator,
Amine compounds such as N, N'-dimethylbenzylamine, N-methyldibutylamine, dimethylaminomethacrylate, ethyl p-dimethylaminobenzoate; phosphite compounds such as dimethylphosphite and dioctylphosphite; and cobalt compounds such as cobalt naphthenate Pyrimidinetriones and the like are preferably used. Specific examples of preferable combinations among these combinations include combinations of camphorquinone / dimethylaminomethacrylate, camphorquinone / ethyl p-dimethylaminobenzoate, and the like.

The amount of the photopolymerization initiator (photosensitizer) and curing accelerator is 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on all monomer components. Is preferred.

The method of curing using the above photopolymerization initiator is not particularly limited. Generally, a unit containing a photosensitizer and a unit containing a curing accelerator are mixed at an appropriate ratio at the time of use to obtain a predetermined ratio. It is preferable to put it in a mold or adjust its shape, and polymerize it at room temperature under light irradiation before use. In the case of photo-curing, the composition can be cured by irradiating ultraviolet rays from a high-pressure, medium-pressure, or low-pressure mercury lamp; or visible light from a halogen lamp or the like.

The crown material or the denture base material of the present invention may have, in addition to the above-mentioned other monomer and polymer components, if necessary, improved fluidity, and various physical properties and properties of the obtained cured product. Inorganic filler for controlling operability; alcohol or plasticizer such as ethanol, dibutyl phthalate and dioctyl phthalate; polymerization inhibitor such as butylhydroxytoluene and methoxyhydroquinone;
Methoxy-2-hydroxybenzophenone, 2- (2-
UV absorbers such as (benzotriazole) -p-cresol; polymerization regulators such as α-methylstyrene dimer; dyes, pigments, fragrances and the like can be added.

The crown material or denture base material of the present invention comprises:
By polymerizing and hardening, it is used for the purpose of prosthesis for loss or loss of teeth, fixing of oscillating teeth, or shaping arrangement.

Specifically, an immediate polymerization resin for denture repair,
Immediate polymerization resin for crown, rapid curing immediate polymerization resin, hard resin for crown, orthodontic resin and other crown materials, or denture base resin, rebase immediate polymerization resin,
It can be suitably used as a denture base material such as an instant polymerization resin for each individual tray and a soft resin for denture base.

The method of using the material for a crown or the material for a denture base of the present invention is not particularly limited, and any method generally used for these materials can be used without any limitation.

For example, when used as an instant polymerization resin for a crown or an instant polymerization resin for a rebase, a powder unit in which a pyrimidinetrione derivative and a cupric or ferric ion-forming compound are blended with a polymer component and a monomer component A liquid unit containing a halogen ion-forming compound may be stored separately, and the two components may be mixed immediately before use and polymerized and cured at room temperature before use.

When used for a soft resin for denture base, a paste-like unit containing a pyrimidinetrione derivative, a cupric or ferric ion forming compound, a filler and a part of a monomer component, and a monomer component are used. A liquid unit in which a halogen ion-forming compound is blended with the remainder may be used by mixing the two components immediately before use and polymerizing and curing at room temperature.

[0085]

EXAMPLES Examples and comparative examples relating to the present invention will be shown below, but the present invention is not limited to these examples.

Next, the substances used in each example and each comparative example will be summarized.

[M-AE Monomer] Compounds having the structures represented by the following abbreviations were used.

[0088]

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[0089]

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The above compounds were prepared in Production Example 1 shown below.
And 2, and methods obtained according to the production examples.

Production Example 1 13.0 g (0.1 mol) of hydroxyethyl methacrylate, 11.6 g (0.1 mol) of levulinic acid, 1 g of paratoluenesulfonic acid, 1 g of hydroquinone monomethyl ether, and 200 ml of toluene were charged at reflux temperature. 2
Allowed to react for hours. After the reaction, the mixture was washed with a 5% aqueous sodium carbonate solution, and the solvent was distilled off to obtain M-AE-413 g.

