JP2016013998A - Composite resin artificial tooth containing chain transfer agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin artificial tooth which reduces a defect occurrence, such as a topical shrinkage, cracking, white turbidity, or chipping by reducing a distortion occurring inside of a composite resin artificial tooth, and which can be molded under a pressurization and heat condition where there are no air bubble-mixing caused by foaming, in a molding step of the composite resin artificial tooth.SOLUTION: The invention relates to a composite resin artificial tooth of a monolayer or multilayer structure, which comprises a composite resin layer containing (a) a polymerizing monomer, (b) a filler, (c) a polymerization initiator, and (d) a chain transfer agent. Preferably, the chain transfer agent is a terpenoid compound, such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α pinene.

Description

The present invention relates to a prosthetic device used for treatment of a denture with a denture in the dentistry field, for example, a composite resin artificial tooth constituting a denture in a partial denture or a complete denture, and more specifically a single layer Alternatively, the present invention relates to a composite resin artificial tooth comprising only a composite resin layer having a multilayer structure, or a composite resin artificial tooth comprising a composite resin layer and an acrylic resin layer having a multilayer structure.

In order to recover the oral function that has been lowered due to a missing tooth, treatment is carried out by mounting a prosthesis = prosthetic device composed of an artificial tooth and a denture base that serves as a substitute for the lost tooth in the oral cavity. Such prosthetic devices include partial dentures that require support for the remaining teeth and full dentures that have no remaining teeth. In addition, there is a denture (implant overdenture) using an artificial root called an implant.
Any denture is manufactured by the following procedure using artificial teeth.
First, after examining and diagnosing the patient's oral cavity, an impression of the mucosal surface is taken, and a plaster model is produced that duplicates the shape of the oral mucosa. Next, a wax bank necessary for obtaining the patient's occlusion is prepared and occlusal is obtained. After obtaining the occlusion, a plaster model is attached to the articulator that reproduces the jaw movement, and artificial teeth are arranged on a horseshoe-shaped wax bank to create a wax denture that matches the patient's jaw movement. The wax denture in which the artificial teeth are arranged is buried in a bisected flask with gypsum, and a split mold is made through a dewaxing process. After filling the acrylic resin for flooring into the split mold leaving the artificial tooth and the floor part being hollow, the resin denture is completed by heat polymerization or room temperature polymerization.

Artificial teeth used for the production of dentures include porcelain teeth mainly composed of inorganic materials and resin teeth mainly composed of organic materials. Since porcelain teeth are hard and have high physical properties, they have less occlusal wear during mastication in the oral cavity, and have superior characteristics such as durability and aesthetics. On the other hand, it is difficult to adjust the occlusion due to the hardness of the material, and because it does not chemically adhere to the floor part (denture base) that supports the porcelain tooth, a maintenance part is required at the base part of the porcelain tooth. The above problems are also recognized. In addition, the frequency of use is decreasing due to the high price.
On the other hand, resin teeth do not have physical properties and durability compared to porcelain teeth, but there are many advantages in use such as easy occlusal adjustment and chemical bonding with denture base. It is recognized and is also widely applied clinically because of its low price.
Resin teeth include acrylic resin artificial teeth based on monofunctional (meth) acrylate monomers and non-crosslinkable organic fillers, fillers consisting of inorganic fillers and organic-composite fillers, and polyfunctional (meth) acrylates. There is a composite resin artificial tooth mainly composed of a monomer.

Although composite resin artificial teeth are characterized by excellent physical properties and aesthetics, problems such as poor color tone stability and easy discoloration and coloring have been pointed out. On the other hand, an acrylic resin artificial tooth is characterized by excellent color tone stability and hardly causing discoloration or coloring, although it has lower physical properties than a composite resin artificial tooth.
As mentioned above, resin teeth have advantages and disadvantages based on the type, properties, and characteristics of the filler component and resin component to be blended. In recent years, however, there are various component compositions for overcoming each disadvantage. Prior art has been proposed. For example, Patent Document 1 includes an artificial tooth including three types of resin components and an inorganic filler, and Patent Documents 2 to 6 include an artificial tooth including a fluorine-containing bisphenol group-containing resin monomer. Although blending these ingredients into the resin teeth can prevent discoloration, the resin teeth are molded products, so they are more susceptible to the component composition and the layer structure due to the mold than the material characteristics. It is important to control the molding characteristics during pressing and heating in order to stabilize the production.

  Resin teeth also provide excellent aesthetics, with complex anatomical forms similar to natural teeth, layer-by-layer structures that make up the forms, and light transmission characteristics and color tones of each layer. Therefore, the mold structure that duplicates the layer structure of the artificial teeth used in the resin tooth molding stage is also important, and the prior art (patent document 7) on artificial teeth having various layer structures and corresponding molds is also proposed. Has been. In addition, a prior art (Patent Document 8) related to artificial teeth molded to an intermediate stage has been proposed. Using the artificial teeth, tailor-made final artificial teeth suitable for each patient are produced at dental clinics and laboratories. It is to do. However, in order to provide a high-quality artificial tooth with aesthetics, a layer of various thicknesses is uniformly polymerized and cured, and several types of layers are laminated to create an anatomical form similar to natural teeth. Properties are more important for manufacturing stability.

