JPH0699265B2 - Dental light opaque coating agent and coating method for dental material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a light-impermeable coating agent used for the purpose of shielding the color of metal castings and discolored teeth in the dental field, and metal castings. Coating method for shielding the metallic color of aluminum.

[Prior Art] In the manufacture of a dental hard resin veneer crown, a coating layer of an opaque resin composition called opaque resin is provided on the surface of a metal frame, and a natural tooth is placed on the layer. Resin composition having the following color tone (hereinafter referred to as body resin)
A method is adopted in which the metal color of the base (or base) is shielded by stacking the layers to reproduce the color tone and form of the natural color.

By the way, in recent years, the polymerization method of the hard resin has been changed from the conventional heat polymerization to photopolymerization, and along with this, the body resin has progressed from the powder-liquid two-division packaging form to the one-paste packaging form, The operability has improved remarkably. However, since opaque resin is essentially impermeable to light, it is extremely difficult to surely cure the opaque resin layer having a sufficient thickness to shield the metallic color of the substrate by photopolymerization.
Therefore, a dental restorative composition using both photopolymerization and compound polymerization has been proposed in JP-A-62-246514. In the composition, a compound X comprising a polymerizable monomer, a photopolymerization initiator and a reducing agent and a compound Y comprising a filler and an organic peroxide are prepared, and the oxidizing agent and the reducing agent are separately packaged separately. , These are mixed and used as a paste. In the composition, the compound X is a liquid and the compound Y is a powder, which is a conventional powder-liquid mixed type.

[Problems to be Solved by the Invention] Such a two-agent (for example, powder-liquid) mixed type composition requires a lot of time and effort for mixing, and care must be taken to ensure uniform mixing. Operability is poor compared to body resin. Therefore, even in the case of a light-impermeable coating agent that uses both photopolymerization and chemical polymerization, it has been desired to convert it into a composition having one paste type and excellent operability.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors applied a solvent containing an oxidizing agent, which is one component of a redox polymerization initiator, to a metal frame. After that, the opaque resin paste containing a photopolymerization initiator and a reducing agent, which is one component of the redox-based polymerization initiator, is laminated and coated on the coated surface and then photocured, whereby the above problems can be solved. The present invention has been completed.

That is, the present invention comprises: a) an organic peroxide, b) a compound [A] containing an organic solvent as a main constituent and c) a polymerizable monomer, d) a photopolymerization initiator, e) a reducing agent, and f) a refractive index The composition [B] containing 2 to 95% by weight of an inorganic filler of 1.9 or more as a main constituent is separately packaged separately, and after the composition [A] is applied to the adherend, the composition [B] is added. A dental light-impermeable coating agent, which is laminated and coated on the compound [A].

Furthermore, the present invention provides a dental material, characterized in that the composition [A] is applied to the surface of a substrate, then the composition [B] is laminated on the composition [A], and the coating layer is polymerized and cured by irradiation with light. It provides a coating method.

In the present invention, the formulation [A] is prepared as a liquid and the formulation [B] is prepared as a paste.

The greatest feature of the present invention is that the composition [A] is applied as a primer on the surface of a substrate, and then the composition [B] is applied as a light-shielding material to a thickness such that the color of the substrate can be sufficiently shielded.
When the surface is irradiated with light, the compounding [B] layer is cured by photopolymerization to a depth at which light can be substantially transmitted, while the deep part where a sufficient amount of light to cause photopolymerization cannot reach is the substrate. The point is that it is cured by redox polymerization with the organic peroxide that diffuses from the formulation [A] applied to the surface and the reducing agent in the formulation [B].

In the present invention, a redox polymerization initiator composed of an organic peroxide-reducing agent is preferably used. As the organic peroxide (a) used in the formulation [A], benzoyl peroxide (abbreviation: BPO), m-toluyl peroxide, p-
Aromatic acyl peroxides such as chlorobenzoyl peroxide and 2,4-chlorobenzoyl peroxide, aliphatic acyl peroxides such as diacetyl peroxide, diisobutyl peroxide, and dilauroyl peroxide, t-butyl peroxide, cumene Examples thereof include hydroperoxides such as hydroperoxide, and dialkyl (or diallyl) peroxides such as di-t-butyl peroxide and dicumyl peroxide.

