JPH0656619A - Dental material having faint smell and low irritation - Google Patents

Abstract

PURPOSE:To obtain a dental material having a faint smell, low irritation, low water absorption ratio of polymer, a proper pasty viscous time and extremely high practical value, comprising a specific methacrylic acid ester-based compound. CONSTITUTION:This dental material having a faint smell and low irritation comprises methacrylic acid ester of formula I ((n) is >=2 integer; R is H or methyl) (e.g. compounds of formula II or formula III). The methacrylic acid ester-based compound is preferably blended with a copolymerizable polyfunctional or trimethylolpropane trimethacrylate). Since this curing material has excellent durability in terms of change in dimension, strength, change of color, etc., even under an extremely severe wetness such as interior of oral cavity, the curing material can be used for a long period of time. On the other hand, treatment can be done safely and hygienically by a dentist or a dental mechanic and the curing material has improved operation efficiency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-odor, low-irritancy dental material prepared by blending a specific methacrylic acid ester compound.

[0002]

2. Description of the Related Art Currently, many dental materials made of synthetic polymers have been developed. For example, (1) crown-restoring materials such as chemically-polymerized and photopolymerizable composites and immediate-curing resins (immediate-polymerization resins), (2) temporary encapsulation and backing materials such as glass ionomer cements and carboxylate cements, (3) Methyl methacrylate-based and polyfunctional methacrylate-based long-term adhesives, (4) Temporary adhesives such as instant adhesives, (5) Chemical polymerization type and photopolymerization type pit fissure sealant (sealant), ( 6) Artificial crown materials such as heat-polymerization type and photo-polymerization type hard crown resins, (7) Temporary crown materials such as polycarbonate crown and crown color immediate hardening resin, (8) Resin teeth, polysulfone teeth And artificial tooth (denture) materials such as polycarbonate teeth, (9)
Denture base materials such as heat polymerization type, room temperature polymerization type (flow-injection type), injection molding acrylic resin and adhesive floor resin, (10) agar, alginate, polysulfide rubber, silicone rubber, polyether rubber and (meth) acrylic Impression materials such as functional impression materials, (1
1) Model materials such as epoxy model materials, (12) wax / wax-shaped materials such as paraffin wax, inlay wax, utility wax, and (13) tray materials such as individual trays and ready-made trays, and the performance required for each material In addition, those having remarkably different functions have been put to practical use.

Of these, for example, dentures, denture bases, dentures or denture base lining materials, and prosthetic materials such as immediate-polymerization resins for repair (rebase) are colorless and transparent, easily colored and aesthetic, and processable. Is required, and from this viewpoint, polymethylmethacrylate (hereinafter abbreviated as PMMA) and polyethylmethacrylate (hereinafter PEMA).
A), a methylmethacrylate (hereinafter abbreviated as MMA) / ethylmethacrylate copolymer, etc., and a polymer component which is mostly powder, and a monofunctional monomer component such as MMA, 1,6-hexanedioldi A mixture of a polyfunctional monomer component such as methacrylate or trimethylolpropane trimethacrylate with a radical polymerization initiator is used. In addition, a composite resin, a resin for hard crown, etc. is a monofunctional monomer, a polyfunctional monomer, and an inorganic filler mixed with a radical polymerization initiator, and is used for a crown resin, a sealant, an adhesive, etc. A combination of a polymerizable monomer, a polyfunctional monomer and a radical polymerization initiator is used, and in each case, a (meth) acrylic monomer such as MMA is used as the monomer.

The above-mentioned prosthesis material is obtained by mixing the monomer component and the polymer component in an appropriate ratio, placing the mixture in a predetermined mold, and polymerizing the mixture at room temperature or under heating. So-called dough stage through the state of pulling a thread from a sandy state wet with water
become. At this stage, the monomer and polymer dissolve in each other, and plasticization progresses, forming a soft dough-like shape that is hard to touch with your hands and separate from the container. The most suitable state for. This process depends on a number of factors, but in the case of prosthesis materials, one of the important points in dental technology is that this mochi-like time is an appropriate length, and in this respect also monomer As a component, a (meth) acrylic monomer such as MMA is suitable. Also recently this MMA
JP-A-62-178502 proposes the use of a specific diester compound as a substitute for the above.

[0005]

However, conventionally, (meth) acrylic monomers such as MMA which have been widely used in dentistry have a strong unpleasant odor. Extremely irritating to skin and mucous membranes. The water absorption of the polymer is high. However, these problems, including the case of the diester compound described in JP-A No. 62-178502, have not been sufficiently improved, and the prosthesis material does not have the above problems and is suitable as a rice cake. It has been desired to provide a monomer having a denaturation time.