  A composite resin artificial tooth is a compression molding method in which paste-like or powdery and liquid-mixed cocoon-like materials are placed in a mold and then pressed and heated, or the material is injected into the mold at a constant pressure. By using a molding method or the like, each layer is polymerized and cured to form a natural tooth-like form while being laminated. However, the thickness of the layers to be stacked is not uniform, and there are thin and thick portions in the same layer, and the positional relationship (in the vicinity of the mold, inside the mold, etc.) where the raw material exists in the mold, etc. Since the method of transferring heat, the speed of polymerization and curing, and the like change, there are problems such as partial shrinkage, cracks, white turbidity, chipping and other defects during molding by pressing and heating. Also, in the stage of laminating each layer while sequentially polymerizing and curing, the familiarity when the raw material for polymerizing and curing the new layer is pressed on the surface of the cured layer and the adhesion between the two when polymerized and cured And the like, and the intended physical properties are not exhibited.

JP 2013-216599 A Japanese Patent No. 2021591 Japanese Patent No. 1651940 JP 62-48647 A Japanese Patent No. 1943819 JP-A-2-40310 JP-A-9-103438 JP 2007-236465 A

The composite resin artificial tooth reproduces the natural tooth-like form while polymerizing and hardening each layer by pressing and heat molding after filling the raw material into the mold, Since the polymerization curing speed and degree of curing change depending on the difference in the composition of each layer and the thickness of the layer structure, and the position of the raw material in the mold, microscopic and macroscopic strains occur and local shrinkage occurs. There were problems such as defects such as cracks, cloudiness, and chipping. In addition, the raw material that is the next layer is placed on the cured layer, and it is polymerized and cured and laminated, but due to the effects of the familiarity of the cured layer surface and the material, polymerization shrinkage stress during polymerization curing, etc., There were also problems such as insufficient adhesion between the layers, resulting in adverse effects on material properties.
The cause of these problems is estimated as follows. The composite resin layer in composite resin artificial teeth contains fillers and polymerizable monomers with different thermal conductivities. Microscopic strain is generated at the interface, which seems to cause the above-mentioned defect. In addition, since the thickness in the same layer structure is partially different, it does not show a uniform polymerization hardening behavior, and the polymerization hardening proceeds preferentially from the thin layer part, generating macro distortion, which is It seems to be connected to the occurrence of defects. Furthermore, a new raw material is placed on the layer that has been polymerized and cured, and polymerized and cured. However, since the layer is thin, rapid polymerization and curing occurs, and the adhesive force on the adhesive surface is directed toward the inside of the layer structure. It seems that the polymerization shrinkage stress is strongly generated, resulting in poor adhesion between layers.
Therefore, the subject of the present invention is not affected by the component composition of each layer, the thickness of the layer structure, etc., in the pressing and heating molding stage in which each layer is polymerized and cured to reproduce a natural tooth-like form. A composite resin artificial material with a single or multi-layer structure that does not cause defects such as local shrinkage, cracking, white turbidity, chipping, etc., and does not adversely affect material properties due to strong adhesion between layers To provide teeth.

In order to solve the above-mentioned problems, the inventors have intensively studied, and in the molding process stage of the composite resin artificial tooth that reproduces the natural tooth-like form while polymerizing and curing each layer, the composite resin artificial tooth By blending a chain transfer agent as a component, the rate of polymerization and curing can be delayed without being affected by the component composition of each layer and the thickness of the layer structure, resulting in uniform polymerization and curing. It has been found that various defects occurring during molding can be reduced by virtue of being able to be firmly bonded, and the present invention has been completed.
In particular,
A single-layer or multilayer composite resin artificial tooth,
Provided is a composite resin artificial tooth characterized in that the composite resin layer contains (a) a polymerizable monomer (b) a filler (c) a polymerization initiator (d) a chain transfer agent.

Also, a composite resin artificial tooth having a multilayer structure,
At least one layer includes (a) a polymerizable monomer, (b) a filler, (c) a polymerization initiator, (d) a composite resin layer made of a chain transfer agent, and a base layer that can be chemically bonded to the denture base. From an acrylic resin layer in which at least one layer comprises (e) a monofunctional (meth) acrylate polymerizable monomer (f) a non-crosslinkable (meth) acrylate polymer (c) a polymerization initiator (d) a chain transfer agent A composite resin artificial tooth is provided.

Furthermore, when each component contained in the composite resin layer of the composite resin artificial tooth has a total of (a) polymerizable monomer and (b) filler of 100 parts by weight,
(A) 10 to 70 parts by weight of a polymerizable monomer,
(B) The filler is contained in the range of 30 to 90 parts by weight, and with respect to 100 parts by weight of the polymerizable monomer,
(C) 0.01-10 parts by weight of a polymerization initiator,
(D) A composite resin artificial tooth characterized in that the chain transfer agent is contained in an amount of 0.001 to 1 part by weight.

Also provided is a composite resin artificial tooth characterized in that (d) the chain transfer agent is a terpenoid compound.

Furthermore, in the above-mentioned method for producing a composite resin artificial tooth, a method for producing a composite resin artificial tooth is provided in which a composite resin layer or an acrylic resin layer is individually polymerized and cured by heating and pressurizing one after another.

The following effects are brought about by the present invention.
The composite resin layer constituting the composite resin artificial tooth of the present invention contains a filler and a polymerizable monomer having different thermal conductivities, but the effect of the chain transfer agent delays the rate of polymerization and curing uniformly. Since it is polymerized and cured, microscopic strain generated at the interface between them can be suppressed, and as a result, defects such as local shrinkage, cracking, white turbidity, and chipping do not occur. In addition, the acrylic resin layer constituting the composite resin artificial tooth of the present invention contains a resin component having a high thermal conductivity and an organic filler as main components. The polymerization transfer rate is delayed by the effect of the chain transfer agent, resulting in uniform polymerization and curing, so micro-distortion is unlikely to occur, and as a result, defects such as local shrinkage, cracks, cloudiness, and chipping do not occur. . Furthermore, although the thicknesses in the same layer are locally different, the rate of polymerization and curing is delayed by the effect of the chain transfer agent, so that it can be uniformly polymerized and cured without being affected by the thickness. Defects such as general shrinkage, cracking, cloudiness, and chipping do not occur.
In addition, when the chain transfer agent is blended, the polymerizable monomer is polymerized and cured with a low degree of polymerization. Therefore, when a raw material is placed on a cured layer and polymerized and cured by pressurization and heating and laminated, the wettability of both is improved, and strong interlayer adhesion can be obtained. As a result, not only defects such as local shrinkage, cracking, white turbidity, and chipping do not occur, but also excellent physical properties can be exhibited.

Simulated artificial teeth used in molded good quality tests The figure which shows the direction of the pressure test in the interface adhesion state confirmation test

The present invention is described in detail below.
The composite resin artificial tooth having a single-layer or multi-layer structure according to the present invention is characterized in that the composite resin layer contains (a) a polymerizable monomer (b) a filler (c) a polymerization initiator (d) a chain transfer agent. And

Further, the dental composite resin artificial tooth having a multilayer structure of the present invention is a composite in which at least one layer is composed of (a) a polymerizable monomer (b) a filler (c) a polymerization initiator (d) a chain transfer agent. At least one layer including a base layer that can be chemically bonded to the resin layer and the denture base is (e) a monofunctional (meth) acrylate polymerizable monomer (f) a non-crosslinkable (meth) acrylate polymer (C) Polymerization initiator (d) It is characterized by comprising an acrylic resin layer comprising a chain transfer agent.

  (A) The polymerizable monomer that can be used in the composite resin layer constituting the composite resin artificial tooth of the present invention is a known monofunctional or polyfunctional polymerizable monomer generally used in the dental field. Can be used from the body without any restrictions. Typical examples that are generally suitably used are (meth) acrylate polymerizable monomers having an acryloyl group and / or a methacryloyl group. In the present invention, both the acryloyl group-containing polymerizable monomer and the methacryloyl group-containing polymerizable monomer are comprehensively described with a (meth) acrylate polymerizable monomer.

A specific example of the (meth) acrylate polymerizable monomer that can be used as the polymerizable monomer (a) is as follows.

Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, glycerol (meta ) Acrylates, (meth) acrylic esters such as isobornyl (meth) acrylate, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylto Examples thereof include silane compounds such as reethoxysilane, and nitrogen-containing compounds such as 2- (N, N-dimethylamino) ethyl (meth) acrylate, N-methylol (meth) acrylamide, and diacetone (meth) acrylamide.

  As the aromatic bifunctional monomer, 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) ) Phenyl) 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- (meth) acryloyloxydipropoxyphenyl) propane, 2, (4- (Meth) acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydieto Cyphenyl) propane, 2 (4- (meth) acryloyloxydiethoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2 (4- (meth) acryloyloxydipropoxyphenyl) -2 (4 -(Meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, etc. Is mentioned.

  Examples of the aliphatic bifunctional monomer include 2-hydroxy-3-acryloyloxypropyl methacrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di ( Examples include meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and glycerol di (meth) acrylate.

  Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.

  Examples of the tetrafunctional monomer include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.

  As the urethane-based polymerizable monomer, a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate And adducts of diisocyanate compounds such as methylcyclohexane diisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylmethylbenzene, 4,4-diphenylmethane diisocyanate. And di (meth) acrylate having a difunctional or trifunctional or higher urethane bond.

  In addition to these (meth) acrylate polymerizable monomers, there is no limitation even if an oligomer or a prepolymer having at least one polymerizable group in the molecule is used. Moreover, there is no problem even if it has a substituent such as a fluoro group in the same molecule. Moreover, the polymerizable monomer described above can be used not only alone but also in combination.

Although the content of the polymerizable monomer (a) that can be used in the composite resin layer constituting the composite resin artificial tooth of the present invention is not particularly limited, the range of 10 to 70 parts by weight is preferable, and more preferable. Is in the range of 10 to 70 parts by weight. (A) When content of a polymerizable monomer is less than 10 weight part, a filler cannot disperse | distribute uniformly and stable material characteristic cannot be expressed. On the other hand, when it exceeds 70 parts by weight, the material properties are lowered, for example, the surface hardness is lowered.

  The composite resin artificial tooth of the present invention is characterized in that at least one layer including a base layer capable of chemically adhering to the denture base is an acrylic resin layer. The (e) monofunctional (meth) acrylate polymerizable monomer that can be used in the acrylic resin layer constituting the composite resin artificial tooth of the present invention is a known monofunctional acryloyl generally used in the dental field. Any (meth) acrylate polymerizable monomer having a group and / or a methacryloyl group can be used without any limitation. In the present invention, the monofunctional (meth) acrylate-based polymerizable monomer comprehensively represents both an acryloyl group-containing polymerizable monomer and a methacryloyl group-containing polymerizable monomer.

(E) Specific examples of the monofunctional (meth) acrylate polymerizable monomer are as follows. Monofunctional (meth) acrylate polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) (Meth) acrylic acid esters such as acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, glycerol (meth) acrylate, isobornyl (meth) acrylate, Silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 2- (N, N-dimethylamino) ethyl (meth) acrylate, N-methylol ( And nitrogen-containing compounds such as (meth) acrylamide. These monofunctional (meth) acrylate polymerizable monomers can be used not only alone but also in combination.
Although there is no restriction | limiting in particular in content of the (e) monofunctional (meth) acrylate type | system | group polymerizable monomer which can be used for the acrylic resin layer which comprises the composite resin artificial tooth of this invention, Among them, 10-70 weight The range is preferably 10 parts by weight, more preferably 10 to 50 parts by weight, and still more preferably 20 to 40 parts by weight. When the content of the monofunctional (meth) acrylate polymerizable monomer is less than 10 parts by weight, the adhesion to the denture base is deteriorated, and when it exceeds 70 parts by weight, the polymerization shrinkage of the resin component is large. Therefore, moldability is deteriorated, and problems such as inability to obtain stable dimensional stability arise.

  As the filler (b) that can be used in the composite resin layer constituting the composite resin artificial tooth of the present invention, a known filler that is generally used for dental composite materials can be used. Examples of the filler include inorganic fillers, organic fillers, organic-inorganic composite fillers, and the like. These fillers can be used not only independently but also in combination regardless of the type of filler.

  Specific examples of inorganic fillers include metal hydroxides such as aluminum hydroxide, calcium hydroxide, strontium hydroxide and magnesium hydroxide, carbonates such as calcium carbonate and strontium carbonate, aluminum sulfate, calcium sulfate and barium sulfate. Such as sulfate, aluminum oxide, metal oxide such as titanium oxide, metal fluoride such as barium fluoride, calcium fluoride, strontium fluoride, talc, kaolin, clay, mica, calcium phosphate, hydroxyapatite, aluminum silicate, alumina , Titania, zirconia, silica, quartz, zeolite, Aerosil (registered trademark), various glasses (fluoroaluminosilicates and borosilicates containing heavy metals such as sodium, strontium, barium, lanthanum and / or fluorine) Aluminum Novo rate, glass such as fluoroaluminosilicate borosilicates) and others as mentioned, but not limited thereto. These inorganic fillers may be used as aggregates, and examples include silica-zirconia composite oxide aggregates obtained by mixing silica sol and zirconia sol, spray drying and heat treatment.

  Specific examples of the organic filler include elastomers such as polyvinyl acetate, polyvinyl alcohol, and styrene-butadiene rubber, and non-crosslinkable (meta) which is a homopolymer of a monofunctional (meth) acrylate-based polymerizable monomer. ) Acrylate polymers, crosslinkable (meth) acrylate polymers obtained by copolymerization of monofunctional (meth) acrylate polymerizable monomers and polymerizable monomers having two or more functional groups. However, it is not limited to these.

Specific examples of organic-inorganic composite fillers are those in which the surface of the inorganic filler is polymerized and coated with a polymerizable monomer, and after mixing and polymerizing the inorganic filler and the polymerizable monomer, suitable particles Examples include, but are not limited to, organic-inorganic composite fillers such as those pulverized to a diameter, or those obtained by dispersing a filler in a polymerizable monomer in advance and emulsion polymerization or suspension polymerization. It is not something.
As these fillers, fillers having an arbitrary shape such as a spherical shape, a needle shape, a plate shape, a crushed shape, and a scale shape can be used. The average particle size of the filler varies depending on the type of filler, and in the case of an inorganic filler, it can be used in the range of 0.05 to 200 μm, preferably 0.5 to 100 μm. It is in the range, more preferably in the range of 1 to 20 μm. In the case of an organic-inorganic composite filler, it can be used in the range of 0.05 to 150, preferably 0.5 to 100 μm, more preferably 1 to 20 μm. is there. Further, in the case of organic fillers, there is no particular limitation on the average particle diameter, and any of the average particle diameters in any range can be used. The information on the average particle diameter can be examined with a laser diffraction particle size measuring machine.
(B) When the filler is an aggregate, the above average particle diameter is the average particle diameter of the aggregate.
Furthermore, the surface of the filler may be multifunctional by a surface treatment method using a surface treatment agent or the like, and these surface treatment fillers can be used without any limitation. Specific examples of the surface treatment agent used to make the surface of the filler multifunctional include surfactants, fatty acids, organic acids, inorganic acids, various coupling materials (titanate coupling agents, aluminate coupling agents and silanes). Coupling agents), metal alkoxide compounds, and the like. Specific examples of the surface treatment method include a method of spraying a surface treatment agent from the top in a state where the filler is flowed, a method of dispersing the filler in a solution containing the surface treatment agent, and several types on the surface of the filler. The method etc. which carry out multilayer processing of the surface treating agent are mentioned. However, the surface treatment agent and the surface treatment method are not limited to these. These surface treatment agents and surface treatment methods can be used alone or in combination.

  The content of the filler (b) that can be used in the composite resin layer constituting the composite resin artificial tooth of the present invention is not particularly limited, but is preferably in the range of 30 to 90 parts by weight in the composite resin layer. More preferably, it is in the range of 30 to 60 parts by weight. If the content of the filler is less than 30 parts by weight, the material properties such as the surface hardness will decrease, while if it exceeds 90 parts by weight, the resin component will decrease and the wettability between the layers will decrease. Since sufficient adhesion cannot be obtained, problems such as deterioration of material properties occur.

  The (f) non-crosslinkable (meth) acrylate polymer that can be used in the acrylic resin layer constituting the composite resin artificial tooth of the present invention is one that swells with a monofunctional (meth) acrylate polymerizable monomer. There is no particular limitation, and a polymer obtained by polymerizing a (meth) acrylate polymerizable monomer alone, a polymer obtained by copolymerizing a plurality of (meth) acrylate polymerizable monomers, and other monofunctionality A polymer or the like copolymerized with the polymerizable monomer can be used without any limitation. Specific examples of these (meth) acrylate polymers include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polypropyl (meth) acrylate, polyisopropyl (meth) acrylate, polyisobutyl (meth) acrylate, polybutyl (meth) ) Homopolymers such as acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) acrylate, etc. Examples thereof include, but are not limited to, a copolymerized copolymer. These non-crosslinkable (meth) acrylate polymers can be used not only alone but also in combination. Among these non-crosslinkable (meth) acrylate polymers, it is preferable to use polymethyl methacrylate, polyethyl methacrylate, and a copolymer copolymer of methyl methacrylate and ethyl methacrylate.

There is no limitation in the polymerization method of these non-crosslinkable (meth) acrylate polymers, and there is no problem even if it is produced by any polymerization method such as emulsion polymerization or suspension polymerization. The shape of these non-crosslinkable (meth) acrylate polymers can be used without any limitation as long as it is spherical, crushed or hollow, but is preferably spherical.
The average particle diameter (50 parts) of the non-crosslinkable (meth) acrylate polymer can be used without any limitation as long as it is in the range of 1 to 300 μm, preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 150 μm. It is a range. The weight average molecular weight of the non-crosslinkable (meth) acrylate polymer can be used without any limitation as long as it is in the range of 1 to 2 million, but is preferably in the range of 5 to 1.5 million, and more preferably 10 to 10 million. 1.5 million.
Surface modification such as coating the surface of organic fillers, inorganic fillers, organic-inorganic composite fillers, organic / inorganic compounds, organic / inorganic pigments with non-crosslinkable (meth) acrylate polymers, etc. Those subjected to secondary processing such as processing and composite processing can be used without any limitation.

The content of the (f) non-crosslinkable (meth) acrylate polymer that can be used in the acrylic resin layer constituting the composite resin artificial tooth of the present invention is 30 to 90 parts by weight, and can be used without any limitation. However, it is preferably 50 to 90 parts by weight, more preferably 60 to 80 parts by weight.
When the content of the non-crosslinkable (meth) acrylate polymer is less than 30 parts by weight, the adhesion to the denture base is deteriorated. On the other hand, when it exceeds 90 parts by weight, the shrinkage of the resin component is increased, and the moldability is increased. And the problem that stable dimensional stability cannot be obtained occurs.

  (C) The polymerization initiator that can be used for the composite resin layer or the acrylic resin layer constituting the composite resin artificial tooth of the present invention is not particularly limited, and a known polymerization initiator, for example, a radical generator can be used without any limitation. . As polymerization initiators, those that start polymerization by mixing (chemical polymerization initiator), those that start polymerization by heating (thermal polymerization initiator), and those that start polymerization by light irradiation (photopolymerization initiator) Although broadly classified, any polymerization initiator can be used without any limitation in the present invention. Moreover, these polymerization initiators can be used not only independently but also in combination of two or more irrespective of a polymerization mode or a polymerization method. Furthermore, these polymerization initiators can be used without any problems even if they are subjected to a secondary treatment such as being encapsulated in a microcapsule in order to realize stabilization of polymerization or delay of polymerization. Among these polymerization initiators, it is preferable to use a thermal polymerization initiator.

Chemical polymerization initiators include organic peroxide / amine compounds or organic peroxides / amine compounds / sulfinates, redox type polymerization initiation systems composed of organic peroxides / amine compounds / borate compounds, oxygen and water, An organometallic polymerization initiator system that reacts to initiate polymerization is used. Further, sulfinates and borate compounds can be used because polymerization can be initiated by reaction with a polymerizable monomer having an acidic group.
Although the specific example of a chemical polymerization initiator is illustrated below, it is not limited to these.

  Specific examples of the organic peroxide include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2 , 5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate and the like.

  Specific examples of the amine compound include secondary or tertiary amines in which an amine group is bonded to an aryl group. Specific examples include pN, N-dimethyl-toluidine, N, N- Dimethylaniline, N-β-hydroxyethyl-aniline, N, N-di (β-hydroxyethyl) -aniline, pN, N-di (β-hydroxyethyl) -toluidine, N-methyl-aniline, p- N-methyl-toluidine and the like can be mentioned.

Specific examples of sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, and the like.
Specific examples of the borate compound include trialkylphenyl boron, trialkyl (p-fluorophenyl) boron (wherein the alkyl group is an n-butyl group, an n-octyl group, an n-dodecyl group, etc.), a sodium salt, lithium Examples include salts, potassium salts, magnesium salts, tetrabutylammonium salts, and tetramethylammonium salts.
Furthermore, specific examples of organometallic polymerization initiators include organoboron compounds such as triphenylborane, tributylborane, and tributylborane partial oxides.
Moreover, as a photoinitiator, what consists of a photosensitizer, a photosensitizer / photopolymerization accelerator etc. are used. Although the specific example of a photoinitiator is illustrated below, it is not limited to these.

  Specific examples of the photosensitizer include benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1 , 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone Thioxanthone such as 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Benzophenones such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Acylphosphine oxides such as oxide, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1, etc. Α-aminoacetophenones, ketals such as benzyldimethyl ketal, benzyl diethyl ketal, benzyl (2-methoxyethyl ketal), bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-pyrrolyl) ) Phenyl]- Tan, bis (cyclpentadienyl) -bis (pentanefluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-4-disiloxyphenyl) -titanium, etc. And titanocenes.

  Specific examples of the photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, pN, N- Dimethyl-toluidine, m-N, N-dimethyl-toluidine, p-N, N-diethyl-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylamino Benzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid aminoester, N, N-dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, pN, N-dihydroxyethyl -Toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl- β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N -Tertiary amines such as dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethanol, secondary amines such as N-phenylglycine, 5-butylbarbitur Acid, 1-benzyl- -Barbituric acids such as phenyl barbituric acid, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversate, dioctyltin bis (mercaptoacetic acid isooctyl ester) salt, tetramethyl-1,3-diacetoxy dista Examples thereof include tin compounds such as noxane, aldehyde compounds such as lauryl aldehyde and terephthalaldehyde, and sulfur-containing compounds such as dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanethiol, and thiosalicylic acid.

Furthermore, in order to improve the photopolymerization promoting ability, in addition to the above photopolymerization accelerator, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropane Addition of oxycarboxylic acids such as acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid and dimethylolpropionic acid is effective.
Specific examples of the thermal polymerization initiator include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, Organic peroxides such as 2,5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate, azobisisobutyronitrile, methyl azobisisobutyrate, azobiscyanovaleric acid, etc. Azo compounds are preferably used. Among these, use of an organic peroxide is preferable, and benzoyl peroxide is more preferable.

  The content of the polymerization initiator (c) that can be used for the composite resin layer or the acrylic resin layer constituting the composite resin artificial tooth of the present invention is the proportion of fillers and polymerizable monomers having different thermal conductivities. It can be appropriately selected depending on the case, but when used in the composite resin layer, it can be used without particular limitation as long as it is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer (A). it can. Preferably it is the range of 0.05-5, More preferably, it is the range of 0.1-5 weight part. (C) When the blending amount of the polymerization initiator is less than 0.01 parts by weight, the polymerization does not proceed sufficiently and the material properties are deteriorated. Defects such as excessive shrinkage, cracking, white turbidity, and chipping may occur.

  As the (d) chain transfer agent that can be used in the composite resin layer or the acrylic resin layer constituting the composite resin artificial tooth of the present invention, a known compound can be used without any limitation. Specifically, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene and α-pinene. , Α-methylstyrene damer, and the like. Among these chain transfer materials, terpenoid compounds are particularly preferable. These chain transfer agents can be used not only alone but also in combination. The content of these chain transfer agents is preferably in the range of 0.001 to 1 part by weight, more preferably 100 parts by weight of the polymerizable monomer (A) when used in the composite resin layer. The range is preferably 0.1 to 0.5 parts by weight. (D) When the chain transfer agent content is less than 0.001 part by weight, rapid polymerization and curing occurs during molding by heating and pressurization, and defects such as local shrinkage, cracking, white turbidity, and chipping may occur. There is sex. On the other hand, when it exceeds 1 part by weight, the polymerization and curing reaction is suppressed, so that the proportion of unreacted polymerizable monomer increases, and as a result, the material characteristics may be deteriorated.

  In addition to the components (a) to (d) above, the composite resin layer or the acrylic resin layer constituting the composite resin artificial tooth of the present invention includes an excipient represented by fumed silica, 2-hydroxy UV absorbers such as -4-methylbenzophenone, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, 2,5-ditertiary butyl-4-methylphenol, discoloration inhibitors, antibacterial materials, color pigments, and other conventionally known Ingredients such as additives can be optionally added as required.

  The method for producing the composite resin artificial tooth of the present invention is not limited at all. Examples include a compression molding method in which a paste-like or powdery material mixed with a liquid material is filled in a mold and heated under pressure, or an injection molding method in which the raw material is driven into the mold at a constant pressure. However, it is not limited to these. Among these, a method of producing a composite resin layer or an acrylic resin layer by individually polymerizing and curing by heating and pressurizing and laminating them is preferable.

  When the composite resin artificial tooth of the present invention has a single layer or a multilayer structure composed of a composite resin layer, chemical adhesion with the denture base cannot be expected, so an adhesive primer is used or a mechanical fit is obtained. Even if a maintenance hole is formed on the surface, there is no limitation. In the composite resin artificial tooth of the present invention, when at least one layer is a composite resin layer and at least one layer including a base layer that can be chemically bonded to the denture base is composed of an acrylic resin layer, There are no restrictions on the number and type, and a multi-layer structure can be adopted. Also, there are no restrictions on the shape and size, and there are no problems even if the shape and size are various.

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. Test methods for evaluating the performance of composite resin artificial teeth prepared in Examples and Comparative Examples are as follows.

(1) Bending test

Purpose of evaluation: To evaluate the bending strength of a test body molded with a composite resin composition.
Evaluation method:
After filling the prepared composite resin composition into a stainless steel mold (25 × 2 × 2 mm: rectangular parallelepiped mold), mold press pressure: 3 t, molding temperature: base layer 100 ° C./enamel layer 120 ° C., press time: 10 minutes Pressurization and thermoforming were performed under the conditions described above. Thereafter, the molded product was taken out from the mold and then immersed in water at 37 ° C. for 24 hours to obtain a test specimen.
The bending strength was measured using an Instron universal testing machine (Instron 5567, manufactured by Instron) at a distance between supporting points of 20 mm and a crosshead speed of 1 mm / min.

(2) Purpose of molded good product test evaluation:
Two-layer structure (acrylic resin composition and composite resin composition) molded using a simulated artificial tooth mold (two-layer structure in which base acrylic resin layer and composite resin layer with different layer thicknesses are laminated: Fig. 1) Evaluate the molding characteristics of the molded product.
Evaluation method:
After filling the acrylic resin composition into the base layer with a transitional change in thickness located at the bottom of the simulated artificial tooth mold (10 mm × 10 mm × 5 mm) shown in FIG. 1, pressurization and thermoforming were performed. . After that, the composite resin composition having a transitionally changing thickness located at the upper part of the cured acrylic resin layer was filled with the composite resin composition, and then subjected to pressure and heat molding. 100 molded articles were produced, and molding characteristics were evaluated by confirming cracks and chips generated in the simulated artificial teeth. The pressurization and thermoforming were performed under the conditions of mold press pressure: 3 t, base layer molding temperature: 100 ° C., composite resin layer molding temperature: 120 ° C., and press time: 10 minutes. As a result, a molded product having no defects such as cracks and chips was regarded as a non-defective product, and the yield rate was calculated. The acceptable range is 90 parts or higher.

(3) Interfacial adhesion confirmation test evaluation purpose:
Two-layer structure (acrylic resin composition and composite resin composition) molded using a simulated artificial tooth mold (two-layer structure in which base acrylic resin layer and composite resin layer with different layer thicknesses are laminated: Fig. 1) Observe the effect on the interface (bonding surface of the base layer and composite resin layer) when a forced pressure load is applied to the molded product.
Evaluation method:
Ten of the 100 artificial artificial teeth determined to be non-defective by the molded non-defective test were randomly selected and used as test specimens. The compression resistance (pressure test) of this specimen was measured using an Instron universal testing machine (Instron 5567, manufactured by Instron). Fig. 2 shows the pressure direction of the specimen. Shown in The measurement conditions were a crosshead speed of 1 mm / min, and the effect produced on the interface when displaced by 0.5 mm was observed and evaluated.
Evaluation criteria were as follows: ○: unchanged, Δ: partially whitened, x: entire interface was whitened or separated at the interface

The compounds used in Examples of the present invention and the abbreviations of the compounds are shown below.
Polymerizable monomer
UDMA: Urethane dimethacrylate
Bis-GMA: 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane
TEGDMA: Triethylene glycol dimethacrylate filler silica: average particle size 0.9 μm, BET specific surface area: 4.0 m ² / g, silane-treated with γ-methacryloxypropyltrimethoxysilane and used for preparation of the composition.
Polymerization initiator
BPO: Benzoyl peroxide monofunctional (meth) acrylate polymerizable monomer
MMA: Methyl methacrylate non-crosslinkable (meth) acrylate polymer
PMMA: Polymethylmethacrylate 50 parts average particle size 50μm

According to the composition shown in Table 1, acrylic resin compositions (B1 to B9 and BC1) were prepared.
According to the composition shown in Table 2, composite resin compositions (E1 to E11 and EC1) were prepared.

