JP2012087086A - Kit for metal color shielding for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop an opaque material for forming a metal color shielding layer in which a shielding effect of a metal color is further enhanced, and brightness of an artificial tooth made from a resin can also be kept good, when a tooth restorative material made from a resin is piled and an artificial tooth is made on a metal substrate, in the opaque material for forming a metal color shielding layer which is made to intervene between both the member materials in order to cover the metal color of the metal substrate.SOLUTION: A kit for metal color shielding for dentistry includes: (A) an opaque material for forming a metal color shielding layer consisting of a photopolymerizable composition; and (B) a surface coating material which comprises a transparency particle in which the average particle size is 1-200 μm, and which has a different refractive index (32°C) with that of a cured product of a polymerizable monomer contained in the opaque material for forming a metal color shielding layer of the (A), or the dispersion thereof, and is used to cover the top surface of the opaque material layer formed by the opaque material for forming a color shielding layer of the (A). In addition, the kit is used.

Description

  The present invention relates to a kit for forming a dental metal color shielding layer, and more particularly, to each of the kits used for shielding a metal color of a metal base material when a resin artificial tooth or a resin artificial gum is created. Is.

  Resin tooth restoration materials made of a curable composition mainly composed of a polymerizable monomer and an inorganic filler are used in the restoration of a tooth caused by caries or the like. That is, the resin tooth restoration material is easier to produce a prosthesis than ceramics and the like, and if it is filled with an inorganic filler at a high density, a resin artificial tooth with high mechanical strength can be formed. Above all, it is easy to adjust the refractive index difference between the matrix resin in which the polymerizable monomer is cured and the inorganic filler. In addition, by blending pigments with appropriate color tone and particle size, the color tone can be synchronized with natural teeth, which is highly advantageous in terms of aesthetics.

  Such resin-made tooth restoration materials are generally used by being built up and cured on a metal substrate provided as a foundation at a treatment site. However, if the resin tooth restoration material is directly built on the metal base material in this way, the resin after treatment is treated even if the color tone of the resin tooth restoration material is synchronized with the color tone of the natural tooth. In the artificial tooth made, it was inevitable that the metal color of the metal base material was seen through and the aesthetics were lowered. Therefore, a metal color shielding layer (opaque material layer) that shields the metal color of the metal base material is formed between the metal base material and the resin tooth restoration material (Patent Document 1). Non-patent documents 1 and 2).

  Here, the opaque material is a layer that shields the metal color of the metal base material by covering the metal base material with the resin artificial tooth and then combining this layer alone or with the color tone of the resin tooth artificial tooth. In addition, a large amount of pigment is contained in the photopolymerizable composition containing a polymerizable monomer and a photopolymerization initiator in order to further impart opacity sufficient to prevent the lower metal color from being seen through. Thus, as the pigment to be contained, white pigments such as petals and titanium white are mainly used.

  Opaque is a material with increased opacity, but in order to sufficiently shield the metallic color of the metal base material, it is not effective with a single application, and the application is repeated many times. (Depending on the case, it is hardened by irradiating light for each serving), and the thickness is often increased. The repetition of this application is complicated, and if the thickness of the metal color shielding layer becomes too thick, there arises a problem that the lightness of the resin artificial teeth is lowered. This is because the opaque material contains a large amount of white pigment and has high saturation, and as the thickness of this layer increases, the lightness of the resin artificial teeth decreases. In addition, if the opaque material is applied multiple times in this way and its thickness is excessively thick, if it is not cured for each application, a curing failure will occur at the bottom, and the adhesive strength with the resin artificial teeth will increase. Decreasing problems are also caused.

  From such a situation, it is preferable to keep the thickness of the metallic color shielding layer made of opaque material as thin as possible. In addition, the metallic color shielding layer made of opaque material may not be thick due to the structure of the treatment site. However, as a matter of course, if the thickness of the shielding layer is too thin, the metallic color shielding effect is not sufficient. Of course, when the increase in the white pigment contained in the opaque material and the application of a stain material or modifier to the surface are used to compensate for this lack of shielding effect, the problem of a decrease in lightness of the resin artificial teeth is caused. Even if the thickness of the metallic color shielding layer is thin, it increases to a level that cannot be ignored.

  From these, it is possible to further improve the shielding effect of the metallic color in the opaque material, develop a method that can sufficiently exhibit the shielding effect even when formed as a thin layer, and can keep the lightness of the resin artificial tooth good. It was desired. Under such circumstances, there has been proposed a method in which a granular polymer to which a coloring component is added is attached onto the coating layer of the opaque material and polymerized to form an opaque material layer (see Patent Document 2). That is, in this method, since the granular polymer adhered to the upper surface of the opaque material layer is colored, the light entering from the outside of the resin artificial tooth can be absorbed by this portion, and reflection on the opaque layer surface is reduced. By doing so, it is said that the transmission of opaque colors can be considerably suppressed (paragraph [0008]).

JP 2008-94732 A JP 7-31631 A

Hidetoshi Takahashi et al., Monthly Dental Technics separate volume Clinical / Technology of Ceramics / Polymer Composite Type Crown Restoration Materials, published by Ishiyaku Shuppan Co., Ltd., 1999, pp. 68-140 Akiyoshi Shintani et al., Separate volume 2003 / practice, restoration of crown color using new materials and techniques, published by Hyoron Publishers Co., Ltd., 2003, pages 65-119

  However, in the method described in Patent Document 2, since the granular polymer attached to the upper surface of the opaque material layer is colored, the saturation becomes high in this portion, and the resin artificial tooth built on the upper portion is The brightness was greatly reduced. In addition, the photopolymerization treatment of the opaque material layer is performed after the granular polymer is adhered. If the granular polymer is deeply colored or the opaque material layer is thickly provided by multiple times of application, the granular material The absorption of light by the polymer tends to cause poor curing of the opaque material layer, and there is a concern that the adhesive strength with the resin artificial teeth is lowered.

  Therefore, it has been strongly desired to develop a measure for satisfactorily improving these problems.

  Moreover, such a subject was applied not only when creating a resin artificial tooth but also when creating a gum part in a denture. That is, the creation of the gum part in the denture is performed by modeling a resin gum preparation material on a metal base material. In this case as well, in order to shield the metal color of the metal base material, Between the base material and the resin gum preparation material, an opaque material layer containing a large amount of a red pigment such as pigment red 166, pigment red 214, pigment red 231 and quinacridone red is formed. Therefore, even in the case of creating this artificial gum, it is required for the same reason to enhance the shielding effect of the metal color without reducing the lightness of the artificial gum. The problem is common with the case.

  In view of the above problems, the present inventors have continued intensive research. As a result, the average particle diameter is 1 to 200 μm on the upper surface of the opaque material layer, and the refractive index is different from that of the cured monomer of the polymerizable monomer contained in the opaque material for forming a metal color shielding layer. The inventors have found that the above problems can be solved by attaching transparent particles, and have completed the present invention.

That is, the present invention shields the metal color of the metal base material when a resin tooth restoration material or a resin gum preparation material is built up on the metal base material to produce an artificial tooth or an artificial gum. A metal color shielding layer forming kit for dental use interposed between the two members,
A) Opaque material for forming a metallic color shielding layer comprising a photopolymerizable composition B) A polymerizable monomer having an average particle diameter of 1 to 200 μm and contained in the above opaque material for forming a metallic color shielding layer The transparent material having a refractive index (32 ° C.) different from that of the cured product, or a dispersion of the transparent material, and the upper surface of the opaque material layer formed by the opaque material for forming the metallic color shielding layer is used. A dental metal color shielding kit comprising a surface coating material.

