JPH0469312A - Composition polymerizable and curable with visible light - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a tetraacrylate monomer, its volatile solvent and a polymerization initiator and quickly curable with irradiation of visible light even in the presence of oxygen to form a smooth hardened surface. CONSTITUTION:The objective composition contains, as essential components, (A) a monomer of formula (R1, R3, R4 and R6 are acryl or methacryl; R2 and R5 are alkyl), (B) a volatile solvent of the above monomer A and having a boiling point of <=100 deg.C [preferably acrylates such as methyl or ethyl (meth) acrylate] and (C) a polymerization initiator (preferably a visible light polymerization catalyst such as camphorquinone, fluorenone and dibenzyl). The composition is especially suitable as an agent for applying surface-smoothness to artificial tooth, a mending agent for defective enamel and discolored part of tooth and manicure and opaquer for tooth because it forms a hardened film having smooth surface by irradiating with a visible light of 400-500mum wavelength.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a visible light polymerizable curable composition, and more particularly, the cured composition has a smooth surface and is particularly suitable for use in artificial teeth. The present invention relates to a visible light polymerizable curable composition suitable for imparting surface smoothness, for repairing tooth enamel defects and discolored areas, for tooth manicure, and as an opaque.

(Prior art) Conventionally, as an acrylate-based photopolymerizable composition, 2
．． Various compositions containing a sensitizing side and an acrylate monomer such as 2-bis[4-3-methacrywaquino-2hydroquinopropoquine)phenyl]propane, triethylene glycol no methacrylate, and 7-opentyl dimethacrylate have been proposed. It is used in a wide variety of fields such as dental materials. However, 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 extrinsic factor, unreacted particles are left on the surface of the cured composition. The 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. For visible light polymerizable dental composite filling materials, after applying the filling material to the affected area for therapeutic purposes,
It is necessary to irradiate visible light and polymerize and cure 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 work has been performed. Similarly, compositions using such a 7-acrylate-based visible polymerizable curable resin as a matrix resin leave unreacted resin residue on the cured surface, making it difficult to cure dental surfaces with a smooth surface that requires a thin film-like resin layer. However, it was not suitable for use in sealants for preventing cavities, opaque materials, nail polish for teeth, etc.

(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 visible light irradiation and forms a smooth cured surface. Another purpose is to cure by irradiation with visible light of 400 to 500 I1m to form a hardened surface that is harmless to the human body and is suitable for dental materials such as tooth surface smoothing hardeners, opaque materials, and nail polish. The present invention provides a polymerizable curable composition. Further objects and effects of the present invention will become clear from the following description.

(Means for solving the problem) The above purpose is to polymerize a tetraacrylate monomer (A) represented by the following formula (1), a volatile solvent (B) for the monomer (A), and This is achieved by a visible light polymerizable curable composition containing an initiator (C).

CHzOR, CHzo R6 R2CCHI OCH2C-R5 CH, OR, CH, OR.

...(1) Examples of the tetraacrylate compounds represented by formula (1) include ditrimethylolethanetetraacrylate, ditrimethylolethanetetramethacrylate, notrimethylolpropanetetraacrylate, ditrimethylolpropanetetramethacrylate, and ditrimethylolbutanetetraacrylate. Examples include acrylate, ditrimethylolbutanetetraacrylate, and the like.

The volatile solvent (B) is a solvent for the tetraacrylate monomer (A) 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 (meth). ) acrylate, ethyl (meth)acrylate, and other acrylates are preferred. The above volatile solvent (B
), acrylate is expressed by formula (1) by irradiation with visible light.
Reacts with the acrylate monomer (A) shown below.

When these acrylates are used as volatile solvents, a cured composition with superior strength can be obtained compared to when a non-reactive volatile solvent is 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, the polymerization initiator (C) applied to the present invention may be appropriately selected from known visible light polymerization catalysts, and if necessary, a reducing agent may be used in combination with the visible light polymerization catalyst.

Preferred visible light polymerization catalysts include camphoraquinone, fluorenone, nohenzil, and the like. Examples of the reducing agent include N, N' dimethylamino P-amino, ethyl fragrant, N, N' dimethylamine ethyl methacrylate, N
-Methyldiphenylamine, N-dimethylpara-toluidine n-butylamine, triethylamine, tri-n-butylphosphine, allylthiourea, S-hensylisothiuronium-P-toluenesulfy7-)-,2-n-butquinethyl-4-dimethylamino Benzoate, 2-dimethylaminoethylhenzoate, P-dimethylaminoamine, isoamyl fragrant, etc., among which N, N' dimethylamino-P-ethyl benzoate, N,
Preferred examples include N'dimethylaminoethyl methacrylate, N-methyldiphenylamine and N-dimethylpara-toluidine. These visible light polymerization catalysts and reducing agents may be added within the ranges normally used.

The visible polymerizable curable composition according to the present invention comprises an acrylate monomer (A) represented by the above formula (1), an rj-generating solvent (B
) and a polymerization initiator (C), but when an acrylate capable of visible light polymerization is added to the above basic composition, the physical and chemical properties of the cured product change.

