JP7416580B2 - Powder-liquid dental resin-reinforced glass ionomer cement composition - Google Patents

Description

The present invention provides a resin-reinforced glass ionomer cement composition for dental fillings for restoring teeth whose form has been partially damaged due to caries, fracture, etc., or a dental prosthesis device that is bonded to a tooth whose form has been damaged. The present invention also relates to a resin-reinforced glass ionomer cement composition for dental luting. More specifically, it exhibits high surface curability even under humid conditions, which prevents the surface from becoming cloudy even if it comes into contact with moisture in the early stages of curing, and the cured product exhibits high mechanical properties while exhibiting low water absorption expansion. This invention relates to a powder-type resin-reinforced glass ionomer cement composition for dental fillings, or a powder-liquid-type resin-reinforced glass ionomer cement composition for dental luting, which exhibits excellent coloring resistance and excellent storage stability. It is.

In clinical dentistry, we fill teeth with composite resin for dental fillings or glass ionomer cement for dental fillings in order to aesthetically and functionally restore teeth whose morphology has been partially damaged due to caries, fracture, etc. Direct restorations are performed, and indirect restorations are performed in which a dental prosthetic device is bonded or bonded to the tooth using a dental adhesive resin cement or a dental bonding glass ionomer cement.

In general, dental resin materials, such as dental filling composite resins and dental adhesive resin cements, include matrix resins made of several types of polymerizable monomers, glass fillers, and organic-inorganic composite fillers. It contains a filler and a polymerization initiator as main components, and is cured by photopolymerization and/or chemical polymerization. Dental resin materials have excellent aesthetic properties due to their high mechanical properties and high transparency, and in the case of photocurable materials, the composition can be cured at the timing intended by the surgeon by light irradiation. It has been widely used in recent years because it has advantages in operability, such as the ability to However, many dental resin materials do not have self-adhesive properties to the tooth structure, and when applying these materials, it is necessary to use a dental primer and/or a dental bonding material, making the operation complicated. be. Further, if moisture remains on the tooth surface of a dental primer and/or a dental bonding material, the permeability and hardenability of the dental primer and/or dental bonding material into the tooth structure will be significantly reduced, so moisture proofing is important when applying them. Therefore, in cases where moisture proofing is difficult, there is a risk of poor adhesion due to the influence of moisture. Furthermore, the effect of preventing secondary caries through sustained release of fluoride ions has only been observed in some commercially available products.

On the other hand, dental glass ionomer cements, such as glass ionomer cements for dental fillings and glass ionomer cements for dental luting, generally contain acid-reactive glasses such as polycarboxylic acid, water, and fluoroaluminosilicate glass. The main component is powder, and it is hardened by an acid-base reaction between polycarboxylic acid and acid-reactive glass powder. Dental glass ionomer cement exhibits self-adhesive properties due to the action of polycarboxylic acid in its components, so it has the advantage of not requiring the use of dental bonding materials or dental primers. It can also be applied to areas where moisture proofing is difficult, such as root caries, because the ingredients contain water. Furthermore, since fluoride ions are continuously and slowly released from the cured product, a preventive effect on secondary caries can be expected. On the other hand, dental glass ionomer cement has lower mechanical properties than dental resin-based materials, so its application is limited to repairing areas where stress is not easily applied. In addition, since dental glass ionomer cement is opaque, it can be used to fill a cavity with glass ionomer cement for dental fillings, or when dental luting glass ionomer cement is used to create a translucent dental implant in areas where tooth morphology has been damaged. When the prosthetic device is bonded, the color compatibility with the teeth or the dental prosthetic device is low, leaving an aesthetic problem. Furthermore, since the hardening of dental glass ionomer cement progresses gradually, the operator cannot carry out the next operations, such as correcting the shape, polishing, or removing excess cement, for several minutes until the hardening has progressed to a certain extent. Furthermore, if moisture comes into contact with the material during the initial stage of curing, the surface may become cloudy.

On the other hand, in order to compensate for the respective drawbacks of dental resin-based materials and dental glass ionomer cement, photopolymerization and/or Dental resin-reinforced glass ionomer cements have been proposed that can be cured through multiple mechanisms of chemical polymerization and acid-base reactions.

For example, Patent Document 1 describes a polycarboxylic acid having a polymerizable group, an acid-reactive powder (fluoroaluminosilicate glass powder, etc.), water, a polymerizable monomer (2-hydroxyethyl methacrylate, etc.), and a photopolymerization initiator. A dental resin-reinforced glass ionomer cement composition has been disclosed that can be cured by both photopolymerization and acid-base reaction mechanisms.

Patent Document 2 discloses that photopolymerization can be carried out by including a polycarboxylic acid, an acid-reactive powder, water, a (meth)acrylate polymerizable monomer, and a photopolymerization initiator and a chemical polymerization initiator as a polymerization initiator. A dental resin-reinforced glass ionomer cement composition is disclosed that is curable by three mechanisms: chemical polymerization, chemical polymerization, and acid-base reaction.

Further, Patent Document 3 proposes a dental resin-reinforced glass ionomer cement composition whose adhesiveness to tooth structure is improved by further adding a polymerizable monomer having an acidic group.

The dental resin-reinforced glass ionomer cement composition shown above combines the respective advantages of dental glass ionomer cement and dental resin-based materials, and has long-term sustained fluoride release, compared to conventional dental glass ionomer cement. It has greater transparency than dental glass ionomer cement. In addition, when photo-curing properties are added, the composition can be cured by light irradiation at the timing the surgeon intends, so unlike conventional dental glass ionomer cements, there is no need to wait for the composition to cure. have. Furthermore, by adding hardenability to the polymerizable monomer through radical polymerization, the surface becomes cloudy due to contact with moisture in the early stage of hardening, which was a problem with conventional dental glass ionomer cement that hardens only through acid-base reactions. is relatively less likely to occur.

However, dental resin-reinforced glass ionomer cement compositions contain water that does not contribute to polymerization hardening, so the hardenability of polymerizable monomers through radical polymerization is low, and hardenability is still low on surfaces that are further inhibited by oxygen. It was insufficient. For this reason, the cured product of the dental resin-reinforced glass ionomer cement composition was easily colored. In addition, dental resin-reinforced glass ionomer cement compositions contain hydrophilic polymerizable monomers as a main component in consideration of compatibility with water contained in the composition. Therefore, the cured product had a large amount of water absorption, which tended to increase the water absorption expansion. Further, there was a need for further improvement in the clouding of the surface due to contact with moisture during the initial stage of curing.

Furthermore, since the liquid material of the dental resin-reinforced glass ionomer cement composition containing polycarboxylic acid and water has a low pH, the coexisting polymerizable monomers are hydrolyzed, causing various problems. Specifically, when a (meth)acrylate polymerizable monomer, which is most commonly used in dental materials, is used, the ester bond of the (meth)acrylate group undergoes hydrolysis, resulting in polymerization. There were problems with storage stability, such as the production of highly active methacrylic acid or acrylic acid, which caused the liquid material to gel during storage and the mechanical properties of the cured product to deteriorate. This tendency was particularly noticeable when the liquid material contained a polymerizable monomer having an acidic group.

On the other hand, techniques have been disclosed for applying (meth)acrylamide-based polymerizable monomers, which are less susceptible to hydrolysis, to various dental materials. For example, in Patent Document 4, by applying a di- to penta-functional (meth)acrylamide-based polymerizable monomer, it is resistant to hydrolysis even in the presence of acidic group-containing polymerizable monomers and has improved storage stability. Techniques for obtaining various superior dental materials are disclosed. However, these patent documents do not suggest any effects other than improvement in storage stability that can be obtained when a (meth)acrylamide-based polymerizable monomer is applied to a dental resin-reinforced glass ionomer cement composition. Moreover, nothing is disclosed about the structure or number of functional groups of a (meth)acrylamide-based polymerizable monomer suitable for application to a dental resin-reinforced glass ionomer cement composition.