  According to the dental metal color shielding kit of the present invention, even when the opaque material layer formed using the metallic color shielding layer forming opaque material is thin or has low opacity, The metallic color can be shielded to a high degree, and the artificial dental teeth and artificial gums are not reduced in lightness, and a natural dental restoration can be performed. Further, it is difficult for the opaque material layer to be hardened, and the adhesive strength between the opaque material layer and the resin artificial teeth and artificial gums (hereinafter also referred to as “resin artificial teeth”) can be stably increased.

  In the present invention, the reason why such excellent effects are exhibited is presumed to be due to the following actions. That is, the B) surface coating material of the present invention is A) a cured product of a polymerizable monomer contained in the opaque material for forming a metal color shielding layer, which is a general tooth temperature in the oral cavity of 32 ° C. In the oral cavity, A) the opaque material layer formed by the opaque material for forming the metallic color shielding layer and the B) adhered to the upper surface thereof. At the contact interface with the surface coating material, irregular reflection of light entering from the outside such as resin artificial teeth occurs violently. The reason why the appearance of resin artificial teeth, etc. is affected by the metal color of the metal base material located underneath is that the light from the outside reaches the metal base material surface and reflects again to make the resin artificial tooth This is because it is released outside the teeth. Then, as described above, if strong irregular reflection occurs at the interface between the opaque material layer and the surface coating material, the external light transmitted through the opaque material layer and reaching the metal substrate surface can be greatly reduced. As a result, the metal color shielding effect of the metal base material by the opaque material layer is remarkably enhanced, and even when the opaque material layer is thin or has low opacity, the effect can be sufficiently exhibited. Will be possible.

  Furthermore, since the particles used for the surface coating material are transparent and usually do not contain a colorant and have low saturation, the brightness of resin artificial teeth and the like built on top can be kept high. Further, even when the opaque material layer is photocured after the surface coating material is attached, the irradiated light is weakened by irregular reflection at the interface between the opaque material layer and the surface coating material. Since a considerable amount of the material layer is sufficiently cured to cure, the problem of poor curing of the opaque material layer can be solved well.

As described above, the kit for forming a metallic color shielding layer of the present invention comprises A) an opaque material for forming a metallic color shielding layer and B) a surface coating material, and the characteristic material is the latter. It explains from.

B) Surface coating material B) The surface coating material is a material used by coating the upper surface of the opaque material layer. This material has an average particle diameter of 1 to 200 μm, and a transparent particle having a refractive index different from that of the cured monomer of a polymerizable monomer contained in the A) opaque material for forming a metallic color shielding layer at 32 ° C. Consists of.

  When the average particle diameter of the transparent particles is smaller than 1 μm, when the particles are attached to the upper surface of the opaque material layer, particularly when the opaque material layer is uncured, the particles are embedded in the inside. The problem is that the diffused reflection of light at the interface between the two members is weakened and the metal shielding property is lowered. Further, even if the average particle diameter of the transparent particles is larger than 200 μm, the specific surface area becomes small, the irregular reflection of light is weakened at the interface between both members, and the metal shielding property is also lowered. Furthermore, if particles having such a large average particle diameter are adhered on the opaque material layer, there is a risk that sufficient thickness of the resin artificial teeth to be formed on the opaque material layer cannot be secured, or the adhesive strength thereof may not be sufficient. Occurs. From these, the average particle diameter of the transparent particles as the surface coating material is particularly preferably 5 to 70 μm.

  In the present invention, the average particle diameter of the particles refers to a value represented by 50% (D50) of the cumulative distribution of particle sizes obtained by the laser light scattering method.

  In addition, transparent particles having a different refractive index at 32 ° C. are used as compared with the cured monomer of the polymerizable monomer contained in the opaque material for forming the metal color shielding layer. That is, due to this requirement, at 32 ° C., which is a general tooth temperature in the oral cavity, light that has entered from the outside of the resin artificial tooth at the contact interface between the transparent particles and the opaque material layer to which the transparent particles adhere. The irregular reflection of the metal occurs violently and the metal color shielding property of the metal base material is greatly improved. The absolute value of the difference in refractive index between the transparent particles and the cured product of the polymerizable monomer contained in the opaque material for forming the metallic color shielding layer is 0.02 to 0.20 in the measurement at 32 ° C. Furthermore, it is preferably 0.05 to 0.10 from the viewpoint of causing violent reflection of the incident light. On the other hand, if the refractive index difference is smaller than 0.02, the diffuse reflection of the intruding light is weakened, and the metal color shielding effect cannot be sufficiently satisfied. Furthermore, even if this refractive index difference is larger than 0.20, the transparency and lightness of the resin artificial tooth to be formed on the upper part are lowered, and it is not fully satisfactory.

  If the relationship between the refractive index difference between the transparent particles and the cured product of the polymerizable monomer contained in the opaque material for forming the metal color shielding layer is specifically shown, for example, as the transparent particles will be described later, In the case of polymethylmethacrylate particles, which is a particularly preferred embodiment in the present invention, the refractive index is 1.49 at 32 ° C., and therefore A) a polymerizable monomer contained in the opaque material for forming a metallic color shielding layer The polymerizable monomer may be selected so that the refractive index of the cured body is 1.51 to 1.69. When the polymerizable monomer contained in the opaque material for forming the metallic color shielding layer is composed of a plurality of types, the refractive index of the cured product in the entire polymerizable monomer composition is a difference in refractive index with respect to the transparent particles. It is sufficient that the requirement is satisfied (that is, if this is satisfied, even if each of the polymerizable monomer components includes a component that deviates from the requirement of the refractive index difference, it is acceptable in the present invention. )

  In the present invention, the particles used as the surface coating material B) are transparent as apparent from the above requirements for the refractive index. Of course, in order to maintain this property, pigments and dyes Such a colorant is usually not used. Because of the transparent particles in this way, the lightness of the resin artificial teeth is excellent, and even if the opaque material layer is polymerized after the particles are attached, the irradiated light is excessively weakened. The opaque material layer can be cured well.

  Here, the transparent particle in the present invention means a particle satisfying the transparency of the particle measured by the following. That is, first, the refractive index of particles at 32 ° C. is measured. Then, the particles are dispersed at a concentration of 50% by mass in an organic solvent having a refractive index difference in the range of ± 0.001 at the same 32 ° C. as the measured refractive index. Then, this dispersion of transparent particles is put into a quartz cell having an optical path length of 0.5 mm, and when the contrast ratio is measured at 32 ° C., the value is 0.1 or less, more preferably 0.05 or less. Say the particles become. The organic solvent in which the transparent particles are dispersed and the refractive index difference at 32 ° C. with respect to the transparent particles is in the range of ± 0.001 is ethanol (refractive index 1.359), toluene (refractive index 1.497). , 2-bromotoluene (refractive index: 1.555), 1-bromonaphthalene (refractive index: 1.658), dibromomethane (refractive index: 2.497), etc., depending on the refractive index of the transparent particles used. The seeds may be appropriately selected and adjusted by changing the mixing ratio.

  The material constituting such transparent particles may be either an organic material or an inorganic material, but an organic resin is preferably used because of its familiarity with the opaque material layer.

  When the organic resin comes into contact with the resin tooth restoration material, it does not dissolve or swell in the polymerizable monomer component, and further, in order to enable an embodiment to be used as a dispersion in an organic solvent described later, Those that are as insoluble as possible to the organic component are preferred. Further, from the viewpoint of easily satisfying the requirement of the difference in refractive index from the cured product of the polymerizable monomer contained in the opaque material for forming the metal color shielding layer, the refractive index at 32 ° C. after curing is 1.45. To 1.70, preferably 1.50 to 1.60.

  Specifically, a crosslinked vinyl polymer such as a crosslinked (meth) acrylate polymer, a crosslinked styrene polymer, a crosslinked acrylonitrile polymer, and a crosslinked olefin polymer is preferable. Here, as the crosslinked (meth) acrylate polymer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) The main component is a monofunctional (meth) acrylate monomer such as acrylate or glycidyl methacrylate, and a crosslinkable monomer such as a polyfunctional polymerizable monomer having two or more polymerizable unsaturated groups is used as a co-polymer. What was polymerized is mentioned.

  Examples of polyfunctional polymerizable monomers include divinylbenzene, divinylsulfone, ethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, hexamethylene di (meth) acrylate, nonamethylene di (meth) acrylate, trimethylolpropane tri ( A meth) acrylate etc. can be illustrated.

  The cross-linked styrene polymer is mainly composed of a monofunctional styrene monopolymer such as styrene, methyl styrene, ethyl styrene, or bromo styrene, and the cross-linkable monomer as exemplified above is copolymerized therewith. Can be mentioned. Examples of the acrylonitrile-based polymer include those in which a monofunctional acrylonitrile-based monopolymer of acrylonitrile and methacrylonitrile is a main component, and a crosslinkable monomer as exemplified above is copolymerized therewith. Furthermore, examples of the olefin polymer include those obtained by copolymerizing a monofunctional olefin monomer such as ethylene, propylene, and various norbornene type compounds as a main component and a crosslinkable monomer.

  In these vinyl polymers, the content of the crosslinkable monomer is in the range of 0.0001 to 5 mol, more preferably 0.001 to 1 mol, with respect to 1 mol of each vinyl monomer. The range of is preferable. Further, the vinyl polymer not only has each vinyl monomer as a main component, but also a part of the vinyl polymer is replaced with another vinyl monomer copolymerizable with each of these vinyl monomers. And may be copolymerized.

  Furthermore, as the organic resin, aromatic polyether resins such as polyether sulfone, epoxy resins, melamine resins, benzoguanamine resins, phenol resins, and the like can be suitably used.

  Even in these organic resins, in addition to high transparency, it is easy to satisfy the requirements for the difference in refractive index from the cured product of the polymerizable monomer contained in the opaque material for forming the metal color shielding layer. Since a metal shielding effect is excellent, a crosslinked (meth) acrylate polymer and a crosslinked styrene polymer are preferable. Particularly preferred organic resin particles used as transparent particles are crosslinked polymethyl methacrylate particles, crosslinked polyethyl acrylate particles, and crosslinked polystyrene particles, and most preferably crosslinked polymethyl methacrylate particles.

  These transparent particles may be of any shape, but B) when used as a surface coating material, from the viewpoint of increasing the diffuse reflectance of light at the interface with the opaque material, the more nearly the shape is more spherical. preferable. If such sphericity organic resin particles are (meth) acrylate polymers, they can be obtained by producing them by suspension polymerization.

  These transparent particles increase the familiarity with the opaque material, and from the viewpoint of increasing the irregular reflection at the interface between the particle and the opaque material, various silicone compounds such as silane coupling agents and polyorganohydrogensiloxane compounds, fatty acid ester compounds, You may use what was surface-treated with the olefin compound etc.

  The method for attaching these transparent particles to the upper surface of the opaque material layer is not particularly limited, and the transparent particles may be applied with a brush, a spatula, or the like, or may be sprinkled from above. When the upper surface of the opaque material layer is observed with an optical microscope from above, at least 40%, more preferably 60%, of the coating is covered with the transparent particles per unit area of 1 cm × 1 cm (of the opaque material layer). It is preferable to carry out at a rate that the upper surface is not exposed.

Further, the amount of the transparent particles attached to the upper surface of the opaque material layer is generally selected from the range of 0.2 mg to 5 mg per cm ² . If a large amount of transparent particles are stacked on the upper surface of the opaque material layer, the adhesive strength of the resin tooth restoration material may be weakened. Therefore, when the transparent particles are used as they are as the B) surface coating material, it is ideal that the transparent particles are attached as a uniform monolayer, and in reality, the attached layer has a maximum particle size of the transparent particles. It is preferable to deposit the thin film so that the thickness is 5 times or less, more preferably 2 times or less. When transparent particles are applied to the upper surface of the opaque material layer or sprinkled, if a large amount of particles are stacked beyond the thickness of the adhesion layer, adjust the thickness to the above level by blowing weak compressed air, etc. Just do it.

  In the present invention, the surface coating material B) may have a form in which the transparent particles are directly adhered to the upper surface of the opaque material layer as described above, but from the viewpoint of facilitating the formation of a uniform layer, the dispersion is dispersed in an organic solvent. It may be used as a liquid form.

  The dispersion liquid dispersed in the organic solvent can be applied to the upper surface of the opaque material layer with a brush or the like, and then the coated surface is dried to evaporate the organic solvent, whereby a uniform layer of transparent particles can be formed with good coatability. In order to perform this transpiration satisfactorily, the organic solvent is preferably volatile. Here, the volatile organic solvent means a solvent having a boiling point at 760 mmHg of 100 ° C. or lower and a vapor pressure at 20 ° C. of 1.0 KPa or higher. Examples of such a volatile organic solvent include alcohol solvents such as methanol, ethanol, n-propanol, and isopropyl alcohol; ketone solvents such as acetone and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary.

  The content of the transparent particles dispersed in the organic solvent is not particularly limited, but is preferably 10 to 90% by mass and more preferably 20 to 70% by mass from the viewpoint of improving the coating property and the like.

  In addition, when the transparent particles are directly attached to the upper surface of the opaque material layer or when used as the dispersion liquid, a small amount of a polymerizable monomer and a polymer are used in order to improve the adhesion to the upper surface of the opaque material layer. An initiator may be added. After attaching transparent particles to the upper surface of the opaque material layer, the polymerizable monomer is cured by a curing method according to the type of the polymerization initiator (light irradiation if the polymerization initiator is a photopolymerization initiator). The adhesive force of the transparent particles can be improved, whereby the adhesive strength of the resin-made artificial teeth can be further increased. As the polymerizable monomer and the polymerization initiator to be used, the same monomers as those described as A) used for the opaque material for forming a metallic color shielding layer described later can be used. It is more preferable to use a polymerizable monomer having a refractive index difference (32 ° C.) between the cured product and the transparent particles in the range of 0.02 to 0.2.

  The amount of the polymerizable monomer is preferably a small amount, specifically, at most 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the transparent particles. When the amount of the polymerizable monomer is too large, transparent particles are embedded in the hardened layer, and the irregular reflection of light at the interface with the opaque material layer is weakened, and the effect of the present invention for shielding the metal color May be damaged. 0.003-5 mass parts is preferable with respect to 100 mass parts of polymerizable monomers, and, as for the usage-amount of a polymerization initiator, 0.01-3 mass parts is more preferable.

A) About the opaque material for forming the metallic color shielding layer The opaque material for forming the metallic color shielding layer only prevents the photopolymerizable composition containing the polymerizable monomer and the photopolymerization initiator from seeing through the lower metallic color. The composition contains a pigment sufficient to impart the opacity. If the opaqueness that does not allow the metal color to be seen through is specifically shown, the contrast ratio of the 0.5 mm thick cured body is preferably in the range of 0.4 to 0.9, and more preferably 0.6 to 0.8. A range is more preferred. When this contrast ratio is larger than 0.4, it is easy to maintain good shielding properties of the underlying metal color even when the thickness of the opaque material for forming the metal color shielding layer cannot be sufficiently secured. When the contrast ratio is less than 0.9, the curing property of the opaque material for forming the metallic color shielding layer can be sufficiently secured, and even when thickly built, the lightness does not decrease, and a resin artificial tooth having a natural feeling like a natural tooth is obtained. There is an advantage that it can be produced.

Here, the contrast ratio of the cured body is a scale representing transparency, and is calculated using the Y value related to brightness among the tristimulus values of the XYZ color system defined in JIS Z8701. More specifically, the black value or white background is brought into contact with a sample plate having a constant thickness (in the present invention, 0.5 mm thickness), and the Y value in the reflected light when the standard light C is irradiated is read. The contrast ratio can be obtained from Yb / Yw, where Yb for a black background is Yb and Y for a white background is Yw. As the contrast ratio value is closer to 1, it is an opaque material, and as it is closer to 0, it is a transparent material. A) A polymerizable monomer used in an opaque material for forming a metallic color shielding layer Any of those known for dentistry can be used without any limitation. The polymerizable monomer that can be suitably used is preferably a (meth) acrylate polymerizable monomer having an acryloyl group or a methacryloyl group as a radical polymerizable monomer, and an oxetane group as a cationic polymerizable monomer. A polymerizable monomer having an epoxy group is preferable in terms of polymerizability, adhesiveness, and ease of handling.

  The polymerizable monomer may be monofunctional or polyfunctional. Specific examples of monofunctional radically polymerizable monomers that are preferably used generally include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (Meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Monofunctional (meth) acrylate monomers such as hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate and methoxydiethylene glycol (meth) acrylate: monofunctional (meth) acrylic such as N-methylol (meth) acrylamide De monomers: styrene, monofunctional styrenic monomers such α- methyl styrene.

  Specific examples of polyfunctional radically polymerizable monomers that are preferably used in general are 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) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meta ) Acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxyethoxyphenyl) 2- (4- (meth) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- ( 4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, 1- ( Aromatic bifunctional (meth) acrylate monomers such as (meth) acryloyloxymethyl-2- (meth) acryloyloxyethyl hydrogen maleate: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acryl , Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, di-2- (meth) acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, N, N′-methylenebis Aliphatic bifunctional (meth) acrylate monomers such as (meth) acrylamide: Bifunctional (meth) acrylic acid amide monomers such as N, N′-methylene (bis) acrylamide: divinylbenzene, α-methyl Bifunctional styrene monomer such as styrene dimer: diallylphthale Bifunctional allyl monomers such as triallyl phthalate and diallyl carbonate: Trifunctional (meth) acrylate monomers such as trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylate: pentaerythritol tetra And tetrafunctional (meth) acrylate monomers such as (meth) acrylate.

  The above radical polymerizable monomers can be used alone or in admixture of two or more.

  Moreover, when the cationically polymerizable monomer generally used suitably is illustrated, the polymerizable monomer which has an oxetane group, and the polymerizable monomer which has an epoxy group are mentioned.

  From the viewpoint of biocompatibility and high polymerizability, the polymerizable monomer is preferably a (meth) acrylate monomer, and particularly preferably a polyfunctional (meth) acrylate monomer.

  As the polymerization initiator used for the opaque material for forming the metallic color shielding layer, a photopolymerization initiator is used. As a typical photopolymerization initiator, when the polymerizable monomer is a radical polymerizable monomer, a combination of α-diketone and tertiary amine, a combination of acylphosphine oxide and tertiary amine, Examples thereof include photopolymerization type radical polymerization initiators such as a combination of thioxanthones and tertiary amines, a combination of α-aminoacetophenones and tertiary amines, a combination of aryl borates and photoacid generators. Such photopolymerization initiators are described in, for example, JP-A-2008-94732 and JP-A-2007-302631.

  Of these, a visible light polymerization initiator that is less harmful to the living body is preferable, and specific examples include α-diketones or a combination of acylphosphine oxide and tertiary amines. Most preferred is a combination of camphorquinone and tertiary amines.

  In addition, when a cationic polymerizable monomer is used as the polymerizable monomer, a compound that generates a Lewis acid or a Bronsted acid by light irradiation is used. It is particularly preferred to employ a photoacid generator.

  These photopolymerization initiators may be used alone or in combination of two or more.

  The amount of the photopolymerization initiator contained in the opaque material for forming the metallic color shielding layer is preferably 0.003 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer from the viewpoint of sufficiently proceeding the polymerization reaction. 0.01-3 mass parts is more preferable.

  From the viewpoint of improving the dispersibility of the pigment, an inorganic pigment is preferably used as the pigment used for the opaque material for forming a metallic color shielding layer of the present invention. And when producing resin artificial teeth, white pigments are mainly used in order to realize metallic color shielding in harmony with the color of the teeth. Examples of such white pigments include titanium oxide, lead white, zinc oxide, antimony white, zirconium white, calcium carbonate, kaolin clay, barium sulfate, alumina white, and talc.

  In addition, if the opaque material for forming a metallic color shielding layer is used in the case of producing an artificial gum made of resin, as a pigment, in order to realize the shielding of the metallic color in harmony with the color of the gum, Pigments are mainly used. Examples of such red pigments include Pigment Red 122, Pigment Red 144, Pigment Red 188, Pigment Red 202, Pigment Red 214, Pigment Red 221, Pigment Red 231, Pigment Red 242, Quinacridone Red, Quinacridone Magenta, Pigment Red 254, and Pigment Red 254. Violet 19, new coxin, red iron oxide, etc. are used.

  Furthermore, even when creating a resin artificial tooth or a resin artificial gum, it is usually required to finely adjust the color tone depending on the surrounding conditions of the treatment site. In this case, as other color pigments, for example, titanium yellow, black iron oxide, yellow iron oxide, pigment yellow 95, pigment blue 60, phthalocyanine blue, phthalocyanine green, quinoline yellow, fast green FCF, etc. may be used. .

  The average particle diameter of these pigments is generally 0.03 to 3.0 μm, but pigments having an average particle diameter of 0.1 to 1.0 μm are preferable because of a small amount and high coloring effect.

  The amount of the pigment used in the opaque material for forming the metallic color shielding layer is an amount that can achieve the purpose of shielding the metallic color of the metallic substrate by combining the opaque material layer alone or the color tone of the resin artificial tooth. If there is no limitation, usually, the amount of contrast ratio of the 0.5 mm thick cured body of the opaque material for forming a metallic color shielding layer described above is 0.4 to 0.9, specifically, It is selected from the range of 10 to 900 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

If the opaque material for forming a metallic color shielding layer used for making resin artificial teeth is prepared by blending pigments in these amounts, the color tone is 0.5 mm in the CIELab color system. As a colorimetric value of the body under a white background condition, L ^* is 40 to 70, a ^* is -3 to 3, b ^* is in the range of 0 to 30, more preferably L ^* is 50 to 65, and a ^* is It is preferable that −1 to 2 and b ^* are adjusted to a range of 5 to 25. On the other hand, if the opaque material for forming a metallic color shielding layer used for producing a resin gum is produced, the color tone is measured by a white background condition of a 0.5 mm cured body in the CIELab color system. As values, L ^* is 40 to 90, a ^* is 2 to 35, b ^* is in the range of 0 to 25, more preferably L ^* is 55 to 85, a ^* is 5 to 30, and b ^* is 3 to 20. It is preferable to adjust to the range.

