JPH0625048B2 - Dental material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a dental material containing a specific (meth) acrylic acid ester compound.

[Conventional technology]

Currently, a number of dental materials made of synthetic polymers have been developed, and some of them have a composition consisting of a monomer, a polymerization initiator, and other components in the form of a material, which is polymerized and hardened at the time of use. . Examples of such materials include crown-restoring materials such as chemically-polymerized and photo-polymerized composites resin and immediate-curing resin (immediate-polymerization resin), composite-resin-tooth substance, metal-tooth substance, and tooth substance. -Long-term and temporary adhesives between teeth, chemical polymerization type and photopolymerization type pit and fissure sealing material (sealant), heat polymerization type and photopolymerization type artificial crown materials such as hard crown resin, Temporary crown materials such as polycarbonate crowns and immediate-curing resins for crowns, heat-curing type, room-temperature-curing type (flow-injection type), injection-molded acrylic resin and denture base materials such as adhesive floor resins, denture base There are lining materials, repair materials such as quick-setting resins for repair, impression materials such as agar, alginate, polysulfide rubber, silicone rubber and (meth) acrylic functional impression materials.

Of these, for example, composite resin and hard dental crown resin are monofunctional monomers, polyfunctional monomers, inorganic fillers mixed with radical polymerization initiators, dental crown resins, sealants, adhesives. Etc., a combination of a monofunctional monomer, a polyfunctional monomer and a radical polymerization initiator is used. Also, denture base, denture base lining material,
Polymethylmethacrylate (hereinafter referred to as PMM) is required for prosthesis materials such as immediate-curing resin for repair, because they are required to be colorless and transparent, easy to be colored, aesthetic, and good in processability.
Abbreviated as A), polyethylmethacrylate (hereinafter PE
A mixture of a polymer component (generally abbreviated as MA) (mostly powder), a monofunctional monomer component, a polyfunctional monomer component and a radical initiator is used.

Examples of these monomers include, as monofunctional monomer components, methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BM).
A), 2-hydroxyethyl methacrylate (HEM
_{A), H 2 C = C} (CH 3) COOC 2 H 4 OCOC 2 H 5 ( JP 62-17
8502) and the like, and as the polyfunctional monomer component, 1,6-hexanediol dimethacrylate (HD), ethylene glycol dimethacrylate (1
G), triethylene glycol dimethacrylate (3
G), bisphenol A diglycidyl dimethacrylate (Bis-GMA), trimethylolpropane trimethacrylate (TMPT), dipentaerythritol pentaacrylate (2P5A) and the like.

[Problems to be Solved by the Invention]

However, it is required that there is no strong unpleasant odor in the composite cavity resin, hard crown resin, immediate-curing resin for crown, sealant, adhesive, etc. because it is directly introduced into the oral cavity, and it does not have a strong unpleasant odor. It is required to have no irritation to skin, mucous membranes, etc. because it is likely to come into contact with the dental pulp, and it does not cause strength deterioration in the environment of the oral cavity because it stays in the oral cavity for a long time after hardening. From this viewpoint, it has been considered inconvenient that the polymer has a high water absorption rate.

In the case of prosthetic materials such as denture bases and denture base lining agents, there is no strong unpleasant odor because the dentist's dental technician manipulates them by hand or directly applies them to the mucous membrane of the oral cavity to perform patterning. It was requested that there should be no irritation to the skin and mucous membranes.

However, there is a problem that the above-mentioned monomer cannot meet any of the above-mentioned requirements (1) to (3).

For example, MMA, EMA, BMA, HEMA, HD, 1
Monomers such as G, 3G, TMPT, and 2P5A are as described above,
H ₂ C = C (CH ₃ ) COOC ₂ H ₄ OCOC ₂ H ₅ , B
Monomers such as is-GMA have a problem that the above cannot be satisfied, and even if these monomers are combined, they cannot satisfy all the above requirements, and it is desired to develop a composition capable of solving them. It was rare.

