JP2017007954A - Temporary sealing material for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a temporary sealing material for dental use, the material being used to be filled in a caries removal part during the course of treatment prior to a final repair of a caries part and being configured to absorb water to swell in the oral cavity to stabilize its property to seal the crypt wall.SOLUTION: A temporary sealing material for dental use is a polymerizable composition consisting of a filler and a matrix, in which a polymer obtained by polymerizing the following compositions (1) to (3) absorbs water and swells while being immersed in water: (1) a matrix-forming component including a polymerizable hydrophilic methacrylate monomer and a methacrylate based crosslinking agent; (2) a polymer or copolymer of a hydrophilic methacrylate (acrylate) monomer or a polymer or copolymer of a hydrophilic methacrylate (acrylate) monomer containing an inorganic compound; and (3) a polymerization catalyst.SELECTED DRAWING: None

Description

The present invention relates to a dental temporary sealing material. Specifically, it is a temporary sealing material that is polymerized and cured, and the sealing property to the fossa wall is stabilized by water absorption expansion in the oral cavity.

Many types of materials are used for dental temporary sealing materials for temporarily filling the cavity between the removal of the carious site in dental treatment and the final repair procedure. Generally, hydraulic temporary sealing materials using hydraulic substances such as gypsum, eugenol cement with analgesic action, room temperature polymerization type resin temporary sealing materials mainly composed of methyl methacrylate, carboxylate cement, glass ionomer cement Dental cements such as the above, and stopping materials used for temporary sealing of root canal treatment are widely used. However, every material has its merits and demerits, and there is no material that is completely satisfactory.

The hydraulic temporary sealing material utilizes the property of hardening by hydration of water such as gypsum. Widely used because it can be used simply by filling the axilla. There are many advantages such as good sealing and less irritation. However, since it cannot be taken as a lump when removing, it is necessary to carefully remove it using a scaler or the like. In addition, the curing performance is slow and the strength is weak and there is a problem in durability such as when the treatment interval needs to be opened.

  Dental Eugenol cement also has analgesic action and can be conveniently used for myelinated teeth. However, if a composite resin or resin cement is subsequently used, care must be taken to prevent curing. Physical properties should also be improved.

  Stopping is widely used for temporary sealing such as root canal treatment. Although it has the great advantage that it can be used easily by heating and has good operability, the temporary sealing of the cavity has the disadvantages that the strength is insufficient and the sealing performance is poor.

  Among dental cements, low-strength carboxylate cements and adhesive glass ionomer cements are often used, but carboxylate cements are poor in durability. It takes time and effort to remove the remaining cement. Although glass ionomer cement has good biocompatibility and can be used conveniently when temporary sealing is required for a long period of time, it is too strong as a temporary sealing material, and it takes time to remove it.

  Resin-based temporary sealing materials are easy to use when aesthetics are required or when you do not want the temporary sealing material to come off over a long period of time, but they are not easy to remove and must be removed. It was. About improvement of operability. For example, Japanese Patent Laid-Open No. 9-268109 discloses an example in which rosin or sandalac is added for the purpose of improving the sealing property and removability. However, since these additives are not contained in the curing system, they are foreign substances from the reaction system, and the problem of polymerization shrinkage, which is a characteristic of the polymerization resin, cannot be solved. Japanese Patent No. 3157922 discloses a technique of mixing a water-absorbing resin in order to compensate for this polymerization shrinkage and improve the compatibility at the edge of the cavity. Water-absorbing resin is widely used in paper diapers, etc., but is completely different from methacrylate-based polymerizable substances widely used in the dental field, and it is assumed that the interface with the matrix part to be polymerized is weak. There is no denying the possibility that the oral substance will be immersed in the mouth. Further, Japanese Patent Application Laid-Open No. 2010-21553 attempts to improve impact properties in order to increase the durability in the oral cavity, but it is not a material that can be completely satisfied in terms of sealing properties.

Patent 3157922 JP-A-9-268109 JP 2010-215538 A

The object of the present invention is to produce a polymerizable temporary sealing material excellent in operability that can be used in a wide range of applications, and in particular, to prepare a resin-based temporary sealing material that can compensate for post-polymerization curing shrinkage.

As a result of investigating the optimum temporary sealing material, we studied mainly soft polymer materials that cause water absorption and swelling in the oral cavity in order to study polymerizable materials with excellent operability. Hydrophilic methacrylate (acrylate) polymer synthesized from various hydrophilic methacrylate (acrylate) monomers is used as filler, hydrophilic methacrylate monomer and methacrylate cross-linking agent are used as matrix, water absorption after polymerization and normal dental filler By using a material that becomes softer than the above, the present invention was completed by successfully producing a temporary sealing material in which temporary sealing performance and operability were balanced.