  In addition, a filler is generally blended in the opaque material for forming a metallic color shielding layer. As such fillers, those known for dentistry can be used without any limitation. By adding a filler, mechanical strength and water resistance can be improved, and the viscosity and fluidity of the opaque material can be easily adjusted. As such a filler, a known organic filler, an inorganic filler, an organic-inorganic composite filler, or a mixture thereof can be used without any limitation.

  Specific examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane trimethacrylate copolymer, polyvinyl chloride. , Particles made of polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, polycarbonate and the like. These are preferably cross-linked products obtained by copolymerizing cross-linkable monomers.

  Specific examples of the inorganic filler include silica-based composite oxides such as quartz, amorphous silica, silica zirconia, and silica titania, silica alumina, fluoroaluminosilicate, barium glass, and the like.

  Of the fillers, amorphous silica, silica-based composite oxides such as silica zirconia and silica titania are particularly preferable in view of the mechanical strength and good dispersibility.

  An inorganic-organic composite filler obtained by pulverizing a composite of an inorganic oxide and a polymer obtained by polymerizing and curing a polymerizable monomer mixture in which the various inorganic fillers are dispersed and contained is also suitable as the filler. Can be used.

  In general, those fillers having an average particle diameter of 0.01 to 100 [mu] m and 0.05 to 5 [mu] m can be suitably used from the viewpoint of strength. If conditions are selected, these include those that can also be used as transparent particles as the above-described B) surface coating material. However, no matter how transparent particles are contained in the opaque material layer, the shielding effect of the metal color cannot be sufficiently exhibited in the opaque material layer. That is, the effect is completely different from that of the present invention in which the transparent particles are attached to the upper surface of the opaque material layer to greatly reduce the amount of transmitted light entering the opaque material layer.

  The shape of the filler is not particularly limited, and may be a pulverized filler or a spherical filler obtained by normal pulverization. Submicron spherical fillers can be suitably used because of their excellent mechanical strength, surface smoothness, operability, and applicability on the cured resin. Most preferably, it is a mixture of spherical inorganic fine particles having an average primary particle size in the range of 0.1 to 1 μm and inorganic fine particles having an average primary particle size in the range of 0.01 to 0.1 μm. .

  Furthermore, these fillers may be used after being treated with a surface treatment agent typified by a silane coupling agent from the viewpoint of improving familiarity with the polymerizable monomer and improving mechanical strength and water resistance.

  The amount of filler contained in the opaque material for forming the metallic color shielding layer is preferably 200 to 1900 parts by mass with respect to 100 parts by mass of the polymerizable monomer, from the viewpoint of imparting sufficient mechanical strength to the cured product. -900 mass parts is more preferable.

  Furthermore, other components can be added to the opaque material for forming a metallic color shielding layer of the present invention as required. Specific examples include organic solvents such as ethanol, polymerization inhibitors such as butylhydroxytoluene and methoxyhydroquinone, and ultraviolet absorbers such as 4-methoxy-2-hydroxybenzophenone and 2- (2-benzotriazole) -p-cresol. , Etc., and other components such as a coloring agent, a coloring matter, and a fragrance can be added.

  In the present invention, the opaque material for forming a metallic color shielding layer forms an opaque material layer by placing and leveling it on a metal substrate with a brush, a spatula or the like. Curing of the formed opaque material layer may be performed by irradiating with light before attaching transparent particles of the surface coating material to the upper surface of the opaque material layer. It is easy to disappear. This is considered to be due to the following reason. When the polymerizable monomer used in the metallic color shielding opaque material is a radical polymerizable monomer, the surface of the cured opaque material layer is about 5 to 20 μm in surface due to inhibition of polymerization by oxygen. Is formed. That is, even when transparent particles of the surface coating material are attached to the upper surface, when the average particle diameter is small, etc., when the resin tooth restoration material is built up from the top after the surface coating material is attached The surface coating material is easily embedded in the surface unpolymerized layer by the pressure applied during the build-up. Then, since the surface unpolymerized layer is cured when the resin tooth restoration material is cured and becomes a surface layer portion of the opaque material layer, the surface coating material is embedded in the opaque material layer. For this reason, it is considered that the irregular reflection of light at the interface with the opaque material layer is slightly weakened and the metal color shielding effect is not sufficiently exhibited. On the other hand, when light irradiation is performed after the transparent particles of the surface coating material are attached, the opaque material immediately below the surface coating material is difficult to come into contact with oxygen, so the amount of surface unpolymerized product is greatly reduced. For this reason, even if a resin tooth restoration material or the like is subsequently built up from above, the phenomenon that the surface coating material is buried in the surface unpolymerized layer by the pressure applied during the build-up hardly occurs. As a result, irregular reflection of light is intensely generated at the interface with the opaque material layer, and it is considered that this curing method has a higher metal color shielding effect.

  The opaque material layer is preferably cured after the transparent particles B) of the surface coating material are adhered to the upper surface thereof. Furthermore, it is also possible to irradiate light after building a resin tooth restoration material or resin gum preparation material on it, and to cure the restoration materials simultaneously with the light transmitted therethrough. However, in the case of the latter method, when the average particle diameter of the transparent particles is still small, the particles are brought into the uncured opaque material layer by the pressure at the time of building the resin tooth restoration material or the resin gum preparation material. Care must be taken because it becomes easier to embed and may weaken the diffuse reflection of light at the interface with the opaque material layer.

  The thickness of the opaque material layer formed on the metal substrate is usually selected from the range of 0.05 to 0.5 mm. As described above, in the kit of the present invention, the effect of the surface coating material can greatly enhance the metal color shielding effect of the metal base material by the opaque material layer. When the thickness cannot be increased, specifically, an excellent metal color shielding effect is obtained even when the opaque material layer is 0.05 to 0.2 mm thin.

  When the opaque material layer is thick, the opaque material may be repeatedly arranged several times. In this case, the arrangement of the lower layer up to the arrangement of the uppermost layer may be carried out by performing a curing process for each arrangement.

  In addition, when placing the opaque material on a metal substrate, the surface of the metal substrate may be subjected to a surface treatment with an adhesive treatment agent in order to enhance the adhesion between them. That is, the metal color shielding layer forming kit of the present invention may include the adhesive treatment agent in the constituent members. As such an adhesive treatment material, an appropriate kind of material is used depending on the type of metal. For example, as an adhesive treatment agent used for a base metal alloy base material, an acidic group-containing polymerizable monomer Examples of the adhesive treating agent used for the organic solvent solution of the body and the base material made of the noble metal alloy include an organic solvent solution of a sulfur atom-containing polymerizable monomer such as a thiouracil-based polymerizable monomer. In addition to the surface treatment with the adhesive treatment agent, the surface of the metal substrate may be sandblasted with alumina particles or the like in order to increase the adhesive strength between the opaque material layer and the metal substrate. good.

  Next, the C) resin tooth restoration material and C ′) resin gum preparation material used in combination with the metal color shielding layer forming kit described above will be described. By such a combination, an artificial tooth preparation kit and an artificial gum preparation kit are provided.

C) Resin tooth restoration material Resin tooth restoration material consists of a curable material containing a polymerizable monomer, a photopolymerization initiator, a filler, and a pigment. These components are not particularly limited and known ones can be used, and the components exemplified in the above A) opaque material for forming a metallic color shielding layer can be preferably used. Of course, white pigments are mainly used as the pigment.

  From the viewpoint of transparency and color tone, the contrast ratio of these resin tooth restoration materials is preferably 0.01 to 0.4, and 0.05 to 0.3. More preferably it is.

  It is only necessary to build up a resin tooth restoration material on the upper surface of the opaque material layer to which the surface coating material has been applied, using a spatula, and shaping the artificial tooth after the build-up has been shaped with a spatula, brush, etc. This may be carried out by performing light irradiation later, or polishing the resin tooth restoration material by light irradiation and then polishing with a polishing bar or the like.

C ′) Resin gum preparation material The composition of the resin gum preparation material is the same as that of the resin tooth restoration material, from a curable material containing a polymerizable monomer, a photopolymerization initiator, a filler, and a pigment. Become. Of course, as the pigment, a red pigment is mainly used.

  From the viewpoint of transparency and color tone, the contrast ratio of these resin gum preparation materials is preferably 0.01 to 0.4, and preferably 0.05 to 0.3. More preferably it is.

  It is only necessary to build up the resin gum preparation material on the upper surface of the opaque material layer to which the surface coating material is attached, using a spatula, and shaping the artificial gum after build-up was shaped with a spatula or brush This may be performed by light irradiation later or by polishing the resin gum preparation material by light irradiation and then polishing with a polishing bar or the like.

D) Metal Substrate As the metal substrate used in the present invention, known materials known as materials for metal frames used in the production of artificial teeth and artificial gums can be used without limitation. Specifically, among metals such as gold, silver, palladium, platinum, indium, zinc, tin, and the like, the metal is mainly alloyed at a predetermined ratio, but the adhesion to the opaque material is good. In view of the above, an alloy mainly composed of gold, silver, palladium or the like is preferable.

  Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the present invention is not limited to these examples.

  In the following Examples and Comparative Examples, various physical properties of particles used in the opaque coating material for forming the metallic color shielding layer and the surface coating material constituting the kit for forming the metallic color shielding layer are implemented by the following measuring methods. did.

<Measurement of contrast ratio and color tone of cured opaque material>
The opaque material is filled into a mold made of Teflon (registered trademark) having a hole with a thickness of 0.5 mm and a diameter of 8 mm, and cured by irradiating with a dental visible light irradiator for 30 seconds to form a 0.5 mm thick cured body. Obtained. This cured product is measured with a color difference meter (product name: 1800MKII, manufactured by Tokyo Denshoku Co., Ltd.) on the black background and the white background of the XYZ color system tristimulus values. The contrast ratio was obtained. In addition, L ^* , a ^* , and b ^* on a white background were measured.

        Yb (Y value of black background) / Yw (Y value of white background) = contrast ratio

<Measurement of refractive index of particles>
The refractive index at a refractive index of 32 ° C. was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.). The refractive index of each particle was measured by the immersion method. That is, the particles are dispersed in ethanol, 1-bromonaphthalene is gradually added dropwise to the slurry, and the refractive index of the dispersion at which the boundary between the particles and the liquid cannot be visually confirmed is defined as the refractive index of the particles. .

<Evaluation of transparency of particles>
Selected from organic solvents (ethanol, toluene, 2-bromotoluene, 1-bromonaphthalene, and dibromomethane having a refractive index difference in the range of ± 0.001 with respect to the refractive index of the particles to be measured (32 ° C.). Prepare a mixture of multiple types with different refractive indices. In this, the particles are dispersed at a concentration of 50% by mass. Then, this particle dispersion is put into a quartz cell having an optical path length of 0.5 mm, and the cell is filled with an XYZ color system with a color difference meter (product name 1800MKII, manufactured by Tokyo Denshoku Co., Ltd.) with a black background and white background. Among these tristimulus values, the Y value related to brightness was measured at 32 ° C., and the contrast ratio was determined by the above formula using the Y value, and this value was defined as transparency.

<Measurement of average particle diameter of particles>
For each particle, the average particle size was measured using a particle size distribution meter (LS230 manufactured by Beckman Coulter, Inc.) by a laser light scattering method, using ethanol as a dispersion medium and treating with ultrasonic waves for 5 minutes before measurement, and then immediately measuring the average particle size. . As the average particle size, a median size value expressed on a volume basis was adopted.

Abbreviations and abbreviations shown in the examples are as follows.
A) Material for opaque material for forming metallic color shielding layer <photopolymerizable composition>
・ M-1
70 g bisphenol A polyethoxymethacrylate, 15 g triethylene glycol dimethacrylate, 15 g 1,6-bis (methacrylethyloxycarbonylamino) trimethyloxane, 0.2 g camphorquinone, 0.2 g p-dimethylaminobenzoate Acid ethyl ester, 0.05 g of hydroquinone monomethyl ether, 0.02 g of dibutylhydroxytoluene dissolved in the dark to make a uniform solution [refractive index of cured product (32 ° C.) 1.55]
・ M-2:
100 g 1,6-hexanediol dimethacrylate, 0.2 g camphorquinone, 0.2 g ethyl p-dimethylaminobenzoate, 0.05 g hydroquinone monomethyl ether, 0.02 g dibutylhydroxytoluene in the dark Dissolved into a uniform solution [refractive index of cured body (32 ° C.) 1.50]
・ M-3:
Dissolve 100 g bisphenol A polyethoxymethacrylate, 0.2 g camphorquinone, 0.2 g p-dimethylaminobenzoic acid ethyl ester, 0.05 g hydroquinone monomethyl ether, 0.02 g dibutylhydroxytoluene in the dark. A uniform solution [refractive index of cured body (32 ° C.) 1.57]
・ M-4:
35 g of bisphenol A polyethoxymethacrylate, 30 g of triethylene glycol dimethacrylate, 35 g of 1,6-bis (methacrylethyloxycarbonylamino) trimethylhexane, 0.2 g of camphorquinone, 0.2 g of p-dimethylaminobenzoate Acid ethyl ester, 0.05 g hydroquinone monomethyl ether, 0.02 g dibutylhydroxytoluene dissolved in the dark to form a uniform solution [refractive index of cured product (32 ° C.) 1.53]

<Pigment blended in photopolymerizable composition>
White pigment: Titanium oxide (average particle size 0.25 μm)
・ Yellow pigment: Pigment Yellow 95
・ Red pigment: Pigment Red 166
・ Blue pigment: Pigment Blue 60

<Filler to be blended in photopolymerizable composition>
・ F-1:
60 g of spherical silica-zirconia [average particle size: 0.4 μm, refractive index (32 ° C.) 1.53], 40 g of spherical silica-titania [average particle size: 0.07 μm, refractive index (32 ° C.) 1.52 ] Which was surface-treated with γ-methacryloyloxypropyltrimethoxysilane.
・ F-2:
59 g of spherical silica-zirconia [average particle size: 0.4 μm, refractive index (32 ° C.) 1.53], 40 g of spherical silica-titania [average particle size: 0.07 μm, refractive index (32 ° C.) 1.52 ] Which was surface-treated with γ-methacryloyloxypropyltrimethoxysilane.

