JPH1036212A - Photopolymerizable composition for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition high in polymerization speed, excel lent in light resistance, usable together with an acidic monomer and good in storage stability by using a polymerizable monomer, a specific photopolymeriza tion initiator and a specified N-phenylglycine derivative as a reducing agent. SOLUTION: This photopolymerization composition comprises a monomer having a polymerizable olefinic unsaturated group, a carbonyl compound absorbing light having wavelengths of 400-700nm as a photopolymerization initiator, and a compound of the formula (R<1> is an electron-attracting group, namely cyano, an alkylcarbonyl, an alkoxycarbonyl, etc.; R<2> is H, an alkyl) as a reducing agent. The introduction of the electron-attracting group to the aromatic ring of the N-phenyl glycine in the compound of the formula enables to shorten the polymerization time and improve the storage stability of the photopolymerization composition. The introduction of the substituent to the N atom enables to improve the solubility of the monomer and the light resistance of the cured product. The compound of the formula is preferably N-(4-cyanophenyl)-N- methylglycine, and the photopolymerization initiator is preferably camphor quinone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dental photopolymerizable composition which has a high polymerization rate, excellent light resistance, can be used in combination with an acidic monomer, and has excellent storage stability.

[0002]

2. Description of the Related Art At present, dental polymerizable resin materials are operable,
Due to its excellent esthetics and strength, it has been widely used in the field of dental treatment. In particular, JP-A-48-498
The visible light polymerization type dental polymerizable resin composition starting with the proposal of the '75 patent can use visible light that is safe for the living body, and has good operability that can be cured at any timing. The strength of the cured product is evaluated, and it is currently most widely used in the field of dental treatment. Conventionally,
The visible light polymerizable dental polymerizable resin composition is known to be composed of a polymerizable monomer, a photopolymerization initiator, and a reducing agent. Among them, α-diketone-based compounds such as benzyl and camphorquinone as photopolymerization initiators or thioxanthone-based compounds are frequently used as visible light polymerization compositions, and various amines have been frequently used as reducing agents. .

[0003]

The polymerization initiator widely used in the current composition for visible light is composed of an α-diketone compound and various amines. Is widely used in the art. Camphorquinone is used as a strong reducing agent for combination with N, N-dimethylaminobenzoic acid ethyl ester (JP-A-60-26002), N, N-dimethylamino Ethyl methacrylate (JP-A-48-4987)
No. 5) is known. However, the polymerization initiator system containing N, N-dimethylaminobenzoic acid ethyl ester has a problem that the polymerization rate cannot be said to be sufficient, and yellowing is caused by exposure to sunlight after polymerization curing. The polymerization initiator system containing dimethylaminomethyl methacrylate still has a problem that the polymerization rate cannot be said to be sufficient, there is a unique amine odor, and it is difficult to polymerize and cure under acidic conditions.

To partially solve the above-mentioned problem, a dental adhesive containing a combination of camphorquinone and N-phenylglycine has been disclosed (Japanese Patent Laid-Open No. 1-2).
No. 30508). In this composition, polymerization curing proceeds in the presence of an acidic adhesion-promoting monomer, but the rate is not sufficient, and the stability of the composition containing N-phenylglycine is insufficient. I had it.
On the other hand, a novel N-aryl-α-amino acid and a photosensitive composition containing the same are disclosed in JP-A-7-267907. This N-aryl-α-amino acid is
It can be considered as a kind of phenylglycine derivative, and the photosensitive composition is provided by using this compound alone or as a mixture with a coumarin compound or an azabenzalcyclohexanone compound. However, exposure to this composition is performed with an ultra-high pressure mercury lamp, and the coumarin compound and azabenzalcyclohexanone compound used in combination are colored, which is unsuitable for dental use.

The inventors of the present invention have made intensive efforts to overcome such disadvantages, and as a result, have a high polymerization rate, can be used in combination with an acidic monomer, have excellent weather resistance of a cured product, and have excellent storage stability of the composition. A photocurable dental composition having no problem was found. That is, by introducing an electron-withdrawing group into the aromatic ring of the reducing agent N-phenylglycine, which was conventionally known to be able to be used in combination with an acidic monomer, the polymerization time was shortened and the storage stability was improved. In addition, by introducing a substituent on the nitrogen atom, the solubility in general-purpose monomers is increased, and at the same time, the weatherability of the cured product is improved, thereby providing a novel dental photopolymerizable composition. Successful.