A bending test was carried out using the prepared composite resin composition, and the results are shown in Table 3.

The composite resin compositions E1 to E3 are systems in which the blending amount of the filler as the component (b) is changed. (B) The bending strength increases as the amount of filler increases.

The composite resin compositions E2 and E4 are systems in which (a) the types of polymerizable monomers (UDMA and Bis-GMA) are partially changed. Although the type and amount of the chain transfer agent were the same, sufficient bending strength was shown although there was a slight difference in bending strength due to the influence of the type of polymerizable monomer.

The composite resin compositions E2, E5, and E6 are systems in which the amount of the (c) polymerization initiator is changed. The type and amount of chain transfer agent were the same and were at the same level without affecting the bending strength.

The composite resin compositions E2, E7, and E8 are systems in which the type (γ-terpinene, α-terpinene, β-terpinene) is changed although the blending amount of the (d) chain transfer agent is the same. Even if the type of chain transfer agent was changed, it was at the same level without affecting the bending strength.

The composite resin compositions E2, E9, E10, and E11 are systems in which the blending amount of the (d) chain transfer agent is changed. In the range of 0.06 (E9) to 0.6 (E10) parts by weight of the chain agent transfer material, the bending strength was not affected, but the level was 1.0 (E11) parts by weight. It was observed that the bending strength slightly decreased.

In composite resin composition EC1, since (d) the chain transfer agent was not blended, a large number of bubbles were involved and cracks were also generated, making it impossible to produce a bending specimen.


Next, using the prepared composite resin composition and acrylic resin composition, a molded good product test and an interfacial adhesion state confirmation test were conducted, and the results are shown in Table 4.

As shown in Table 4, in Examples 1 to 16, simulated artificial teeth were molded using an acrylic resin composition and a composite resin composition containing a chain transfer agent. As a result, generation of bubbles was not observed at all, while cracks were partially generated but extremely small, and the yield rate was 90 parts or more. Moreover, as a result of conducting an interfacial adhesion confirmation test using the good artificial artificial teeth, it was confirmed that there were no problems at the interface and the two compositions were firmly bonded.

As shown in Table 4, in Comparative Examples 1 and 2, simulated artificial teeth were molded using a composite resin composition in which no chain transfer agent was blended. In any case, the occurrence of bubbles and cracks was very large, and it was confirmed that the artificial artificial teeth could not be molded, and the yield rate was 16 parts in Comparative Example 1 and 8 parts in Comparative Example 2, which was very low. Among them, samples that were non-defective were taken out and subjected to an interface adhesion status confirmation test. As a result, it was confirmed that the entire interface where the two compositions were bonded to each other was whitened or separated and dropped.

By adding a chain transfer agent to the composite resin artificial tooth composition, it is possible to uniformly polymerize and harden the material properties due to the addition of the chain transfer agent. Suppresses cloudiness and chipping, and achieves excellent physical properties.

Claims (5)

A single-layer or multilayer composite resin artificial tooth,
(A) polymerizable monomer (b) filler (c) polymerization initiator, and
(D) A composite resin artificial tooth comprising a composite resin layer containing a chain transfer agent.
The composite resin artificial tooth has a multilayer structure,
At least one of the composite resin layers;
(E) monofunctional (meth) acrylate polymerizable monomer (f) non-crosslinkable (meth) acrylate polymer (c) polymerization initiator, and
(D) comprising at least one acrylic resin layer containing a chain transfer agent,
The composite resin artificial tooth according to claim 1, wherein a base layer capable of being chemically bonded to a denture base is composed of the acrylic resin layer.
In each component contained in the composite resin layer of the composite resin artificial tooth (a) 10 to 70 parts by weight of the polymerizable monomer,
(B) 30 to 90 parts by weight of filler
And with respect to 100 parts by weight of the polymerizable monomer,
(C) 0.01-10 parts by weight of a polymerization initiator,
(D) Chain transfer agent is contained in 0.001-1 weight part, The composite resin artificial tooth of Claim 1-2 characterized by the above-mentioned.
The composite resin tooth according to claim 1, wherein the (d) chain transfer agent is a terpenoid compound.
5. The method of manufacturing a composite resin artificial tooth according to claim 1, wherein the composite resin artificial tooth is laminated by polymerizing and curing the composite resin layer alone or the composite resin layer and the acrylic resin layer sequentially under heating and pressing conditions. Production method.