JPH04366111A - 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 plurality of specific catalysts. 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), an alpha-aminoacetophenone photopolymerization catalyst (e.g. 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one), and a thioxanthone photopolymerization catalyst (e.g. 2, 4-dimethylthioxanthone).

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. 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.

[0004] 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 resin as a matrix resin leave unreacted resin monomers on the cured surface, so they can be used as surface lubricating hardeners for dental applications, which require a thin resin layer.
It was unsuitable for sealants for preventing cavities, opaque materials, nail polish for teeth, etc.

[0005] In addition, the inventors have previously discovered a visible light polymerizable curing composition for the same purpose (Japanese Patent Application Laid-Open No. 183904/1983).
Publication No. 183905/1983), which exemplify camphorquinone, benzyl, and fluorenone as visible light polymerization catalysts, and these visible light polymerization catalysts are all yellowish. However, the visible light polymerizable composition also had a strong yellowish tinge, and the color of the cured film obtained by visible light irradiation also remained yellowish.

[0006]

[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.

[0007]

[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) and a thioxanthone-based photopolymerization catalyst (D).

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. Further, as the α-aminoacetophenone photopolymerization catalyst (C) applied to the present invention, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one is particularly preferable, but 2-benzyl-2 -dimethylamino-1-
(4-morpholinophenyl)-butanone and the like are also suitable. In addition, as the thioxanthone photopolymerization catalyst (D),
2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,
4-dichlorothioxanthone, or 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-
1-propanaminium chloride and the like are preferred. These polymerization catalysts (C) are usually used together with a reducing agent.

α-aminoacetophenone-based photopolymerization catalyst (
C) Alternatively, there is a method of using each of the thioxanthone photopolymerization catalysts (D) alone, but the maximum absorption wavelengths of (C) and (D) are 305 nm and 384 nm, respectively, which are far below the light emitted by a normal visible light irradiator. Since the maximum absorption wavelength is shifted to the lower wavelength side compared to 470 nm, it is necessary to use (C) or (D) to make the reaction rate in the oral environment and the physical properties of the cured film sufficient as a dental material. need to be used in large quantities.

Surprisingly, however, when (C) and (D) are used in combination, there is a spectral sensitization effect, and the absorption wavelength of the combined catalyst shifts to the high frequency side, so even if both (C) and (D) are used in relatively small amounts, The above-mentioned required performance can now be achieved. The amounts of (C) and (D) added to the total amount of the composition are (C) 0.1 to 5% by weight and (D) 0.01%.
~0.5% by weight is preferred. In order to achieve a total balance of reaction rate, cured film physical properties, and cured film color tone of the visible light polymerizable curable composition, (C) should be added in an amount of 1 to 4% by weight based on the total amount of the composition.
and (D) 0.1 to 0.4% by weight are particularly preferred.

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), a thioxanthone photopolymerization catalyst (D), and a reducing agent, but visible light polymerization is possible with the above basic composition. When acrylate is added and blended, the physical and chemical properties of the cured product 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, glycerol acrylate/methacrylate, tris(acryloxyethyl) isocyanate, diacrylated isocyanate, caprolactone modified dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate.

When these acrylates are blended into 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
- An aminoacetophenone photopolymerization catalyst (C), a thioxanthone photopolymerization catalyst (D), and a reducing agent are dissolved to prepare a basic composition of a visible light polymerization curable composition. If necessary, visible light polymerizable acrylates, fillers, pigments, etc. may be added to the basic composition while stirring.

[0019]

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, and forms 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), thioxanthone photopolymerization catalyst (D), etc. according to the present invention, 400-50
It forms a colorless, non-sticky, smooth cured film when irradiated with visible light in the 0 μm wavelength range, so it can be applied to the surface of dental plastic materials such as tooth filling materials, dentures, and denture base resins, and irradiated with visible light. By polymerizing it, it can be used as a surface coating material for dental plastic materials.

The composition of the present invention can also be used as an aesthetic restoration material for discolored teeth due to enamel defects, etc., and as a nail polish and opaque for teeth by incorporating fillers, pigments, etc. The present invention will be specifically explained below with reference to Examples.

[0021]

[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 in a room for 24 hours, and 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.

[0023]

[0024]

[Table 1]

[0025]

[C6]

[0026]

[C7]

[0027]

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

[0028]

[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.

[0029]

[Comparative Example 2] α-aminoacetophenone-based photopolymerization catalyst (
C) and thioxanthone-based photopolymerization catalyst (D) instead of
A visible light-curable composition was prepared in the same manner as in Example 1 Table 2 and Table 3 Experiment Nos. 1 to 4, except that 1 part by weight of camphorquinone was used, and a visible light-curable composition was prepared in the same manner as in Example 1. The color tones of the compositions before and after irradiation with visible light were observed, and each had a strong yellow tinge before irradiation with visible light, and the cured film had a slight yellow tinge even after irradiation with visible light.

[0030]

[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.

[0031]

[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.

[0032]

[Comparative Example 4] α-aminoacetophenone-based photopolymerization catalyst (
C) and thioxanthone-based photopolymerization catalyst (D) instead of
A visible light curable 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, and a visible light curable composition was prepared in the same manner as in Example 2. The color tone of the composition before and after irradiation with visible light was observed, and the cured film had a strong yellow tinge before irradiation with visible light, and the cured film had a slight yellow tinge even after irradiation with visible light.

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Chemical formula 9]

[0036]

[Chemical formula 10]

Claims (2)

[Claims] [Claim 1] Polyfunctional acrylate monomer (A),
Visible light polymerization curing characterized by containing a volatile solvent (B) for the monomer (A), an α-aminoacetophenone photopolymerization catalyst (C), and a thioxanthone photopolymerization catalyst (D). sexual composition. [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: