JP2008081446A - Photopolymerizable resin composition for manufacturing dental prosthesis pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable resin composition for manufacturing a dental prosthesis (e.g. clasp) pattern, which has proper viscosity before polymerization, excellent operability and moldability, high toughness after polymerization and is not broken at the time of attachment and detachment from a gypsum mold. <P>SOLUTION: The photopolymerizable resin composition comprises (a) 100 parts by wt. of a polymerizable unsaturated monomer containing ≥3 wt.% of an unsaturated monomer having at least one caprolactone unit in one molecule, (b) 50-400 parts by wt. of an organic filler, (c) 0.001-5 parts by wt. of a photopolymerization initiator and (d) 0.01-10 parts by wt. of a reducing agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photopolymerization resin composition for producing a dental prosthesis pattern. More specifically, the present invention provides, for example, a metal component that provides denture gripping (resistance to lateral movement), maintenance (resistance to attachment / detachment), and support (resistance to occlusal pressure) in making a partial denture. The present invention relates to a photopolymerization resin composition suitable for producing a casting clasp prototype, that is, a clasp pattern showing a theoretical shape with respect to maintenance force, durability, and the like when a casting clasp is produced by the lost wax method. .

Clasps are used in more than 90% of main and indirect maintenance devices for partial dentures. However, the manufacturing method is particularly complicated in a casting clasp, and the present situation is that the maintenance force, the fitting accuracy, the form of a given arm portion, etc. are not always satisfactory.
In the conventional casting clasp manufacturing method, first, a jaw impression in a patient's oral cavity is collected, and a working model is made of cemented gypsum or the like. Next, in order to design a clasp as a maintenance device, the maintenance tooth portion on the work model is surveyed. The survey here is to find the remaining teeth on the model and the maximum ridges of the ridge, and at the same time, to investigate the parallel relationship between them, determine the denture attachment / detachment direction, determine the maintenance teeth, block out part This is an extremely important task in the production of dentures, such as clarification, measurement of undercut amount, and determination of clasp position.

Important factors that affect the clasp maintenance force include the length, thickness, cross-sectional shape of the clasp arm, the Young's modulus of the alloy used, the set undercut amount, the curvature of the maintenance tooth surface, and the like. When manufacturing a casting clasp using a paraffin wax pattern, the maintenance force of the clasp can be controlled by selecting the amount of undercut to be used, the thickness of the pattern, and different cross-sectional shapes. When designing a denture, a clasp design corresponding to the state of the maintenance periodontal tissue is required.
When the design / blocking out of the working model is completed, the maintenance tooth portion blocked out according to the design is taken again (double impression) in order to produce a clasp wax pattern, and the working model is replaced with a model investment material. Next, with consideration given to accurately controlling the clasp maintenance force, the paraffin wax clasp pattern is affixed to the model investment using an adhesive while bending with fingers, and the rest and legs are molded. , Plant sprue. Next, without removing the paraffin wax clasp pattern from the model investment material, the model investment material was buried in the casting investment material, and after the investment material was cured, the paraffin type clasp pattern was heated in the furnace. After incineration, the melted metal is poured into the mold of the Kraspup pattern that is created, and after cooling, index polishing is performed to complete the clasp. (Hereafter, this method is referred to as “mold burying method”.)

As described above, the manufacturing method of the casting clasp and the material for forming the clasp pattern are paraffinic waxes, and thus the following problems are involved.
(A) Paraffinic wax cannot be elastically deformed and plastically deformed, and therefore cannot be removed from the undercut portion of the maintenance tooth on the work model through the maximum ridge.
If it is forcibly removed, it will be permanently deformed and accurate adaptation will not be obtained. This makes it impossible to create an accurate clasp with controlled maintenance. Therefore, the paraffin wax clasp pattern always makes a double impression of the working model, replaces it with a model investment material, forms a clasp pattern on the model investment material, and embeds the model investment material with the casting investment material. You must carry out the “Buying method for each mold”. For this reason, the clasp manufacturing process is complicated and requires a long time, and the material cost is also great.

  (B) The paraffin wax clasp pattern does not adhere to the model investment material or plaster, so a special adhesive must be used. Accordingly, the clasp having an error of about 50 μm in thickness of the adhesive cannot be obtained, and a clasp having a good fit cannot be obtained.

