Dental resin-reinforced glass ionomer cement kit

Abstract

To provide a dental resin-reinforced glass ionomer cement kit comprising a dental tooth surface treatment material composition and a dental resin-reinforced glass ionomer cement composition, which exhibits high adhesiveness to tooth structure with a simple procedure without complicated operations.SOLUTION: A dental resin-reinforced glass ionomer cement kit is provided, including a dental tooth surface treatment material composition (i) and a dental resin-reinforced glass ionomer cement composition (ii), wherein the dental tooth surface treatment material composition (i) includes: (A) 20 mass% or more and 79 mass% or less of a water-soluble organic solvent; (B) 20 mass% or more and 79 mass% or less of water; and (C) 1 mass% or more and 30 mass% or less of a polymerizable monomer having acid anhydride structure, and wherein the dental resin-reinforced glass ionomer cement composition (ii) includes: (D) an acid-reactive glass powder; (B) water; (E) a polymer of acidic group-containing polymerizable monomer; (F) a trifunctional or higher functional (meth)acrylamide polymerizable monomer; (G) a (meth)acrylate polymerizable monomer having a hydroxyl group; and (H) a polymerization initiator.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dental resin-reinforced glass ionomer cement kit for repairing teeth whose shape has been partially damaged mainly due to caries, fractures, etc., or for bonding or adhering dental prosthetic devices to teeth whose shape has been damaged. [Background technology]

[0002] In clinical dentistry, in order to aesthetically and functionally restore teeth that have been partially damaged by caries, fractures, etc., direct restoration is performed by filling the tooth with a dental composite resin for filling or a dental glass ionomer cement for filling, and indirect restoration is performed by adhering or bonding a dental prosthetic device to the tooth using a dental adhesive resin cement or a dental glass ionomer cement for bonding.

[0003] In general, dental resin-based materials, such as dental filling composite resins and dental adhesive resin cements, have high mechanical properties and excellent aesthetics due to their high transparency, and also have the advantage of ease of use, so they have been widely used in recent years. However, many dental resin-based materials do not have self-adhesive properties to tooth structure, and when applying these materials, it is necessary to use a dental primer and / or a dental bonding material in combination.

[0004] In contrast, dental glass ionomer cement (for filling or luting) has the advantage that it exhibits self-adhesion to tooth structure due to the action of polycarboxylic acid in its components, so there is no need to use a dental bonding material or dental primer in combination. In addition, fluoride ions are continuously released from the hardened material, which is expected to have a preventive effect against secondary caries. On the other hand, dental glass ionomer cement has lower mechanical properties compared to dental resin-based materials, so it is often used to repair areas that are not easily subjected to strong stress. In addition, dental glass ionomer cement is opaque, leaving aesthetic issues to be addressed.

[0005] On the other hand, in order to compensate for the respective drawbacks of dental resin-based materials and dental glass ionomer cements, dental resin-reinforced glass ionomer cements have been proposed that combine the component composition of dental resin-based materials with the component composition of dental glass ionomer cements.

[0006] Dental resin-reinforced glass ionomer cement combines the advantages of both dental glass ionomer cement and dental resin-based materials, and has a long-term sustained release of fluoride ions, transparency and mechanical properties that exceed those of conventional dental glass ionomer cement. In addition, when photocuring is imparted, the composition can be cured by light irradiation at the timing intended by the surgeon, which has the advantage that there is no need to wait for curing, unlike conventional dental glass ionomer cement.

[0007] Another feature of dental resin-reinforced glass ionomer cement is its self-adhesiveness to tooth structure. However, there are cases where it is desirable to improve adhesion to tooth structure, such as in the restoration of the occlusal surface of a molar tooth where occlusal forces are applied. In such cases, tooth surface preparation may be performed before applying dental resin-reinforced glass ionomer cement to the restoration site.

[0008] Patent Document 1 proposes a type of tooth surface treatment material that dissolves and removes the smear layer (tooth cutting debris) that remains on the tooth surface after cavity formation and acts as an adhesion inhibitor. Patent Document 2 also proposes a type of tooth surface treatment material that modifies the hydrophilic tooth surface, including the smear layer, to be somewhat hydrophobic, thereby improving the affinity of dental resin-reinforced glass ionomer cement, which has intermediate properties between hydrophobic and hydrophilic, to tooth tissue. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 8-217612 [Patent Document 2] Japanese Patent Application Publication No. 9-249514 Summary of the Invention [Problem to be solved by the invention]

[0010] The tooth surface treatment material in Patent Document 1 is mainly composed of an aqueous polycarboxylic acid solution, and is used by applying it to the tooth surface after cavity formation, leaving it for a certain period of time, rinsing with water, and drying. By applying this tooth surface treatment material, the smear layer dissolves in the tooth surface treatment material and is removed when rinsing with water, improving the adhesion of dental resin-reinforced glass ionomer cement to tooth structure. However, this type of tooth surface treatment material requires thorough rinsing with water after application to the tooth surface, making the process complicated.

[0011] The tooth surface treatment material of Patent Document 2 is composed mainly of an organic compound having a phosphate group or the like, a (meth)acrylate polymerizable monomer, and water, and is used by applying it to the tooth surface after cavity formation, leaving it for a certain period of time, and then drying it without rinsing with water. By applying this tooth surface treatment material, the smear layer dissolves and the (meth)acrylate polymerizable monomer penetrates into the tooth surface while incorporating the smear layer, improving the affinity between the polymerizable monomer contained in the dental resin-reinforced glass ionomer cement and the tooth surface, thereby improving adhesion.

