JPH0193507A - Photopolymerizable dental material - Google Patents

Abstract

PURPOSE:To obtain the titled material, consisting of a photopolymerization initiator consisting of a photosensitizer of an alpha-ketocarbonyl compound and a reducing agent of a glycine compound and aromatic sulfinic acid or salt thereof and a radically polymerizable monomer. CONSTITUTION:A photopolymerizable dental material consisting of a radically polymerizable monomer and a photopolymerization initiator. In the above- mentioned material, the photopolymerization initiator consists of a photosensitizer and a reducing agent and an alpha-ketocarbonyl compound (e.g. diacetyl or benzil) is used as the photosensitizer and a glycine compound expressed by the formula [R1 and R2 are H or alkyl (which may be substituted by vinyl, acyl, alkoxy, etc.); R3 is H, alkyl or aromatic group] and an aromatic sulfinic acid or salt thereof (e.g. benzenesulfinic acid) are used as the reducing agent. The above-mentioned polymerizable dental material has improved photopolymerizability within a low temperature region near ordinary temperature and the resultant material has excellent storage stability, color tone, etc.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a polymerizable dental material used as a composite resin for teeth or a hard resin for teeth, which has excellent properties particularly in the low temperature region around room temperature. Has photopolymerizability,
The present invention also relates to a photopolymerizable dental material that has excellent storage stability and color tone.

[Conventional technology and its problems]

Conventionally, composite resins for teeth or hard resins for teeth were used.
As polymerizable dental materials such as resin, polymerizable materials comprising radically polymerizable monomers such as (meth)acrylic acid ester monomers and curing agents are known.

Polymerizable dental materials such as composite resins for teeth and hard resins for teeth have excellent mechanical strength and
It must have excellent curing performance, storage stability, color tone, etc. in the low-temperature region around room temperature.In particular, tooth restoration technology has made significant progress recently, and with this, the above-mentioned performance requirements for polymerizable dental materials have also improved. Things are getting tougher.

In conventional polymerizable dental materials made of radically polymerizable monomers such as (meth)acrylic acid ester monomers and polymerization initiators, by photopolymerizing using a photoinitiator as the polymerization initiator, Techniques for achieving the above-mentioned required performance have also been proposed.

For example, Japanese Patent Publication No. 54-10986 discloses a method of polymerization in the presence of a photopolymerization initiator consisting of a carbonyl compound such as α-diketone and amines.

However, when a (meth)acrylic acid ester-based radically polymerizable monomer is photopolymerized using a photopolymerization initiator that combines the above-mentioned carbonyl compound and amines and used as a dental material, Even if the photopolymerizability in the low temperature region is poor or the polymerization rate is sufficient,
There are drawbacks such as the polymer being markedly colored and the color tone changing significantly over time under sunlight or in water, and thus does not fully satisfy the above-mentioned required performance.

Also, JP-A-60-26002 and JP-A-60-7
Publication No. 1602 describes a photocurable composition with excellent photopolymerizability at low temperatures around room temperature, containing α-diketone and 4
- Compositions using photopolymerization initiators in combination with dimethylbenzoate, etc. have been proposed;
Although these have excellent photopolymerizability, they have poor storage stability and do not fully satisfy the above-mentioned required performance.

Further, JP-A-56-120610 discloses a photopolymerizable dental material comprising a vinyl monomer having an acidic group in the molecule, an α-diketone, and an aromatic sulfinate salt. However, although this material has excellent color tone, it has insufficient photopolymerizability and does not satisfy the above-mentioned required performance.

[Means for solving problems]

The present invention allows photopolymerization to proceed sufficiently by short-time light irradiation even in a low temperature region near room temperature, has excellent mechanical strength such as hardness, bending strength, and compressive strength, and has excellent storage stability, color tone, etc. Regarding excellent photopolymerizable dental materials.

