JPH0977623A - Dental photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new dental composition having a rapid polymerization rate and less in the elution of a low molecular weight compound from its cured material by combining a specific photopolymerization initiator with a specific reducing agent and using them with a monomer having a polymerizable olefinic unsaturated group. SOLUTION: This dental photopolymerizable composition is obtained by containing a photopolymerization initiator containing a carbonyl compound having an absorption at 400-700nm and a copolymerizable aromatic tertiary amine-type reducing agent having one or more polymerizable olefinic unsaturated group, a nitrogen atom binding with an aromatic ring and H atom in at least one C atom adjacent to the nitrogen atom in a monomer having a polymerizable olefinic unsaturated group. As the reducing agent, a compound of the formula [R1 is H or methyl; R2 is a 1-6C organic residue; R3 is an electron attracting group; (a) is 1, 2; (b) is 0, 1; A is a 1-3C organic residue] is preferable. As the photopolymerization initiator, an a-diketone compound having an absorption in 400-500nm, especially bicyclo [2, 2, 1] heptane-2, 3-dione, etc., are preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dental photocurable composition having a high polymerization rate and a low elution of a low molecular weight compound from a cured product.

[0002]

2. Description of the Related Art Currently, dental polymerizable resin materials are easy to operate,
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 ray-curable dental polymerizable resin composition starting with the proposal of Japanese Patent No. 75 can use visible light that is safe for the living body and has good operability that can be cured at any timing. The cured product has been evaluated for its high strength, and is now most widely used in the dental treatment field. 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, as a visible light polymerization composition, benzyl as a photopolymerization initiator, an α-diketone compound such as camphorquinone, or a thioxanthone compound is often used, and various amines have been often used as a reducing agent. .

[0003]

The polymerization initiator which is widely used in the present composition for visible light is composed of an α-diketone compound and various amines, and is most preferable as the polymerization initiator. A potent and widely used one is camphorquinone, and the most potent reducing agent to combine with it is believed to be N, N-dimethylaminobenzoic acid ethyl ester (JP-A-60-26002). . However, the polymerization rate is not sufficient for this polymerization initiator system, and since dimethylaminobenzoic acid ester, which is one component of this initiator system, is gradually eluted from the cured product due to its hydrophilicity, There was also concern about adverse effects on the living body. The present invention seeks to overcome such drawbacks,
It is an object of the present invention to provide a novel dental photocurable composition that has a high polymerization rate and little elution of a low molecular weight compound from a cured product.

According to the reaction kinetics / molecular collision theory, the conventional photopolymerizable composition is composed of a photopolymerization initiator, a reducing agent and a polymerizable monomer. Requires a multi-molecular reaction due to, and moreover, the collision needs to be between the convenient positions, and it is not enough that each component only collides. The present inventor considered that the first addition reaction of radicals generated by the photopolymerization initiator and the reducing agent to the monomer is a very important point among these processes. That is,
This reaction is a reaction in which a relatively stable radical is added to the polymerizable double bond to generate a more unstable carbon radical, and increasing the efficiency of this process is an important point for improving the polymerization rate. I thought there was. The present inventor, while repeatedly studying the above, in order to obtain a sufficient polymerization rate, in order to obtain a sufficient polymerization rate, a radical capable of receiving a radical in the molecule of a reducing agent that forms a photoexcited complex with a photopolymerization initiator to generate a primary radical. Recall that the presence of a saturated group eliminates the need for another monomer molecule to collide with the reducing agent and favors the process of first adding the radicals generated on the reducing agent molecule to the polymerizable double bond. However, as a result of various searches based on such a concept, one or more polymerizable olefinic unsaturated groups in the molecule, a nitrogen atom bonded to the aromatic ring, and a hydrogen atom at the adjacent carbon atom are found. It is particularly preferable that the copolymerizable aromatic tertiary amine type reducing agent possessed is excellent in polymerization initiation performance, and in particular, that the unsaturated group is present around the 6th atom counted from the atom in which the primary radical is generated. Things Idashi, ranged to the present invention.

