JPH04366112A - Composition polymerizable and curable by visible ray - Google Patents

Abstract

PURPOSE:To obtain a composition which polymerizes and cures by visible rays to give a cured film having a smooth and glossy surface and is useful, for example, as a surface smoothness-and gloss-imparting agent for artificial teeth, by blending a specific monomer with a specific solvent and a specific catalyst. CONSTITUTION:The title composition comprises a polyfunctional monomeric acrylate, preferably a dipentaerythritol acrylate monomer represented by the formula (wherein R1 to R6 each is H or (meth)acryloyl, provided that at least four of R1 to R6 are (meth)acryloyl), a volatile solvent for the monomer (e.g. methyl methacrylate), and an alpha-aminoacetophenone photopolymerization catalyst (e.g. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone).

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a visible light polymerizable curable composition, and more particularly, the cured composition has a surface smoothness, and in particular, an agent for imparting surface lubricity to artificial teeth. The present invention relates to a visible light polymerizable curable composition suitable as a repair agent for tooth enamel defects and discolored areas, a tooth manicure, and an opaque.

0002

[Prior Art] Conventionally, as an acrylate-based photopolymerizable composition,

[Chemical formula 2] Various compositions containing acrylate monomers such as triethylene glycol dimethacrylate and neopentyl dimethacrylate and sensitizers have been proposed, and are used in a wide variety of fields such as dental materials. .

By the way, when an acrylate-based photopolymerizable curable composition is irradiated with light, a radical polymerization chain reaction is initiated, but since oxygen in the air acts as a polymerization inhibiting factor, the surface of the cured composition is Unreacted composition remains. Therefore, there is a problem that the surface of the cured composition lacks smoothness and remains sticky for some time.

[0004] This tendency was particularly remarkable in the case of photopolymerization using visible light rather than ultraviolet light. For example, there is a visible light polymerizable tooth composite filling material as a product using such an acrylate visible light polymerizable curable composition as a matrix resin.

[0005] For dental composite filling materials that are polymerizable and hardenable with visible light, after the filling material is applied to the affected area, it is necessary to irradiate it with visible light and polymerize and harden it in about 30 seconds. Due to the limitations of the light source and curing time, it becomes more difficult to form a smooth cured surface. Therefore, conventionally, in order to form a composite resin surface with a smooth surface, unreacted matrix resin monomer remaining on the surface has been removed and careful polishing has been performed.

Similarly, compositions using such acrylate-based visible light polymerizable curable resins as matrix resins leave unreacted resin monomers on the cured surface, making them difficult to use for dental surface lubrication, which requires a thin film-like resin layer. It was unsuitable for hardening agents, sealants for preventing cavities, opaque materials, and tooth nail polish. In addition, the inventors have previously discovered a visible light polymerization curing composition for the same purpose (Japanese Unexamined Patent Application Publications No. 183904/1983 and No. 183905/1983). Camphorquinone, benzyl, and fluorenone are exemplified, and since these visible light polymerization catalysts all have a yellowish tinge, their visible light polymerizable compositions also have a strong yellowish tinge, and the curing obtained by visible light irradiation is There was also a problem in that the color of the film remained yellowish.

[0007]

[Problems to be Solved by the Invention] The present inventors have completed the present invention as a result of intensive research in view of the above-mentioned problems of existing acrylate-based visible light polymerizable curable compositions. The object of the present invention is to provide a visible light polymerizable curable resin composition that is rapidly cured by irradiation with visible light to form a smooth cured surface. Another object is to provide a visible light polymerizable curable composition that is almost colorless before and after irradiation with visible light. Another purpose is to cure by irradiation with visible light of 400 to 500 μm to form a strong hardened surface that is harmless to the human body and non-stick, making it suitable for dental materials such as tooth surface smooth hardening materials, opaque materials, and nail polish. The present invention provides a visible light polymerizable curable composition. Further objects and effects of the present invention will become clear from the following description.

[0008]

[Means for Solving the Problems] The above-mentioned object consists of a polyfunctional acrylate monomer (A), a volatile solvent (B) for the monomer (A), and an α-aminoacetophenone photopolymerization catalyst (
C) is achieved by a visible light polymerizable curable composition.

As the polyfunctional acrylate monomer (A), the following formula (I) is used.

[Chemical formula 3] (However, in the formula, R1 to R6 represent hydrogen, an acrylic group, or a methacryl group, and at least 4 out of R1 to R6
is an acrylic or methacrylic group. ) dipentaerythritol acrylate monomers are particularly preferred, but others of the following formula (II)

[Chemical formula 4] (However, in the formula, R1, R3, R4, R6 represent an acrylic group or a methacryl group, and R2, R5 represent an alkyl group.) A tetramethylolmethane acrylate monomer represented by the following formula ( III)

[Chemical formula 5] (where m = an integer from 1 to 3, R1 and R2 are H
Alternatively, a caprolactone-modified dipentaerythritol hexaacrylate monomer or a polyfunctional urethane-based acrylic monomer, where CH3, a, and b are integers and a+b=6), is preferable.