Further, in the case of a prosthesis material, a monomer component and a polymer component are mixed at an appropriate ratio and put in a predetermined mold, or introduced into the oral cavity to perform molding, and then taken out and polymerized at room temperature or under heating. It is important to be in a so-called dough stage for a suitable time during this molding, has no strong unpleasant odor, is hypoallergenic, and has an appropriate dough-forming time. It was desired to have a composition that also has:

[Means for solving problems]

In view of such a current situation, as a result of intensive studies to solve the above problems, the present inventors have found that the specific (meth) acrylic acid ester-based monomer has low odor and low irritation, and water absorption of the polymer. The present inventors have found that the rate is small and also have an appropriate dough-forming time, and have reached the present invention.

That is, the gist of the present invention is the following general formula [1] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkylene group having 1 to 15 carbon atoms, R ₃
Represents an alkylene group having 1 to 10 carbon atoms, and R ₄ has 1 carbon atom.
~ 15 alkyl groups are shown. ) A dental material containing a specific (meth) acrylic acid ester compound represented by the formula (4), a dental material containing a polyfunctional methacrylate copolymerizable with the compound, and further a monomer thereof. It is a dental material in which an organic polymer capable of dissolving or swelling is blended in the components.

Hereinafter, the case of using it as a prosthetic material will be mainly described, but the dental material of the present invention is not limited to this, and it is also suitably used for composites resin, crown resin, sealant, adhesive, etc. It is a thing.

In the present invention, conditions desired as a dental material, that is, low odor, low irritation, and water absorption rate of the polymer, mechanical strength, and further a dough-forming time required when used as a two-component prosthesis material In consideration of the above, in the above general formula [1],
The alkyl group of R ₁ preferably has 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, for the same reason, R ₂ and R ₃ in the general formula [1] are alkylene groups, but may be linear methylene or polymethylene, or may be polymethylene having a side chain, R ₂
Preferably has 1 to 10 carbon atoms, and 1 to 6
Is more preferable. For the same reason, R ₃ preferably has 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. Furthermore, for the same reason as above, R ₄ in the general formula [1] preferably has 1 to 10 carbon atoms in the alkyl group, and more preferably 1 to 7 carbon atoms. From the above, as specific examples of the specific (meth) acrylic acid ester-based compound that is particularly preferably used in the present invention,
The following compounds may be mentioned.

(Meta) represented by the above-mentioned general formula [1] in the present invention
Acrylic ester compound is a specific unsaturated carboxylic acid It is made by esterification reaction of alkyl alcohol (R ₄ -OH) with other unsaturated alcohols. And ester group-containing carboxylic acid Reaction with unsaturated carboxylic acids And ester group-containing alcohol It can also be produced by a reaction with, a reaction using a carboxylic acid halide instead of the above-mentioned carboxylic acid, a transesterification reaction between unsaturated carboxylic acid esters, and the like.

In the present invention, if necessary, other monomers copolymerizable with the specific (meth) acrylic acid ester compound represented by the general formula [1] may be used as long as they can maintain low odor and low irritation. Ingredients can also be included. Specific examples of the monomer include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate,
Cyclohexyl (meth) acrylate, n-hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di (meth) acrylate, nonaethylene glycol di ( (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1 9- nonanediol di (meth) acrylate, 1,10-decanediol di (meth)
Acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4
-Methacryloyloxypolyethoxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy-
2-hydroxypropoxy) phenyl] propane, di (methacryloyloxyethyl) trimethylhexamethylenediurethane, tetramethylolmethane tri (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate and the like can be mentioned. One or more of these can be blended, among which ethylene glycol di Methacrylate, triethylene glycol dimethacrylate, 1,6
-Hexanediol methacrylate, 2,2-bis (4
-Methacryloyloxyethoxyphenyl) propane,
It is preferable to use a polyfunctional methacrylate such as neopentyl glycol dimethacrylate or trimethylolpropane trimethacrylate as another copolymerizable monomer component in consideration of the mechanical strength of the obtained cured product.

The blending ratio of the (meth) acrylic acid ester compound represented by the general formula [1] of the present invention to the other monomer component capable of copolymerization depends on the degree of irritation of the other monomer component capable of copolymerization. The amount of the (meth) acrylic acid ester compound represented by the general formula [1] is 20% by weight, though it can be appropriately selected within a range that maintains low odor and low irritation.
It is preferably at least 30% by weight, and more preferably at least 30% by weight.