[0006]

That is, the present invention provides:
A dental photopolymerizable composition comprising (a) a monomer having a polymerizable olefinically unsaturated group, (b) a photopolymerization initiator, and (c) a reducing agent, wherein the photopolymerization initiator is used. (B) is a carbonyl compound exhibiting absorption at 400 to 700 nm, and the reducing agent (c) is represented by the following general formula:

Embedded image (Wherein, R ¹ is a substituent selected from an electron-withdrawing group, and represents a substituent selected from cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, halogen, and halogenoalkyl; R ² represents a hydrogen atom; )
A alkyl group that may be substituted with an acroyl group or a hydroxyl group).

[0007] The polymerizable monomer that can be used in the present invention may be any known monomer having an olefinically unsaturated group, as long as it can be easily polymerized without special reaction conditions. However, a meta (acrylate) -based monomer is preferred from the viewpoint of simplicity of the polymerization operation and safety for the living body. The (meth) acrylate monomer used in the present invention includes:
(Meth) acrylic acid esters (in the case of alkyl esters, the alkyl group has 1 to 12 carbon atoms; in the case of esters containing aromatic groups, those having 6 to 12 carbon atoms; those containing a substituent such as a polyethylene glycol chain in these groups are Carbon number), polyalkylene glycol di (meth) acrylate (alkylene group having 2 to 20 carbon atoms), ethylene glycol oligomer di (meth) acrylate (2 to 10-mer), di (meth) Urethane (meth) acrylates which are reaction products of 2 moles of (meth) acrylate having a hydroxyl group and 1 mole of diisocyanate. Specifically, JP-B-55-33687 and JP-A-56-1524
No. 08 is preferred.

As specific examples of these, examples of monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-
Ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate,
Glycerol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate , Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, caprolactone-modified dipentaerythritol (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth)
And (meth) acrylates such as acrylate.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol. Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nempentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, glycerol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A glycidyl di (meth) acrylate, ethylene oxide modified Bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A Gurishijiruji (meth) acrylate, 2,2-bis (4-
(Methacryloxypropoxyphenyl) propane, 7,
7,9-trimethyl-4,13-dioxa-3,14-
Dioxo-5,12-diazahexadecane-1,16-
Diol di (meth) acrylate, neopentyl glycol hydroxypivalate ester di (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol ester di (meth) acrylate,

Trimethylolethanedi (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolmethanetri (meth) acrylate,
Trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 3-chloro-2
Reaction products of 2-hydroxypropyl (meth) acrylate and methylcyclohexane diisocyanate, reaction products of 2-hydroxypropyl (meth) acrylate and methylcyclohexane diisocyanate, 2-hydroxypropyl (meth) acrylate and methylene bis (4
-Cyclohexyl isocyanate), 2
Reaction product of hydroxypropyl (meth) acrylate and trimethylhexamethylene diisocyanate, 2
Reaction products of -hydroxyethyl (meth) acrylate and isophorone diisocyanate, and reaction products of 3-chloro-2-hydroxypropyl (meth) acrylate and isophorone diisocyanate.

Further, specific examples of acidic monomers known to have an adhesion promoting effect include the following.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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As the photopolymerization initiator, dicarbonyl compounds, benzophenone compounds, thioxanthone compounds, and acylphosphine oxide compounds are effective. Specifically, as the dicarbonyl compound, camphorquinone, diacetyl, 2,3-pentanedione, 2,3-heptanedione, benzyl, 4,4′-dichlorobenzyl, 4,4′-dimethoxybenzyl, benzyl Sodium 4-methanesulfonate, dinaphthyl,
Acenaphthenequinone, 9,10-phenanthraquinone,
Examples include anthraquinone, 2-ethylanthraquinone, and 3-acetylcoumarin.

Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-hydroxybenzophenone, 4-methylthiobenzophenone, 4-benzoyl-diphenylsulfide, and 4-benzoyl-
4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bis (N, N-dimethylamino) benzophenone, 4,4 ′
-Bis (N, N-diethylamino) benzophenone, 4
-(Acryloyloxyethoxy) benzophenone, trimethyl (3-benzoylphenyl) methylammonium and the like. Thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone,
Methylthioxanthone, 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylcoxanthone,
2,4-diisopropylthioxanthone, sodium thioxanthone-2-oxyethanesulfonate, and the like.

As acylphosphine oxide compounds, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-
Diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,4
And methyl 6-trimethylbenzoyl-phenylphosphinate.