The present invention is a photopolymerizable dental material comprising a radically polymerizable monomer and a photopolymerization initiator, the photopolymerization initiator comprising a photosensitizer and a reducing agent, and the photosensitizer is an α-ketocarbonyl compound, and the reducing agent has the general formula t
"Carboxyl group, hydroxyl group, amide group, -CN
, -NO,, -NO, may be substituted with a halogen atom, and R represents a hydrogen atom, an alkyl group, a cyanoalkyl group, an aromatic group] Glycine compounds and aromatic sulfinic acids or their The present invention relates to a photopolymerizable dental material characterized by a reducing agent comprising salts.

As the radically polymerizable monomer, acrylic ester,
In addition to ethylenically unsaturated compounds such as methacrylic acid esters and monohydric or polyhydric alcohols having ethylenically unsaturated bonds, urethane-acrylate copolymers, urethane-
Examples include methacrylate copolymers and reaction products of bisphenol A and glycidyl methacrylate. Furthermore, two or more of these radically polymerizable monomers may be used in combination.

More specific examples include methyl (meth)acrylate,
Alkyl (meth)acrylates such as ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
(meth)acrylic acid-2-hydrooxypropyl, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, meth)acrylate, hexylene glycol di(meth)acrylate, 2.2-bis[4-(meth)acryloyloxyphenyl]propane, 2.2-bis[4-(meth)acryloyloxycyclohexyl]propane, 2,
2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 4-(meth)acrylate ) Acryloyloxyethoxycarbonyl phthalic anhydride, etc.

As a photosensitizer, an α-ketocarbonyl compound is used. Examples of α-ketocarbonyl compounds include α-diketones, α-ketoaldehydes, α-ketocarbonic acids, α-
Examples include ketocarboxylic acid esters. α− above
Among the ketocarbonyl compounds, alpha-diketones are preferred due to their excellent stability. Among the α-diketones, diacetyl, benzyl, and camphorquinone are particularly preferred.

The α-ketocarbonyl compound is preferably 0.001 to 10% by weight based on the radically polymerizable monomer, preferably i;;0.
Used on box surfaces with 0.05 to 5.0%.

If the α-ketocarbonyl compound is less than 0.001% by weight, a sufficient photosensitizing effect cannot be obtained, and if it exceeds 10% by weight, the photosensitizing effect will not be improved any further, and it may be meaningless. Therefore, the storage stability of the obtained photopolymerizable dental material is unfavorable.

As a reducing agent, use the following formula: R/ ,-CN,
Glycine compounds and aromatic sulfinic acids or their salts represented by -N (h, -NO, which may be substituted with a halogen atom, and represents a hydrogen atom, an alkyl group, a cyanoalkyl group, or an aromatic group) A reducing agent consisting of is used.

Specific examples of glycine compounds include N,N-diethylglycine methyl, N,N-diethylglycine 2゜6-
Xyrel, N,N-dihexylglycine ethyl, N+todihydroxyethylglycine, N,N-diisobutylglycine ethyl, N,N-dimethylglycine 2- (1-
naphthylmethyl), N,N-dipentylglycine ethyl, N,N-dipropylglycine 2,6-xyrel, glycine ethyl, N-ethyl-N-hydroxyglycine,
N-(4-hydroxybutyl)-N-nitrosoglycine methyl, N-hydroxymethyl-N-nitrosoglycine methyl, N-nitroglycine, Tautoro N-butylglycine ethyl, N-nitro-N-2,2,2- 1-IJ
Nido.

Ethylglycine methyl, glycine-2-phenyloctyl, N,N-bis(2-(bis(carboxymethyl)amino)ethyl)glycine, N,N-bis(2-chloroethyl)glycine, N,N-bis(2 -chloropropyl)
Glycine ethyl, N,N-bis(2-cyanoethyl)glycine, N-carboxyglycine, N,N-dimethylglycine 2-cyanoethyl, N-acetylglycineethyl, N-methoxyglycineethyl, N-(2-cyanoethyl)glycine , N, N-diallylglycineethyl, N,
Examples include ethyl N-dibutylglycine and N-acetamidoglycine.