In the present invention, an organic polymer may be further blended and used as another component that can be dissolved or swelled in the monomers. Specific examples of the polymer component include PMM.
A, PEMA, MMA / EMA copolymer, MMA / BM
A copolymer, polystyrene, polybutyl methacrylate, MMA / styrene copolymer, EMA / BMA copolymer, EMA / styrene copolymer, polyacrylate, polymethacrylate, polyacrylonitrile, styrene /
Examples thereof include acrylonitrile copolymer, styrene / acrylonitrile / butadiene copolymer, polycarbonate resin, polyvinyl chloride, etc. Among them, PMMA, PE
MA, MMA / EMA copolymer, MMA / BMA copolymer, polystyrene, polybutyl methacrylate, MMA
/ Styrene copolymer, EMA / BMA copolymer, EMA
A / styrene copolymer and a mixture of these polymers with other polymers are preferable in order to exhibit appropriate solubility and swellability.

The molecular weight and the average particle diameter of the polymer are not particularly limited, but in view of the solubility / swellability with the monomer component of the present invention and the mechanical strength of the obtained cured product, the molecular weight is 10,000 to 1,500,000. Preferably 5
It is more preferable that the average particle size is 1 μm to 150 μm, and 10 is more preferable.
More preferably, it is in the range of μm to 100 μm.

Although the blending ratio of the polymer component and the total monomer component can be selected from a wide range, especially considering the mechanical strength of the cured product, the total monomer component is 1 to 140 parts by weight with respect to 10 parts by weight of the polymer component. To be a department
Preferably, the amount is 2 to 110 parts by weight, more preferably 4 to 85 parts by weight.

As a polymerization and curing agent for forming a prosthesis material, any of known compounds can be used, but in the case of curing by heating, a substance capable of decomposing upon heating to initiate polymerization, for example, benzoyl peroxide. , Cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, azobisisobutyronitrile and the like. In the case of polymerizing and curing at room temperature, for example, peroxides and amines,
A combination of peroxides and sulfinic acids, or peroxides and cobalt compounds can be used. When a combination of polymerization initiators is used, the composition may be divided into two, one may be blended with a peroxide and the other may be blended with an amine, a sulfinic acid, or a cobalt compound. The amount of the above curing agent used is 0.
It is preferably from 01 to 15% by weight, and 0.05 to 1
More preferably 0% by weight, 0.1 to 7% by weight
Is more preferable.

Further, in the case of performing polymerization curing by irradiation of light such as ultraviolet rays and visible light, any known photosensitizer can be used, for example, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin propyl ether, Α-diketones such as benzyl, biacetyl and camphorquinone, and benzophenones such as benzophenone and methoxybenzophenone are preferably used. Further, in the case of the above photocuring, a curing accelerator can be further added to the photosensitizer. As the curing accelerator, aminobenzoic acid ester, toluidine, benzylamine,
Amine such as aminomethacrylate is preferably used.

The amount of these photo-curing agents used is preferably 0.01 to 15% by weight based on the total amount of monomers,
It is more preferably from 10 to 10% by weight, particularly preferably from 0.1 to 7% by weight.

In the present invention, an inorganic filler may be blended in addition to the monomers, polymer component and polymerization initiator. Specific examples of the inorganic fillers include the periodic law Nos. I, II, III and IV.
Group, transition metals and their oxides, hydroxides, chlorides,
Sulfates, sulfites, carbonates, phosphates, silicates, borates and mixtures thereof, complex salts and the like,
Among them, silicon dioxide, quartz powder, aluminum oxide, barium sulfate, titanium oxide, talc, glass powder, glass beads, glass fiber, glass filler containing barium salt or strontium salt, silica gel, colloidal silica, carbon fiber, zirconium oxide, Examples thereof include tin oxide and other ceramic powders. The above-mentioned fillers were organically composited by the method described in Japanese Unexamined Patent Publication (Kokai) No. 60-81116, etc., untreated fillers, surface-treated fillers such as silane coupling agents, titanate coupling agents, and polymer-coated fillers. It can be applied to any of the fillers.

For example, compression molding, injection molding, injection molding, and other conventionally known molding techniques can be applied as a molding method for mechanical molding such as denture, denture base, and denture base lining material.

If necessary, the dental material of the present invention may further contain a colorant, a polymerization inhibitor, an ultraviolet absorber, an oxidation stabilizer and the like.

In the present invention, it is also used for dental materials other than prosthetic materials.