Production Example 2 10 g (0.07 mol) of cyclohexylurea, 13.2 g (0.07 mol) of diethyl methylmalonate, 4.8 g (0.07 mol) of sodium ethoxide, ethanol 1
Then, the reaction was carried out at reflux temperature for 5 hours. After the reaction, the reaction solution was added to 500 ml of water, and acidified with hydrochloric acid.
After the precipitated oil was extracted with diethyl ether, dried over magnesium sulfate, and filtered, the solvent was distilled off to obtain a brown solid. The obtained solid was recrystallized from methanol to obtain 8 g of c-Hex-MePTO.

[Other Monomers] Each abbreviation represents a compound having the structure shown on the right. In addition, the following OTM-1 ~
OTM6 is shown in (A)-
This corresponds to the compound of (F).

[0094]

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MMA: Methyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) IBM: Isobutyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) HDM: 1,6-hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) NMA : 1,9-nonanediol dimethacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) DDM: 1,10-decanediol dimethacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) NPG: neopentyl glycol dimethacrylate (new BPMA: bisphenol A dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) TMPT: trimethylolpropane trimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) UDMA: urethane dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) DMA: Dimer diol dimethacrylate (Toa) [Polymer component] PMMA30: polymethyl methacrylate (average molecular weight 250,000, average particle size 30 μm) (manufactured by Sekisui Chemical Co., Ltd.) PEMA10: polyethyl methacrylate (average molecular weight 250,000, average) PEMA30: polyethyl methacrylate (average molecular weight 250,000, average particle size 30 μm) (manufactured by Sekisui Plastics Co., Ltd.) PEMA35: polyethyl methacrylate (average molecular weight) PMMA-PEMA: polymethyl methacrylate-polyethyl methacrylate copolymer (average molecular weight: 500,000, average particle size: 50 μm) (Sekisui Plastics Co., Ltd.) PHMA: poly-n-hexyl methacrylate (average molecular weight 200,000, average particle size 10 μm) (Aldrich) PST: polystyrene (average molecular weight 1,000,000, average particle size 10 μm) (Aldrich) [Radical polymerization catalyst] AIBN: 2,2′-azobisisobutyronitrile (Tokyo Chemical Co., Ltd.) CNVA: 4,4'-azobis (4-cyanovaleric acid)
(Manufactured by Aldrich) ADMBN: azobisdimethylvaleronitrile (manufactured by Aldrich) DPO: decanoyl peroxide (manufactured by NOF Corporation) LPO: lauroyl peroxide (manufactured by NOF Corporation) BPO: benzoylper Oxide (manufactured by NOF Corporation) DLPO: dilauroyl peroxide (manufactured by NOF Corporation) DCBPO: di-p-chlorobenzoyl peroxide (manufactured by NOF Corporation) Me-c-HexPTO: 1-cyclohexyl-5-methylpyrimidinetrione s-Bu-c-HexPTO: 5-sec-butyl-1
-Cyclohexylpyrimidinetrione c-Hex-HexPTO: 1-cyclohexyl-5
Hexylpyrimidinetrione c-Hex-OcPTO: 1-cyclohexyl-5-octylpyrimidinetrione c-Hex-c-HexPTO: 1,5-dicyclohexylpyrimidinetrione CQ: camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) DET: 2 4-Diethylthioxanthone (Tokyo Kasei Co., Ltd.) BZ: Benzyl (Tokyo Kasei Co., Ltd.) [Curing accelerator] DEPT: N, N′-di (β-hydroxyethyl) -p
-Toluidine (manufactured by Tokyo Kasei Co., Ltd.) DMPT: N, N'-dimethyl-p-toluidine (manufactured by Tokyo Kasei Co., Ltd.) CuAcAc: Copper acetylacetone (manufactured by Tokyo Kasei Co., Ltd.) DLDMAC: dilauryl dimethyl ammonium chloride ( CuAc: cupric acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) LDMVAC: lauryl dimethylbenzylammonium chloride (manufactured by Takemoto Yushi Co., Ltd.) DMBA: N, N'-dimethylbenzylamine (manufactured by Air Brown Co., Ltd.) DMABAE: Ethyl p-dimethylaminobenzoate (Tokyo Kasei Co., Ltd.) DMAEMA: Dimethylaminoethyl methacrylate (Tokyo Kasei Co., Ltd.) [Polymerization inhibitor] MEHQ: Hydroquinone monomethyl Ether (manufactured by Tokyo Chemical Industry Co., Ltd.) BHT: butylhydroxytoluene ( (Manufactured by Tokyo Chemical Industry Co., Ltd.) and a monomer (M-AE monomer and other monomers)
The evaluation method of the cured product obtained by curing the curable composition is as follows.

1. Evaluation method of monomer (1) [Evaluation of irritation to the skin (hereinafter, also simply referred to as irritation)] The irritation is measured by the Draize method and the degree of pain felt when attached to the tongue. evaluated.
In addition, the evaluation by the Draize method evaluated the above-mentioned M-AE-1 to 8 on the left side of the shaved part of the Angora rabbit whose back was shaved with a clipper.
, OTM1-6, MMA, IBM
And DDM were applied in an amount of 0.05 ml each, and the inflammatory state after 24 hours was scored according to the evaluation table in Table 1 to give
The average score for wings and above was determined. The smaller this average point, the smaller the skin irritation.

[0097]

[Table 1]

The evaluation based on the pain felt when attached to the tongue was performed by dropping one drop of the monomer at the tip of the tongue.
The pain after one minute was evaluated on four scales: "no irritation", "very weak pain", "weak pain", and "strong pain".

(2) [Evaluation of odor] The odor was evaluated as "odorless" by smelling.
The evaluation was made in four stages of "smell odor", "irritating odor" and "strong irritating odor".

(3) [Evaluation of polymer swelling property when polymer component is used] PEMA30 was used as a polymer, and the weight ratio of polymer to monomer was fixed at 1.6. And IGK-1 (manufactured by Ishida Giken Co., Ltd.), and the time-dependent change in viscosity was measured for 4 minutes. When the monomer is MMA, the viscosity rises too fast,
A30 was used. The degree of the initial increase in viscosity was evaluated from the change in viscosity after 4 minutes. It is preferable that the initial rise in viscosity is large because the waiting time after kneading during actual use is short.

2. Evaluation method of cured body [Evaluation of flexural modulus] First, a curable composition was 25 mm long.
The mixture was poured into a mold having a width of 4 mm and a thickness of 2 mm, polymerized and cured under predetermined conditions, and the obtained cured product was polished with a 1500-grade water-resistant abrasive paper to prepare a measurement sample. Measure the sample at 23 ° C
For 24 hours, a bending test was conducted with a tensile tester at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min to measure the flexural modulus.

[Evaluation of Unpolymerized Amount] First, the curable composition was poured into a Teflon mold having a length of 20 mm, a width of 20 mm and a thickness of 1 mm, and was polymerized and cured under predetermined conditions. The thickness of the obtained cured product was measured at five places with a micrometer, and the average value (D
1) was determined. After immersion in methanol for 1 minute, the surface unpolymerized layer was removed, and the thickness of the cured product was measured at five places with a micrometer, and the average value (D2) was obtained. D1-D2
Was defined as the surface unpolymerized layer thickness, and the unpolymerized amount was evaluated based on the thickness.

Reference Examples 1 to 8 and Reference Comparative Examples 1 to 9 Various monomers shown in Table 2 were evaluated for polymer swellability, irritation and odor. Table 2 shows the results.

[0104]

[Table 2]

From the results of Reference Examples 1 to 8, it is understood that the M-AE monomer is lower in both the trade method and tongue stimulation than the monomers used in Reference Comparative Examples 1 to 9. Further, it can be seen that the odor and polymer swellability are equivalent to those of other monomers. Therefore, it can be seen that the crown material or the denture base material of the present invention using the M-AE monomer has low odor and irritation, and has good operability when used in combination with the polymer component.

Examples 1 to 8 Based on 100 parts by weight of each M-AE monomer of Reference Examples 1 to 8, c-HexMePTO2 was used as a radical polymerization initiator.
Parts by weight, 0.001 parts by weight of CuAcAc and DLDMA
After mixing 0.3 parts by weight of C, the mixture was cured at room temperature. All of the obtained cured products had characteristics of high transparency and strength equal to or higher than those of conventional products, and were sufficiently usable as an instant polymerization resin for rebase.