Japanese Unexamined Patent Publication No. 1-308855 Patent No. 3288698 Japanese Patent Application Publication No. 2014-152179 Patent No. 4171600

Conventional dental resin-reinforced glass ionomer cements are photopolymerized and/or chemically polymerized, which makes the surface of the cured product less likely to become cloudy due to contact with moisture in the early stage of curing, but this has been sufficiently improved. However, there was a need for further improvement in surface hardening properties. In addition, since the cured product expands greatly after absorbing water, the patient may feel uncomfortable due to the restoration being lifted up, and in some cases, there is a risk that the occlusion with the opposing teeth may deteriorate. Furthermore, the property of being easily colored has not yet been improved, and it has not been possible to maintain the aesthetic appearance of the repaired site over a long period of time. Therefore, the present invention maintains the excellent properties of conventional dental resin-reinforced glass ionomer cement compositions, further improves surface hardening properties, exhibits less water absorption expansion and excellent coloring resistance, and further improves various properties. An object of the present invention is to provide a dental resin-reinforced glass ionomer cement composition that can stably express the following over a long period of time and has excellent storage stability.

The present inventors conducted intensive studies to solve the above problems, and found that the basic components of conventional dental resin-reinforced glass ionomer cement are acid-reactive glass powder, typified by fluoroaluminosilicate glass powder, and water. , and polymers of acidic group-containing polymerizable monomers represented by polyacrylic acid, polymerizable monomers, and polymerization initiators, (meth)acrylate-based polymerizable monomers having hydroxyl groups as polymerizable monomers. By simultaneously blending trifunctional or higher-functional (meth)acrylamide-based polymerizable monomers with polymers, the curing properties of the polymerizable monomers in the coexistence of water are dramatically improved, resulting in an excellent surface. It has been found that while exhibiting curability, the surface of the cured product is less likely to be colored, and furthermore, water absorption and expansion are reduced. In addition, the storage stability of the liquid material was improved by blending trifunctional or higher functional (meth)acrylamide polymerizable monomers, and acidic group-containing polymerizable monomers were blended to improve adhesion to tooth structure. It has been found that excellent storage stability is exhibited even in cases where Furthermore, as the (meth)acrylate polymerizable monomer having a hydroxyl group, a monofunctional (meth)acrylate polymerizable monomer having a hydroxyl group and a di- to tetrafunctional (meth)acrylate polymerizable monomer having a hydroxyl group are used. When both of these are included in a specific ratio, and/or when a tetrafunctional or higher (meth)acrylamide polymerizable monomer is blended as a trifunctional or higher functional (meth)acrylamide polymerizable monomer, the surface It was discovered that the curability and coloring resistance were further improved, and the water absorption expansion was further reduced, leading to the completion of the present invention.

That is, the above-mentioned problem is (a) a powder material containing an acid-reactive glass powder, (b) water, (c) a polymer of an acidic group-containing polymerizable monomer, and (d) a (meth)acrylate system having a hydroxyl group. It is composed of a liquid material containing a polymerizable monomer, and (e) a trifunctional or higher functional (meth)acrylamide polymerizable monomer, and (f) polymerization initiation is applied to at least one of the powder material and the liquid material. This is achieved by the dental resin-reinforced glass ionomer cement composition of the present invention containing the agent.

Further, the dental resin-reinforced glass ionomer cement composition of the present invention preferably further includes (g) an acidic group-containing polymerizable monomer in at least one of the powder material and the liquid material.

Further, it is preferable that the polymer of the acidic group-containing polymerizable monomer (c) is a polymer of α,β-unsaturated carboxylic acid.

In addition, the (d) hydroxyl group-containing (meth)acrylate polymerizable monomer is a hydroxyl group-containing monofunctional (meth)acrylate polymerizable monomer and a hydroxyl group-containing 2- to 4-functional (meth)acrylate polymerizable monomer. and a monofunctional (meth)acrylate polymerizable monomer having a hydroxyl group and a di- to tetrafunctional (meth)acrylate polymerizable monomer having a hydroxyl group in a weight ratio. , preferably 1:2 to 4:1.

Further, the (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer is preferably a tetrafunctional or higher functional (meth)acrylamide polymerizable monomer.

Moreover, it is more preferable that the (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer is a compound represented by the following formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, which may be the same or different from each other. R ² is a straight chain or branched chain having 2 to 6 carbon atoms that may have a substituent. represents an alkylene group, and may be the same or different.)

Further, in the compound represented by formula (1), it is more preferable that all R ¹ are hydrogen atoms.

Moreover, it is more preferable that the (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer is a compound represented by the following formula (2).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

Furthermore, in the compound represented by formula (2), it is more preferable that all R ¹ are hydrogen atoms.

The dental resin-reinforced glass ionomer cement composition of the present invention exhibits high surface hardening properties even under wet conditions. This makes it difficult for the surface to become cloudy due to poor curing even in cases where it is difficult to remove moisture. Furthermore, since the cured product exhibits excellent mechanical properties and color resistance, the initial repaired state can be maintained for a long period of time. Furthermore, because there is little water absorption and expansion, discomfort during occlusion due to lifting of the restoration is less likely to occur. In addition to these, it has excellent storage stability, so it can stably exhibit its properties over a long period of time.

The present invention will be explained in more detail below.
The dental resin-reinforced glass ionomer cement composition of the present invention comprises (a) a powder material containing an acid-reactive glass powder, (b) water, (c) a polymer of an acidic group-containing polymerizable monomer, ( d) A liquid material containing a (meth)acrylate polymerizable monomer having a hydroxyl group, and (e) a trifunctional or higher functional (meth)acrylamide polymerizable monomer, and a combination of the powder material and the liquid material. At least one of them contains (f) a polymerization initiator, and optionally at least one of the powder material and the liquid material contains (g) an acidic group-containing polymerizable monomer. In this specification, (meth)acrylate comprehensively represents both acrylate and methacrylate, (meth)acryloyl comprehensively represents both acryloyl and methacryloyl, and (meth)acrylamide comprehensively represents acrylamide and methacrylamide.

The acid-reactive glass powder (a) that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention must contain an acid-reactive element and fluorine. By containing an acid-reactive element, the acid-reactive glass powder undergoes an acid-base reaction with the acidic group of the polymer of (c) acidic group-containing polymerizable monomer, which will be described later, in the presence of water. . Specific examples of acid-reactive elements include, but are not limited to, sodium, potassium, calcium, strontium, barium, lanthanum, aluminum, and zinc. One type or two or more types of these acid-reactive elements may be included, and the content thereof is not particularly limited.

Furthermore, in order to impart X-ray contrast properties to the dental resin-reinforced glass ionomer cement composition of the present invention, it is desirable to include an X-ray opaque element in the acid-reactive glass powder. Specific examples of X-ray opaque elements include, but are not limited to, strontium, lanthanum, zirconium, titanium, yttrium, ytterbium, tantalum, tin, tellurium, tungsten, and bismuth. Further, there are no particular limitations on other elements contained in the acid-reactive glass powder, and the acid-reactive glass powder in the present invention can contain various elements.

Acid-reactive glass powder includes aluminosilicate glass, borosilicate glass, aluminoborate glass, boroaluminosilicate glass, phosphate glass, which contains the acid-reactive element shown above, fluorine, and an X-ray opaque element. Examples include boric acid glass and silica glass, but are not limited to these.

Furthermore, the shape of the acid-reactive glass powder is not particularly limited, and any particle shape such as spherical, acicular, plate-like, crushed, and scaly shapes can be used without any restriction. These acid-reactive glass powders can be used alone or in combination.

The method for producing these acid-reactive glass powders is not particularly limited, and any production method such as a melting method, a gas phase method, a sol-gel method, etc. can be used without any problem. Among these, it is preferable to use acid-reactive glass powder produced by a melting method or a sol-gel method, which allows easy control of the types and contents of elements contained in the acid-reactive glass powder.

Acid-reactive glass powder that is generally sold as a filler can be used without any processing such as pulverization, but the use of the dental resin reinforced glass ionomer cement composition of the present invention is Depending on the purpose, it can be appropriately pulverized to adjust to a desired average particle size. The pulverization method is not particularly limited, and any pulverization method, wet or dry, can be used. Specifically, it can be pulverized using a high-speed rotating mill such as a hammer mill or a turbo mill, a container-driven media mill such as a ball mill or a vibration mill, a media stirring mill such as a sand grinder or an attritor, a jet mill, or the like.

For example, when using the dental resin-reinforced glass ionomer cement composition of the present invention as a material for filling or building an abutment, the average particle size of the acid-reactive glass powder is It is preferably in the range of 0.01 to 30.0 μm, more preferably in the range of 0.01 to 10.0 μm.

Furthermore, when the dental resin-reinforced glass ionomer cement composition of the present invention is used for bonding, the average particle diameter of the acid-reactive glass powder is 0.01 to 10.0 μm because a thin coating is required. It is preferably in the range of 0.01 to 5.0 μm, and more preferably in the range of 0.01 to 5.0 μm.