According to the present invention, it is possible to provide a temporary sealing material that is durable with simple operability, has good adhesion at the cavity edge, is not colored at the edge, and can be used stably for a long time without invasion of bacteria.

We investigated a temporary sealing material that has better operability than the currently used resin-based materials and can be used stably in the oral cavity. The resin-based temporary sealing material compensates for polymerization shrinkage by utilizing water absorption expansion, and after curing As a result, the present invention was completed by successfully producing an optimal temporary sealing material.

The configuration of the present invention is as follows:
A polymerizable composition consisting of a filler and a matrix.
(1) A matrix-forming component comprising a polymerizable hydrophilic methacrylate monomer and a methacrylate-based crosslinking agent.
(2) A polymer or copolymer of a hydrophilic methacrylate (acrylate) monomer, or a polymer or copolymer of a hydrophilic methacrylate (acrylate) monomer containing an inorganic compound.
(3) A dental temporary sealing material that causes water absorption expansion in a state in which a polymer obtained by polymerizing a composition comprising a polymerization catalyst is immersed in water.

The polymerizable hydrophilic methacrylate monomer as the matrix forming component is typically a polymerizable methacrylate monomer having a hydrophilic group, and is hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerol diester. A typical example is methacrylate.

Typical examples of the crosslinking agent include monomers and oligomers having two or more double bonds in one molecule that are compatible with these hydrophilic methacrylate monomers. As the crosslinking agent, any monomer that is hydrophobic but compatible with a hydrophilic monomer, such as urethane dimethacrylate, Bis-GMA, can be used. Specifically, in addition to urethane dimethacrylate and Bis-GMA, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate such as diethylene glycol dimethacrylate and triethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, block type Polyethylene glycol and polypropylene glycol dimethacrylate, random polyethylene glycol and polypropylene glycol dimethacrylate, glycerol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3 butanediol dimethacrylate, tricyclodecanol dimethacrylate, Ethoxylated glycerin trimeta Relate can select ethoxylated pentaerythritol penta methacrylate, ethoxylated dipentaerythritol polymethacrylate, ethoxylated polyglycerol glycol polymethacrylate, etc. multifunctional urethane methacrylate as a crosslinking agent.

For the matrix component, a non-hydrophilic monofunctional monomer such as methyl methacrylate or ethyl methacrylate may be used for the preparation. Moreover, acidic monomers such as 4-META and M10P widely used for dental materials can also be included.

In addition, the hardness of a hardening body is controllable by combining a crosslinking agent and a monomer moderately. The hardness of the cured product is complicated such as control of monomer mixing ratio, filler hardness, filler and monomer mixing ratio, and catalyst amount. However, it is important to balance in order to exhibit contradictory performance that is easy to fill, durable in the oral cavity, and easy to remove, which is an important factor.

Polymer or copolymer of hydrophilic methacrylate (acrylate) monomer used for filler or polymer or copolymer of hydrophilic methacrylate (acrylate) monomer containing inorganic compound is a polymerizable hydrophilic methacrylate monomer or hydrophilic A filler based on a polymer or copolymer containing an acrylate, and a filler containing an inorganic compound in a polymer or copolymer of a polymerizable hydrophilic methacrylate monomer or hydrophilic acrylate monomer is also included in the present application. The hydrophilic monomer used for the filler need not be the same material as the matrix. Of course, there is no problem even if the same one is used. Since the filler is polymerized and the skin irritation of the acrylate monomer is almost eliminated, it may be synthesized from the acrylate monomer. Specifically, the above-mentioned hydrophilic methacrylate monomers can be listed. Examples thereof include hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, ethylene glycol diacrylate or dimethacrylate, polyethylene glycol diacrylate or dimethacrylate, glycerol diacrylate or dimethacrylate, and the like. The hydrophilic monomer used for the filler may be homopolymerized or may be copolymerized with other monomers. In the case of a copolymer, the hydrophilic monomer is preferably as much as possible from the viewpoint of water absorption, but it is generally preferable to contain 50 mol% or more. Although there is no restriction | limiting in particular as a copolymer component, Specifically, the crosslinking agent and monomer which can be used for the matrix mentioned above can also be used.

Further, the filler may take the form of a composite filler with an inorganic compound. In this case, the inorganic compound is generally 0 to 80% by weight based on the whole filler. There are no particular restrictions on the inorganic compounds used, but feldspar, silica, finely divided silica, strontium glass, barium glass, dental glass ionomer cement fluoroaluminosilicate glass, silicate glass, oxidation used in dental fillers Zinc, alumina, zirconia, or the like can be used. These are used in the form of powder, and those having an average particle size of about 0.02 to 30 microns are usually easy to use.

  The composition of the present application can be selected from either photopolymerization or chemical polymerization. In the case of photopolymerization, the catalyst is camphorquinone, which is a representative of α-diketone widely used in the dental field, (2,4,6-trimethylbenzoyldiphenylphosphine oxide) which is representative of (bis) acylphosphine oxide and its salts. And bis- (2,4,6 trimethylbenzoyl) phenylphosphine oxide can be conveniently used. Further, in addition to these photopolymerization initiators, other photopolymerization initiators can be combined. The catalyst system for photopolymerization is not particularly limited if a photopolymerization initiator that works in the visible light region of 400 nm or more is selected. For example, water-soluble acylphosphine oxide, thioxanthone, ketal, benzoyl alkyl ether and the like can be combined. Further, combining a reducing agent with an initiator is usually a good catalyst for improving curing performance. The reducing agents used are tertiary aliphatic amines typified by triethanolamine and N-methyldiethanolamine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-dimethyl-p-toluidine, 4-N , N-dimethylaminobenzoic acid ethyl ester and other aromatic amines, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, etc. Is easy to use. When photopolymerization is selected, the composition can be made into a one-paste system, so that the work of kneading is omitted and the operability is generally good. On the other hand, when a chemical polymerization system is selected, an operation of mixing two components such as powder and liquid is required, but there is an advantage that fluidity can be adjusted. As the chemical polymerization catalyst, for example, a redox polymerization catalyst widely used in dentistry can be conveniently used. A typical example is a combination of an organic peroxide such as benzoyl peroxide and the above reducing agent.

  A plasticizer may be included to adjust the fluidity. However, in the present application, it is preferable not to include a plasticizer because the performance in the oral cavity can be made constant without the plasticizer.

  The present invention will be specifically described with reference to examples.

Example 1. 9.8 g of hydroxyethyl methacrylate and 0.2 g of triethylene glycol dimethacrylate were mixed, and 0.1 g of benzoyl peroxide was added. The solution was slowly added dropwise to 100 ml of 1 wt% carboxymethylcellulose sodium salt (CMCNa) having an average molecular weight of about 100,000 which had been heated to 80 ° C. over about 3 hours for polymerization. After the polymerization, CMCNa was removed and dried at 60 ° C. for 24 hours to obtain a filler. 50% by weight of this filler, 30% by weight of hydroxyethyl methacrylate, 15% by weight of urethane dimethacrylate, 5% by weight of ethyl methacrylate, 1% by weight of camphorquinone, 1% by weight of sodium benzenesulfinate, and 1% by weight of hydroquinone are added. Then, a photopolymerizable temporary sealing material was produced. The cured body after 24 hours with respect to the cured body after polymerization exhibited 2% water absorption expansion. A 3 mm square, 2 mm deep cavity was dug into the bovine teeth and filled. One day after storage in water, it was judged that it was compatible with no gap on the fossa wall and could be used as a temporary sealant.

Example 2 95 g of hydroxypropyl methacrylate and 5 g of glycerol dimethacrylate were mixed, and 1 g of benzoyl peroxide was added. The solution was slowly dropped and polymerized over about 5 hours while stirring vigorously in distilled water heated to 80 ° C. After the polymerization, it was dried at 60 ° C. for 24 hours to obtain a filler. 50% by weight of this filler, 20% by weight of hydroxyethyl methacrylate, 15% by weight of hydroxypropyl methacrylate, 10% by weight of glycerol dimethacrylate, 5% by weight of ethyl methacrylate, 1% by weight of camphorquinone and 1% by weight of triethanolamine, 1% by weight of hydroquinone was added to prepare a photopolymerizable temporary sealing material. The cured body after 24 hours with respect to the cured body after polymerization exhibited 2% water absorption expansion. In addition, 3 mm square and 2 mm deep cavity was dug into the bovine teeth and filled. One day after storage in water, there is no gap on the fossa wall and it is compatible and can be used as a temporary sealing material.

Example 3 FIG. Hydroxypropyl methacrylate (65 g), fluoroaluminosilicate glass (FujiI powder manufactured by GC) (30 g) and triethylene glycol dimethacrylate (5 g) were mixed, and benzoyl peroxide (1 g) was added. The solution was slowly added dropwise and polymerized over about 5 hours while stirring vigorously in distilled water containing 1% of triethanolamine heated to 80 ° C. After polymerization, the mixture was filtered with a filter paper and dried at 60 ° C. for 24 hours to obtain a filler. 50% by weight of this filler, 30% by weight of hydroxyethyl methacrylate, 15% by weight of urethane dimethacrylate, and 5% by weight of glycerol dimethacrylate are mixed, 1% by weight of camphorquinone and 1% by weight of dimethylparatoluidine are added as a catalyst, and light is added. A polymerization type temporary sealing material was produced. The cured body after 24 hours with respect to the cured body after polymerization exhibited 2% water absorption expansion. A cavity with a depth of 3 mm and a depth of 2 mm was dug into the bovine teeth and filled. One day after storage in water, there is no gap on the fossa wall and it is compatible and can be used as a temporary sealing material.