[0005]

That is, the present invention provides a monomer (a) having a polymerizable olefinic unsaturated group.
And a dental photopolymerizable composition comprising a photopolymerization initiator (b) and a reducing agent (c), comprising a carbonyl compound exhibiting absorption at 400 to 700 nm as the photopolymerization initiator (b), A copolymerizable aroma having one or more polymerizable olefinic unsaturated groups in the molecule as a reducing agent (c), a nitrogen atom bonded to an aromatic ring and a hydrogen atom on at least one carbon atom adjacent to the nitrogen atom. A dental photopolymerizable composition containing a group III tertiary amine-type reducing agent,

The copolymerizable aromatic tertiary amine type reducing agent has the following general formula:

Embedded image (In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an organic residue having 1 to 6 carbon atoms, R3 represents an electron-withdrawing group, a represents an integer of 1 or 2, and b represents Represents an integer of 0 or 1, A represents an organic residue having 1 to 3 carbon atoms), the dental photopolymerizable composition as described above,

The photopolymerization initiator is an α-diketone compound which absorbs at 400 to 500 nm.
The above-mentioned dental photopolymerizable composition, wherein the photopolymerization initiator is bicyclo [2,2,1] heptane-2,3-dione or an alkyl group, an alkoxy group, a sulfonyl group-substituted derivative, benzyl or an alkyl thereof. A dental photopolymerizable composition, which is a group, an alkoxy group or a halogen group substituted derivative, a thioxanthone or an alkyl group thereof, or a halogen group substituted derivative.

Polymerizable monomers that can be used in the present invention are easily polymerized without being exposed to special reaction conditions such as acrylic monomers, epoxy resins, urethane resins and silicone resins. Any compound can be used as long as it can be used, but a meth (acrylate) -based monomer is preferable from the viewpoint of convenience of the polymerization operation and safety to the living body. The meta (acrylate) -based monomer used in the present invention is a (meth) acrylic acid ester (in the case of an alkyl ester, an alkyl group having 1 to 12 carbon atoms, and an ester containing an aromatic group has a carbon number of 6 to 1).
2. Those having a substituent such as a polyethylene glycol chain in these groups also include their carbon number), polyalkylene glycol di (meth) acrylate (alkylene group having 2 to 20 carbon atoms), ethylene glycol oligomer di (meth A) acrylate (2-10 mer), di (meth) acrylate derived from bisphenol A, trifunctional or higher polyvalent (meth) acrylate, etc., and 2 mol of (meth) acrylate having a hydroxyl group and diisocyanate Urethane (meth) acrylates which are reaction products with 1 mole, specifically, JP-B-55-3
The monomers disclosed in 3687 and JP-A-56-152408 are suitable. Specific examples of these include monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and 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) acrylate, and other (meth) acrylates.

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 hydroxypivalic acid ester di (meth) acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethylolmethane tri (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 , A reaction product of 3-chloro-2-hydroxypropyl (meth) acrylate and methylcyclohexane diisocyanate, a reaction product of 2-hydroxypropyl (meth) acrylate and methylcyclohexane diisocyanate, and 2-hydroxypropyl (meth) acrylate Reaction product of methylenebis (4-cyclohexylisocyanate), reaction product of 2-hydroxypropyl (meth) acrylate with trimethylhexamethylene diisocyanate, reaction product of 2-hydroxyethyl (meth) acrylate with isophorone diisocyanate, 3 Examples include a reaction product of -chloro-2-hydroxypropyl (meth) acrylate and isophorone diisocyanate.

As the photopolymerization initiator, dicarbonyl compounds, benzophenone compounds and thioxanthone compounds are effective. Specifically, dicarbonyl compounds include camphorquinone, diacetyl, 2,3
-Pentanedione, 2,3-heptanedione, benzyl, 4,4'-dichlorobenzyl, 4,4'-dimethoxybenzyl, benzyl-4-methanesulfonate sodium, dinaphthyl, acenaphthenequinone, 9,10-phenanthate Raquinone, anthraquinone, 2-ethylanthraquinone, 3-acetylcoumarin and the like can be mentioned. Examples of the benzophenone compound include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-hydroxybenzophenone, 4-
Methylthiobenzophenone, 4-benzoyl-diphenyl sulfide, 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 chloride and the like.
Thioxanthone compounds include thioxanthone, 2
-Chlorothioxanthone, 2-methylthioxanthone,
2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,
4-diethylcoxanthone, 2,4-diisopropylthioxanthone, sodium thioxanthone-2-oxyethanesulfonate, etc. may be mentioned. Examples of the acylphosphine oxide-based compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,6-
Examples thereof include dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide and methyl 2,4,6-trimethylbenzoyl-phenylphosphinate.

However, many photopolymerization initiators having an aromatic ring do not have good resistance to ultraviolet light, and therefore initiators containing no aromatic ring, that is, aliphatic α-diketones,
Alicyclic α-diketones are preferable, and camphorquinone is particularly preferable. These photopolymerization initiators are used in the range of 0.01-5% by weight with respect to the polymerizable monomer.