[0006] Further, in terms of applications such as composite resins, resins for hard crowns, resins for crowns, sealants, adhesives, etc., moistening time is not necessary, but strong unpleasant odor and high irritation become problems. There has also been a demand for the provision of a monomer having no problem in the use of.

[0007]

[Means for Solving the Problems] In view of such a situation,
As a result of intensive studies to solve the above problems, the present inventors have found that a specific methacrylic acid ester compound has low odor and low irritation, has a low water absorption rate of the polymer, and further has a polymer powder. The present invention was found to have a suitable length of dough time when mixed with.

That is, the gist of the present invention is the following general formula [I]

[0009]

[Chemical 4] (In the formula, n represents an integer of 2 or more, and R represents a hydrogen atom or a methyl group.) A low odor / low irritation dental material containing a specific methacrylic acid ester compound. Further, a dental material containing a polyfunctional methacrylate copolymerizable with the above compound, and a low odor / low irritation dental composition containing an organic polymer soluble or swellable in these monomer components. In the material.

The integer n of 2 or more representing the ethylene glycol unit of the general formula [I] can be basically used without any limitation, but it is a condition desired as a low odor and low irritation dental material, that is, Considering the low odor, low irritation, water absorption of the polymer, mechanical strength, and the dough-forming time required when used as a two-component prosthesis material, the integer n in the general formula [I] Is preferably 2 to 10,
More preferably, it is in the range of 2-5.

From the above, specific examples of the specific methacrylic acid ester compounds which are particularly preferably used in the present invention include the following compounds.

[0012]

[Chemical 5] In the present invention, if necessary, other monomer components copolymerizable with the specific methacrylic acid ester compound represented by the general formula [I] are blended as long as the low odor and low irritation can be maintained. You can also Specific examples of the monomer include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid. n-hexyl,
Tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di (meth) Pentaethylene glycol 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) acrylic acid, di (meth) acrylic Acid 1,4-butanediol, di (meth) acrylic acid 1,5
-Pentanediol, di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,7-heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1 , 9-nonanediol, 1,10-decanediol di (meth) acrylic acid,
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,
Tri (meth) acrylic acid tetramethylolmethane, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid trimethylolethane, tetra (meth) acrylic acid
Tetramethylol methane acrylate and the like can be mentioned, and one or more of these can be blended, but among them, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 2,2 Polyfunctional methacrylates such as -bis (4-methacryloyloxyethoxyphenyl) propane, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate are mentioned, and they are adopted in terms of improving the mechanical strength of the resulting cured product. preferable.

The blending ratio of the specific methacrylic acid ester compound of the present invention to the other copolymerizable monomer component can be arbitrarily set as long as it is within a range of maintaining low odor and low irritation. The content of the specific methacrylic acid ester compound of the present invention is preferably 20% by weight or more, particularly preferably 30% by weight or more.

In the present invention, an organic polymer may be further added as another component capable of being dissolved or swelled in the above-mentioned monomers. Specific examples of the organic polymer include PMM.
A, PEMA, MMA / ethylmethacrylate copolymer, MMA / butylmethacrylate copolymer, polystyrene, polybutylmethacrylate, methylmethacrylate / styrene copolymer, ethylmethacrylate / butylmethacrylate copolymer, ethylmethacrylate / styrenecopolymer , Polyacrylate, polymethacrylate, polyacrylonitrile, styrene / acrylonitrile copolymer, styrene / acrylonitrile / butadiene copolymer, polycarbonate resin, polyester resin,
Polyethylene resin, polypropylene resin, polyvinyl chloride resin, silicone resin, etc. may be mentioned, among which P
MMA, PEMA, MMA / ethylmethacrylate copolymer, MMA / butylmethacrylate copolymer, polystyrene, polybutylmethacrylate, MMA / styrene copolymer, ethylmethacrylate / butylmethacrylate copolymer, ethylmethacrylate / styrene copolymer and A mixture of these organic polymers and other polymers is preferable in order to exhibit appropriate solubility.

The molecular weight and average particle size of the organic polymer are not particularly limited, but when used as a prosthesis material such as a denture, a denture base, a denture or a denture base lining material, an instant polymerization resin for repair, etc. Considering the solubility with the monomer component and the mechanical strength of the obtained cured product, the molecular weight is in the range of 10,000 to 1,500,000, preferably 50,000 to 1,000,000, and the average particle size is in the range of 1 μm to 15 μm.
It is in the range of 0 μm, preferably 10 μm to 100 μm.

Although the compounding ratio of the organic polymer component and the total monomer component containing the methacrylic acid ester compound of the present invention can be selected from a wide range, for example, when it is used for a prosthetic material similar to the above, it is particularly cured. Considering the mechanical strength of the product, the total monomer component containing the methacrylic acid ester compound of the present invention is 1 to 140 parts by weight, preferably 2-1 to 10 parts by weight of the organic polymer component.
10 parts by weight, particularly preferably 4 to 85 parts by weight.

A known compound can be used as a polymerization and curing agent for forming a prosthetic material, but in the case of curing by heating, a substance that can decompose to initiate polymerization when heated,
For example, benzoyl peroxide, cumene hydroperoxide,
Examples thereof include t-butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, and azobisisobutyronitrile. In the case of polymerizing and hardening at room temperature, for example, a combination of peroxide and amine, peroxide and sulfinic acid, or peroxide and cobalt compound can be used. When the polymerization initiator is used in combination, the composition may be divided into two parts, one may be mixed with a peroxide, and the other may be mixed with an amine, a sulfinic acid, or a cobalt compound and used. . The amount of the above curing agent used is 0.
01 to 15% by weight, preferably 0.05 to 10% by weight,
It is particularly preferably 0.1 to 7% by weight.

In the case of carrying out polymerization and curing by irradiation with light such as ultraviolet rays and visible rays, known photosensitizers are used, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and other benzoin alkyl ethers, Α-diketones such as benzyl, biacetyl and camphorquinone, and benzophenones such as benzophenone and methoxybenzophenone are preferably used. Further, in the case of the photo-curing, a curing accelerator can be further added to the photosensitizer. As the accelerator, amines such as aminobenzoic acid ester, toluidine, benzylamine and aminomethacrylate are preferably used.

The amount of these photo-curing agents used is 0.01 to 15% by weight, preferably 0.05, based on the total amount of monomers.
It is from 10 to 10% by weight, particularly preferably from 0.1 to 7% by weight.

Further, as a molding method in the case of mechanically molding a denture or a denture base material, for example, conventionally known molding techniques such as compression molding, injection molding and injection molding can be applied.

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

[0022]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Examples 1-8, Comparative Examples 1-4 The odor test, irritation test and polymer solubility test were carried out using the compounds shown below as specific methacrylic acid ester compounds according to the present invention.

[0023]

[Table 1] The outline of each test method is shown below, and the results are summarized in Table 2. [Test Method] Odor test : Five unspecified persons aged 20 to 30 were selected as testers, 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> ○: Slight odor Δ: Weak odor ×: Strong irritating stimulus ・Irritation test : Five unspecified persons aged 20 to 30 years were selected as testers, and one sample was placed on the tongue of each person. Drop a drop,
The test was carried out on the condition of pain after 1 minute according to the following evaluation criteria.

<Evaluation Criteria> ○: Almost no pain △: Slight pain ×: Very strong pain ・Polymer solubility test : 20% by weight of polyethylmethacrylate powder having an average molecular weight of 230 × 10 ³ and an average particle diameter of 25 μm %, The state after 5 hours of mixing and stirring was tested according to the following evaluation criteria.

<Evaluation Criteria> S: Soluble SW: Swelling IS: Insoluble • Primary skin irritation test (1) Test animals and number of animals Rabbit Japanese white system (Shizuoka experimental animal) 6 (2) Test reagents, coating Method and Period The hair on the back of the rabbit was shaved with an electric hair clipper, and the hair was separated into 4 sections and dehaired with a depilatory, and one day passed after washing the depilatory with hot water, and no redness was observed. The application sites were non-rubbed and rubbed skin (preparation of # -shaped rubs using an 18-gauge blood transfusion needle) for one sample of the test article.

The amount of the sample was 0.5 ml per section, and it was pressed with gauze and covered with an oil gummy, Ami Hotai, and tape to remove them, and after 24 hours, they were removed and observed until 72 hours. The degree of reaction was evaluated by the following scores, and shown as an average value of 6 animals and 4 sections.

Degree of reaction Score No irritation 0 Very mild erythema (slightly identifiable) 1 Erythema and edema are observed on the application site 2 Erythema and edema are observed on areas other than the application site 3 Severe erythema (Beet red) and edema (about 1 mm or more) 4

[0029]

[Table 2] Examples 9 to 19 Tests were performed in the same manner as in Example 2 except that the test compound was used as a mixed monomer, and the results are shown in Table 3.