Example 4 50 g of hydroxyethyl methacrylate, 30 g of strontium silicate glass (average particle size 2 μm) and 20 g of triethylene glycol dimethacrylate were mixed, and 1 g of benzoyl peroxide was added. The solution was slowly added dropwise and polymerized over about 5 hours while stirring vigorously in distilled water containing 1 g of triethanolamine heated to 80 ° C. After polymerization, the mixture was filtered with a filter paper and dried at 60 ° C. for 24 hours to obtain a filler. 50% by weight of this filler, 30% by weight of hydroxyethyl methacrylate, 15% by weight of urethane dimethacrylate, and 5% by weight of glycerol dimethacrylate are mixed, and 1% by weight of camphorquinone and 1% by weight of sodium p-toluenesulfinate are added as catalysts. Then, a photopolymerizable temporary sealing material was produced. The cured body after 24 hours with respect to the cured body after polymerization exhibited 2% curing expansion. A cavity with a depth of 3 mm and a depth of 2 mm was dug into the bovine teeth and filled. One day after storage in water, there is no gap on the fossa wall and it is compatible and can be used as a temporary sealing material.

Example 5 FIG. A filler was produced in the same manner as in Example 2. 100 g of the prepared filler was mixed with 2 g of benzoyl peroxide to prepare a powder. On the other hand, 70 g of hydroxypropyl methacrylate, 25 g of triethylene glycol dimethacrylate and 5 g of glycerol dimethacrylate were mixed, and 2% by weight of dimethylparatoluidine and 1% by weight of hydroquinone were added to prepare a chemical polymerization temporary sealing material. The cured body after 24 hours had a water absorption expansion of 3% with respect to the cured body after polymerization. A 3mm square, 2mm deep cavity was dug into the bovine teeth and filled. One day after storage in water, there is no gap on the fossa wall and it is compatible and can be used as a temporary sealing material.

Example 6 A filler was prepared in the same manner as in Example 3. Powder A was prepared by adding 1 g of benzoyl peroxide to 100 g of the prepared filler. On the other hand, 50% by weight of hydroxyethyl methacrylate, 10% by weight of ethyl methacrylate, 10% by weight of urethane dimethacrylate, and 30% by weight of glycerol dimethacrylate were mixed, and further 1% by weight of triethanolamine was added to prepare Solution B. Powder A and solution B were cured to produce a chemical polymerization temporary sealing material. The cured body after being immersed in water for 24 hours with respect to the cured body after polymerization exhibited 3% curing expansion. In addition, a 3 mm square, 2 mm deep cavity was dug into the bovine teeth and filled. One day after storage in water, it was confirmed that it was compatible with no gap on the fossa wall and could be used as a temporary sealant.

Comparative Example 1 1 g of benzoyl peroxide was added to 10 g of methyl methacrylate. The solution was slowly dropped and polymerized over about 5 hours while stirring vigorously in distilled water heated to 80 ° C. After polymerization, the mixture was filtered with a filter paper and dried at 60 ° C. for 24 hours to obtain a filler. 50% by weight of this filler, 35% by weight of urethane dimethacrylate and 15% by weight of triethylene glycol dimethacrylate are mixed, 1% by weight of camphorquinone and 1% by weight of sodium benzenesulfinate are added as a catalyst, and photopolymerization type temporary sealing A material was prepared. The cured body after 24 hours had 3% curing shrinkage relative to the cured body after polymerization. In addition, a 3 mm square, 2 mm deep cavity was dug into the bovine teeth and filled. One day after storage in water, a gap in the fossa was observed.

Claims (1)

A polymerizable composition comprising a filler and a matrix, (1) a matrix-forming component comprising a polymerizable hydrophilic methacrylate monomer and a methacrylate-based crosslinking agent.
(2) A polymer or copolymer of a hydrophilic methacrylate (acrylate) monomer, or a polymer or copolymer of a hydrophilic methacrylate (acrylate) monomer containing an inorganic compound.
(3) A dental temporary sealing material that causes water absorption expansion in a state in which a polymer obtained by polymerizing a composition comprising a polymerization catalyst is immersed in water.