The reducing agent used in the present invention has 1 in the molecule.
An aromatic amine compound having at least one polymerizable olefinic unsaturated group and a tertiary amino group having a hydrogen atom on at least one carbon atom adjacent to a nitrogen atom, and having the following general formula:

Embedded image (In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an organic residue having 1 to 6 carbon atoms which may have an ether bond, a thioether bond or the like in the molecular chain, and R3
Represents an electron-withdrawing organic group, a represents an integer of 1 or 2, b represents an integer of 0 or 1, and A represents an organic residue having 1 to 3 carbon atoms. ), In which R1
Is a hydrogen atom or a methyl group, R2 represents a lower alkyl group or a lower alkenyl group, and these are substituted with a halogen atom, a hydroxy group, an alkoxy group, a mercapto group, an alkylthio group, an aryl group, a formyl group, an alkoxycarbonyl group or the like. It may have been done. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, cyclohexyl group, chloroethyl group, hydroxyethyl group, methoxyethyl group, methylthioethyl group, ethoxycarbonyl. Represents a methyl group, an allyl group, a 5-hexenyl group, and the like,
R3 represents an electron-withdrawing group, for example, COOR4, CN,
CHO, COR5, CF3, and a halogen atom are represented, and R4 is a carbon atom which may be substituted with a halogen atom, a hydroxy group, an alkoxy group, a mercapto group, an alkylthio group, an aryl group, a formyl group, a dimethylamino group, or the like. R6 represents an alkyl group or an alkenyl group, wherein R5 is a halogen atom, a hydroxy group, an alkoxy group, a mercapto group, an alkylthio group, an aryl group, a formyl group, a dimethylamino group, or the like, having 1 to 10 carbon atoms. It shows up to 6 alkyl groups, alkenyl groups or aryl groups, but is not limited thereto.

Examples of reducing agents of the present invention are:
p-bis-N, N- (2-methacryloxyethyl) aminobenzoic acid ethyl ester, p-bis-N, N- (2-
Methacryloxyethyl) aminobenzoic acid butoxyethyl ester, p-bis-N, N- (2-methacryloxyethyl) aminobenzonitrile, p-bis-N, N- (2
-Methacryloxyethyl) aminobenzaldehyde, p
-Bis-N, N- (2-methacryloxyethyl) aminoacetophenone, p-bis-N, N- (2-methacryloxyethyl) aminobenzophenone, p-fluoro-bis-N, N- (2-methacryloxy) Ethyl) aniline,
p-chloro-bis-N, N- (2-methacryloxyethyl) aniline, p-bromo-bis-N, N- (2-methacryloxyethyl) aniline, p-trifluoromethyl-bis-N, N- (2-methacryloxyethyl) aniline, p-N-methyl-N- (2-methacryloxyethyl) aminobenzoic acid ethyl ester, p-N-methyl-
N- (2-methacryloxyethyl) aminobenzoic acid butoxyethyl ester, p-N-methyl-N- (2-methacryloxyethyl) aminobenzonitrile, p-N-methyl-N- (2-methacryloxyethyl) Aminobenzaldehyde, p-N-methyl-N- (2-methacryloxyethyl) aminobenzophenone, p-fluoro-N-
Methyl-N- (2-methacryloxyethyl) aniline,
p-chloro-N-methyl-N- (2-methacryloxyethyl) aniline, p-bromo-N-methyl-N- (2-
Methacryloxyethyl) aniline, p-trifluoromethyl-N-methyl-N- (2-methacryloxyethyl)
Aniline, p-N-ethyl-N- (2-methacryloxyethyl) aminobenzoic acid ethyl ester, p-N-ethyl-N- (2-methacryloxyethyl) aminobenzoic acid butoxyethyl ester, p-N-ethyl -N- (2-
Methacryloxyethyl) aminobenzonitrile, p-N
-Ethyl-N- (2-methacryloxyethyl) aminobenzaldehyde, p-bis-N, N- (2-acryloxyethyl) aminobenzoic acid ethyl ester, p-bis-
N, N- (2-acryloxyethyl) aminobenzoic acid butoxyethyl ester, p-bis-N, N- (2-acryloxyethyl)] aminobenzonitrile, p-bis [N, N- (2-acryloyl) Roxyethyl) -aminobenzaldehyde, p-bis-N, N- (2-acryloxyethyl) aminoacetophenone, p-bis-N, N- (2
-Acryloxyethyl) -aminobenzophenone, p-
Fluoro-bis-N, N- (2-acryloxyethyl)
-Aniline.