When the average particle size of the acid-reactive glass powder is less than 0.01 μm, its surface area increases and it becomes impossible to include it in a large amount in the composition, which may cause a decrease in mechanical properties. In addition, the viscosity of the kneaded product may increase, resulting in poor operability.

When used as a material for filling or building an abutment, if the average particle diameter of the acid-reactive glass powder exceeds 30.0 μm, the surface of the material after polishing becomes rough, which may cause discoloration. In addition, when used as a bonding material, if the average particle size of the acid-reactive glass powder exceeds 10.0 μm, the coating thickness becomes thick and the bonded dental prosthetic device lifts, making it impossible to obtain the intended fit. There is a fear.

For the purpose of adjusting the operability, hardening characteristics, mechanical properties, etc. of the dental resin-reinforced glass ionomer cement composition of the present invention, the acid-reactive glass powder is composed of (c) an acidic group-containing polymerizable monomer as described below. Various surface treatments and heat treatments, agglomeration treatments in liquid phase or gas phase, microencapsulation treatment to cover the surface with organic matter, or surface It is possible to perform a treatment such as grafting, which functionalizes it with an organic substance. Moreover, there is no problem in performing these treatments alone or in combination of several types. Among these, it is preferable to perform surface treatment or heat treatment because it is easy to control various properties and has excellent productivity.

Specific examples of surface treatment methods for acid-reactive glass powder include cleaning with an acid such as phosphoric acid or acetic acid, surface treatment with an acidic compound such as tartaric acid or polycarboxylic acid, surface treatment with a fluoride such as aluminum fluoride, Examples include surface treatment with a silane compound such as γ-methacryloyloxypropyltrimethoxysilane or tetramethoxysilane. The surface treatment methods that can be used in the present invention are not limited to those described above, and these surface treatment methods can be used alone or in combination.

A specific example of a heat treatment method for acid-reactive glass powder includes a treatment method in which the powder is heated at a temperature of 100 to 800° C. for 1 to 72 hours using an electric furnace or the like. The heat treatment method that can be used in the present invention is not limited to the above-described method, and there is no problem whether the heat treatment is performed at a single temperature or at multiple temperatures.

(b) Water that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention does not have an adverse effect on various properties such as hardenability and mechanical properties of the dental resin-reinforced glass ionomer cement composition. It can be used without any restrictions as long as it does not contain any impurities. Specifically, it is preferable to use distilled water or ion-exchanged water.

The polymer of (c) acidic group-containing polymerizable monomer that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention is a polymerizable monomer containing at least one acidic group in the molecule. Any polymer obtained by polymerizing a polymer can be used without any restrictions. Although it is preferable that the polymer of (c) acidic group-containing polymerizable monomer be blended into the liquid material, there is no problem even if a part of it is blended into the powder material.

(c) The acidic group-containing polymerizable monomer that can be used to obtain a polymer of the acidic group-containing polymerizable monomer is not limited to the type of acidic group, and any polymerizable monomer having an acidic group can be used. Even monomers can be used. Moreover, the number (monofunctional or polyfunctional) of radically polymerizable unsaturated groups possessed by this acidic group-containing polymerizable monomer and the types thereof can be used without any restriction.

Specific examples of the acidic group possessed by the acidic group-containing polymerizable monomer include a phosphoric acid group, a pyrophosphoric acid group, a phosphonic acid group, a carboxyl group, a sulfonic acid group, a thiophosphoric acid group, but are limited to these. It is not something that will be done.

Specific examples of the polymerizable unsaturated group possessed by the acidic group-containing polymerizable monomer include (meth)acryloyl group, (meth)acrylamide group, styryl group, vinyl group, allyl group, etc. It is not limited to. Among these unsaturated groups, a (meth)acryloyl group or a (meth)acrylamide group is preferable, and a (meth)acryloyl group is more preferable.

Furthermore, these acidic group-containing polymerizable monomers can also have other functional groups such as an alkyl group, a halogen, an amino group, a glycidyl group, and/or a hydroxyl group in the molecule.

Specific examples of acidic group-containing polymerizable monomers that can be used to obtain a polymer of (c) acidic group-containing polymerizable monomer and that have a (meth)acryloyl group as an unsaturated group are listed below. .

Examples of the acidic group-containing polymerizable monomer having a phosphoric acid group include (meth)acryloyloxymethyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, and 3-(meth)acryloyloxypropyl dihydro. Genphosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl Dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyl Oxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, bis [2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[3-(meth)acryloyloxypropyl] hydrogen phosphate, bis[4-(meth)acryloyloxybutyl] hydrogen phosphate, bis[6-(meth) ) acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] Hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl 2'-bromoethyl hydro Examples include, but are not limited to, gen phosphate and the like.

In addition, examples of the acidic group-containing polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[3-(meth)acryloyloxypropyl] pyrophosphate, and bis[4-(meth)acryloyloxypropyl] pyrophosphate. (meth)acryloyloxybutyl], bis[5-(meth)acryloyloxypentyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[7-(meth)acryloyloxyheptyl] pyrophosphate, Bis[8-(meth)acryloyloxyoctyl] pyrophosphate, Bis[9-(meth)acryloyloxynonyl] pyrophosphate, Bis[10-(meth)acryloyloxydecyl] pyrophosphate, Bis[12-(meth)pyrophosphate ) acryloyloxydodecyl], tris[2-(meth)acryloyloxyethyl] pyrophosphate, tetra[2-(meth)acryloyloxyethyl] pyrophosphate, and the like, but are not limited to these.

In addition, examples of the acidic group-containing polymerizable monomer having a phosphonic acid group include 5-(meth)acryloyloxypentyl-3-phosphonopropionate and 6-(meth)acryloyloxyhexyl-3-phosphonopropionate. pionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate, Examples include (meth)acryloyloxyethyl phenylphosphonate, but are not limited thereto.

In addition, examples of the acidic group-containing polymerizable monomer having a carboxyl group include (meth)acrylic acid, 2-chloroacrylic acid, 3-chloro(meth)acrylic acid, 2-cyanoacrylic acid, aconitic acid, mesaconic acid, Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, glutaconic acid, citraconic acid, utraconic acid, 1,4-di(meth)acryloyloxyethylpyromellitic acid, 6-(meth)acryloyloxynaphthalene- 1,2,6-tricarboxylic acid, 1-butene-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, N-(meth)acryloyl-p-aminobenzoic acid, N- (meth)acryloyl-5-aminosalicylic acid, 4-(meth)acryloyloxyethyltrimellitic acid and its anhydride, 4-(meth)acryloyloxybutyltrimellitic acid and its anhydride, 2-(meth)acryloyloxybenzoic acid Acid, β-(meth)acryloyloxyethyl hydrogen succinate, β-(meth)acryloyloxyethyl hydrogen maleate, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, p-vinyl Benzoic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxybutyloxycarbonylphthalic acid, 4-(meth)acryloyloxyhexyloxycarbonylphthalic acid, 4-(meth)acryloyloxyoctyloxy Carbonyl phthalic acid, 4-(meth)acryloyloxydecyloxycarbonylphthalic acid and their acid anhydrides, 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, Examples include 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, etc. However, it is not limited to these.

In addition, examples of acidic group-containing polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth)acrylate, and 4-(meth)acrylate. ) acryloyloxybenzenesulfonic acid, 3-(meth)acryloyloxypropanesulfonic acid, etc., but are not limited to these.

In addition, examples of the acidic group-containing polymerizable monomer having a thiophosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, and 4-(meth)acryloyloxyethyl dihydrogenthiophosphate. ) Acryloyloxybutyldihydrogenthiophosphate, 5-(meth)acryloyloxypentyldihydrogenthiophosphate, 6-(meth)acryloyloxyhexyldihydrogenthiophosphate, 7-(meth)acryloyloxyheptyldihydrogenthiophosphate phosphate, 8-(meth)acryloyloxyoctyldihydrogenthiophosphate, 9-(meth)acryloyloxynonyldihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, etc. It is not limited to.

The acidic group-containing polymerizable monomers shown above may be used alone or in combination to synthesize a polymer of acidic group-containing polymerizable monomers without any problem. In addition, an acidic group-containing polymerizable monomer having at least one or more acidic groups in the molecule and a polymerizable monomer not having an acidic group can be copolymerized to form an acidic group-containing polymerizable monomer. There is no problem in synthesizing this polymer.