As the reducing agent (e) used in the formulation [B], N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N
-Aromatic tertiary amines such as diethanol-p-toluidine, aromatic sulfonates such as sodium benzenesulfinate and sodium p-toluenesulfinate, thioureas such as thiourea and tetramethylthiourea, Fe Metal ions such as ²⁺ , Cu ⁺ and Cu2 ⁺ can be mentioned.

Next, the organic solvent (b) used in the formulation [A] means a liquid organic compound capable of substantially stably dissolving an organic peroxide, and accordingly, a non-polymerizable compound such as benzene, hexane, acetone or the like. Besides compounds, polymerizable organic compounds such as methyl methacrylate, trimethylene glycol dimethacrylate, and styrene, that is, polymerizable monomers are also included. However,
Organic solvents having a function of significantly promoting the decomposition of dissolved organic peroxides, such as tertiary amines for benzoyl peroxide, cannot be used in practice.

Non-polymerizable organic solvents preferably used in the present invention include n-hexane, dodecane, benzene, xylene, 1,
Hydrocarbons such as 2-dichloroethane, tert-butanol, tert-pentanol, tertiary alcohols such as 4-methyl-4-heptanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, ethyl acetate, Examples include esters such as butyl acetate, isopentyl ethyl dihydrogen phosphite butyrate, and triethyl phosphate; carboxylic acids such as acetic acid and oleic acid.

In addition, as the polymerizable organic solvent (polymerizable monomer) that is preferably used, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate. , Neopentyl glycol
Di (meth) acrylate, 1,10-decanediol Di (meth) acrylate, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (sometimes referred to as Bis-GMA) , 2,2-
Bis [(meth) acryloyloxypolyethoxyphenyl] propane, trimethylolpropane tri (meth) acrylate, 2-methacryloyloxyethyl dihydrodiene phosphate, bis (2-methacryloyloxyethyl) hydrogen diphosphate, 2-methacryloyloxyethyl Phenyl hydrogen
Phosphate, (meth) acrylic acid γ-methacryloyloxypropyltrimethoxysilane and other (meth) acrylate-based polymerizable monomers, styrene, p-methylstyrene, α-methylstyrene, divinylbenzene and other styrene-based polymerizable monomers And other polymerizable monomers such as vinyl acetate and 1,1-dichloroethylene. These organic solvents may be used alone or as a mixture of two or more.

In addition, the above-mentioned "(meth) acrylate" means "methacrylate or acrylate".

Further, in the present invention, as long as the mixed system is liquid,
A solid organic compound is used in addition to the above organic solvent.
Examples of the compound include 10-methacryloyloxydecyl
Dihydrodiene phosphate, 4- (2-methacryloyloxyethoxycarbonyl) phthalic acid, 4- (2-
Methacryloyloxyethoxycarbonyl) phthalic anhydride and other known polymerizable monomers having metal adhesion, bisphenol A dimethacrylate, tris (2-
Examples thereof include polymerizable monomers such as hydroxyethyl) isocyanuric acid trimethacrylate.

The suitable addition ratio of the organic peroxide (a) to the organic solvent (b) is 0.1 to 10% by weight.

Next, as the polymerizable monomer of the formulation [B], various (meth) acrylate-based polymerizable monomers used in known dental compositions are preferably used. For example, methyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,10-decanediol di (meth)
Acrylate, Bis-GMA, 2,2-bis [(meth) acryloyloxypolyethoxyphenyl] propyne, trimethylolpropane tri (meth) acrylate, 2,2,4
-Addition compound of 1 mole of trimethylhexamethylene diisocyanate and 2 moles of glycerin di (meth) acrylate, γ-methacryloyloxypropyltrimethoxysilane, 2- (dimethylamino) ethyl methacrylate, 10-methacryloyloxydecyl dihydrodiene phosphate, 4- (2-methacryloyloxyethoxycarbonyl) phthalic acid, 4- (2-methacryloyloxyethoxycarbonyl) phthalic anhydride and the like. These polymerizable monomers are usually used as a mixture of two or more kinds for the purpose of satisfying various performances required for the formulation [B], such as viscosity, crosslink density and polarity.