[0030]

[Table 3] Examples 20 to 26, Comparative Examples 5 to 6 0.5% by weight of benzoyl peroxide (relative to the monomer solution) was dissolved in the monomer solution shown in Table 4, the solution was sealed in a glass tube, and the solution was kept at 60 ° C. for 24 hours. Heat, then 100 ℃, 2
It was heat-polymerized for 4 hours to obtain a cured product. Next, performance evaluation of the cured product was carried out by the method shown below, and the results are summarized in Table 4. Method of evaluating the performance of cured products・ Indirect tensile strength (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. Use the test method and calculate the value from the following formula.

[0031]

[Equation 1] ・ Water absorption amount The test piece was a disc of 1 × 10 mmφ, and was measured after being stored in water at 37 ° C. for 7 days.

[0032]

[Table 4] Examples 27 to 37 Polymer powders shown in Table 5 and a monomer liquid in which 0.5% by weight of benzoyl peroxide (relative to the monomer liquid) were dissolved were mixed in a weight ratio of 30/70, and a mixed liquid was sealed in a glass tube. Then 6
After heating at 0 ° C. for 24 hours and then at 100 ° C. for 24 hours, heat polymerization was performed to obtain a cured product. Next, the performance of the cured product was evaluated in Example 20.
The same method was used, and the results are summarized in Table 5.

[0033]

[Table 5] Polymer properties : average molecular weight (abbreviated as MW), average particle size (abbreviated as PS), copolymer composition (abbreviated as CP) (* 1) MW: 480 × 10 ³ , PS: 15 μm (* 3) MW: 230 × 10 ³ , PS: 25 μm (* 3) CP: 40/60, MW: 320 × 10 ³ , P
S: 20 μm (* 4) CP: 40/60, MW: 60 × 10 ³ , P
S: 23 μm (* 5) MW: 120 × 10 ³ , PS: 30 μm (* 6) MW: 360 × 10 ³ , PS: 42 μm (* 7) CP: 75/25, MW: 85 × 10 ³ , P
S: 84 μm (* 8) CP: 50/50, MW: 780 × 10 ³ , P
S: 12 μm (* 9) CP: 50/50, MW: 520 × 10 ³ , P
S: 18 μm Examples 38 to 40 PEMA powder having various average particle diameters shown in Table 6 (average molecular weight = 230 × 10 ³ ) and compound A / dimethacrylic acid 1,6-hexanediol = 36/64 (weight Table 6 shows the results obtained by mixing the mixed monomer consisting of (1) to (2) in 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 A predetermined amount of the polymer powder and the monomer liquid are weighed in a weighing bottle (inner diameter 47 mm, height 2 cm), stirred for 20 seconds, covered with a lid of reinforced glass and left for 5 minutes. After stirring again for 20 seconds, the reinforcing bottle is capped on the weighing bottle and left for 5 minutes. The time when the surface of the sample is no longer sticky when the surface of the sample is touched with a fingertip is defined as the start time of the rice cake. Separate the wall from the sample with a metal needle along the inner wall of the weighing bottle. Insert the handle of the spoon into the sample, and set the time for which the sample can be inverted as the dough-like finish time. The pot life was also determined by the end time of rice cake-the start time of rice cake.

[0034]

[Table 6]

[0035]

As described above, the dental material prepared by blending the specific methacrylic acid ester compound according to the present invention has a lower odor and a lower irritation as compared with the conventional materials, and is heavy. The coalescence has a low water absorption rate, and also has an appropriate dough-like time. That is, for patients treated with these materials, even when directly treated in the oral cavity, they do not experience discomfort due to odorous surfaces and mucous membrane irritation, etc. Also, since the durability in terms of dimensional change, strength and discoloration is excellent, it can be used for a long time. On the other hand, it also improves safety, hygiene, and work efficiency for the dentist or dental technician who performs the treatment.

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

Claims (3)

[Claims] 1. The following general formula [I]: (In the formula, n represents an integer of 2 or more, and R represents a hydrogen atom or a methyl group.) A low odor / low irritation dental material containing a methacrylic acid ester compound. 2. The following general formula [I]: (In the formula, n represents an integer of 2 or more, and R represents a hydrogen atom or a methyl group.) A compound obtained by blending a methacrylic acid ester compound and a polyfunctional methacrylate copolymerizable with the compound. Odor / low irritation dental material. 3. The following general formula [I]: (In the formula, n represents an integer of 2 or more, and R represents a hydrogen atom or a methyl group), a polyfunctional methacrylate copolymerizable with the compound, and a monomer component thereof. A low odor and low irritation dental material containing a soluble or swellable organic polymer.