Among these acidic group-containing polymerizable monomers, α,β-unsaturated carboxylic acid-based acidic group-containing polymerizable monomers are preferably used. The α,β-unsaturated carboxylic acid group-containing polymerizable monomer that can be used at this time is not particularly limited, and the number of carboxyl groups in the molecule, carboxylic acid anhydride, or other substituent It can be used regardless of the presence or absence of etc.

Specific examples of these α,β-unsaturated carboxylic acid group-containing polymerizable monomers include (meth)acrylic acid, 2-chloroacrylic acid, 3-chloro(meth)acrylic acid, and 2-chloro(meth)acrylic acid. Cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, glutaconic acid, citraconic acid, utraconic acid, tiglic acid, 1-butene-1,2,4-tricarboxylic acid Examples include, but are not limited to, acid, 3-butene-1,2,3-tricarboxylic acid, and the like.

The method of polymerizing various polymerizable monomers is not particularly limited, and any method such as solution polymerization, suspension polymerization, emulsion polymerization, etc. can be used without any restriction. Furthermore, the polymerization initiator and chain transfer agent that can be used during the synthesis of the polymer may be appropriately selected in order to obtain the desired polymer. The polymer of the acidic group-containing polymerizable monomer thus obtained can be used alone or in combination of several types.

The resulting polymer of acidic group-containing polymerizable monomers is treated with sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. for the purpose of adjusting operating margin time and curing time, or improving storage stability. using an alkali metal hydroxide, or an alkali metal carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate, or an alkali metal hydrogen carbonate such as sodium hydrogen carbonate, potassium hydrogen carbonate, or lithium hydrogen carbonate, etc. It may be used after neutralizing some of the acidic groups. The compounds used for this neutralization are not limited to these, and may be used alone or in combination without any problem.

Furthermore, there is no problem even if the polymer of the acidic group-containing polymerizable monomer has an unsaturated group capable of radical polymerization. However, (b) polymers of acidic group-containing polymerizable monomers having unsaturated groups tend to have relatively low solubility in water, and their blending amount tends to be low. It is more preferable that the polymer of the acidic group-containing polymerizable monomer does not have unsaturated groups, since the physical properties may deteriorate.

Among these, polymers of acidic group-containing polymerizable monomers (polyacrylic acid) synthesized using only acrylic acid as a starting material, acrylic acid and maleic acid, acrylic acid and maleic anhydride, acrylic acid and itaconic acid, It is more preferable to use a copolymer of acidic group-containing polymerizable monomers synthesized using two or more types of starting materials, such as acrylic acid and 3-butene-1,2,3-tricarboxylic acid.

Further, the weight average molecular weight of the polymer of the acidic group-containing polymerizable monomer is preferably in the range of 10,000 to 500,000, more preferably in the range of 20,000 to 300,000, More preferably, it is in the range of 20,000 to 200,000. If the weight average molecular weight of the polymer of the acidic group-containing polymerizable monomer is less than 10,000, the mechanical properties of the cured product will become too low, which may cause problems in durability. On the other hand, if the weight average molecular weight exceeds 500,000, the viscosity of the kneaded product increases when the dental resin-reinforced glass ionomer cement composition is kneaded, which may cause problems in operability.

(d) The (meth)acrylate polymerizable monomer having a hydroxyl group that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention is capable of radical polymerization with at least one hydroxyl group in the molecule. Any polymerizable monomer having at least one (meth)acrylate group as an unsaturated group can be used without any restriction.

(d) Examples of (meth)acrylate polymerizable monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate (2-HEMA), 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono( meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, glycerin Mono(meth)acrylate, erythritol mono(meth)acrylate, addition products of phenols and glycidyl(meth)acrylate, such as 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-hydroxy-3-naphthoxy Monofunctional (meth)acrylate polymerizable monomers such as propyl (meth)acrylate, 2-hydroxypropyl-1,3-di(meth)acrylate (GDMA), 3-hydroxypropyl-1,2-di(meth)acrylate ) acrylate, bisphenol A diglycidyl (meth)acrylate (Bis-GMA), and polyfunctional (meth)acrylate-based polymerizable monomers such as 2-hydroxy-3-acryloyloxypropyl methacrylate (GDA). In addition, sugar alcohols (erythritol, arabinitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, etc.), monosaccharides (arabinose, xylose, mannose, galactose, fructose, etc.), disaccharides (sucrose, maltose, lactose, trehalose, etc.) ), and polyfunctional (meth)acrylate polymerizable monomers in which two or more hydroxyl groups of trisaccharides (maltotriose, raffinose, etc.) are substituted with substituents having polymerizable unsaturated groups. The body can also be suitably used, but is not limited thereto.

Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate, bisphenol A diglycidyl (meth)acrylate (Bis-GMA), 2-hydroxypropyl-1 , 3-di(meth)acrylate (GDMA), and 2-hydroxy-3-acryloyloxypropyl methacrylate (GDA) are particularly preferred. Note that two or more types of these (meth)acrylate polymerizable monomers having a hydroxyl group may be used in combination as desired.

In the dental resin-reinforced glass ionomer cement composition of the present invention, (d) a (meth)acrylate polymerizable monomer having a hydroxyl group is a monofunctional (meth)acrylate polymerizable monomer having a hydroxyl group; Contains both a monofunctional (meth)acrylate polymerizable monomer having a hydroxyl group and a 2- to 4-functional (meth)acrylate having a hydroxyl group. The blending ratio of the polymerizable monomers is preferably 1:2 to 4:1 by weight. By using such combinations and blending ratios of (meth)acrylate polymerizable monomers having hydroxyl groups, (b) water, (c) a polymer of acidic group-containing polymerizable monomers, and (e) Since trifunctional or higher functional (meth)acrylamide polymerizable monomers are more likely to be uniformly compatible with each other, mechanical properties and transparency after curing can be improved. Furthermore, the 2- to 4-functional (meth)acrylate polymerizable monomer having a hydroxyl group is more preferably a difunctional (meth)acrylate polymerizable monomer having a hydroxyl group.

The (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention has three or more (meth)acrylamide groups in the molecule. Any polymerizable monomer can be used without any restrictions. Note that (e) trifunctional or higher functional (meth)acrylamide polymerizable monomers that do not have acidic groups and/or hydroxyl groups are more effective in improving surface hardening properties and coloring resistance, and reducing water absorption expansion. It is preferred because it is easy to obtain.

(e) Specific examples of trifunctional or higher functional (meth)acrylamide polymerizable monomers include those represented by the following formula (1) and the following formula (3).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, which may be the same or different from each other. R ² is a straight chain or branched chain having 2 to 6 carbon atoms that may have a substituent. represents an alkylene group, and may be the same or different.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group. m represents an integer of 2 to 4. n represents an integer of 2 to 4. k represents 0 or 1. Plural R ¹ , m represents They may be the same or different.)

More specific (e) trifunctional or higher functional (meth)acrylamide polymerizable monomers include those represented by the following formulas (2) and (4) to (7).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

Among these, a (meth)acrylamide polymerizable monomer having four or more functionalities is preferable, a polymerizable monomer represented by the above formula (1) is more preferable, and a polymerizable monomer represented by the above formula (2) is preferable. It is more preferably a polymerizable monomer represented by the formula (2) above, and most preferably a polymerizable monomer in which all R ¹ are hydrogen atoms.

As the polymerization initiator (f) that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention, any known photopolymerization initiator and/or chemical polymerization initiator can be used without any restriction. Note that (f) the polymerization initiator may be blended in at least one of the powder material and the liquid material as long as it can sufficiently harden the resin component, and various polymerization initiator systems may be used. I can do it.

Examples of the photopolymerization initiator include those made of a photosensitizer, photosensitizer/photopolymerization accelerator, and the like. Specific examples of photosensitizers include benzyl, camphorquinone, α-naphthyl, acetonaphcene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1 , 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone , 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, thioxanthone such as 2,4-diisopropylthioxanthone, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone benzophenones such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl) ) Acyl phosphine oxides such as phenylphosphine oxide, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone- α-aminoacetophenones such as 1st class, ketals such as benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2-methoxyethyl ketal), 3-(4-methoxybenzoyl)coumarin, 3-benzoyl-5,7-dimethoxycoumarin , coumarins such as 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin), bis(cyclopentadienyl)-bis[2,6-difluoro- 3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro- Examples include, but are not limited to, titanocenes such as (4-disiloxyphenyl)-titanium.