As the aromatic sulfinic acid or its salts, at least one selected from aromatic sulfinic acids or their alkali metal salts, alkaline earth metal salts, amine salts, and ammonium salts is used. As alkali metal salts, lithium salts,
Examples of alkaline earth metal salts include magnesium salts, calcium salts, strontium salts, barium salts, etc., and amine salts include methylamine, ethylamine, propylamine, butylamine, aniline, toluidine, and phenylene. Salts of primary amines such as diamine and xylylenediamine; salts of secondary amines such as dimethylamine, diethylamine, dipropylamine, dibdelamine, piperidine, N-methylaniline, N-ethylaniline, diphenylamine, and N-methyltoluidine; trimethylamine, triethylamine, pyridine,
N,N-dimethylaniline, N,N-di(β-hydroxyethyl)aniline, N,N-diethylaniline, N,
Salts of tertiary amines such as N-dimethyltoluidine, N,N-bis(β-hydroxyethyl)toluidine, etc.; examples of ammonium salts include ammonium salts, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, and trimethylbenzyl salts; Examples include ammonium salts.

More specific examples of aromatic sulfinic acids include benzenesulfinic acid, 0-)toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphzenesulfinic acid. Examples include polyphosphorus sulfinic acid.

More specific examples of aromatic sulfinic acid salts include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, and benzenesulfinate. Barium, benzenesulfinic acid butylamine salt, benzenesulfinic acid aniline salt, benzenesulfinic acid toluidine salt, benzenesulfinic acid phenylenediamine salt, benzenesulfinic acid diethylamine salt, benzenesulfinic acid diphenylamine salt, benzenesulfinic acid triethylamine salt, benzenesulfinic acid Ammonium, tetramethylammonium benzenesulfinate, trimethylbenzylammonium benzenesulfinate, sodium o-toluenesulfinate, calcium 0-toluenesulfinate, aniline o-toluenesulfinate, ammonium 0-toluenesulfinate, 0-toluenesulfinic acid Tetramethylammonium, p-) Lithium toluenesulfinate, p
-sodium toluenesulfinate, I)-)/L/potassium ensulfinate, barium p-toluenesulfinate, I)-toluenesulfinate ethylamine salt,
Toluidine p-toluenesulfinate, N-methylaniline p-toluenesulfinate, pyridine p-toluenesulfinate, ammonium toluenesulfinate, tetrabutylammonium toluenesulfinate, sodium β-naphthalenesulfinate, β- Strontium naphthalenesulfinate, triethylamine β-naphthalenesulfinate, N-methyltoluidine β-naphthalenesulfinate, ammonium β-naphthalenesulfinate, trimethylbenzylammonium β-naphthalenesulfinate, and the like. Among these, lithium salts and sodium salts of benzenesulfinic acid and p-)luenesulfinic acid are preferred.

Glycine compounds and aromatic sulfinic acids or their salts exhibit excellent action as reducing agents due to their synergistic effect. As for the blending amount, the total amount of the glycine compound and aromatic sulfinic acid or its salts is 0.6 % based on the polymerizable monomer.
001 to 10% by weight, particularly O: 05 to 5% by weight is suitable.

If the total amount of the glycine compound and aromatic sulfinic acid or its salts is less than 0% by weight, a sufficient reducing effect cannot be obtained, and if it exceeds 10% by weight, the resulting photopolymerizable dental material cannot be stored. Unfavorable due to low stability.

The ratio of the glycine compound to the aromatic sulfinic acid or its salt is preferably 179 to 9/1, particularly preferably 515 to 8/2. If the blending ratio is outside this range, the synergistic effect between the glycine compound and the aromatic sulfinic acid or its salts will not be sufficiently exhibited, and the reducing effect will be extremely low, which is not preferable.

The photopolymerizable dental material of the present invention may further contain other components as necessary, such as a powdered filler, a tackifier, an ultraviolet absorber, a photosensitizer other than an α-ketocarbonyl compound, and a polymerization control agent. Agents, polymerization inhibitors, X-ray contrast agents, pigments, etc. can also be blended.