The addition of the acrylate to the basic composition is also effective depending on the application. Examples of such visible light polymerizable acrylates include dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, triallyl cyanurate,
Pentaerythritol tetramethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate-1, tetraethylene glycol diacrylate, tetraethylene glycol diacrylate methacrylate, 1.
3-butanediol acrylate, 1.4-butanediol diacrylate, 1.4-diol methacrylate,
Opentyl glycol noacrylate, neopentyl glycol dimethacrylate, 1,6-hexanethiol dimethacrylate trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
Examples include pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, tricyclodecane diacrylate, glycerol dimethacrylate, glycerol acrylate/methacrylate diacrylated isocyanate, caprolactone-modified dipentaerythritol hexaacrylate, and nottrimethylolpropane 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 may be 50% by weight or less, preferably 5 to 30% by weight.

Furthermore, when an inorganic or organic filler is added to the basic composition, the visible light irradiation time required for polymerization is significantly shortened, and the strength of the cured product is improved and opacity 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 the treatment of discolored areas of teeth due to enamel defects, etc., and as a dental manicure and opaque. be able to. An example of an inorganic or organic filler that can be incorporated into the basic composition is silica. Examples include titanium dioxide, zirconium oxide, silicon nitride, calcium carbonate, polymethyl methacrylate, polyethylene methacrylate, and the like.

To prepare a composition using these components, no special method is required; for example, the tetraacrylate monomer represented by formula (1) is prepared in a completely sealed brown bottle. While stirring the polymer (A) into the volatile solvent (B)? Then, the polymerization initiator (C) is further dissolved to prepare a basic composition of a visible light polymerizable curable composition. If necessary, visible polymerizable acrylates, fillers, pigments, etc. may be added to the basic composition while stirring.

(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 will exhibit outstanding effects when used in various applications such as dental materials. That is, by combining the tetraacrylate monomer (A) represented by the formula (1) according to the present invention with a specific volatile solvent (B) and a polymerization initiator (C),
A smooth cured film is formed by irradiation with visible light in the 00 μm wavelength range, so it can be applied to the surface of dental plastic materials such as tooth filling materials and denture base resin, and irradiated with visible light to polymerize. 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 restorative 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.

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 surface of a cured composite resin for photopolymerization (product name: Helfeel Mark ■, manufactured by Kanebo ■) was prepared into a disk shape of 1 cm in diameter and 2 mm in thickness using the composition, and the surface was wet-polished using abrasive paper with a grain size of 600. After applying a thin layer with a small brush, place it in a dental visible light irradiator (trade name: LIGHTACE manufactured by Yoshida) for 1 minute and 3 minutes.
Light irradiation was performed for 5 minutes, 10 minutes, and 20 minutes.

After irradiation with light, the cured composition was left indoors for 24 hours, and the surface was wiped with a cloth soaked in ethyl alcohol, and evaluated by inspection using the evaluation criteria shown below. The results are shown in Table 1.

ゝ＼ (hereinafter referred to as tS white) ´To Comparative Example 1 2,2 bis (P
A visible light polymerizable curable composition was prepared in the same manner as in Example 1, except that -2'-hydroxy-3'-methacryloxypropoquinphenyl)propane was used, and the surface smoothness was determined in the same manner as in Example 1. In the evaluation, even after 20 minutes of light irradiation, liquid unreacted monomer remained on the surface of the cured composition and adhered to the cloth.

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

Comparative Example 2 2,2-bis(P-2'-hydroquine-3'
Example 2 except that -methacryloxypropoxyphenyl)propane is used. A visible light polymerizable curable composition was prepared in the same manner as in Experiment No. 1.2.3 of Table 2, and the surface smoothness was evaluated in the same manner as in Example 1. Even after 20 minutes of light irradiation, the surface of the cured composition remained Unreacted liquid scum remained and adhered to the cloth.

Example 3 A visible light polymerizable curable composition was prepared in the same manner as in Example 1 except that the composition shown in Table 3 was used instead of the composition shown in Table 1, and a comparison was made in the same manner as in Example 1. Example 3 2,2-bis(P-2'-hydroquine-
A visible light polymerizable curable composition was prepared in the same manner as in Example 3, Table 3, Experiment No. 1.2.3, except that 3'-methacryloxypropoxyphenyl)propane was used, and the surface was cured in the same manner as in Example 1. Although the smoothness was evaluated, even after 20 minutes of light irradiation, liquid unreacted monomer remained on the surface of the cured composition and adhered to the cloth.

Example 4 A visible light polymerizable curable composition was prepared in the same manner as in Example 1, except that the composition shown in Table 4 was used instead of the composition shown in Table 1, and a comparison was made in the same manner as in Example 1. Example 4 2,2-bis(P-2'-hydroxy-3
A visible light polymerizable curable composition was prepared in the same manner as in Example 4, Table 4, Experiment Nos. 1 to 5, except that propane ('-methacryloquine propoxyphenyl) was used. The glossiness was evaluated, but even after 20 minutes of light irradiation, liquid unreacted monomer remained on the surface of the cured composition and adhered to the cloth.

Example 5 A visible light polymerizable curable composition was prepared in the same manner as in Example 1, except that the composition shown in Table 4 was used instead of the composition shown in Table 1. The surface smoothness was evaluated. The results are shown in Table 5.

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

Claims (1)

[Claims] A tetraacrylate monomer represented by the following formula (1) (
A visible light polymerizable curable composition comprising: A), a volatile solvent (B) for the monomer (A), and a polymerization initiator (C). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) [However, in the formula, R_1, R_3, R_4, and R_6 represent an acrylic group or a methacrylic group, and R_2 and R_5 represent an alkyl group. ]