The addition amount of these amines is usually in the range of 0.1 to 20% by weight, preferably 0.1% by weight, based on the polymerizable monomer.
Used in the range of 5-5% by weight.

Further, a polymerization inhibitor, an ultraviolet absorber and a pigment can be added to the dental photopolymerizable composition in the present invention, if desired.

When used as a filling / restoring agent for caries cavities, the polymerizable monomer: 10-80% by weight and the filler:
The basic composition is 90-20% by weight, to which a photopolymerization initiator and a reducing agent are added. As the filler, an inorganic material or an organic material and a mixture thereof are used, and examples of the inorganic filler include soda glass, barium glass, strontium glass, borosilicate glass, crystalline quartz, fused silica, alumina silicate, amorphous silica, and glass. Examples include ceramics 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 sizes may be mixed and used. The inorganic filler is preferably subjected to a known surface treatment. Examples of surface treatment agents 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 polymerized powder of the polymerizable monomer may be used. Further, 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 is used as a dental restoration filling material, an adhesive, a resin cement, a sealant, etc. with or without addition of a filler, and a coating agent for general industry, It can also be used as an adhesive or a filler.

[0018]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples. Example 1

Under nitrogen atmosphere, p-aminobenzoic acid ethyl ester 1.65 g, bromoethanol 6.25 g, sodium carbonate 2.12 g, in a 100 ml three-headed flask,
0.6 g of sodium iodide and 10 ml of N, N-dimethylformamide were charged, and the mixture was heated and stirred at 140 ° C for 15 hours. The reaction mixture was poured into 150 ml of saturated saline solution,
It was extracted with ethyl acetate. The combined organic layers were washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and p-N, N-bis (2
1.82 g (72%) of -hydroxyethyl) -aminobenzoic acid ethyl ester were obtained. 50 ml under nitrogen atmosphere
In a round-bottomed flask, 1.82 g of p-N, N-bis (2-hydroxyethyl) aminobenzoic acid ethyl ester, 1.24 g of methacrylic acid distilled immediately before use, 30 mg of N, N-dimethylaminopyridine and dry methylene chloride. 30 ml was charged. Ethyl (N, N-dimethylaminopropyl) carbodiimide hydrochloride (2.75 g) was added thereto, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into 200 ml of saturated saline and extracted with ethyl acetate. The combined organic layers were washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and p-N, N-bis (2
1.64 g (59%) of -methacryloxyethyl) aminobenzoic acid ethyl ester was obtained as a pale yellow oil. 1H-NMR (270 MHz, CDCl3) δ 1.
36 (3H, t), 1.90 (6H, s), 3.74
(4H, t), 4.29 (2H, q), 4.31 (4
H, t), 5.58 (2H, s), 6.06 (2H,
s), 6.77 (2H, d), 7.90 (2H, d)

Example 2 Under a nitrogen atmosphere, p-aminobenzoic acid ethyl ester 1.65 g, bromoethanol 5.02 g, sodium carbonate 1.06 g, sodium iodide 0.3 g and dimethylformamide 10 ml were placed in a 50 ml three-headed flask. After charging, the mixture was heated and stirred at 80 ° C. for 8 hours and then cooled to room temperature. Methyl iodide (1.56 g) was added thereto, and the mixture was heated with stirring at 50 ° C. for 12 hours. The reaction mixture was poured into 150 ml of saturated saline and extracted with ethyl acetate. The combined organic layers were washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and p-N-methyl-N- was used.
1.14 g (51%) of (2-hydroxyethyl) aminobenzoic acid ethyl ester was obtained as a yellow oil. Under a nitrogen atmosphere, 1.50 g of p-N-methyl-N- (2-hydroxyethyl) aminobenzoic acid ethyl ester obtained above in a 50 ml eggplant type flask, 0.43 g of methacrylic acid distilled immediately before use, N , N-dimethylaminopyridine 20 mg and dry methylene chloride 20 ml were charged. Ethyl (N, N-dimethylaminopropyl) carbodiimide hydrochloride (0.96 g) was added thereto, and the mixture was heated with stirring at room temperature overnight. The reaction mixture was poured into 100 ml of saturated saline and extracted with ethyl acetate. The combined organic layers were washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and p-N-methyl-N- (2-methacryloxyethyl) aminobenzoic acid ethyl ester 0.95 g (65 %) Was obtained. 1H-NMR (270 MHz, CDCl3) δ 1.
36 (3H, t), 1.90 (3H, s), 3.07
(3H, s), 3.72 (2H, t), 4.29 (2
H, q), 4.31 (2H, t), 5.57 (1H,
s), 6.04 (1H, s), 6.69 (2H, d),
7.91 (2H, d)