For example, in an adhesive / sealant, in addition to the (meth) acrylic acid ester-based compound represented by the general formula [1] of the present invention, other monomer components copolymerizable with the compound similar to the prosthetic material, polymerization initiation Agents, etc., and if necessary, a polymer, an inorganic filler, a colorant, a polymerization inhibitor,
It is also possible to add an ultraviolet absorber, an oxidation stabilizer and the like.

In addition, in composites resin, hard crown resin, immediate-curing resin for crown, etc., a (meth) acrylic acid ester compound represented by the general formula [1] of the present invention can be used in the same manner as the prosthesis material. An inorganic filler or the like is blended and used in addition to the other monomer component and the polymerization initiator which are copolymerizable with the compound. As the inorganic filler, those which can be used for the prosthetic material are similarly used. Further, if necessary, a polymer, a colorant, a polymerization inhibitor, an ultraviolet absorber, an oxidation stabilizer and the like may be added.

〔Example〕

 Next, the present invention will be further described with reference to examples.

The (meth) acrylic acid ester compound represented by the general formula [1] of the present invention has low odor and low irritation, but does not change in reactivity from conventional monomers.

Therefore, the prosthesis material will be mainly described in the following examples.

Synthesis example 1 A 2000 ml four-necked flask equipped with a cooling pipe, a nitrogen introduction pipe, a stirring rod, and a thermocouple for detecting the internal temperature was used as an unsaturated carboxylic acid, and acrylic ester SA produced by Mitsubishi Rayon Co., Ltd.
_{(CH 2 = C (CH 3} ) COOC 2 H 4 -OCOC 2 H 4 COOH) 115g, methanol 500 ml, a mixture of concentrated hydrochloric acid 2.5g and a small amount of hydroquinone, at room temperature (about 20 degrees), 3 days I left it in the dark. Then, after adding and diluting 500 ml of water and extracting twice with 200 ml of methylene chloride, the methylene chloride solution was separated from the aqueous layer. The methylene chloride solution was diluted with 300 ml of water to 2 times.
After washing with water once, it was washed once with saturated NaHCO ₃ water, and the methylene chloride solution was separated from the aqueous layer again. Anhydrous magnesium sulfate was added to the methylene chloride solution, and water in the solution was dehydrated and filtered. The solvent in the filtrate was evaporated under reduced pressure with an aspirator, and finally the solvent was removed at 50 ° C. for 30 minutes to obtain a specific methacrylic acid ester compound B as a target. The yield of the product was 100.1 g. The IR chart of the product is shown in FIG.

Other compounds represented by the general formula [1] can also be synthesized by the same reaction using a suitable unsaturated carboxylic acid and alcohol.

Examples 1 to 5 and Comparative Examples 1 to 3 As typical examples of the (meth) acrylic acid ester compound represented by the general formula [1] according to the present invention, the following compounds are used, and an odor test, an irritation test and Polymer solubility experiments were performed.

Compound A Compound B Compound C Compound D Compound E The outline of each test method is shown below, and the results are summarized in Table 1.

[Test method] Odor test: Five unspecified persons were selected as testers from the age of 20 to 30 and the test was conducted according to the following evaluation criteria.
When the evaluations differed among the testers, the test was repeated until three or more testers made the same evaluation.

<Evaluation Criteria> 〇: Slight odor Δ: Weak odor ×: Strong irritating stimulus Stimulation test: Five unspecified persons were selected as testers from the age of 20 to 30 and sampled on the tongue of each person. The test was carried out according to the following evaluation criteria for the condition of pain one minute after dropping 1 drop of.

<Evaluation Criteria> ○: Almost no pain △: Slightly painful ×: Very severe pain Polymer solubility test: average molecular weight of 230 × 10 ³ , polyethylmethacrylate powder concentration of average particle diameter 25 μm The test was carried out in accordance with the following evaluation criteria for the situation after 5 hours of mixing and stirring at 20% by weight.

<Evaluation criteria> S: Soluble SW: Swelling IS: Insoluble Examples 6 to 16 except that the test compounds were mixed monomers shown in Table 2,
The test was carried out in the same manner as in Example 2, and the results are shown in Table 2.

Examples 17 to 22 and Comparative Examples 4 to 5 To the monomer solutions shown in Table 3, benzoyl peroxide 0.5 was added.
Wt% (to the monomer solution) is dissolved, the solution is sealed in a glass tube, heated at 60 ° C. for 24 hours, and then continuously heated at 100 ° C.
It was heat-polymerized for 24 hours to obtain a cured product. Next, the performance evaluation of the cured product was carried out by the method described below, and the results are summarized in Table 3.

[Cured Product Performance Evaluation Method] Indirect tensile (diametral) strength The test piece is a 6 × 6 mmφ cylinder, and when a compressive force is applied in the diametrical direction, tensile stress is generated in the direction perpendicular to the compressive force. The tensile test method is adopted and the value is calculated from the following formula.

Water absorption The test piece is a cylinder of 1 x 10 mmφ, and it is measured after being stored in water at 37 ° C for 7 days.

Examples 23 to 33 Polymer powders shown in Table 4 and benzoyl peroxide 0.5
A monomer liquid in which a weight% (to the monomer liquid) is dissolved is mixed at a weight ratio of 30/70, and the mixed liquid is sealed in a glass tube.
Continuously at 60 ° C. for 24 hours, followed by heat polymerization at 100 ° C. for 24 hours to obtain a cured product. Next, performance evaluation of the cured product was carried out in the same manner as in Example 18, and the results are summarized in Table 4.

Examples 34 to 36 PEMA powders (average molecular weight 230 × 10 ³ ) having various average particle sizes shown in Table 5 and compound B / 1,6-hexanediol dimethacrylate = 36/64 (weight ratio) Table 5 shows the results of mixing the mixed monomer with a weight ratio of 2: 1 and measuring the dough-like time of the mixture by the test method shown below.

[Mochi-like time test method] Predetermined polymer powder and monomer liquid are weighed in a measuring bottle (inner diameter 47
mm, height 2 cm), stir for 20 seconds, cover the weighing bottle with a lid of tempered glass, and leave for 5 minutes. After stirring again for 20 seconds, the tempering glass is capped with a tempered glass and left for 5 minutes. The mochi-like start time is defined as the time when the sample surface is touched with the fingertip and when it is not sticky. Along the inner wall of the weighing bottle, the sample is separated from the wall surface with a metal needle. Insert the handle of the spoon into the sample and allow the sample to turn over to make the dough-like finish time. The pot life was calculated as the rice cake-like end time minus the rice cake-like start time.

[Effects of the Invention] As described above, the dental material containing the specific (meth) acrylic acid ester compound according to the present invention is
It has low odor and low irritation as compared with conventional materials, has a low water absorption of the polymer, and has an appropriate dough-forming time when used as a prosthetic material. That is, the patient receiving the treatment with the material does not experience any discomfort due to the odor surface or mucous membrane stimulation even during direct treatment in the oral cavity, and the cured material itself is Even under extremely severe wet conditions, since the water absorption rate is small and the durability in terms of dimensional change, strength, discoloration, etc. is excellent, long-term use is possible. On the other hand, the dentist who performs the treatment brings safety, hygiene and work efficiency improvement to the dental technician.

Therefore, the material of the present invention has a great practical value in the dental field.

[Brief description of drawings]

 FIG. 1 shows the IR chart of compound B.

Claims (3)

[Claims] 1. The following general formula [1] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkylene group having 1 to 15 carbon atoms, R ₃ represents an alkylene group having 1 to 10 carbon atoms, R _{3 Four}
Represents an alkyl group having 1 to 15 carbon atoms. ) A dental material containing a specific (meth) acrylic acid ester compound represented by: 2. The following general formula [1] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkylene group having 1 to 15 carbon atoms, R ₃ represents an alkylene group having 1 to 10 carbon atoms, R _{3 Four}
Represents an alkyl group having 1 to 15 carbon atoms. ) A dental material comprising a specific (meth) acrylic acid ester compound represented by the formula (4) and a polyfunctional methacrylate copolymerizable with the compound. 3. The following general formula [1] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkylene group having 1 to 15 carbon atoms, R ₃ represents an alkylene group having 1 to 10 carbon atoms, R _{3 Four}
Represents an alkyl group having 1 to 15 carbon atoms. ) A dental material comprising a specific (meth) acrylic acid ester-based compound represented by the formula (1), a polyfunctional methacrylate copolymerizable with the compound, and an organic polymer soluble or swellable in these monomer components.