Examples 9 to 26 The crown material or the denture base material of the present invention was polymerized using various radical polymerization initiators shown in Tables 3 and 4, and the flexural modulus and the flexural modulus of the obtained cured product were determined. The surface unpolymerized layer thickness was measured. The results are shown in Tables 3 and 4. In addition, the photopolymerization was performed by irradiating light for 20 minutes using a commercially available visible light irradiator “Triad Cure Unit” (manufactured by Dentsply).

[0108]

[Table 3]

[0109]

[Table 4]

A denture base and a rebase were produced by heating polymerization or room temperature polymerization using the crown material or denture base material obtained in Examples 9 to 22 according to a conventional method. And rebase. Also,
When the material for the crown or the material for the denture base of Examples 14 to 22 was used as an instant polymerization resin for a tray and a rapid curing instant polymerization resin, a tray and a provisional tooth were produced, respectively.
Sufficient performance was obtained. At this time, when a combination of a pyrimidinetrione derivative, a halogen ion-forming compound and a cupric or ferric ion-forming compound is used as the radical polymerization catalyst, a particularly thin surface unpolymerized layer is obtained. Was done.

Furthermore, denture bases and rebases were produced by photopolymerization using the materials for crowns or denture bases of Examples 23 to 26 according to a conventional method, and denture bases and rebases having sufficient strength were obtained. .

Examples 27 to 32 Table 5 shows the polymer components and the monomer components in Example 18.
The polymerization was carried out in the same manner as in Example 18, except that the polymerization was changed as shown in Table 1. The results are shown in Table 5.

[0113]

[Table 5]

Comparative Examples 1 to 9 A predetermined amount of each component shown in Table 6 was mixed to prepare a curable composition. The flexural modulus of the obtained curable composition was measured. Table 6 shows the results.

[0115]

[Table 6]

From the results of Examples 9 to 32 and Comparative Examples 1 to 9, the cured product obtained from the dental crown material or the denture base material of the present invention using the M-AE monomer was determined by the type of polymerization catalyst. Regardless, it can be seen that the material exhibits the same bending elastic modulus as when the current material for crown or denture base is used. Further, when the polymerization catalyst is a combination of a pyrimidinetrione derivative, a halogen ion-forming compound and a cupric or ferric ion-forming compound, the surface unpolymerized layer thickness becomes about 1/3 as compared with other polymerization catalysts. You can see that.

[0117]

The crown material or denture base material of the present invention using the M-AE monomer has a lower odor and lower irritation than the conventional crown material or denture base material. Further, the crown material or denture base material of the present invention used in combination with the polymer component has a good operability at the time of use as well as a cured product after curing because the polymer component easily swells. The strength becomes excellent.

For this reason, when a patient is treated using the material for a crown or the material for a denture base of the present invention, the patient has an unpleasant odor and a stimulating surface even in the case of direct treatment in the oral cavity. Nothing. In addition, the cured product obtained at that time has excellent mechanical properties, so that reliable treatment can be performed.

Claims (3)

[Claims] (1) The following general formula (1): (Wherein, R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ represent an alkylene group, R ² and R ³ may be different, and R ⁴ represents an alkyl group). (Meta)
A crown material or a denture base material containing an acrylate polymerizable monomer and a radical polymerization initiator. 2. The following general formula (1): (Wherein, R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ represent an alkylene group, R ² and R ³ may be different, and R ⁴ represents an alkyl group). (Meta)
An acrylic acid ester polymerizable monomer, a monomer component comprising a radical polymerizable monomer other than the (meth) acrylic acid ester polymerizable monomer, and a compound represented by the following general formula (2): (Wherein, R ⁵ is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms), a halogen ion-forming compound, a cupric ion or a ferric ion A material for a crown or a denture base, comprising a radical polymerization initiator comprising an ion-forming compound. 3. The material for a crown or a denture base according to claim 2, further comprising a polymer component.