However, many photopolymerization initiators having an aromatic ring have poor light resistance to ultraviolet light, and initiators containing no aromatic ring, ie, aliphatic α-diketones,
Alicyclic α-diketones are preferred, and camphorquinone is particularly preferred. These photopolymerization initiators are used in an amount of 0.01 to 5% by weight based on the polymerizable monomer.

The reducing agent used in the present invention is an N-phenylglycine derivative having a substituent selected from an electron-withdrawing group on an aromatic ring and optionally having a substituent on a nitrogen atom. Yes, the following general formula

[0025]

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Wherein R ¹ is a substituent selected from an electron-withdrawing group, and represents a substituent selected from cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, halogen and halogenoalkyl, and R ² is a hydrogen atom , A (meth) acryloyl group or an alkyl group which may be substituted with a hydroxyl group).

Specific examples of R ¹ include cyano, acetyl, ethyloyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl, fluorine atom, chlorine atom, bromine atom, trichloromethyl, trifluoromethyl and the like. Specific examples of R ² include a hydrogen atom, an acryloyl group, a methacryloyl group, a methyl group, an ethyl group,
Examples thereof include an n-propyl group, an i-propyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

Examples of the reducing agent of the present invention are shown below. N-
(4-cyanophenyl) glycine, N- (4-ethoxycarbonylphenyl) glycine, N- (2-ethoxycarbonylphenyl) glycine, N- (4-acetylphenyl) glycine, N- (4-chlorophenyl) glycine, N -(4-trifluoromethylphenyl) glycine, N- (4-cyanophenyl) -N-methylglycine, N- (4-ethoxycarbonylphenyl) -N-methylglycine, N- (4-methylsulfonylphenyl)
-N-methylglycine, N- (4-acetylphenyl)
-N-methylglycine, N- (4-chlorophenyl)-
N-methylglycine, N- (4-trifluoromethylphenyl) -N-methylglycine, N- (4-cyanophenyl) -N-ethylglycine, N- (4-cyanophenyl) -NN-propylglycine N- (4-cyanophenyl) -Ni-propylglycine, N- (4-cyanophenyl) -NN-butylglycine, N- (4-cyanophenyl) -N-methacryloylglycine, N-
(4-methylsulfonyl) -N-methacryloylglycine, N- (4-cyanophenyl) -N-acryloylglycine, N- (4-methylsulfonyl) -N-acryloylglycine, N- (4-cyanophenyl) -N -(2
-Hydroxyethyl) glycine, N- (4-methylsulfonylphenyl) -N- (2-hydroxyethyl) glycine.

The amount of these amines added is usually in the range of 0.1 to 20% by weight, preferably 0.1 to 20% by weight, based on the polymerizable monomer.
It is used in the range of 1 to 5% by weight. The dental photopolymerizable composition according to the present invention further includes a polymerization inhibitor if desired,
UV absorbers and pigments can be added.

When the photopolymerizable composition of the present invention is used as a composite material for filling and restoring dental cavities, a polymerizable monomer:
The basic composition is 10-80% by weight and filler: 90-20% by weight, and a photopolymerization initiator and a reducing agent are added thereto. As the filler, an inorganic or organic substance and a composite thereof are used. Examples of the inorganic filler include soda glass, lithium borosilicate glass, barium glass, strontium glass, zinc glass, fluoroaluminum borosilicate glass, borosilicate glass,
Examples thereof include crystal quartz, fused silica, synthetic silica, alumina silicate, amorphous silica, glass ceramic, and mixtures thereof. The particle size of the inorganic filler is not particularly limited, but is usually 150 μm or less, preferably 100 μm or less. Also, several kinds of fillers having different particle diameters may be mixed and used.

The above-mentioned inorganic filler is preferably subjected to a known surface treatment. Examples of the surface treatment agent include silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrisilane. Methoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like are used. As the organic filler, a polymer powder of the polymerizable monomer may be used. A powder (composite filler) obtained by dispersing and polymerizing the inorganic filler in the polymerizable monomer can also be used.

As described above, the photopolymerizable composition of the present invention can be used as a dental restorative filling material, an adhesive, a resin cement, a sealant, etc., with or without a filler. It can also be used as an adhesive, a filler and the like.

[0033]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples. Examples 1-6 and Comparative Examples 1-2 To measure the curing activity, a mixture of a monomer, a photoinitiator and a reducing agent of the present invention was prepared. The composition was bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate / camphorquinone / reducing agent = 50/50/1/2 (weight ratio). The mixture was placed in a colorless glass sample tube, the tip of a thermocouple was inserted into the center of the sample tube, and irradiated from below the sample tube using a dental light irradiator Lightel II (manufactured by Morita Seisakusho) to observe the heat of polymerization. Was reached as the curing time.
Table 1 shows the amines according to the invention and N, N- as comparative examples.
The results for dimethylaminobenzoic acid ethyl ester are shown, from which it is clear that the curing time of the composition containing the reducing agent of the present invention is short.

[0034]

[Table 1]

Examples 7 to 9 and Comparative Examples 3 to 4 In order to measure the curing activity when using an acidic monomer, a mixture of a monomer, an acidic monomer, a photoinitiator and the reducing agent of the present invention was prepared. The composition is as follows: bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate / 10-methacryloyloxydecyl dihydrogen phosphate / camphorquinone / reducing agent = 5
0/45/5/1/1 (weight ratio). The curing time of the mixture was measured in the same manner as in Example 1. Table 2 shows the results of the reducing agent according to the present invention and N-phenylglycine and N, N-dimethylaminoethyl methacrylate as comparative examples. From this, it can be seen that the curing time of the reducing agent of the present invention is remarkable even when an acidic monomer is used in combination. It is clear that there is no significant extension.

[0036]

[Table 2]

Examples 10 to 12 and Comparative Examples 5 to 6 In order to evaluate the light fastness of the cured product, a mixture comprising a monomer, a photoinitiator and the reducing agent of the present invention was prepared. The composition was bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate / camphorquinone / reducing agent = 50/50/1/1 (weight ratio). The mixture was poured into a mold having a diameter of 20 mm and a thickness of 1 mm, and both sides were irradiated for 1 minute using a slide projector. Half of the cured product is covered with aluminum foil,
Light of 150,000 Lx was irradiated in water at 37 ° C. for 24 hours. The color difference in the L * a * b * color system was measured for the non-irradiated surface and the irradiated surface. Table 3 shows the results obtained using the amine according to the present invention and N, N-dimethylaminobenzoic acid ethyl ester as a comparative example. Where ΔE = (ΔL * ² + Δa * ² Δb *
² ) ^1/2 , which represents the color difference between the non-irradiated surface and the irradiated surface. This clearly shows that the composition of the present invention has little discoloration after light irradiation and is excellent in light resistance.

[0038]

[Table 3]

Example 13 and Comparative Example 7 In order to evaluate the storage stability of the composition of the present invention, a mixture comprising a monomer, a photoinitiator and a reducing agent was prepared.
Its composition is bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate / 10-
Methacryloyloxydecyl dihydrogen phosphate / camphorquinone / reducing agent = 50/45/5/1 /
1 (weight ratio). The mixture was stored at a constant temperature, and the time until solidification was examined. The results are shown in Table 4, from which it is clear that the composition of the present invention is excellent in storage stability.

[0040]

[Table 4]

[0041]

The photopolymerizable dental composition of the present invention has a high polymerization rate, is excellent in light resistance, can be used in combination with an acidic monomer, has excellent storage stability, and has excellent physical and clinical properties. It is excellent.

Claims (4)

[Claims] 1. A dental photopolymerizable composition comprising (a) a monomer having a polymerizable olefinically unsaturated group, (b) a photopolymerization initiator, and (c) a reducing agent. The photopolymerization initiator (b) is a carbonyl compound exhibiting absorption at 400 to 700 nm, and the reducing agent (c) is represented by the following general formula: (Wherein, R ¹ is a substituent selected from an electron-withdrawing group, and represents a substituent selected from cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, halogen, and halogenoalkyl; R ² represents a hydrogen atom; )
An alkyl group which may be substituted with an acroyl group or a hydroxyl group). 2. The reducing agent (c) has the following general formula: (Wherein R ¹ represents a substituent selected from cyano, ethoxycarbonyl, methoxycarbonyl, and methylsulfonyl, and R ² is a methyl group).
Dental photopolymerizable composition. 3. The dental photopolymerizable composition according to claim 1, wherein said reducing agent (c) is N- (4-cyanophenyl) -N-methylglycine. 4. The photopolymerization initiator (b) is camphorquinone, and the reducing agent (c) is N- (4-cyanophenyl)
The dental photopolymerizable composition according to claim 1, which is -N-methylglycine.