As the photopolymerization initiator, known initiator systems such as α-diketone-reducing agent, ketal-reducing agent and thioxanthone-reducing agent are preferably used. As α-diketone, camphorquinone, benzyl, 2,3-pentadione, 3,4-
Heptadione, etc. can be mentioned. Examples of the ketal include benzyl dimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl ketal) and the like. Examples of thioxanthone include thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. The reducing agent as one component of the photopolymerization initiator includes 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, tertiary amines such as N-methyldiethanolamine, lauryl aldehyde, dimethylaminobenzaldehyde, and terephthalate. Aldehydes such as aldehydes, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid,
Examples thereof include compounds having a thiol group such as thiobenzoic acid.

The reducing agent as one component of these photopolymerization initiators may be the same as or different from the reducing agent (e) paired with the above-mentioned organic peroxide.

The photopolymerization initiator is usually 0.1 to 100 parts by weight of the polymerizable monomer.
Used within the range of 10 parts by weight. The reducing agent (e) is also 0.1 to 1
Use within the range of 0 parts by weight is preferable.

In the present invention, an inorganic filler (f) having a refractive index of 1.9 or more is added to the compound [B] as a light shielding agent. Examples of the filler include titanium oxide (n = 2.49 to 2.90), zirconium oxide (n = 2.13 to 2.19), zinc oxide (n = 2.00 to 2.02),
And so on. The proportion of the inorganic filler in the blend [B] is 2 to 95% by weight, more preferably 4 to 60%.
% By weight.

In the present invention, in addition to the inorganic filler (f), various fillers may be added to the compound [B]. As these fillers, quartz, glass, barium sulfate, aluminum oxide, inorganic fillers having a refractive index of less than 1.9 such as hydroxyapatite, PMMA, polyvinyl chloride, organic polymer fillers such as phenol resin, silica fine powder with methacrylate resin. Examples thereof include organic / inorganic composite fillers formed by compounding. The amount of these fillers added is not particularly limited as long as the blend [B] is a paste having an appropriate viscosity, but is usually 0 with respect to the total amount of the blend [B].
The amount added is up to 80% by weight.

Coloring pigments such as red iron oxide, phthalocyanine blue, and various azo dyes may be further mixed in the composition [B] for the purpose of coloring.

Next, the coating method will be described. In the coating agent of the present invention, it is blended on the surface of the substrate (metal or tooth) [A]
Is further applied, and the compound [B] is further laminated and coated thereon in a thickness of 0.01 to 0.5 mm, and thereafter, the compound [B] layer is irradiated with ultraviolet rays and / or visible light to polymerize and cure. As the light source, a xenon lamp, a halogen lamp, a mercury lamp or the like is preferably used. The irradiation time depends on the amount of light, but it can be cured in 10 seconds to 10 minutes by using a dental irradiation device. When the coating agent of the present invention is used by coating it in a relatively thin layer, photopolymerization and chemical polymerization can be used in combination to sufficiently cure the composition.

EFFECTS OF THE INVENTION According to the present invention, in the production of a dental hard resin veneer crown, the work of forming a light-impermeable coating on the surface of the metal frame is simplified as compared with the conventional method, and the work of the technical work is simplified. Efficiency improvement is achieved. Furthermore, the present invention is also extremely effective as a coating for shielding undesired colors of discolored teeth.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to such embodiments.