EXAMPLE 3 Ethyl iodide 1.69 in place of methyl iodide 1.56 g
Using the same procedure as in Example 2 except that g is used, p
0.64 g (21%) of -N-ethyl-N- (2-methacryloxyethyl) aminobenzoic acid ethyl ester was obtained. 1H-NMR (270 MHz, CDCl3) δ 1.
12 (3H, t), 1.36 (3H, t), 1.90
(3H, s), 2.75 (2H, q), 3.72 (2
H, t), 4.29 (2H, q), 4.31 (2H,
t), 5.57 (1H, s), 6.04 (1H, s),
6.72 (2H, d), 7.90 (2H, d)

Example 4 The same procedure as in Example 1 was repeated except that 1.18 g of p-aminobenzonitrile was used in place of 1.65 g of ethyl p-aminobenzoate and the reaction time was extended to 36 hours. This was performed to obtain 0.62 g (18%) of p-bis-N, N- (2-methacryloxyethyl) aminobenzonitrile as a pale yellow oily substance. 1H-NMR (270 MHz, CDCl3) δ 1.
90 (6H, s), 3.73 (4H, s), 4.31
(4H, s), 5.59 (2H, s), 6.06 (2
H, s), 6.84 (2H, d), 7.55 (2H,
d)

Example 5 p-N-Methyl-N was prepared in the same manner as in Example 2 except that 1.18 g of p-aminobenzoic acid ethyl ester was replaced with 1.18 g of p-aminobenzonitrile. −
0.45 g (15%) of (2-methacryloxyethyl) aminobenzonitrile was obtained as a yellow oil. 1H-NMR (270 MHz, CDCl3) δ 1.
90 (3H, s), 3.09 (3H, s), 3.72
(2H, t), 4.30 (2H, t), 5.57 (1
H, s), 6.04 (1H, s), 6.86 (2H,
d), 7.56 (2H, d)

Example 6 The procedure of Example 1 was repeated except that 1.35 g of p-aminobenzoic acid ethyl ester was replaced with 1.35 g of p-aminoacetophenone, and p-bis-N, N- was used.
2.26 g (63%) of (2-methacryloxyethyl) aminoacetophenone was obtained as a yellow oil. 1H-NMR (270 MHz, CDCl3) δ 1.
90 (6H, s), 2.55 (3H, s), 3.73
(4H, s), 4.31 (4H, s), 5.59 (2
H, s), 6.06 (2H, s), 6.80 (2H,
d), 7.81 (2H, d)

Example 7 The procedure of Example 1 was repeated except that 1.21 g of p-aminobenzaldehyde was used in place of 1.65 g of p-aminobenzoic acid ethyl ester, and p-bis-N, N-
(Methacryloxyethyl) aminobenzaldehyde 1.
Obtained 17 g (34%) as a yellow oil. 1H-NMR (270 MHz, CDCl3) δ 1.
90 (6H, s), 3.73 (4H, s), 4.31
(4H, s), 5.58 (2H, s), 6.05 (2
H, s), 6.88 (2H, d), 7.75 (2H,
d), 9.80 (1H, s)

Example 8 1.11 g of p-fluoroaniline was used in place of 1.65 g of p-aminobenzoic acid ethyl ester, and the reaction temperature was 1.
The same operation as in Example 1 was carried out except that the temperature was set to 00 ° C.,
1.37 g (41%) of p-fluoro-bis-N, N- (2-methacryloxyethyl) aniline was obtained as a yellow oil. 1H-NMR (270 MHz, CDCl3) δ 1.
90 (6H, s), 3.73 (4H, s), 4.31
(4H, s), 5.59 (2H, s), 6.06 (2
H, s), 6.66 (2H, d), 6.93 (2H,
d)

Example 9 The same operation as in Example 1 was carried out except that 1.61 g of p-trifluoromethylaniline was used in place of 1.65 g of ethyl p-aminobenzoate and the reaction temperature was 90 ° C. And p-trifluoromethyl-bis-N, N- (2
-Methacryloxyethyl) aniline 0.85 g (22
%) As a yellow oil. 1H-NMR (270 MHz, CDCl3) δ 1.
90 (6H, s), 3.73 (4H, s), 4.31
(4H, s), 5.59 (2H, s), 6.06 (2
H, s), 6.80 (2H, d), 7.51 (2H,
d)