As the volatile solvent (B) for the polyfunctional acrylate monomer (A), solvents having a boiling point of 100° C. or lower, such as alcohols such as methanol and ethanol, ketones such as acetone, esters such as ethyl acetate, and methyl Preferred examples include acrylates such as (meth)acrylate and ethyl (meth)acrylate. Among the volatile solvents (B), acrylate reacts with the polyfunctional acrylate monomer (A) upon irradiation with visible light.

When these acrylates are used as volatile solvents, cured compositions with superior strength can be obtained compared to when non-reactive volatile solvents are used. Furthermore, it is suitable as a dental material in terms of reaction rate in the oral cavity environment, physical properties of the cured product, etc. Also, α applied to the present invention
-As the aminoacetophenone photopolymerization catalyst (C),
2-Methyl-2-morpholino(4-thiomethylphenyl)propan-1-one is particularly preferred, but 2-benzyl-
2-dimethylamino-1-(4-morpholinophenyl)
- Butanone etc. are also suitable. These polymerization catalysts are usually used together with a reducing agent.

[0012] A suitable amount of addition is 5 to 15% by weight, but if it is less than 5%, the reaction rate and surface curing properties are insufficient, and if it exceeds 15% by weight, the cured film will turn yellow. The cured film becomes tastier and the strength of the cured film becomes weaker because the amount of catalyst in the monomer increases. A particularly preferable addition amount is 6 to 10% by weight, judging from overall aspects such as reaction rate, surface curing property, color tone of cured film, and strength of cured film.

Next, as the reducing agent, for example, triethanolamine, N,N-dimethylaminoethanol, N-
Methyldiethanolamine, N,N-dimethylethanolamine, N,N-dimethylamino P-ethyl benzoate, N,N-dimethylaminoethyl methacrylate, N-
Methyldiphenylamine, N-dimethylpara-toluidine,
n-Butylamine, triethylamine, tri-n-butylphosphine, allylthiourea, S-benzylisothiuronium-P-toluenesulfinate, 2-n-butoxyethyl-4-dimethylaminopenzoate, 2-dimethylaminoethyl Examples include benzoate and isoamyl P-dimethylaminobenzoate, among which,
Triethanolamine, N,N-dimethylaminoethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, etc. are suitable.

These visible light polymerization catalysts and reducing agents may be added within the ranges normally used. The visible light polymerizable curable composition according to the present invention contains a polyfunctional acrylate monomer (A
), a volatile solvent (B), an α-aminoacetophenone photopolymerization catalyst (C), and a reducing agent, but when an acrylate that can be polymerized with visible light is added to the above basic composition, the cured product becomes Physical and chemical properties change. The addition of the acrylate to the basic composition is extremely effective depending on the application.

Examples of such visible light polymerizable acrylates include caprolactone-modified tris(acryloxyethyl)isocyanate, dipentaerythritol monohydroxypentaacrylate, triallyl cyanurate,
Pentaerythritol tetramethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,
3-butanediol acrylate, 1,4-butanediol diacrylate, 1,4-diol methacrylate, neopentyl glycol diacrylate.

Neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, tricyclodecane diacrylate, glycerol dimethacrylate, Examples include glycerol acrylate/methacrylate, tris(acryloxyethyl) isocyanate, diacrylated isocyanate, caprolactone-modified dipentaerythritol hexaacrylate, and ditrimethylolpropane tetraacrylate.

When these acrylates are added to the basic composition, a dental material suitable for the reaction rate in the oral environment, physical properties of the cured product, toxicity, etc. can be obtained. The amount of the acrylate added to the basic composition is 30% by weight or less, preferably 1 to 10% by weight.
It is preferable to express it in weight %. Furthermore, when an inorganic or organic filler is added to the basic composition, the visible light irradiation time required for polymerization can be significantly shortened, and the strength of the cured product can be improved and an opaque feeling can be developed.

Furthermore, when a colored substance such as a pigment is added and blended, a colored cured product can be obtained, and the composition containing the colored substance can be used for treatment of discolored areas of teeth due to enamel defects, etc., tooth manicure, and opaque. It can be used as Examples of inorganic or organic fillers that can be incorporated into the basic composition include silica, titanium dioxide, zirconium oxide, silicon nitride, calcium carbonate, polymethyl methacrylate, and polyethyl methacrylate.

To prepare a composition using these components, no special means or methods are required; for example, the polyfunctional acrylate monomer (
A) is dissolved in a volatile solvent (B) with stirring, and further α
-Dissolving the aminoacetophenone photopolymerization catalyst (C),
A basic composition of a visible light and reducing agent polymerization curable composition is prepared. If necessary, visible light polymerizable acrylates, fillers, pigments, etc. may be added to the basic composition while stirring.