Specific examples of photopolymerization accelerators include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, and N,N-dimethylaniline. p-Toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylamino Benzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N,N-dimethylanthranilic acid methyl ester, N,N-dihydroxyethylaniline , N,N-dihydroxyethyl-p-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α - Naphthylamine, N,N-dimethyl-β-naphthylamine, triethanolamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylhexylamine, N,N-dimethyldodecyl Tertiary amines such as amines, N,N-dimethylstearylamine, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, 2,2'-(n-butylimino)diethanol, N-phenylglycine Secondary amines such as 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3,5-trimethylbarbituric acid, sodium 1,3,5-trimethylbarbiturate, 1 , barbituric acids such as calcium 3,5-trimethylbarbiturate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversate, dioctyltin bis(mercaptoacetic acid isooctyl ester) salt, tetramethyl-1, Examples include tin compounds such as 3-diacetoxydistanoxane, aldehyde compounds such as lauryl aldehyde and terephthalaldehyde, and sulfur-containing compounds such as dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanethiol, and thiosalcylic acid. , but not limited to these.

Furthermore, in order to improve photopolymerization promotion ability, in addition to the photopolymerization promoters mentioned above, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropane It is effective to add oxycarboxylic acids such as 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, dimethylolpropionic acid, but not limited thereto.

As the chemical polymerization initiator, peroxide/amine compound, peroxide/amine compound/aromatic sulfinic acid or its salt, aromatic sulfonyl compound, peroxide/amine compound/(thio)barbituric acid compound, or Redox type polymerization initiator system consisting of (thio)barbiturate compound, peroxide/amine compound/borate compound, peroxide/ascorbic acid compound, peroxide/thiourea/vanadium compound or copper compound, oxygen Examples include organometallic polymerization initiator systems that initiate polymerization by reacting with water and water. Furthermore, aromatic sulfinates, borate compounds, and (thio)barbiturates can initiate polymerization by reacting with acidic compounds, but are not limited thereto.

Peroxides include sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, sodium peroxodiphosphate, potassium peroxodiphosphate, ammonium peroxodiphosphate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2 , 4-dichlorobenzoyl peroxide, diacetyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetra Methyl butyl hydroperoxide, t-amyl hydroperoxide, iso-propylbenzene hydroperoxide, 5-phenyl-4-pentenyl hydroperoxide, t-butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, 1,1-bis( Examples include, but are not limited to, t-butylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, and t-butylperoxybenzoate.

As the amine compound, aromatic secondary or aromatic tertiary amines are preferable, and specific examples include N-methyl-p-toluidine, N-(2-hydroxyethyl)-p-toluidine, and p-methylamino. Ethyl benzoate, N-methylaniline, N-(2-hydroxyethyl)aniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-bis(2-hydroxyethyl) -p-toluidine, ethyl p-dimethylaminobenzoate, N,N-dimethylaniline, N,N-bis(2-hydroxyethyl)aniline and the like, but are not limited to these.

Examples of aromatic sulfinic acids or salts thereof, or aromatic sulfonyl compounds include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, Isopropylbenzenesulfinic acid and its sodium, potassium, lithium or ammonium salts, or benzenesulfonyl chloride, benzenesulfonyl fluoride, benzenesulfonamide, benzenesulfonyl hydrazide, p-toluenesulfonyl chloride, p-toluenesulfonyl fluoride , p-toluenesulfonamide, p-toluenesulfonyl hydrazide and the like, but are not limited to these.

Examples of the (thio)barbituric acid compound or (thio)barbiturate compound include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-Butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 5-laurylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3- Dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1, 3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-phenyl-5-benzylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, thiobarbituric acid, 1 , 3-dimethylthiobarbituric acid, 5-phenylthiobarbituric acid, and their alkali metal salts (lithium, sodium, potassium salts, etc.), alkaline earth metal salts (calcium, strontium, barium salts, etc.), ammonium salts , tetramethylammonium salt, and tetraethylammonium salt, but are not limited thereto.

Examples of borate compounds include trialkyl phenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, Monoalkyltriphenylboron, monoalkyltris(p-chlorophenyl)boron, monoalkyltris(p-fluorophenyl)boron, monoalkyltris(p-butylphenyl)boron, monoalkyltris(p-butyloxyphenyl)boron, Tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron (alkyl group is n-butyl group, n- octyl group, n-dodecyl group, etc.) sodium salt, potassium salt, lithium salt, magnesium salt, tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, methylpyridinium salt, ethylpyridinium salt, methylquinolinium salt, Examples include, but are not limited to, ethylquinolinium salts.

Examples of ascorbic acid compounds include L(+)-ascorbic acid, isoascorbic acid, sodium L(+)-ascorbate, potassium L(+)-ascorbate, calcium L(+)-ascorbate, sodium isoascorbate, etc. Examples include, but are not limited to.

Examples of thiourea compounds include 1,3-dimethylthiourea, tetramethylthiourea, 1,1-diethylthiourea, 1,1,3,3-tetraethylthiourea, 1-allyl-2-thiourea, 1,3-diallylthio Urea, 1,3-dibutylthiourea, 1,3-diphenyl-2-thiourea, 1,3-dicyclohexylthiourea, ethylenethiourea, N-methylthiourea, N-phenylthiourea, N-benzoylthiourea, N-acetylthiourea Examples include, but are not limited to, urea and the like.

Examples of the vanadium compound include, but are not limited to, vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, and the like.

Copper compounds include, but are not limited to, copper chloride, copper acetate, copper naphthenate, copper salicylate, copper gluconate, copper oleate, copper benzoate, copper acetylacetonate, copper naphthenate, etc. isn't it.

Examples of organometallic polymerization initiators include, but are not limited to, organoboron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide.

These polymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method. In addition, there is no problem even if these polymerization initiators are subjected to secondary treatment such as being encapsulated in microcapsules, if necessary.

The dental resin-reinforced glass ionomer cement composition of the present invention may optionally contain (g) an acidic group-containing polymerizable monomer in order to improve adhesion to teeth, base metals, alumina, zirconia, etc. I can do it. (g) The acidic group-containing polymerizable monomer may be the same as the acidic group-containing polymerizable monomer that can be used to obtain the polymer of (c) the acidic group-containing polymerizable monomer. can. Furthermore, (g) the acidic group-containing polymerizable monomer may be used alone or in combination without any problem. Note that (g) the acidic group-containing polymerizable monomer may be blended in at least one of the powder material and/or the liquid material.

Among these, the acidic group-containing polymerizable monomer (g) is preferably a carboxyl group-containing polymerizable monomer, and more preferably has two or more carboxyl groups. By containing the carboxyl group-containing polymerizable monomer, it becomes easier to obtain a dental resin-reinforced glass ionomer cement composition that has an excellent balance between adhesiveness to teeth and mechanical properties.

The main components used in the dental resin-reinforced glass ionomer cement composition of the present invention are (a) acid-reactive glass powder, (b) water, and (c) polymerization of the acidic group-containing polymerizable monomer. (d) a (meth)acrylate polymerizable monomer having a hydroxyl group, (e) a trifunctional or more functional (meth)acrylamide polymerizable monomer, (f) a polymerization initiator, and (g) an acidic group. It is a polymerizable monomer contained, and its preferable content is as follows.

(a) The acid-reactive glass powder is preferably contained in an amount of 20 to 85 parts by weight per 100 parts by weight of the total weight of the composition excluding (f) the polymerization initiator. When the content of the acid-reactive glass powder is less than 20 parts by weight, the mechanical strength of the cured product becomes too low, which may cause problems in durability. If it exceeds 85 parts by weight, the viscosity of the kneaded product becomes high when kneaded, which may cause problems in operability. In addition, curing may be rapid and sufficient operating margin time may not be obtained.

(b) Water is preferably contained in an amount of 1 to 55 parts by weight per 100 parts by weight of the total weight of the liquid material excluding (f) the polymerization initiator. If the water content is less than 1 part by weight, acid-base reactions are less likely to occur, which may result in poor curing. When the amount exceeds 55 parts by weight, the mechanical strength of the cured product becomes too low, which may cause problems in durability.