Examples 1 to 5 and Comparative Examples 1 to 3 A formulation [A] whose composition is shown in Table 1 and a formulation [B] whose composition is shown in Table 2 were prepared. For each combination of the formulation [A] and the formulation [B] shown in Table 3, using a metal as a substrate
The following three items were evaluated: 1. The property of shielding the color of the substrate, 2. The curability, and 3. The adhesiveness to the substrate, and the results are summarized in Table 3. The experimental conditions are as follows.

Sample preparation Gold-silver-palladium alloy for dental casting "Castwell M.
Use C "(manufactured by Jitsu Dental Industry Co., Ltd.) to cut a square plate of 10 x 10 x 1 mm.
Cast. One side of this square plate is a 1000th silicone car
After polishing with Bide polishing paper, sand with 50μ alumina abrasive
Blasted (4 atm). Furthermore, for this face
Electrodepositor "Claace" (made by Nippon Avionics Co., Ltd.)
I went to Suzuki. The surface that has been subjected to the above processing is the base
As a surface, a coating layer is formed on the surface by the following method
did. 0.10 mm thick adhesive tape with a hole of 7 mm diameter
Was attached to the surface of the substrate. Compound [A] in the tape opening
Apply lightly with a brush, leave for 1 minute, and then mix [A]
Of volatile components (tertiary butanol, n-butyl acetate)
Let it dry. Next, mix [B] to the same thickness as the tape
As described above, the sample was applied to the opening, and then the sample was applied to a photopolymerizer “J.M.α-
Light "(using 5 150W tungsten halogen lamps,
Irradiation for 3 minutes at Morita Tokyo Mfg. Co., Ltd.
Layers were formed. The following evaluation was performed using this sample.

Shielding property The sample was exposed to α-light for 20 minutes, and d,
After the color of l-camphorquinone was completely faded, the color was visually compared with that of the reference sample, and the case in which the metallic color of the substrate was clearly observed was x, the case in which a slight metallic color was observed was Δ, and the one slightly observed was observed. Those that could not be evaluated were rated as ○.

The reference sample is a sample obtained by repeating coating with the combination of A-1 and B-5 three times, that is, the coating layer has a thickness of 0.3 mm, and the α-light is used after the third lamination.
It is a sample irradiated for a minute.

After irradiating with curable α-light for 3 minutes, the coating layer was immediately peeled off with a razor to confirm the presence or absence of an uncured portion. The sample in which the uncured portion was present was evaluated as x, and the sample that was not cured was evaluated as o.

Adhesiveness A 9 mmφ × 25 mm stainless steel is placed on the coating layer of the above sample.
Use a dental adhesive "Panavia EX" (made by Kuraray Co., Ltd.)
Adhesion, dipping the adhered sample in water at 37 ° C for 1 day, then
Tensile bond strength (kg
/cm²) Was measured (cross head speed = 2 mm / min).
The cast well used in this experiment The square plate of M.C.
Stainless steel plate (12 × 12 × 4m for the purpose of mechanical reinforcement
m), and then the coating layer is formed.
It was Tensile adhesion using 8 samples in each Example and Comparative Example
Strength (kg / cm²) Was measured and the average value is shown in Table 3.
It was

Claims (2)

[Claims] 1. A blend [A] containing a) an organic peroxide and b) an organic solvent as main constituents, and c) a polymerizable monomer, d) a photopolymerization initiator, e) a reducing agent, and f) a refractive index. The composition [B] whose main constituent is 2 to 95% by weight of an inorganic filler of 1.9 or more is separately packaged separately, and the composition [A] is applied to the adherend before use, and then the composition [B] A non-transparent dental dental coating agent, which is obtained by laminating and coating the above composition [A]. 2. After coating a metal surface with a mixture [A] containing a) an organic peroxide and b) an organic solvent as main constituents, c) a polymerizable monomer, d) a photopolymerization initiator, and e) reduction. And f) a mixture [B] containing 2 to 95% by weight of an inorganic filler having a refractive index of 1.9 or more as a main component is laminated and coated on the mixture [A], and the coating layer is polymerized and cured by irradiation with light. The coating method of the characteristic dental material.