B) Material for surface coating material <Transparent particles and comparative particles>
・ P-1:
Spherical cross-linked polymethylmethacrylate (manufactured by Sekisui Chemical Co., Ltd., MBX-50) [average particle diameter 50 μm, refractive index (32 ° C.) 1.49, particle transparency; contrast ratio 0.01]
・ P-2:
Spherical cross-linked polymethyl methacrylate (manufactured by Sekisui Chemical Co., Ltd., MBX-20) [average particle diameter 20 μm, refractive index (32 ° C.) 1.49, particle transparency; contrast ratio 0.01]
・ P-3:
Spherical cross-linked polymethylmethacrylate (manufactured by Sekisui Chemical Co., Ltd., MBX-8) [average particle diameter 8 μm, refractive index (32 ° C.) 1.49, particle transparency; contrast ratio 0.01]
・ P-4:
Spherical cross-linked polymethylmethacrylate particles (manufactured by Nippon Shokubai Co., Ltd., MA1002) [average particle diameter 2 μm, refractive index (32 ° C.) 1.49, particle transparency; contrast ratio 0.01]
・ P-5:
Spherical silica, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (SE-30, manufactured by Tokuyama Co., Ltd.) [average particle size 30 μm, refractive index (32 ° C.) 1.45, particle transparency; contrast ratio 0.03]
・ P-6:
Amorphous barium glass, surface-treated product of γ-methacryloyloxypropyltrimethoxysilane (manufactured by Schott, G018-159) [average particle 30 μm, refractive index (32 ° C.) 1.61, particle transparency; contrast ratio 0.04]
・ P-7:
Spherical cross-linked polystyrene (manufactured by Sekisui Chemical Co., Ltd., SBX-8) [average particle diameter 8 μm, refractive index (32 ° C.) 1.59, particle transparency; contrast ratio 0.07]
・ P-8:
Spherical cross-linked polystyrene (manufactured by Sekisui Chemical Co., Ltd., XS-10) [average particle diameter 1000 μm, refractive index (32 ° C.) 1.59, particle transparency; contrast ratio 0.06]
・ P-9:
Synthetic spherical silica [average particle size: 0.4 μm, refractive index (32 ° C.) 1.45, transparency of particles; contrast ratio 0.03]
・ P-10:
Amorphous barium glass, surface-treated γ-methacryloyloxypropyltrimethoxysilane (Shot, G018-186) [average particle 30 μm, refractive index (32 ° C.) 1.83, particle transparency; contrast ratio 0.08]
・ P-11:
100 parts by weight of spherical crosslinked polymethylmethacrylate (manufactured by Sekisui Chemical Co., Ltd., MBX-50), 5 parts by weight of titanium oxide (average particle size 0.25 μm), 0.3 part by weight of Pigment Yellow 95, and 0 by Pigment Red 166 .2 parts by weight and 0.05 parts by weight of Pigment Blue 60 were mixed in a mortar for 30 minutes, and composite particles in which titanium oxide was adsorbed on the particle surface [average particle diameter of 50 μm, refractive index (32 ° C.) 1. 49, particle transparency; contrast ratio 0.50]

<Volatile organic solvent>
EtOH: ethanol

Example 1
With respect to 100 parts by weight of the photopolymerizable composition M-1, 0.2 parts by weight of titanium oxide as a pigment, 450 parts by weight of F-1 as a filler, 0.015 parts by weight of Pigment Yellow 95, Pigment Red 166 And 0.12 parts by weight of Pigment Blue 60 and 0.002 parts by weight of Pigment Blue 60 were defoamed to produce an opaque material for forming a metallic color shielding layer to be used for producing resin artificial teeth. The contrast ratio of the cured opaque material was measured and found to be 0.70. Moreover, the color tone of the hardening body was L ^* : 68, a ^* :-1, b ^* : 20.

Next, a dispersion liquid in which transparent particles P-1 were dispersed in ethanol at a concentration of 50% by mass was prepared as a surface coating material. The transparent particle P-1 dispersion was combined with the metal color shielding layer forming opaque material to produce a dental metal color shielding kit. About the obtained dental metal color shielding kit, <Evaluation of metal color shielding property>, <Lightness change before and after formation of opaque material layer (ΔL ^* )>, <Resin artificial tooth (artificial gum) The adhesive bending strength> of each was measured, and the results are shown in Table 3.

<Evaluation of metal color shielding>
A Teflon (registered trademark) mold having a hole with a thickness of 0.1 mm and a diameter of 8 mm is placed on one side of a dental gold-silver-palladium alloy “Golden Para 12” (10 × 10 × 3 mm, manufactured by Tokuyama Dental Co., Ltd.) The manufactured opaque material is filled in the holes, and the surface coating material is applied to the uncured surface of the opaque material with a brush so that the amount of transparent particles attached is 0.2 mg (0.4 mg per 1 cm ^{2 of the} opaque material upper surface). After applying and evaporating the volatile organic solvent, it was cured by irradiating light for 30 seconds with a dental visible light irradiator. Further, a Teflon (registered trademark) mold having a hole with a thickness of 0.5 mm and a diameter of 8 mm is placed on the Teflon (registered trademark) mold used for filling and curing the opaque material. The resin tooth restoration material “Pearl Este (color tone CD3)” was filled in the hole, pressed with a transparent polyethylene film, and then cured by irradiation with a dental visible light irradiator for 30 seconds.

The color tone of the obtained cured product was visually observed and evaluated according to the following criteria.
◎: The metallic color of the dental gold-silver-palladium alloy located in the lower layer cannot be seen through at all, and the cured material of the opaque material can be observed in a bright color tone. ○: The dental gold-silver-palladium alloy located in the lower layer Although the metallic color is not seen through, the opaque cured material feels a slightly darker color. Δ: The metallic color of the dental gold-silver-palladium alloy located in the lower layer can be seen through slightly. The metal color of the dental gold-silver-palladium alloy is clearly identified

<Lightness change before and after opaque material layer formation (ΔL ^* )>
In the same manner as in the above <Evaluation of metal color shielding>, a dental metal color shielding kit is applied on a dental gold-silver-palladium alloy “Gold Para 12” to form an opaque material layer. After the surface coating material was processed on the upper surface, a cured body of a resin tooth restoration material was formed. With respect to this specimen, the lightness (L ^* ) of the cured body surface of the resin tooth restoration material in the white background was measured with a color difference meter.

On the other hand, as a control, a Teflon (registered trademark) mold having a hole with a thickness of 0.5 mm and a diameter of 8 mm is filled with “Pearl Este (color tone CD3)”, the same resin tooth restoration material, and pressed with a transparent polyethylene film Then, it was cured with a dental visible light irradiator. For this cured product, the lightness (L ^* ) in the white background was also measured with a color difference meter.

Wherein as compared with the brightness of the specimen (L ^*) control of lightness (L ^*), it was evaluated when the value drops as a negative number.
<Method for measuring bending strength adhesive strength>
A Teflon (registered trademark) mold having a thickness of 0.1 mm, a length of 2 mm, and a width of 25 mm is prepared, and the opaque material for forming a metallic color shielding layer is filled in the groove. After the surface coating material is applied to the uncured surface of the material with a brush so that the amount of the transparent particles attached is 0.2 mg (0.4 mg per 1 cm ^{2 of the} upper surface of the opaque material layer), the volatile organic solvent is evaporated. Then, it was cured by irradiating with a dental visible light irradiator for 30 seconds. Further, a Teflon (registered trademark) mold having a thickness of 0.5 mm, a groove of 2 mm in length and 25 mm in width was used for filling the opaque material. It was placed on a Teflon (registered trademark) mold so that the groove hole part overlapped, and the resin tooth restoration material “Pearl Este (color tone CD3)” was filled in the hole and pressed with a transparent polyethylene film. In this state, the position was changed so that the entire surface was exposed to light from one side for 30 seconds × 3 times, and light irradiation was carried out by closely contacting the polypropylene with a dental visible light irradiator. Subsequently, the opposite surface was similarly adhered to polypropylene and irradiated with light for 30 seconds × 3 times to obtain a cured product. The Teflon (registered trademark) mold was removed and the cured body was taken out. The surface was lightly polished with a # 1500 water-resistant abrasive paper to obtain a 0.6 × 2 × 25 mm prismatic test piece. This test piece was mounted on a testing machine (manufactured by Shimadzu Corp., Autograph AG5000D), and the three-point bending fracture strength was measured at a distance between supporting points of 20 mm and a crosshead speed of 1 mm / min.

Examples 2-15
Each opaque material for forming a metallic color shielding layer was produced in the same manner as in Example 1 except that the composition shown in Table 1 was used. The contrast ratios of the cured bodies of these opaque materials were as shown in Table 1, and the color tones of the cured bodies were L ^* : 68, a ^* :-1, and b ^* : 20.

Next, as a surface coating material, a dispersion liquid in which each transparent particle shown in Table 1 is dispersed in ethanol at a concentration of 50% by mass is prepared, and these are combined with the above opaque materials as shown in Table 1. A dental metal color shielding kit was manufactured. For the obtained dental metal color shielding kit, <Evaluation of metal color shielding property>, <Change in brightness before and after formation of opaque material layer (ΔL ^* )>, <Adhesive bending strength of resin artificial teeth (artificial gums) > Was measured and evaluated. The results are shown in Table 3.

Example 16
In Example 1, <Evaluation of metal color shielding>, <Lightness change before and after formation of opaque material layer (ΔL ^* )>, <Adhesive bending strength of resin artificial tooth (artificial gum)> The dental metal color shielding is carried out in the same manner as in Example 1 except that the thickness of the Teflon (registered trademark) mold for filling the material into the holes to form the opaque material layer is changed from 0.1 mm to 0.3 mm. The kit was evaluated. The results are shown in Table 3.

Example 17
In Example 1, the dental metal color shielding kit was used in the same manner as in Example 1 except that the transparent particle P-1 was used as it was without being dispersed in ethanol. The shielding kit was evaluated. In addition, application | coating to the uncured surface of an opaque material of the surface coating material which consists of transparent particle P-1 was implemented by apply | coating with a brush so that the adhesion amount of transparent particle might be 0.2 mg. The results are shown in Table 3.

Example 18
100 parts by weight of the photopolymerizable composition shown in Table 1, 450 parts by weight of filler, 0.2 part by weight of titanium oxide as a pigment, 0.01 part by weight of Pigment Yellow 95, 0.05 part by weight of Pigment Red 166, Opaque material for forming a metallic color shielding layer used for preparing resin gums was prepared by blending 0.002 parts by mass of Pigment Blue 60 and defoaming. The contrast ratio of the cured product of the opaque material is as shown in Table 1, and the color tone of the cured product was L ^* : 68, a ^* : 10, and b ^* : 12.

Next, as a surface coating material, a dispersion liquid in which transparent particles P-1 were dispersed in ethanol at a concentration of 50% by mass was prepared, and these were combined with the opaque material to produce a dental metal color shielding kit. . About this dental metal color shielding kit, <Evaluation of metal color shielding property>, <Lightness change before and after formation of opaque material layer (ΔL ^* )>, <Adhesion of resin artificial teeth> Bending strength> was measured, and the results are shown in Table 3.

Comparative Example 1
Using the same opaque material for forming a metallic color shielding layer as in Example 1 and using no surface coating material, <Evaluation of metallic color shielding property>, <Change in brightness before and after the opaque material layer formation (ΔL ^* )>, <Adhesive bending strength of resin artificial teeth (artificial gums)> was measured. The results are shown in Table 4.

Comparative Examples 2-4
In Example 1, it carried out similarly to Example 1 except having changed into the aspect using the dispersion liquid which disperse | distributed each particle | grain shown in Table 2 to ethanol by the density | concentration of 50 mass% as a surface coating material. The results are shown in Table 4.

Comparative Example 5
Using the same opaque material for forming a metallic color shielding layer as in Example 11 and using no surface coating material, <Evaluation of metallic color shielding property>, <Change in brightness before and after the opaque material layer was formed (ΔL ^* )>, <Adhesive bending strength of resin artificial teeth (artificial gums)> was measured and evaluated. The results are shown in Table 4.

Comparative Example 6
In Comparative Example 1, <Evaluation of metal color shielding>, <Lightness change before and after formation of opaque material layer (ΔL ^* )>, <Adhesive bending strength of resin artificial tooth (artificial gum)> The same as Example 1 except that the thickness of the Teflon (registered trademark) mold for filling the material into the holes to form the opaque material layer is changed from 0.1 mm to 0.3 mm. The opaque material for forming a metallic color shielding layer was used, and the surface coating material was not used. The results are shown in Table 4.

Comparative Example 7
In Comparative Example 2 (using P-11 comparative particles as the surface coating material), <Evaluation of metal color shielding>, <Lightness change before and after formation of opaque material layer (ΔL ^* )>, <Resin artificial tooth ( The thickness of the Teflon (registered trademark) mold that forms the opaque material layer by filling the opaque material in the hole is changed from 0.1 mm to 0.3 mm for each measurement of the adhesive bending strength> of the artificial gum). The dental metal color shielding kit was evaluated in the same manner as in Comparative Example 2 except that it was carried out. The results are shown in Table 4.

Claims (7)

When an artificial tooth or artificial gum is produced by building up a resin tooth restoration material or resin gum preparation material on a metal base material, the metal base material is shielded between the two members in order to shield the metal color. A metal color shielding layer forming kit for dental use,
A) Opaque material for forming a metallic color shielding layer comprising a photopolymerizable composition B) A polymerizable monomer having an average particle diameter of 1 to 200 μm and contained in the above opaque material for forming a metallic color shielding layer The transparent material having a refractive index (32 ° C.) different from that of the cured product, or a dispersion of the transparent material, and the upper surface of the opaque material layer formed by the opaque material for forming the metallic color shielding layer is used. A dental metal color shielding kit comprising a surface coating material.   B) The refractive index difference (32 ° C.) between the transparent particles used in the surface coating material and the cured product of the polymerizable monomer contained in the A) opaque material for forming the metallic color shielding layer is 0.02 to 0. The dental metal color shielding kit according to claim 1, which is in the range of .20.   B) The metal color shielding kit for metal tooth restoration material according to claim 1, wherein the transparent particles used in the surface coating material are organic resin particles not containing a colorant.   The metal color shielding kit for metal tooth restoration material according to claim 3, wherein the organic resin constituting the organic resin particles not containing a colorant is polymethyl methacrylate.   A) The contrast ratio of the 0.5 mm thick cured body of the opaque material for forming a metallic color shielding layer is 0.4 to 0.9. 5. The dental metallic color shielding kit according to claim 1. . An artificial tooth preparation kit comprising the dental metal color shielding kit according to any one of claims 1 to 5, and C) a resin tooth restoration material. An artificial gum preparation kit comprising the dental metal color shielding kit according to any one of claims 1 to 5, and C ') a resin gum preparation material.