(c) The polymer of the acidic group-containing polymerizable monomer is preferably contained in an amount of 0.1 to 40 parts by weight in 100 parts by weight of the total weight of the composition excluding (f) the polymerization initiator. If the content of the acidic group-containing polymerizable monomer is less than 0.1 part by weight, acid-base reactions are less likely to occur, which may result in poor curing. If it exceeds 40 parts by weight, the viscosity of the kneaded product becomes high when kneaded, which may cause problems in operability. In addition, curing may be rapid and sufficient operating margin time may not be obtained.

(d) The (meth)acrylate polymerizable monomer having a hydroxyl group is 100% of the total weight of the total polymerizable monomer, (b) water, and (c) the acidic group-containing polymerizable monomer. It is preferable that 3 to 60 parts by weight is contained in each part by weight. If the content of the (meth)acrylate polymerizable monomer having a hydroxyl group is less than 3 parts by weight, the compatibility of each polymerizable monomer, water, and the polymer of the acidic group-containing polymerizable monomer becomes poor; If the cured product becomes non-uniform, mechanical properties and transparency may deteriorate. If the amount exceeds 60 parts by weight, the curability of the polymerizable monomer mixture may deteriorate and the mechanical properties may deteriorate.

(e) The trifunctional or higher functional (meth)acrylamide polymerizable monomer is the total weight of the total polymerizable monomer, (b) water, and (c) acidic group-containing polymerizable monomer. It is preferably contained in an amount of 1 to 30 parts by weight per 100 parts by weight. If the content of the trifunctional or higher functional (meth)acrylamide polymerizable monomer is less than 1 part by weight, the curability of the polymerizable monomer mixture may deteriorate and the mechanical properties may deteriorate. In addition, storage stability may also deteriorate. If the amount exceeds 30 parts by weight, the compatibility of each polymerizable monomer, water, and the acidic group-containing polymerizable monomer will deteriorate, and the cured product will become non-uniform, resulting in poor mechanical properties and transparency. It may decrease.

(f) The polymerization initiator is preferably added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total weight of all polymerizable monomers. If the content of the polymerization initiator is less than 0.01 parts by weight, curability may be poor and mechanical properties may be deteriorated. If it exceeds 10 parts by weight, storage stability may deteriorate.

(g) The acidic group-containing polymerizable monomer is contained in 100 parts by weight of the total weight of all the polymerizable monomers, (b) water, and (c) the acidic group-containing polymerizable monomer. It is preferable that the content is between 20 parts by weight. If the content of the acidic group-containing polymerizable monomer is less than 1 part by weight, the adhesiveness to tooth structure may decrease. If it exceeds 20 parts by weight, curability may deteriorate and mechanical properties may deteriorate. In addition, storage stability may deteriorate.

In the dental resin-reinforced glass ionomer cement composition of the present invention, (d) a (meth)acrylate-based polymerizable monomer having a hydroxyl group is added for the purpose of improving mechanical properties within a range that does not adversely affect various properties. (e) trifunctional or higher functional (meth)acrylamide-based polymerizable monomer, and (g) acidic group-containing polymerizable monomer. As such a polymerizable monomer, there are no restrictions on the number (monofunctional or polyfunctional) of radically polymerizable unsaturated groups or their types, and known ones can be used. The polymerizable monomer having a (meth)acryloyl group as an unsaturated group will be specifically shown below as a representative example.

Monofunctional polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, and cyclohexyl (meth)acrylate. Acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ) acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, etc., but are not limited to these.

Examples of aromatic bifunctional polymerizable monomers include 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2, 2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypenta) ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2(4-(meth)acryloyloxyethoxyphenyl)-2(4-(meth)acryloyloxydiethoxyphenyl) Propane, 2(4-(meth)acryloyloxydiethoxyphenyl)-2(4-(meth)acryloyloxytriethoxyphenyl)propane, 2(4-(meth)acryloyloxydipropoxyphenyl)-2(4-( meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 2, Examples include, but are not limited to, 2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, and the like.

Examples of aliphatic bifunctional polymerizable monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. meth)acrylate, neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1, Examples include, but are not limited to, 10-decanediol di(meth)acrylate.

Examples of the trifunctional polymerizable monomer include, but are not limited to, trimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate, trimethylolmethanetri(meth)acrylate, etc. .

Examples of the tetrafunctional polymerizable monomer include, but are not limited to, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like.

As the urethane-based polymerizable monomer, polymerizable monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-chloro-2-hydroxypropyl (meth)acrylate are used. 2 derived from adducts with diisocyanate compounds such as methylcyclohexane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylbenzene, 4,4-diphenylmethane diisocyanate. Examples include di(meth)acrylates having a functional or trifunctional or more functional urethane bond, but are not limited thereto.

In addition to the (meth)acrylate group-containing polymerizable monomers mentioned above, polymerizable monomers having a sulfur atom in the molecule, polymerizable monomers having a fluoro group, and oligomers having at least one polymerizable group Alternatively, a polymer may be used. These polymerizable monomers can be used alone or in combination as necessary.

It should be noted that a polymerizable monomer having one or two (meth)acrylamide groups in the molecule may be included as long as it does not affect the properties of the dental resin-reinforced glass ionomer cement composition of the present invention. There is no problem in letting it happen.

(d) Polymerization of a (meth)acrylate polymerizable monomer having a hydroxyl group, (e) a trifunctional or higher functional (meth)acrylamide polymerizable monomer, and (g) an acidic group-containing polymerizable monomer. The content of the monomer is preferably within 5.0 parts by weight per 100 parts by weight of the total weight of the liquid material.

The dental resin-reinforced glass ionomer cement composition of the present invention includes a controlled acid-base reaction between (a) an acid-reactive glass powder and (c) a polymer of an acidic group-containing polymerizable monomer. For the purpose of adjusting the margin time and curing time, polybasic carboxylic acid, phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, etc. can be included, but the composition is not limited to these.

Specific examples of polybasic carboxylic acids that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention include tartaric acid, citric acid, maleic acid, fumaric acid, malic acid, aconitic acid, and tricarbaryl. acid, itaconic acid, 1-butene-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, and the like. The polybasic carboxylic acids described above are not limited to these, and can be used without any restrictions.

Moreover, these polybasic carboxylic acids, phosphoric acid, pyrophosphoric acid and/or tripolyphosphoric acid can be used alone or in combination of several types. The polybasic carboxylic acid, phosphoric acid, pyrophosphoric acid and/or tripolyphosphoric acid is preferably contained in an amount of 0.1 to 15.0 parts by weight per 100 parts by weight of the total weight of the composition.

Furthermore, the dental resin-reinforced glass ionomer cement composition of the present invention may contain a surfactant for the purpose of improving kneading properties, as long as it does not affect various properties. The surfactant that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention may be either an ionic surfactant or a nonionic surfactant.

Specific examples of ionic surfactants include aliphatic carboxylic acid metal salts such as sodium stearate, sulfated aliphatic carboxylic acid metal salts such as sodium dioctyl sulfosuccinate, and stearyl sulfate. Examples include metal salts of higher alcohol sulfate esters such as sodium.

Examples of the cationic surfactant include adducts of higher alkylamines and ethylene oxide, amines made from lower amines, and alkyltrimethylammonium salts such as lauryltrimethylammonium chloride. Furthermore, examples of the amphoteric surfactant include metal salts of higher alkylaminopropionic acids such as sodium stearylaminopropionate, betaines such as lauryl dimethyl betaine, and the like.

In addition, nonionic surfactants include polyethylene glycol type or polypropylene glycol type in which ethylene oxide or propylene oxide is added to higher alcohols, alkylphenols, fatty acids, higher aliphatic amines, aliphatic amides, etc. Examples include polyhydric alcohols, diethanolamines, and polyhydric alcohol types in which sugars and fatty acids are ester bonded.

The surfactants described above are not limited to these, and can be used without any restrictions. Further, these surfactants can be used alone or in combination. The surfactant is preferably contained in an amount of 0.001 to 5.0 parts by weight per 100 parts by weight of the total weight of the composition.

Furthermore, non-acid-reactive powder may be added to the dental resin-reinforced glass ionomer cement composition of the present invention for the purpose of adjusting operability, mechanical properties, or hardening properties, as long as it does not adversely affect various properties. can be included.

The non-acid-reactive powder that can be used in the dental resin-reinforced glass ionomer cement composition of the present invention is any powder that does not contain any element that reacts with the acidic groups of the acidic group-containing polymerizable monomer. It can be used without particular limitation.

Examples of the non-acid-reactive powder include those known as dental filling materials, such as inorganic fillers, organic fillers, and organic-inorganic composite fillers, and there are no restrictions when these powders are used alone or in combination. It can be used without Among them, it is particularly preferable to use inorganic fillers. Further, the shape of these non-acid-reactive powders is not particularly limited, and may be any particle shape such as spherical, acicular, plate-like, crushed, scale-like, or aggregates thereof; It is not limited. The average particle diameter of these non-acid-reactive powders is not particularly limited, but is preferably in the range of 0.001 to 30 μm.

Specific examples of inorganic fillers include quartz, amorphous silica, ultrafine silica, various glasses that do not contain elements that react with acidic groups (glass produced by melting method, synthetic glass produced by sol-gel method, and synthetic glass produced by gas phase reaction). Examples include, but are not limited to, silicon nitride, silicon carbide, boron carbide, etc.

The non-acid-reactive powder is preferably contained in an amount of 0.001 to 40 parts by weight per 100 parts by weight of the total weight of the composition.

The dental resin-reinforced glass ionomer cement composition of the present invention may optionally contain various known additives, if necessary. Examples of additives that can be used in the present invention include polymerization inhibitors, chain transfer agents, colorants, anti-discoloration materials, fluorescent materials, ultraviolet absorbers, antibacterial materials, preservatives, and the like.

The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Components (a) to (g) and other components used to prepare the dental resin-reinforced glass ionomer cement compositions of Examples and Comparative Examples and their abbreviations are as follows.

[(a) Acid-reactive glass powder]
・CK-Si-1: Silane-treated fluoroaluminosilicate glass powder 1
(50% particle size: 4.5 μm)
・CK-Si-2: Silane-treated fluoroaluminosilicate glass powder 2
(50% particle size: 8.0 μm)

[(b) Water]
·Distilled water

[(c) Polymer of acidic group-containing polymerizable monomer]
・PCA1: Acrylic acid homopolymer powder (weight average molecular weight: 50,000)
・PCA2: Acrylic acid-3-butene-1,2,3-tricarboxylic acid copolymer powder (weight average molecular weight: 80,000)
・PCA3: Acrylic acid-maleic acid copolymer powder (weight average molecular weight: 60,000)

[(d) (meth)acrylate polymerizable monomer having hydroxyl group]
・HEMA: 2-hydroxyethyl methacrylate ・Bis-GMA: Bisphenol A diglycidyl methacrylate ・GDMA: Glycerin dimethacrylate ・GDA: 2-hydroxy-3-acryloyloxypropyl methacrylate

[(e) Trifunctional or higher functional (meth)acrylamide polymerizable monomer]
Tetrafunctional acrylamide polymerizable monomer・FAM-401 (manufactured by Fujifilm Corporation): Compound represented by formula (2), in which all R ¹ are hydrogen atoms・FAM-402 (manufactured by Fujifilm Corporation) : Compound represented by formula (5) Trifunctional acrylamide polymerizable monomer・FAM-301 (manufactured by Fujifilm Corporation): Compound represented by formula (4)・FAM-302L (Fujifilm Corporation) ): Compound represented by formula (7)

[(f) Polymerization initiator]
・CQ: dl-camphorquinone ・DMBE: ethyl p-dimethylaminobenzoate ・DM-3B: N,N-dimethylaminoethyl methacrylate ・APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide ・Bis-APO: Bis (2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure 819)
・p-TSNa: Sodium p-toluenesulfinate ・KPS: Potassium peroxodisulfate ・AA: Ascorbic acid

[(g) Acidic group-containing polymerizable monomer]
・4-MET: 4-methacryloxyethyl trimellitic acid ・4-AET: 4-acryloxyethyl trimellitic acid ・10-MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[others]
・14EG: Polyethylene glycol #600 dimethacrylate ・HEAA: Hydroxyethyl acrylamide ・2AM: N,N'-methylenebismethacrylamide

The method for producing fluoroaluminosilicate glass powder is as follows.

[Production of fluoroaluminosilicate glass powder 1]
Various raw materials for silicon dioxide, aluminum oxide, sodium fluoride, and strontium carbonate (glass composition: SiO ₂ 26.4% by weight, Al ₂ O ₃ 29.3% by weight, SrO 20.5% by weight, P ₂ O ₅ 10. 9, 2.5% by weight of Na ₂ O, 10.4% by weight of F), and then the raw material mixture was melted at 1400° C. in a melting furnace. Glass was obtained by taking out the melt from the melting furnace and quenching it in water. The obtained glass was crushed to obtain fluoroaluminosilicate glass powder 1. The 50% particle size of this glass powder was measured using a laser diffraction particle size analyzer (Microtrac MT3300EXII, manufactured by Nikkiso Co., Ltd.) and was found to be 4.5 μm.

[Production of fluoroaluminosilicate glass powder 2]
After obtaining glass in the same manner as fluoroaluminosilicate glass powder 1, fluoroaluminosilicate glass powder 2 having a 50% particle size of 8.0 μm was obtained by adjusting the grinding time.

The method for silane treatment of fluoroaluminosilicate glass powder is as follows.

[Silane treatment of fluoroaluminosilicate glass powders 1 and 2]
After dispersing 200 g of fluoroaluminosilicate glass powder 1 or 2 in 500 mL of water, 2 g of 3-methacryloyloxypropyltrimethoxysilane was added and stirred at room temperature for 2 hours. After distilling off the solvent under reduced pressure, the powders were further dried at 100° C. for 5 hours to obtain silane-treated fluoroaluminosilicate glass powders 1 and 2: CK-Si-1 and CK-Si-2.

[Preparation of powder materials and liquid materials]
Each component was mixed in the ratios shown in Tables 1 to 3 to prepare powder and liquid materials for dental resin-reinforced glass ionomer cement compositions used in Examples and Comparative Examples.

Regarding the dental resin-reinforced glass ionomer cement compositions (Examples 1 to 9, Comparative Examples 1 to 6) in which these powder materials and liquid materials were kneaded in the combinations shown in Table 4 and in the powder/liquid ratio, the surface Curability, storage stability, coloring resistance (coloring test), water absorption linear expansion coefficient, and compressive strength were evaluated. In addition, a commercially available dental resin-reinforced glass ionomer cement (Fuji II LC (color tone: A2)/GC) was similarly evaluated (Comparative Example 7). The test results are shown in Table 4. The evaluation method is as shown below.

<Surface hardening>
A stainless steel mold (diameter 10 mm x thickness 0.5 mm: disk shape) was placed on a glass plate placed in a constant temperature bath at a temperature of 37°C and a humidity of 100%, and a dental resin-reinforced mold shown in Examples or Comparative Examples was prepared. A kneaded glass ionomer cement composition was filled into a mold. After removing the excess kneaded material so that the surface is flat, with the surface open, a light irradiator for dental polymerization (trade name: Penbrite, manufactured by Shofusha Co., Ltd.) is used for 10 minutes from a height of 5 mm. The kneaded product was cured by irradiation with light for seconds, and was used as a test specimen. The surface of the test piece was strongly rubbed using a plastic spatula to check the surface condition such as the presence or absence of scratches and the extent of the scratches. After that, water was dropped on the surface and left for 1 minute, then the moisture was wiped off with a nonwoven cloth and the surface condition (white turbidity of the surface) was checked again. The evaluation criteria are as follows.
◎: There is no stickiness on the surface of the test specimen, and there are almost no scratches or cloudiness.
○: The surface of the test piece is not sticky, but there are some scratches and cloudiness in some parts.
Δ: The surface of the test piece was slightly sticky due to the residual unpolymerized polymerizable monomer, and there were some scratches and cloudiness in most parts.
×: The surface of the test specimen was sticky due to the residual unpolymerized polymerizable monomer, and there were many scratches and cloudy whiteness on the entire surface.
In addition, ◎, 〇, and △ are those that can withstand clinical use.

<Evaluation of storage stability>
The compatibility of the dental resin-reinforced glass ionomer cement compositions shown in Examples and Comparative Examples was evaluated immediately after preparation. After storing the powder material and liquid material in a thermostatic chamber at 50° C. for 2 months, the kneading properties were evaluated again and compared with the kneading properties immediately after preparation. The evaluation criteria are as follows.
A: Almost no change.
B: Kneadability decreases.
C: Separation or gelation of the liquid material occurs, or the kneading property is significantly reduced.
In addition, A and B were determined to be durable for clinical use even after storage.

<Coloring test>
Place a stainless steel mold (diameter 10 mm x thickness 1 mm: disk shape) on a smooth glass plate, and fill the mold with a kneaded product of the dental resin-reinforced glass ionomer cement composition shown in Examples or Comparative Examples. did. After curing the kneaded product by irradiating it with light for 10 seconds using a dental polymerization light irradiator (trade name: Pembrite, manufactured by Shofusha), the cured product was taken out of the mold and used as a test specimen. Measure the L*, a*, b ^* values of the L ^* a ^* b ^* color space using a colorimeter (Konica Minolta CM-5) using the SCI method, light source ^D65 , viewing angle 2 ^° , and on a white plate. did. After the measurement, the test specimen was immersed in 5 mL of rhodamine solution (0.1%) at 37° C. for 24 hours, then washed with water and dried. After removing the side surface of the specimen (side surface of the disk (unpolymerized layer)) with #600 abrasive paper, the L ^* , a ^* , and b ^* values were measured again, and the color difference before and after immersion in the rhodamine solution was calculated using the following formula. Calculated. Measurements were performed on three specimens per sample, and the average value was determined.
ΔE = ((L ^* ₁ - L ^* ₂ ) ² + (a ^* ₁ - a ^* ₂ ) ² + (b ^* ₁ - b ^* ₂ ) ² ) ^1/2
Each parameter shown on the right side of the formula is as follows.
L ^* ₁ : L ^* value before coloring L ^* ₂ : L ^* value after coloring a ^* ₁ : A ^* value before coloring a ^* ₂ : A ^* value after coloring b ^* ₁ : B ^* value before coloring b ^* ₂ : b ^* value after coloring The criteria for the "coloring test" shown in the table are as follows.
A: ΔE is 0 to less than 40: The test specimen is not colored to slightly colored.
B: ΔE is 40 to less than 50: The test specimen is colored to some extent.
C: ΔE is 50 or more: The specimen is significantly colored.
Note that A and B can withstand long-term clinical use. If it is 50 or more, it will not be in complete harmony with the natural teeth.

<Water absorption linear expansion coefficient>
A divisible stainless steel mold (diameter 4 mm x height 6 mm: cylindrical shape) was placed on a smooth glass plate, and a kneaded product of the dental resin-reinforced glass ionomer cement composition shown in Examples or Comparative Examples was placed in the mold. filled inside. After pressing the top surface of the filled kneaded product with a smooth glass plate, the kneaded product is cured by irradiating it with light for 10 seconds using a dental polymerization light irradiator (trade name: Penbrite, manufactured by Shofusha). I let it happen. After leaving it for 1 hour in a constant temperature and humidity chamber at 37° C. and 100% relative humidity, the cured product was taken out of the mold and used as a test specimen. The length of the test piece in the axial direction was measured using a micrometer (manufactured by Mitutoyo), and this was used as the initial value. After the test specimen was immersed in distilled water at 37° C. for 24 hours from the end of kneading, the length in the axial direction was similarly measured, and this was taken as the test value. Using the obtained values, the water absorption linear expansion coefficient was calculated using the following formula. Measurements were performed on three specimens per sample, and the average value was determined.
Water absorption linear expansion coefficient (%) = (test value - initial value) x 100/initial value A value of less than 1.0 means that it can withstand long-term clinical use. If it exceeds 1.0, there is a risk that the tooth root etc. will break.

<Compressive strength test>
A divisible stainless steel mold (diameter 4 mm x height 6 mm: cylindrical shape) was placed on a smooth glass plate, and a kneaded product of the dental resin-reinforced glass ionomer cement composition shown in Examples or Comparative Examples was placed in the mold. filled inside. After pressing the top surface of the filled kneaded product with a smooth glass plate, the kneaded product is cured by irradiating it with light for 10 seconds using a dental polymerization light irradiator (trade name: Penbrite, manufactured by Shofusha). I let it happen. After leaving it in a constant temperature and humidity chamber at 37°C and 100% relative humidity for 1 hour, the cured product was removed from the mold and immersed in distilled water at 37°C for 24 hours after kneading was completed. . According to JIST6609-1 (ISO9917-1), using a universal testing machine (Instron 5567A: manufactured by Instron Japan), a cylindrical test specimen was tested in the axial direction at a crosshead speed of 1.0 mm/min. A load was applied under these conditions, and the compressive strength (MPa) was measured. Measurements were performed on five specimens per sample, and the average value was determined.
In addition, as stated in the ISO9917-1 standard, a value of 100 or more is suitable for clinical use.

As shown in Table 4, the dental resin-reinforced glass ionomer cement compositions of Examples 1 to 9 had excellent surface hardening properties and exhibited high compressive strength. Furthermore, the cured product had little coloring and a low coefficient of water absorption linear expansion. Furthermore, the powder material and liquid material maintained their kneading properties immediately after preparation even after being stored at 50° C. for 2 months. On the other hand, the dental resin-reinforced glass ionomer cement compositions of Comparative Examples 1 to 6 and the commercially available dental resin-reinforced glass ionomer cement (Comparative Example 7) were the dental resin-reinforced glass ionomer cement compositions of Examples 1 to 9. Compared to cement compositions, they were inferior in any of the properties of surface hardening, compressive strength, coloring resistance, coefficient of water absorption linear expansion, or storage stability.

The dental resin-reinforced glass ionomer cement composition of the present invention is useful for filling restorations of teeth whose morphology has been partially damaged due to caries or fracture, and for bonding dental prosthetic devices to teeth whose morphology has been impaired. It can be used for etc.

Claims (8)

(a) Powder material containing acid-reactive glass powder, (b) water, (c) polymer of acidic group-containing polymerizable monomer, (d) (meth)acrylate-based polymerizable monomer having hydroxyl group , and (e) a liquid material containing a trifunctional or higher functional (meth)acrylamide polymerizable monomer, and at least one of the powder material and the liquid material contains (f) a polymerization initiator;
The (d) hydroxyl group-containing (meth)acrylate polymerizable monomer is a hydroxyl group-containing monofunctional (meth)acrylate polymerizable monomer and a hydroxyl group-containing 2- to 4-functional (meth)acrylate polymerizable monomer. The blending ratio of a monofunctional (meth)acrylate polymerizable monomer having a hydroxyl group and a di- to tetrafunctional (meth)acrylate polymerizable monomer having a hydroxyl group is 1 by weight. :2 to 4:1, a dental resin-reinforced glass ionomer cement composition. The dental resin-reinforced glass ionomer according to claim 1, wherein the (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer is a tetrafunctional or higher functional (meth)acrylamide polymerizable monomer. cement composition. (a) Powder material containing acid-reactive glass powder, (b) water, (c) polymer of acidic group-containing polymerizable monomer, (d) (meth)acrylate-based polymerizable monomer having hydroxyl group , and (e) a liquid material containing a trifunctional or higher functional (meth)acrylamide polymerizable monomer, and at least one of the powder material and the liquid material contains (f) a polymerization initiator;
A dental resin-reinforced glass ionomer cement composition, wherein the (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer is a compound represented by the following formula (1).
(In the formula, R ¹ represents a hydrogen atom or a methyl group, which may be the same or different from each other. R ² is a straight chain or branched chain having 2 to 6 carbon atoms that may have a substituent. represents an alkylene group, and may be the same or different.) The dental resin-reinforced glass ionomer cement composition according to claim 3, wherein in the compound represented by formula (1), all R ¹ are hydrogen atoms. (a) Powder material containing acid-reactive glass powder, (b) water, (c) polymer of acidic group-containing polymerizable monomer, (d) (meth)acrylate-based polymerizable monomer having hydroxyl group , and (e) a liquid material containing a trifunctional or higher functional (meth)acrylamide polymerizable monomer, and at least one of the powder material and the liquid material contains (f) a polymerization initiator;
A dental resin-reinforced glass ionomer cement composition, wherein the (e) trifunctional or higher functional (meth)acrylamide polymerizable monomer is a compound represented by the following formula (2).
(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other.) The dental resin-reinforced glass ionomer cement composition according to claim 5, wherein in the compound represented by formula (2), all R ¹ are hydrogen atoms. The dental resin-reinforced glass ionomer cement composition according to any one of claims 1 to 6, wherein at least one of the powder material and the liquid material further contains (g) an acidic group-containing polymerizable monomer. The dental resin-reinforced glass ionomer cement according to any one of claims 1 to 7, wherein the polymer of the acidic group-containing polymerizable monomer (c) is a polymer of α,β-unsaturated carboxylic acid. Composition.