  (C) The paraffin wax clasp pattern is pressed with fingers using an adhesive and adhered to the model investment material. At that time, the investment material is low in strength and the particles of the investment material are peeled off. The form and surface properties deteriorate. Further, the particles from which the investment material has peeled off adhere to the clasp pattern of the paraffinic wax, and a casting clasp having a good surface property cannot be obtained.

  (D) The paraffin wax used for the clasp pattern is a polymer having a high crystallinity and a relatively low molecular weight, and is a metal-like substance having a glass transition temperature Tg and a melting point Tm very close to each other and having the same melting point and glass transition point. Therefore, if the temperature rise rate is too high when the wax is heated and incinerated, the melted wax will boil, and the wax that has become gas will expand, so it will be pressurized rapidly, causing cracks in the investment material or roughening of the inner surface of the investment material May occur.

  Instead of paraffin wax, it has been proposed to use a dental material using a photopolymerization resin for the production of a clasp pattern, which has been put to practical use. For example, a clasp pattern production photopolymerization resin using an unsaturated monomer that is solid at room temperature, which is an application of the present applicant (Patent Document 1), a material for producing a similar pattern, and a urethane acrylate resin liquid A mixture of polymer powders such as styrene (Patent Document 2), a mixture of polyethylene glycol dimethacrylate resin liquid and polymethyl methacrylate macromonomer (Patent Document 3), etc. have been proposed. Dissatisfaction remained in terms of sex. In addition, a polymer liquid of polycaprolactone mixed with a resin liquid such as polyethylene glycol dimethacrylate (Patent Document 4) has been proposed. However, polycaprolactone powder can be chemically bonded to an unsaturated monomer. Since it does not have a functional group, there remains anxiety about deformation and breakage due to stress when it is detached from the plaster model.

Japanese Unexamined Patent Publication No. 1-110609 JP-A-62-115013 JP-A-5-132408 Japanese Patent Laid-Open No. 8-119823

  As a result of diligent research in view of conventional techniques, the present inventors have completed the present invention, and the present invention has an appropriate viscosity before polymerization, excellent operability and formability, and toughness after polymerization. Providing a photopolymerization resin composition for producing a dental prosthesis pattern that can be stably attached to and detached from a plaster model, and that does not break, and more specifically, operability before polymerization is conventionally known. It is more equivalent to the paraffinic wax used as this kind of material, has sufficient toughness after polymerization, can be detached from the plaster model stably, does not break, and has excellent strength and durability An object of the present invention is to provide a photopolymerization resin composition for producing a prosthesis pattern.

  In order to solve the above-mentioned problems, the working photopolymerization resin composition for producing a dental prosthesis pattern according to the present invention is a) Polymerizable containing 3% by weight or more of an unsaturated monomer having at least one caprolactone unit in one molecule. 100 parts by weight of an unsaturated monomer, b) 50 to 400 parts by weight of an organic filler, c) 0.001 to 5 parts by weight of a photopolymerization initiator, and d) 0.01 to 10 parts by weight of a reducing agent. Features.

Photopolymerization resin composition for the production of dental prosthesis patterns can be used for clasp patterns, inlay patterns, onlay patterns, lingual bar patterns, paratalbar patterns, skeleton patterns, cast floor patterns, crown bridge patterns and other dental prosthetic casting patterns. Used for production. Hereinafter, the case where it uses for manufacture of a clasp pattern is demonstrated.
Since this photopolymerization resin composition has the same viscosity, operability, and moldability as conventional paraffin wax for producing clasp patterns before polymerization, a plaster model (work model) A clasp pattern can be formed above and cured by irradiation with polymerization light. Of moderate viscosity, operability, and moldability required before polymerization, moderate viscosity is mainly necessary because the clasp pattern is stuck to the extent that it does not peel off or fall off from the plaster model. Yes, operability and formability are characteristics that are mainly necessary for forming a clasp pattern on a plaster model. The polymer obtained by polymerizing this clasp pattern working photopolymerization resin composition has sufficient toughness (energy value until failure), and this clasp pattern cured product is removed from the undercut portion of the plaster model to the maximum height. Even if it is spread over the part and removed from the gypsum model, it will return to its original shape accurately without any breakage, and a stable operation can be performed. The clasp pattern cured product removed from the gypsum model forms a sprue, buried with a casting investment material, and after the investment material is cured, the clasp pattern cured product is incinerated, and then the clasp pattern formed on the investment material. A metal clasp can be obtained by pouring molten metal into the negative cavity, taking it out after cooling, and polishing.
The production of the dental prosthesis pattern other than the clasp pattern may be performed in accordance with the above description.

  The polymerizable unsaturated monomer preferably contains 5 to 20% by weight of an unsaturated monomer having at least one caprolactone unit in the molecule.

  Moreover, it is preferable that the number of repeating units of the caprolactone unit of the unsaturated monomer having at least one caprolactone unit in one molecule is in the range of 1 to 10.

  The photopolymerization initiator is preferably at least one of an α-diketone compound, a ketal compound, an anthraquinone compound, a thioxanthone compound, a benzoin alkyl ether compound, and derivatives thereof.

Since the present invention is configured as described above, the following effects can be obtained.
In other words, the viscosity before polymerization is appropriate, the operability and moldability are excellent, and the toughness (energy value until failure) after polymerization is high, and it does not break when it is detached from the plaster model. Thus, it is possible to obtain a photopolymerization resin composition for producing a dental prosthesis pattern which is excellent in strength and durability, yet returns to its original shape and can be stably operated.

The best mode for carrying out the invention will be described below, and the present invention will be described in more detail. Of course, the present invention is not limited to the following embodiments.
The unsaturated monomer having at least one caprolactone unit in one molecule used in the present invention is a polymerizable unsaturated monomer that exhibits high toughness in the cured product after polymerization, and has the following general formula (1 ) Represented by polycaprolactone-modified alkyl (meth) acrylate. Specific examples include polycaprolactone-modified hydroxyethyl (meth) acrylate, polycaprolactone-modified hydroxypropyl (meth) acrylate, and polycaprolactone-modified hydroxybutyl (meth) acrylate. Etc.

As the repeating number m of the caprolactone unit of the unsaturated monomer having at least one caprolactone unit in one molecule, 1 to 25 can be adopted. If the number of repetitions m of caprolactone units exceeds 25, the molecular chain becomes long, leading to a decrease in the cross-linking density after polymerization, and the strength and durability are inferior. Among these, 1-10 are preferable.
As the repeating number n of methylene of an unsaturated monomer having at least one caprolactone unit in one molecule, 1 to 10 can be adopted. When the number of methylene repeats exceeds 10, the molecular chain becomes long, leading to a decrease in the crosslink density after polymerization, and the strength and durability are inferior. Among these, 2-4 are preferable.
Moreover, the urethane (meth) acrylate obtained by making organic isocyanate and the said polycaprolactone modified | denatured alkyl (meth) acrylate react is also mentioned.
These unsaturated monomers having at least one caprolactone unit in one molecule can be used alone or in admixture of two or more.

As the polymerizable unsaturated monomer used in combination with an unsaturated monomer having at least one caprolactone unit in one molecule, a polymerizable unsaturated monomer usually used in a dental photopolymerization resin is used. Monofunctional (meth) acrylate and polyfunctional (meth) acrylate can be exemplified.
Monofunctional (meth) acrylates include methyl methacrylate (MMA), ethyl methacrylate (EMA), isopropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxypropyl methacrylate, tetrahydroflur Mention may be made of furyl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, and acrylates thereof.

  Polyfunctional (meth) acrylates include 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis (methacryloxyphenyl) propane, 2,2-bis [4- (2-hydroxy-3-methacrylic). Roxypropoxy) phenyl] propane, bisphenol A type epoxy diacrylate, bisphenol A type epoxy dimethacrylate, phenol A (PO) (EO) modified diacrylate, phenol A (PO) (EO) modified dimethacrylate, (EO) modified ethylene Glycol diacrylate, (EO) modified ethylene glycol dimetallate, 1,4-butadiol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate Dipropylene glycol diglycidyl ether diacrylate, triglycerol diacrylate, glycerol dimethacrylate, glycerol acrylate / methacrylate, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxypoly) Ethoxyphenyl) propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butane Diol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylol proppant Methacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, pentaerythritol tetramethacrylate, di-2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate and their acrylates, and molecules Mention may be made of methacrylates and acrylates having urethane bonds. In the polyfunctional (meth) acrylate, (EO) means ethylene oxide, and (PO) means propylene oxide.

  The polymerizable unsaturated monomer used in combination with the unsaturated monomer having at least one caprolactone unit in one molecule is a (meth) acrylic acid ester derivative or alkylene glycol di (meth) acrylate. , Alkyl di (meth) acrylates, bisphenol A-alkyl di (meth) acrylates, urethane di (meth) acrylates, urethane tri (meth) acrylates, urethane tetra (meth) acrylates, hydroxyalkyl (meth) acrylates, etc. Can also be classified.

These polymerizable unsaturated monomers are used by mixing so as to be compatible with an unsaturated monomer having at least one caprolactone unit in one molecule. These polymerizable unsaturated monomers can be used alone or in admixture of two or more. These polymerizable unsaturated monomers are compatible with an unsaturated monomer having at least one caprolactone unit in one molecule, and are preferably liquid at room temperature. Even if it is solid, it cannot be used. In the case of a solid at normal temperature, it may be used, for example, in a liquid state in a heated atmosphere.
Then, these polymerizable unsaturated monomers and unsaturated monomers having at least one caprolactone unit in one molecule are used in the form of a mixture beforehand. A polymerized resin composition (for example, for clasps, a clasp pattern-forming photopolymerization resin composition; the same shall apply hereinafter) may be prepared, and each may be prepared as a dental prosthesis pattern-forming photopolymerization resin. It may be used to mix in preparing the composition.

  The content of the unsaturated monomer having at least one caprolactone unit in one molecule needs to be 3% by weight or more based on the total polymerizable unsaturated monomer. If it is less than 3% by weight, the toughness of the cured product after polymerization is low, and it tends to break when it is removed from the plaster model. In addition, if the content of the unsaturated monomer having at least one caprolactone unit in one molecule is excessively large, the degree of polymerization during light irradiation may decrease, and a large amount of unpolymerized portions may remain on the surface of the cured product. The content of the unsaturated monomer having at least one caprolactone unit in one molecule is preferably 3 to 30% by weight, more preferably 5 to 20% by weight.

  Examples of the organic filler used in the present invention include polyolefin powder (polyethylene powder, polypropylene powder, etc.), polyethylene-polyvinyl acetate powder, polyacrylate powder (polymethyl acrylate, polyethyl acrylate, etc.), polymethacrylate. Acid ester powder (polymethyl methacrylate, polyethyl methacrylate, etc.), methacrylate copolymer powder (copolymer of polymethyl methacrylate and polyethyl methacrylate, etc.), acrylate copolymer powder (poly Copolymer of methyl acrylate and polyethyl acrylate), cross-linked methacrylate powder (polymethyl methacrylate cross-linked with trimethylolpropane trimethacrylate, etc.), styrene-butadiene copolymer powder Acrylonitrile - styrene copolymer powder, acrylonitrile - styrene - butadiene copolymer powder, there are nylon powder and the like, they are alone or may be used as a mixture of two or more. The addition amount is preferably 50 to 400 parts by weight with respect to 100 parts by weight of the polymerizable unsaturated monomer. The organic filler is mainly used to ensure molding operability before polymerization of the dental prosthesis pattern production photopolymerization resin composition, and within this range, it is the same as paraffinic wax Such as high viscosity, shape retention, and plasticity that can be deformed with a finger. When the organic filler is less than 50 with respect to 100 parts by weight of the polymerizable unsaturated monomer, the photopolymerization resin composition for producing a dental prosthesis pattern before polymerization is too soft and has a strong adhesiveness. Prosthesis pattern (for example, clasp pattern; the same applies hereinafter) becomes difficult, and when it exceeds 400 parts by weight, the photopolymerization resin composition for producing a dental prosthesis pattern becomes hard, and the dental prosthesis on the plaster model The moldability of the pattern is poor and cracks occur, and it is not preferable because it does not stick to the gypsum model and peels off or falls.

  As the photopolymerization initiator used in the present invention, α-diketone compounds, ketal compounds, anthraquinone compounds, thioxanthone compounds, and benzoin alkyl ether compounds are effective, specifically, α-diketone compounds. As the compound, d, l camphorquinone, benzyl, diacetyl, acenaphthenequinone, 9,10-phenanthrenequinone and the like are effective. Of these, d, l camphorquinone and benzyl are particularly preferred. Ketal compounds include benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl di (β-phenylethyl) ketal, benzyl di (2-methoxyethyl) ketal, benzyl di (2-ethoxyethyl) ketal, benzyl di (2-methoxy Ethoxyethyl) ketal, benzyldi (2-ethoxyethoxyethyl) ketal, 4,4'-dimethylbenzyldimethyl ketal, 2,2-dimethoxybenzyl diethyl ketal, 4,4'-dichlorobenzyl-diethyl ketal, 4,4'- Dichlorobenzyldipropyl ketal and the like are effective. Of these, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl) ketal, and 4,4'-dichlorobenzyl dimethyl ketal are particularly preferred.

As anthraquinone compounds, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone and the like are effective. Among these, anthraquinone, 1-chloroanthraquinone, and 1,2-benzanthraquinone are particularly preferable. Thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethyloxanthone, 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone, 2 -Chloro-7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide and the like are effective. Among these, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone are particularly preferable.
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin butyl ether and the like are effective as the benzoin alkyl ether compounds. Of these, benzoin butyl ether is particularly preferred.

  The above photopolymerization initiators may be used alone or in combination of two or more. These photopolymerization initiators are blended in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of a polymerizable unsaturated monomer containing 3% by weight or more of an unsaturated monomer having at least one caprolactone unit in one molecule. It is preferable that When the blending amount is less than 0.001 part by weight, the reactivity is poor, the curing time becomes long, and the curing depth becomes small. If the blending amount exceeds 5 parts by weight, the excess catalyst functions as a plasticizer, so that the strength of the cured product is lowered.

As the reducing agent used in the present invention, the photosensitizer is reduced when the reverse sensitizer is in an excited state, but when the photosensitizer is not excited by the active energy ray, the photosensitizer is used. Those that have a reduction ability that cannot be reduced are used. Examples of reducing agents include propylamine, n-butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, di-n-butylamine, dipentylamine, 2-dimethylaminoethanol, trimethylamine, triethylamine, tripropyl. There are amines, tri-n-butylamine, tripentylamine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, triethanolamine and long chain aliphatic amines.
Examples of reducing agents containing aromatic groups include N, N'-dimethylaniline, N, N'-dimethyl-p-toluidine, p-tolyldiethanolamine, m-tolyldiethanolamine, N-methyldiphenylamine, 2-dimethylaminobenzoic acid. Examples include ethyl acetate, ethyl 4-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate.

  The amount of these reducing agents added is 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymerizable unsaturated monomer containing 3% by weight or more of an unsaturated monomer having at least one caprolactone unit in one molecule. It is preferable. When the addition amount is less than 0.01 parts by weight, the reactivity is poor, the curing time is prolonged, and the curing depth is reduced. If the added amount exceeds 10 parts by weight, the storage stability is deteriorated, and the technical operation margin time in normal room lighting becomes very short.

  In addition, a polymerization inhibitor, a colorant, an ultraviolet absorber and the like can be added to the composition of the present invention as desired.

  When this dental prosthesis pattern production photopolymerization resin composition is used to produce a clasp pattern, it is desirable to provide a ready-made product that is pre-shaped into a shape suitable for producing a clasp pattern, Table 1 shows an example of the shape.

  These shapes are important when controlling the maintenance force at the time of partial denture attachment and detachment and mastication, but are not limited to those shown in Table 1.

  Next, although an example is shown and explained in more detail with a comparative example, the present invention is not limited by these examples.

(Example 1)
As an unsaturated monomer having one caprolactone unit in one molecule, polycaprolactone-modified hydroxyethyl methacrylate (HEMA: 1 mol of caprolactone of hydroxyethyl methacrylate) was used. As the polymerizable unsaturated monomer used in combination, a blend of polyethylene glycol dimethacrylate and glycerol dimethacrylate in a weight ratio of 90:10 was used.
100 parts by weight of a mixture prepared by adding 5% by weight of polycaprolactone-modified hydroxyethyl methacrylate to this blend, 0.5 parts by weight of d, l camphorquinone as a photopolymerization initiator, and p-tolyldiethanolamine 0% as a reducing agent The liquid component was prepared by adding and dissolving 5 parts by weight.
To the liquid component, 150 parts by weight of polymethyl methacrylate powder and 25 parts by weight of polyethylene-polyvinyl acetate copolymer powder are added as an organic filler, and the mixture is stirred and mixed. A polymerized resin composition was prepared.

  About the obtained photopolymerization resin composition, bending strength, a strain energy value, and surface unpolymerization were evaluated according to the following evaluation methods. The results are as shown in Table 2. When the viscosity, operability, and moldability of the photopolymerized resin composition before polymerization were confirmed with a finger, there was no stickiness, it was rich in plasticity, and was equivalent to a paraffin wax pattern.

(1) Bending strength and strain energy value Using a mold having a 2 mm thick stainless steel plate with a 2 mm wide and 25 mm long hole, the resulting photopolymerization resin composition was filled, and a polyethylene film was applied from above and below. In the state where the glass plate was pressed through, a visible light irradiator Labolite-LVII (manufactured by GC) was irradiated with light for 5 minutes from the upper and lower surfaces. The test piece was released from the mold. The obtained test piece was measured using an autograph tester (MODEL AGF-500D: manufactured by Shimadzu Corporation) at a crosshead speed of 1.0 mm / min and a distance between fulcrums of 20 mm.
The strain energy value was calculated from the bending strength and the energy required to break from the obtained maximum load.

(2) Unpolymerized surface About 1 g of the obtained photopolymerized resin composition was collected on a glass plate and shaped into a disk having a diameter of about 10 mm using a plastic spatula, and then the visible light irradiator Labolite-LVII ( For 5 minutes. The situation when the light irradiation surface of the cured body was scratched with the spatula was evaluated. Evaluation was made according to the following criteria.
○: The surface is not scratched and there is almost no unpolymerized layer. Δ: The surface is scratched, but there are few unpolymerized layers (minor scratches).
X: Scratches on the surface and many unpolymerized layers (scratches with a depth of about 1 mm)

(Examples 2 and 3)
Example 2 was the same as Example 1 except that 100 parts by weight of the mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 1 was 10% by weight was used. Example 1 is the same as Example 1 except that 100 parts by weight of a mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 1 is 20% by weight is used.

The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Example 2 and Example 3 in Table 2.
Moreover, when the viscosity, operability and moldability before polymerization of the photopolymerized resin compositions obtained as Example 2 and Example 3 were confirmed with fingers, they were all non-sticky, rich in plasticity, and paraffinic wax. It was equivalent to the pattern.

(Comparative Examples 1 and 2)
Comparative Example 1 was the same as Example 1 except that 100 parts by weight of a mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 1 was 1% by weight was used. Comparative Example 2 was an example. Example 1 is the same as Example 1 except that 100 parts by weight of a mixture prepared without using polycaprolactone-modified hydroxyethyl methacrylate is used.

The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Comparative Example 1 and Comparative Example 2 in Table 2.
In addition, when the viscosity, operability and moldability before polymerization of the photopolymerized resin compositions obtained as Comparative Examples 1 and 2 were confirmed with fingers, none of them were sticky, rich in plasticity, and paraffinic wax It was equivalent to the pattern.

  According to Table 2, it can be seen that when the unsaturated monomer having a caprolactone unit in one molecule is not used or the amount used is small, the strain energy value is clearly lowered.

Example 4
As an unsaturated monomer having five caprolactone units in one molecule, polycaprolactone-modified hydroxyethyl methacrylate (HEMA containing 5 mol of caprolactone) was used. As the polymerizable unsaturated monomer used in combination, a blend of polyethylene glycol dimethacrylate and glycerol dimethacrylate in a weight ratio of 90:10 was used.
100 parts by weight of a mixture prepared by adding 5% by weight of polycaprolactone-modified hydroxyethyl methacrylate to this blend, 0.5 parts by weight of d, l camphorquinone as a photopolymerization initiator, and p-tolyldiethanolamine 0% as a reducing agent The liquid component was prepared by adding and dissolving 5 parts by weight.
To the liquid component, 250 parts by weight of polymethyl methacrylate powder and 10 parts by weight of polyethylene-polyvinyl acetate copolymer powder are added as organic fillers, mixed with stirring, and further put into a vacuum deaerator to remove bubbles, and light. A polymerized resin composition was prepared.

The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Example 4 in Table 3.
Further, when the viscosity, operability, and moldability before polymerization of the obtained photopolymerization resin composition were confirmed with a finger, there was no stickiness, it was rich in plasticity, and was equivalent to a paraffin wax pattern.

(Examples 5 and 6)
Example 5 was the same as Example 4 except that 100 parts by weight of the mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 4 was 10% by weight was used. Example 4 is the same as Example 4 except that 100 parts by weight of the mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Step 4 is 20% by weight is used.

The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Example 5 and Example 6 in Table 3.
Further, when the viscosity, operability and moldability before polymerization of the photopolymerized resin compositions obtained as Example 5 and Example 6 were confirmed with fingers, none of them were sticky, rich in plasticity, and paraffinic wax. It was equivalent to the pattern.

(Comparative Example 3)
Example 4 is the same as Example 4 except that 100 parts by weight of a mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate is 31% by weight is used.
The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Comparative Example 3 in Table 3.
When the viscosity, operability and moldability before polymerization of the obtained photopolymerization resin composition were confirmed with a finger, there was no stickiness, it was rich in plasticity, and was equivalent to a paraffin wax pattern.

  According to Table 3, when the usage-amount of the unsaturated monomer which has a caprolactone unit increases, superposition | polymerization by light irradiation will fall, a surface unpolymerized part will increase on the hardened | cured body surface, and it turns out that bending strength falls.

(Example 7)
As an unsaturated monomer having 10 caprolactone units in one molecule, polycaprolactone-modified hydroxyethyl methacrylate (HEMA containing 10 mol of caprolactone) was used. As the polymerizable unsaturated monomer used in combination, a blend of polyethylene glycol dimethacrylate and glycerol dimethacrylate in a weight ratio of 90:10 was used.
100 parts by weight of a mixture prepared by adding 3% by weight of polycaprolactone-modified hydroxyethyl methacrylate to this blend, 0.5 parts by weight of d, l camphorquinone as a photopolymerization initiator, and p-tolyldiethanolamine 0% as a reducing agent The liquid component was prepared by adding and dissolving 5 parts by weight.
To the liquid component, 400 parts by weight of polymethyl methacrylate powder as an organic filler was added and mixed with stirring. The mixture was further placed in a vacuum defoamer to remove bubbles to prepare a photopolymerization resin composition.

The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Example 7 in Table 4.
Further, when the viscosity, operability, and moldability before polymerization of the obtained photopolymerization resin composition were confirmed with a finger, there was no stickiness, it was rich in plasticity, and was equivalent to a paraffin wax pattern.

(Examples 8 and 9)
Example 8 is the same as Example 7 except that 100 parts by weight of the mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 7 is 5% by weight is used. Example 7 was the same as Example 7 except that 100 parts by weight of a mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 7 was 10% by weight was used.

The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Example 8 and Example 9 in Table 4.
Further, when the viscosity, operability and moldability before polymerization of the photopolymerized resin compositions obtained as Example 8 and Example 9 were confirmed with fingers, none of them were sticky, rich in plasticity, and paraffinic wax. It was equivalent to the pattern.

(Comparative Example 4)
Example 7 is the same as Example 7 except that 100 parts by weight of the mixture prepared so that the polycaprolactone-modified hydroxyethyl methacrylate in Example 7 is 31% by weight is used.
The resulting photopolymerized resin composition was evaluated for bending strength, strain energy value, and surface unpolymerization according to the evaluation method described in Example 1. The results are as shown in Comparative Example 4 in Table 4.
When the viscosity, operability and moldability before polymerization of the obtained photopolymerization resin composition were confirmed with a finger, there was no stickiness, it was rich in plasticity, and was equivalent to a paraffin wax pattern.

  According to Table 4, when the amount of the unsaturated monomer having a caprolactone unit is increased, the polymerization due to light irradiation is decreased, the surface unpolymerized portion is slightly increased on the cured body surface, and the bending strength is decreased. .

Claims (5)

a) 100 parts by weight of a polymerizable unsaturated monomer containing 3% by weight or more of an unsaturated monomer having at least one caprolactone unit in one molecule;
b) 50 to 400 parts by weight of organic filler,
c) 0.001 to 5 parts by weight of a photopolymerization initiator,
d) A dental prosthesis pattern-working photopolymerization resin composition comprising 0.01 to 10 parts by weight of a reducing agent.   2. The process for producing a dental prosthesis pattern according to claim 1, wherein the polymerizable unsaturated monomer contains 5 to 20% by weight of an unsaturated monomer having at least one caprolactone unit in the molecule. Photopolymerization resin composition.   The dental prosthesis pattern according to claim 1 or 2, wherein the number of repeating units of the caprolactone unit of an unsaturated monomer having at least one caprolactone unit in one molecule is in the range of 1 to 10. Production photopolymerization resin composition.   The photopolymerization initiator is one or more of α-diketone compounds, ketal compounds, anthraquinone compounds, thioxanthone compounds, benzoin alkyl ether compounds, and derivatives thereof. Or the dental prosthesis pattern manufacturing action photopolymerization resin composition of 3.   5. The photopolymerization resin composition for producing a dental prosthesis pattern according to claim 1, wherein the composition is for producing a clasp pattern.