[0020]

Effects of the Invention The visible light polymerizable curable composition of the present invention rapidly cures even in the presence of oxygen by irradiation with visible light to form a smooth cured surface. Since the visible light polymerizable curable composition of the present invention has excellent properties as described above,
It exhibits outstanding effects when applied to various uses such as dental materials.

That is, by combining the polyfunctional acrylate monomer (A), volatile solvent (B), α-aminoacetophenone photopolymerization catalyst (C), reducing agent, etc. according to the present invention, It forms a colorless, non-sticky, smooth surface cured film when irradiated with visible light in the wavelength range of By polymerizing it, it can be used as a surface coating material for dental plastic materials. Furthermore, the composition of the present invention can also be used as an aesthetic restorative material for discolored teeth due to enamel defects, etc., and as a nail polish and opaque for teeth by incorporating fillers, pigments, and the like. The present invention will be specifically explained below with reference to Examples.

[0022]

[Example 1] The components shown in Table 1 below were blended with thorough stirring in a completely closed brown bottle to prepare a visible light polymerizable curable composition. The composition is 1 cm in diameter and 2 mm in thickness.
The surface of the cured composite resin for photopolymerization (product name: Bellfeel Mark II, manufactured by Kanebo Co., Ltd.) prepared in the form of a disc was wet-polished using abrasive paper with a grain size of 600, and then a thin layer of 2. After applying several coats, use a dental visible light irradiator (
Manufactured by Yoshida Co., Ltd. Product name: LIGHTACE
)) and irradiated with light for 1 minute.

After irradiation with light, the cured composition was left indoors for 24 hours, the surface was gently wiped with a cloth soaked in ethyl alcohol, and the composition was inspected and evaluated according to the evaluation criteria shown in the table below. Regarding the surface curability of the cured film, the color tone of the visible light polymerizable curable composition before and after visible light irradiation was also observed.

[0025]

[Table 1]

[0026]

[C6]

[0027]

[C7]

[0028]

[Chemical formula 8] The results are shown in Table 1.

[0029]

[Comparative Example 1] Table of Example 1 except that 2,2-bis(P-2'-hydroxy-3'-methacryloxypropoxyphenyl)propane was used instead of the polyfunctional acrylate monomer (A). 1 A visible light polymerizable curable composition was prepared in the same manner as in Experiment Nos. 1 to 4, and the surface smoothness was evaluated in the same manner as in Example 1. Unreacted monomer remained and adhered to the cloth.

[0030]

[Comparative Example 2] α-aminoacetophenone-based photopolymerization catalyst (
A visible light polymerizable composition was prepared in the same manner as in Example 1, Table 1, Experiment Nos. 1 to 4, except that 1 part by weight of camphorquinone was used in place of C), and in the same manner as in Example 1. The color tone of the visible light curable composition was observed before and after visible light irradiation.
Each had a strong yellow tinge before visible light irradiation, and the cured film remained slightly yellowish even after visible light irradiation.

[0031]

[Example 2] A visible light polymerizable curable composition was prepared in the same manner as in Example 1, except that the compositions shown in Tables 2 and 3 were used instead of the composition shown in Table 1. The surface smoothness was evaluated. The results are shown in Table 3.

[0032]

[Comparative Example 3] 2,2-bis(P-2'-hydroxy-3'-methacrylate Example 2 Table 2 except that Roxypropoxyphenyl)propane is used
, Table 3 A visible light polymerizable curable composition was prepared in the same manner as in Experiment Nos. 1 to 5, and the surface smoothness was evaluated in the same manner as in Example 1. However, even after 20 minutes of light irradiation, there was no liquid on the surface of the cured composition. Unreacted monomer remained and adhered to the cloth.

[0033]

[Comparative Example 4] α-aminoacetophenone-based photopolymerization catalyst (
A visible light polymerizable composition was prepared in the same manner as in Example 2 Table 2 and Table 3 Experiment Nos. 1 to 5, except that 1 part by weight of camphorquinone was used in place of C). Similarly, the color tone of the visible light curable composition before and after irradiation with visible light was observed, and in each case, the color tone was strong yellowish before irradiation with visible light, and the cured film was slightly yellowish even after irradiation with visible light.

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Chemical formula 9]

[0037]

[Chemical formula 10]

Claims (2)

[Claims] [Claim 1] Polyfunctional acrylate monomer (A),
A visible light polymerizable curable composition comprising a volatile solvent (B) for the monomer (A) and an α-aminoacetophenone photopolymerization catalyst (C). [Claim 2] The polyfunctional acrylate monomer (A) has the following formula (I) [Formula 1] (wherein R1 to R6 represent hydrogen, an acrylic group, or a methacrylic group; Both 4
is an acrylic or methacrylic group. The visible light polymerizable curable composition according to claim 1, which is a dipentaerythritol acrylate monomer represented by: