JPH0745374B2 - Dental photocurable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a dental dental composition which has less residual monomers, catalysts and other eluates from a cured polymer and exhibits complete and excellent physical and clinical properties. The present invention relates to a photocurable composition.

[Prior Art] Since a polymerizable resin material is excellent in strength, aesthetics, operability, etc., its use amount is rapidly increasing as a material replacing the conventional cement-based restorative material in the dental treatment field. It is coming. These polymerizable resin materials are adjusted so that the polymerization is started by means of kneading with a polymerization initiator or irradiation, from the viewpoints of storability and operability during use. In the kneading method with the polymerization initiator, since the curing reaction starts immediately after the kneading, the application to the adhesive surface such as filling of the dental cavity must be completed within a predetermined time and the operability is poor. In addition, the leftover material is uneconomical because it hardens and becomes useless, so it must be discarded.

On the other hand, in the light irradiation method, it can be provided (enclosed in a light-shielding bottle) in a pack of a composition in which a polymerizable monomer and a photocuring catalyst are mixed, and therefore, there is no need for kneading and entrapment of air at the time of use. It has high utility value.

[Problems to be Solved by the Invention] However, the polymerizable resin material of the type in which polymerization is initiated by light irradiation has the following problems. That is, in general, the polymerizable resin material is inevitably translucent and has a shallow light reaching depth, so that the polymerization at the deep portion in direct contact with the tooth structure becomes incomplete, and the unpolymerized monomer is gradually aged. It is known that the catalyst component elutes and causes dental pulp irritation and other toxicity, and the large amount of the eluting component causes problems in strength and other physical properties and aesthetics of the cured polymer.

Among the components that are easily eluted, there are substances that were originally not expected to directly participate as a polymerization component and were used as accelerators, such as the amine compounds described below.

Diethanolamine, triethanolamine, dimethylethanolamine, N-methyldiethanolamine, propylamine, butylamine, hexylamine, dimethylamine, diethylamine, pentylamine, dipropylamine, dibutylamine, dihexylamine, trimethylamine, triethylamine, tripropylamine, triethylamine Butylamine, tripentylamine, trimethylenediamine, tetramethylenediamine, pentanemethylenediamine, hexamethylenediamine, N, N-dimethylaniline, N, N-dimethylaminotoluidine, N, N-dimethylaminobenzoic acid, N, N- Methyl dimethylaminobenzoate, propyl N, N-dimethylaminobenzoate, butyl N, N-dimethylaminobenzoate and the like.

Other amino compounds include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like disclosed in Japanese Examined Patent Publication No. 54-10986, but these have an aromatic group like the photopolymerization accelerator of the present invention described later. On the other hand, N is not directly bonded, the reaction activity is not particularly excellent, and it seems inevitable that a small amount is eluted with the residual monomer.

Therefore, in the present invention, not only high activity as a photopolymerization accelerator, but also by itself participating in the polymerization,
Dental-like photopolymerization that can form a stable and cured polymerized product that exhibits stable and excellent physical and clinical properties, as well as photopolymerization accelerators and little elution of other residual monomers and catalysts. Various studies were conducted to provide a sexual composition.

[Means for Solving the Problems] The present invention that has been able to solve the above problems comprises (a) a photopolymerizable monomer, (b) a photosensitizer, and (c) a photopolymerization accelerator. A dental photocurable composition comprising the following: (a) the photopolymerizable monomer is an acrylate derivative or a methacrylate derivative, and (b) the photosensitizer exhibits clear absorption at a wavelength of 380 to 500 nm. A diketone or quinone derivative, wherein the (c) photopolymerization accelerator is an amine compound represented by the following general formula, (Wherein R ¹ and R ² are hydrogen or a lower alkyl group, R ³ is an alkylene group substituted or unsubstituted by hydroxy or halogen, and R ⁴ is hydrogen or a methyl group). To do.

[Function] The dental photopolymerizable composition in the present invention comprises (a) a photopolymerizable monomer, (b) a photosensitizer and (c) a photopolymerization accelerator, and particularly Since the photopolymerization accelerator itself has a high activity and participates in the polymerization, it is possible to provide a safe and strong polymerized cured product with a small amount of eluted components.

The (a) photopolymerizable monomer is an acrylate derivative or a methacrylate derivative that initiates polymerization upon irradiation with light. Typical examples are as follows.

For example, 2,2'-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane, 2,2'-bis (4- (meth) acryloyloxyphenyl) propane, 2,2 ' -Bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypropoxy Phenyl) propane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3- Butanediol di (meth) acrylate, trimethylolpropa Tri (meth) acrylate, trimethylolethane (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include pentaerythritol tetra (meth) acrylate, and a methacrylate derivative having a urethane bond or a phosphate phosphene skeleton.

The photosensitizer in the present invention has an α having an apparent absorption at 380 to 500 nm in its ultraviolet and visible absorption spectra.
A diketone or quinone derivative, such as diacetyl, 2,3-pentanedione, 2,3- or 3,4-hexanedione, 2,3- or 3,4-heptanedione, 2,3-
(Or 3,4-or 4,5-) chain α-diketone compounds such as octanedione, camphorquinone [1,7,
Alicyclic α-diketone compounds such as 7-trimethylbicyclo (2,2,1) heptane-2,3-dione] and bicyclo (2,2,1) heptane-2,3-dione, and further 9, Polynuclear quinones such as 10-phenanthraquinone, 9,10-anthraquinone, acenaphthenequino, α- (or β-) naphthoquinone, 2-methyl-1,4-naphthoquinone (vitamin K
₃ ), 2-tertiary butyl-9,10-anthraquinone, 2-
Ethylanthraquinone, 1-chloroanthraquinone, 1,
2-benzo anthraquinone, 2-methyl anthraquinone, 2-methyl-3-Fuichiru-1,4-naphthoquinone (vitamin K _1), 2-methyl-3-geranyl-1,4-naphthoquinone (vitamin K _2), 2, Included are polynuclear quinone derivatives such as 3-dimethoxy-5-methyl-1,4-benzoquinone (coenzyme Q ₀ ). Among these, camphorquinone, phenanthraquinone, acenaphthenequinone, β-naphthoquinone, anthraquinone, 2,3-pentanedione,
2,3- (or 3,4-) heptanedione, 2,3- (or 3,4- or 4,5-) octanedione and the like are particularly preferable. These sensitizers are used in the range of 0.01 to 5% by weight based on the polymerizable monomer.

The polymerization accelerator of the present invention is an amine compound which is an esterified product of para-aminobenzoic acid in which an N atom is directly bonded to an aromatic group having an acryloyloxy group or a methacryloyloxy group in the molecule and is represented by the general formula: Wherein R ¹ and R ² are hydrogen, a lower alkyl group such as methyl, ethyl, propyl, etc., and R ³ is a hydroxy group or a halogen atom such as F, Cl, Br, I, or is substituted. It is a lower alkylene group such as methylene, ethylene, propylene and the like, and R ⁴ is hydrogen or a methyl group.

These are shown in more detail by the chemical structural formulas as follows.

The amount of these amines added is usually 0.
Although it is determined in the range of 1 to 20% by weight depending on the polymerization system, 0.5 to 5% by weight is preferable in consideration of problems such as reaction activity and elution property.

Furthermore, a polymerization inhibitor, a colorant, an ultraviolet absorber, etc. can be added to the dental photocurable composition in the present invention, if desired.

When used as a filling / restoring material for a caries cavity, the polymerizable monomer: 10 to 80% by weight (preferably 15 to 50% by weight) and the filler: 90 to 20% by weight (preferably 85 to 50% by weight) A basic composition is prepared, and a photopolymerization sensitizer and an accelerator are added to this.

As the filler, inorganic substances, organic substances, and mixtures thereof are used. Examples of the inorganic filler include soda glass, barium glass, strontium glass, borosilicate glass, crystalline quartz, fused silica, alumina silicate, amorphous silica, glass. Examples include ceramics and mixtures thereof. The particle size of the inorganic filler is not particularly limited, but usually 150 μm or less, preferably 100 μm or less is suitable. Also, several kinds of inorganic fillers having different particle sizes 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-
Methacryloyloxypropyltrimethoxysilane, γ
Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane or titanium compounds such as isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, tetraoctyldi (tridecylphosphite) Titanate, dicumylphenolate oxyacetate titanate, diisostearoyl ethylene titanate 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.

In this way, 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, as well as a coating agent and an adhesive for general industrial use. It can also be used as a filler or the like.

[Examples] Examples 1 to 4 and Comparative Examples 1 to 3 The components shown in Table 1 were each mixed with the amine compound shown in Table 2 to prepare a dental filling / restoring composite material, and each test described below was conducted. The results are shown in the lower column of Table 2. The photopolymerization accelerator compounded with the amine compound specified in the present invention was used as an example, and the photopolymerization accelerator compounded with a non-specified amine compound was used as a comparative example.

The pastes obtained according to the blending amounts shown in Tables 1 and 2 were thawed with Sancurelite (Sankin Kogyo Co., Ltd. photopolymerizer).
A test piece cured by irradiating with a light of 0 to 500 nm for 40 seconds was tested under the following conditions.

Compressive strength: A cylindrical test piece having a diameter of 4 mm and a height of 5 mm was immersed in distilled water at 37 ° C for 24 hours and then compressed at a speed of 10 mm / min to obtain the strength.

Tensile strength: A disc test piece having a diameter of 6 mm and a thickness of 3 mm was immersed in distilled water at 37 ° C for 24 hours, and then the pulling speed was calculated at a speed of 1 mm / min.

Knoop hardness: A test piece with a diameter of 4 mm and a height of 2 mm is immersed in distilled water at 37 ° C for 24 hours, and then the light irradiation surface is loaded with a Knoop hardness meter.
It was measured at 50 g and a pressing time of 15 seconds.

Water absorption and dissolution: 3 disc test pieces with a diameter of 20 mm and a thickness of 1.5 mm
After immersing in distilled water at 7 ° C for 4 weeks, it was determined by the following calculation method.

Method for calculating water absorption and dissolution W ₁ : Weight of dry test piece before immersion in water (mg) W ₂ : Weight of water absorption test piece after immersion in water (mg) W ₃ : Weight of dry test piece after immersion in water (mg) S: Test piece surface area (cm ² ) Examples 5 and 6 and Comparative Examples 4 and 5 Dental sealants were prepared by blending the components shown in Table 3 with the amine compounds shown in Table 4, and the components not involved in the polymerization were measured by the test method described below. , The results are shown in FIGS. 1 and 2.
As shown in the figure. The photopolymerization accelerator compounded with the amine compound specified in the present invention was used as an example, and the photopolymerization accelerator compounded with a non-specified amine compound was used as a comparative example.

A cured product prepared by irradiating a test piece with a diameter of 15 mm and a thickness of 0.5 mm with a light of 380 to 500 nm for 90 seconds with a sun cure light (manufactured by Sankin Industry Co., Ltd.) is immersed in methanol 10 minutes after the initiation of polymerization. Then, the components (dissolved amount) that could not participate in the polymerization were quantified daily by high performance liquid chromatography (HPLC).

<Measurement Conditions> Shimazu LC-6A Snim-pack CLC-ODS (0.15mX6.0mmφ) Solvent MeOH / H 2 O = 80/20 (wt) Flow Rate 1ml / min Oven Temp.40 ℃ Detecter Shimazu SPD-6AV UV- 230 nm, VIS-480 nm Data Prosessor Shimazu C-R3A Samples Size 10 μl Comparative Examples 6 to 9 (Curing experiment with peroxide) 100 g of the compounding ingredients shown in Table 5 and the amine compound having the number of moles shown in Table 6 The resulting paste was allowed to stand at 23 ° C. for 15 minutes under light shielding to cure, and then the above-mentioned compressive strength test was conducted. The results obtained are shown in Table 6. The amine compounds conventionally used are cured to some extent even with peroxides (Comparative Examples 7 to 9), but it was revealed that the photopolymerization accelerator defined in the present invention was not cured with peroxides (Comparative). Example 6).

[Advantages of the Invention] As described above, the dental photopolymerizable composition of the present invention has little residual monomer, catalyst and other eluates, and is excellent in physical and clinical properties.

[Brief description of drawings]

FIGS. 1 (a), (b), (c), and (d) are diagrams showing changes with time of the amount of dental sealant dissolved using a photopolymerizable composition.

Claims (1)

[Claims] 1. A dental photocurable composition comprising (a) a photopolymerizable monomer, (b) a photosensitizer and (c) a photopolymerization accelerator, which comprises (a) a photopolymerizable composition. The monomer is an acrylate derivative or a methacrylate derivative, (b) the photosensitizer is an α-diketone or quinone derivative that exhibits obvious absorption at a wavelength of 380 to 500 nm, and (c) the photopolymerization accelerator is the following general compound. An amine compound represented by the formula: (Wherein R ¹ and R ² represent hydrogen or a lower alkyl group, R ³ represents an alkylene group substituted or unsubstituted by hydroxy or halogen, and R ⁴ represents hydrogen or a methyl group) Dental photocurable composition.