Example 10 and Comparative Examples To measure the curing activity, a mixture of monomer, photoinitiator and copolymerizable reducing agent of the present invention was prepared. The composition was bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate / camphorquinone / reducing agent = 50/50/2/4 (weight ratio).
The mixture was put in a colorless glass sample tube, the tip of a thermocouple was inserted in the center of the sample tube, and irradiation with a dental light irradiator Litel II (Morita Manufacturing Co., Ltd.) was applied from below the sample tube to observe the heat of polymerization. The time when the maximum temperature was reached was defined as the curing time. Table 1 shows the results of the amine according to the present invention and N, N-dimethylaminobenzoic acid ethyl ester as a comparative example. From this, it is clear that the curing time of the composition containing the reducing agent of the present invention is short.

[0029]

[Table 1]

Example 10 To measure the polymerization inhibitory ability of a reducing agent, a mixture of a monomer, a photoinitiator and a copolymerizable reducing agent of the present invention was prepared. Its composition is bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate /
Camphorquinone / reducing agent = 50/50/1 / x (weight ratio). The curing time of the mixture was measured in the same manner as in Example 11. Table 2 shows the results of the reducing agent according to the present invention and N, N-dimethylaminobenzoic acid ethyl ester as a comparative example. From this, it can be seen that the reducing agent of the present invention significantly increases the curing time even if the addition amount is increased. Obviously not.

[0031]

[Table 2]

Example 11 To measure the elution of the initiator from the cured product, a mixture of monomer, photoinitiator and the copolymerizable amine of the present invention was prepared. Its composition is bisphenol A diglycidyl methacrylate / triethylene glycol dimethacrylate / camphorquinone / reducing agent = 50/50 /
It was set to 1/5 (weight ratio). The mixture was poured into a mold having a diameter of 20 mm and a thickness of 1 mm and irradiated with a dental irradiator α-light (manufactured by Morita Manufacturing Co., Ltd.) for 5 minutes, and the surface and the side surface of the obtained cured product were polished with polishing paper. A 50 ml round bottom flask equipped with a reflux condenser was charged with 10 ml of methanol and three pieces of the cured product weighed, and heated at a temperature at which methanol gently refluxed for 5 hours. The methanol solution was analyzed by gas chromatography (manufactured by Hitachi Ltd.) to quantify the eluted amine. Table 2 shows the results using the amine according to the present invention and N, N-dimethylaminobenzoic acid ethyl ester as a comparative example. It is clear from this that the reducing agent contained in the composition of the present invention does not elute in methanol at all. Is.

[0033]

[Table 3]

[0034]

Industrial Applicability The dental photopolymerizable composition of the present invention has a high curing rate, a small polymerization inhibition, a small elution from the cured product, and excellent physical and clinical properties.

Claims (4)

[Claims] 1. A monomer (a) having a polymerizable olefinic unsaturated group, a photopolymerization initiator (b) and a reducing agent (c).
A photopolymerizable composition for dental use comprising: a photopolymerization initiator (b) containing a carbonyl compound exhibiting absorption at 400 to 700 nm; and a reducing agent (c) having at least one polymerizable compound in its molecule. A olefinically unsaturated group, a nitrogen atom bonded to an aromatic ring, and a hydrogen atom on at least one carbon atom adjacent to the nitrogen atom, and a copolymerizable aromatic tertiary amine type reducing agent. Dental photopolymerizable composition. 2. The copolymerizable aromatic tertiary amine type reducing agent is represented by the following general formula: (In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an organic residue having 1 to 6 carbon atoms, R3 represents an electron-withdrawing group, a represents an integer of 1 or 2, and b represents The dental photopolymerizable composition according to claim 1, wherein A represents an integer of 0 or 1, and A represents an organic residue having 1 to 3 carbon atoms. 3. The photopolymerization initiator is an α-diketone compound that absorbs at 400 to 500 nm.
The dental photopolymerizable composition according to claim 1 or 2. 4. The photopolymerization initiator is bicyclo [2,2,1].
Heptane-2,3-dione or its alkyl group, alkoxy group, sulfonyl group substituted derivative, benzyl or its alkyl group, alkoxy group or halogen group substituted derivative, thioxanthone or its alkyl group, halogen group substituted derivative The dental photopolymerizable composition according to claim 1 or 2.