Powdered fillers include inorganic powders such as quartz, alumina, glass, kaolin, talc, calcium carbonate, barium aluminosilicate glass, titanium oxide, borosilicate glass, and colloidal silica, and colloidal silica solidified with polymers. Pulverized so-called organic composite filler powder or powder of resin such as polymethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, etc. Can be mentioned.

Moreover, two or more of these powders can also be used in combination.

When using the filler made of the inorganic powder, it is preferable to use it after surface treatment.

As the surface treatment agent, silane coupling agents such as T-methacryloxypropyltrimethoxysilane, vinyltrichloroO'/lan, vinyltriethoxysilane, titanate coupling agents, aluminate coupling agents, etc. can be used. .

The photopolymerizable dental material of the present invention, like conventional photopolymerizable materials, can be photopolymerized by light from a halogen lamp, xenon lamp, fluorescent lamp, sunlight, or the like as a light source.

The temperature during photopolymerization is usually 0 to 80°C, preferably 5 to 80°C.
The temperature range is 50℃, and the light irradiation time is usually 1 second to 5 seconds.
It's a minute.

The present invention will be explained in detail below using Examples and Comparative Examples.

Example In a dark room, 2,2-bis(4-(3-methacryloxy-2
-Hydroxypropoxy)-phenyl] 70 parts by weight of propane and 30 parts by weight of triethylene glycol dimethacrylate are mixed, and 0.0% of camphorquinone is added to this mixture.
A monomer-photosensitizer type material was prepared by adding 2% by weight. This prepared solution was divided into beakers, and N,N-diethylglycine methyl and sodium p-)luenesulfinate were added to each beaker in the proportions shown in Table 1, and the monomer-photosensitizer was added. - A reducing agent-based photopolymerizable material was prepared.

To 18 parts of each photopolymerizable material prepared as above, T-
Quartz powder surface treated with methacryloxypropyltrimethoxysilane (■Tatsumori: CR32107-05) 82
% and knead it in an agate mortar to make a paste,
This paste was used to measure the depth of cure.

[Curing depth]

10m thick polytetrafluoroethylene sheet,
A through hole with a diameter of 4 m is provided, and the hole is filled with the paste. The surface is covered with cellophane and irradiated with light for 30 seconds using a visible light irradiation device for dental filling resin polymerization (Translux, manufactured by Kulzer). Next, the polymerized paste (cylindrical shape) is taken out from the light irradiated surface through the hole, and the unpolymerized portion is removed with a canter knife, and the length is measured and determined as the hardening depth.

The results of cure depth are shown in Table 1.

Comparative Examples 1 to 2 Monomer-photosensitizer materials were prepared in the same manner as in Examples 1 to 3. In Comparative Example 1, only sodium p-)luenesulfinate was used, and in Comparative Example 2, N, N - Only diethylglycine methyl was added as a reducing agent to prepare a monomer-photoenhancing agent-reducing agent photopolymerizable dental material. Pastes were prepared in the same manner as in the examples, and the curing depth was measured using the pastes.

The results of cure depth are shown in Table 1.

Table 1 DEGM: N,N-diethylglycine methyl PTSS:
p-) Sodium luenesulfinate As is clear from Table 1, N was used in Examples 1 to 3.

Due to the synergistic effect of N-diethylglycine methyl and sodium p-)luenesulfinate, polymerization progresses sufficiently deep, resulting in a large curing depth. On the other hand, when either one is used alone, the hardening depth is small even if the same amount as the total amount in the example is added.

Examples 4 to 11 Monomer-photosensitizer materials were prepared in the same manner as in Examples 1 to 3. This prepared solution was divided into beakers, and various reducing agents were added to each beaker in the proportions shown in Table 2 to prepare a monomer-photosensitizer-reducing agent system photopolymerizable material. A paste was prepared using this photopolymerizable material in the same manner as in Examples 1 to 3.

The depth of cure was measured as described above using the above paste. In addition, storage stability, Brinell hardness, compressive strength, and bending strength were measured as follows, and at the same time, the color tone of the cured product was examined.

[Storage stability]

The paste log is placed in a glass container with a lid (capacity: 30 d), left standing in a dry oven at 60°C while shielded from light with aluminum foil, and the number of days until hardening is measured.

[Brinell hardness, compressive strength]

A through hole with a diameter of 4 nn was provided in a polytetrafluoroethylene sheet having a thickness of 5 plates, a glass plate was placed on one side of the sheet, and the paste was filled into the hole from the opposite side. The surface was covered with cellophane and irradiated with light for 30 seconds using the irradiation device. Next, the sheet was turned over and irradiated with light for 30 seconds from the glass side as well. The polymerization product (cylindrical shape) was taken out from the hole, and its Brinell hardness and compressive strength were measured.

Measurements are based on JIS T6506 and ADA standard N, respectively.
It was carried out in accordance with O-27.

[Bending Strength] A rectangular hole with a width of 21 and a length of 25 mg+ was provided in a polytetrofluoroethylene sheet having a thickness of 2 g, a glass plate was placed on one side of the sheet, and the hole was filled with the paste from the opposite side. Cover the surface with cellophane and use the dental crown t@
Light was irradiated for 90 seconds using a visible light irradiation device for J-lipid polymerization (Dentacolor XS, manufactured by Kulzer). Then, the polymerization product (2 x 25 x 2 m square) was taken out from the hole, and the bending strength was measured according to ISO standard 4049.

The measurement results are shown in Table 2.

Comparative Examples 3 to 8 Monomer-photosensitizer materials were prepared in the same manner as Examples 1 to 3. This prepared solution was divided into beakers, and various reducing agents were added to each beaker in the proportions shown in Table 2 (in Comparative Example 3, no reducing agent was added), monomer −
A photosensitizer-reducing agent type photopolymerizable dental material was prepared, and a paste was prepared using this photopolymerizable material in the same manner as in Examples 1 to 3.

Using the paste, cure depth, storage stability, Brinell hardness, compressive strength, and bending strength were measured, and color tone was examined.

The results are shown in Table 2.

As is clear from Table 2, in Examples 4 to 11, due to the synergistic effect of the glycine compound and the aromatic sulfinic acid or its salt, the polymerization progressed sufficiently deep, and the curing depth was large. The hardness and mechanical strength of the polymer are also excellent. It also has excellent storage stability and color tone. On the other hand, in Comparative Example 3, in which no reducing agent was added, although the storage stability and color tone were excellent, there was no crosslinking except for a small IB thickness on the surface layer, and the hardness and mechanical strength measurements were poor. It was possible. In Comparative Examples 4 to 8 using reducing agents other than the present invention,
No material with good cure depth, hardness, mechanical strength, storage stability and color matching has been obtained.

〔Effect of the invention〕

When a photopolymerizable material is produced using the reducing agent of the present invention,
Its photopolymerizability is very good, and crosslinking progresses sufficiently to the inside of the material. The storage stability of the material before polymerization is excellent, and there is no discoloration of the material due to polymerization.

In addition, the obtained photopolymerizable material has high hardness and mechanical strength, and can be widely applied to the field of dental materials such as composite resins for teeth, tooth sealants, dental crowns, and resin denture bases. .

Claims (1)

[Scope of Claims] A photopolymerizable dental material consisting of a radically polymerizable monomer and a photopolymerization initiator, the photopolymerization initiator consisting of a photosensitizer and a reducing agent, and the photosensitizer being a photopolymerization initiator. It is an α-ketocarbonyl compound, and the reducing agent has a general formula, ▲mathematical formula, chemical formula, table, etc.▼ [In the formula, R_1 and R_2 represent a hydrogen atom or an alkyl group,
Some of the alkyl groups are vinyl groups, acyl groups, alkoxy groups, carboxyl groups, hydroxyl groups, amide groups, -CN
, -NO_2, -NO, which may be substituted with a halogen atom, and R_3 represents a hydrogen atom, an alkyl group, a cyanoalkyl group, or an aromatic group] and an aromatic sulfinic acid or a salt thereof. A photopolymerizable dental material characterized by being a reducing agent consisting of.