[0012] However, it has been suggested that in order to further improve the adhesiveness of this type of tooth surface treatment material to tooth structure, it is necessary to add a chemical polymerization initiator to the two-liquid mix type, or add a photopolymerization initiator to the one-liquid type to impart polymerization hardening properties to the tooth surface treatment material. However, the former requires mixing of two liquids and requires waiting time until hardening, while the latter requires light irradiation, making the operation complicated. Furthermore, this type of tooth surface treatment material has a problem in that the ester bond of the (meth)acryloyloxy group is hydrolyzed to produce acrylic acid or methacrylic acid, which have high polymerization activity, and the gradual polymerization of these acids causes an increase in viscosity over time.

[0013] Therefore, an object of the present invention is to provide a dental tooth surface treatment composition that exhibits high adhesion to tooth substance through a simple procedure without complicated operations, and a dental resin-reinforced glass ionomer cement kit that includes a dental tooth surface treatment composition. Another object of the present invention is to provide a dental tooth surface treatment composition that has excellent storage stability and can be used with the same operational feel for a long period of time. [Means for solving the problem]

[0014] As a result of intensive research conducted by the inventors to solve the above-mentioned problems, they found that a dental tooth surface treatment composition containing as its main components a polymerizable monomer having an acid anhydride structure and water has excellent storage stability, and when combined with a dental resin-reinforced glass ionomer cement composition containing a tri- or higher functional (meth)acrylamide-based polymerizable monomer, it exhibits specifically high adhesion to tooth substance even with an extremely simple tooth surface treatment procedure, thereby completing the present invention.

[0015] That is, the present invention provides a dental resin-reinforced glass ionomer cement kit comprising a dental tooth surface treatment composition (i) and a dental resin-reinforced glass ionomer cement composition (ii), The dental tooth surface treatment composition (i) comprises (A) a water-soluble organic solvent in an amount of 20% by mass or more and 79% by mass or less; (B) 20% by mass or more and 79% by mass or less of water, and (C) a polymerizable monomer having an acid anhydride structure in an amount of 1% by mass or more and 30% by mass or less, Including, The dental resin-reinforced glass ionomer cement composition (ii) comprises: (D) acid-reactive glass powder; (B) Water; (E) a polymer of an acidic group-containing polymerizable monomer, (F) a trifunctional or higher (meth)acrylamide polymerizable monomer, (G) a (meth)acrylate polymerizable monomer having a hydroxyl group, and (H) a polymerization initiator, The present invention provides a dental resin-reinforced glass ionomer cement kit comprising:

[0016] The present invention also provides a method for applying a dental resin-reinforced glass ionomer cement kit to tooth structure, comprising: a first step of applying a dental tooth surface treatment composition (i) to a tooth surface; a second step of immediately drying the applied surface without rinsing with water; a third step of applying the dental resin-reinforced glass ionomer cement composition (ii) to the dried surface without irradiating it with light; and a fourth step of irradiating the applied dental resin-reinforced glass ionomer cement composition (ii) with light to harden it. Effect of the Invention

[0017] The dental resin-reinforced glass ionomer cement kit of the present invention can improve the adhesion of the dental resin-reinforced glass ionomer cement composition to tooth structure by simple operations only, without the need for complicated operations such as leaving, rinsing, polymerization, etc. after applying the dental tooth surface treatment composition to the tooth surface. Furthermore, the dental resin-reinforced glass ionomer cement kit of the present invention exhibits little change in properties over time and can be used with the same feel over a long period of time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below. In this specification, the term "water-soluble" means that the solubility in water at 25°C is 3% by mass or more.

[0019] In addition, in this specification, (meth)acrylate refers to both acrylate and methacrylate, (meth)acryloyl refers to both acryloyl and methacryloyl, (meth)acrylic acid refers to both acrylic acid and methacrylic acid, and (meth)acrylamide refers to both acrylamide and methacrylamide.

[0020] The dental resin-reinforced glass ionomer cement kit of the present invention includes a dental tooth surface treatment material composition (i) and a dental resin-reinforced glass ionomer cement composition (ii). The dental tooth surface treatment material composition includes, as essential components, (A) a water-soluble organic solvent, (B) water, and (C) a polymerizable monomer having an acid anhydride structure. The dental resin-reinforced glass ionomer cement composition (ii) includes, as essential components, (D) an acid-reactive glass powder, (B) water, (E) a polymer of an acidic group-containing polymerizable monomer, (F) a trifunctional or higher (meth)acrylamide-based polymerizable monomer, (G) a (meth)acrylate-based polymerizable monomer having a hydroxyl group, and (H) a polymerization initiator.

[0021] The dental resin-reinforced glass ionomer cement kit of the present invention can be composed of a dental tooth surface treatment material composition (i) and a dental resin-reinforced glass ionomer cement composition (ii).

[0022] In the dental resin-reinforced glass ionomer cement kit of the present invention, the (C) polymerizable monomer having an acid anhydride structure may be a compound represented by the following formula (1). [ka] (In the formula, X represents an ether bond, an amide bond, an ester bond, and / or a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, and A represents a (meth)acryloyloxy group or a (meth)acrylamide group.)

[0023] In the dental resin-reinforced glass ionomer cement kit of the present invention, the (C) polymerizable monomer having an acid anhydride structure may be at least one selected from the group consisting of 4-(meth)acryloyloxyethyl trimellitic anhydride, 4-(meth)acryloylaminoethyl trimellitic anhydride, 4-(meth)acryloyloxyethyl trimellitic amide anhydride, and 4-(meth)acryloylaminoethyl trimellitic amide anhydride.

[0024] In the dental resin-reinforced glass ionomer cement kit of the present invention, the (A) water-soluble organic solvent may be at least one selected from the group consisting of ethanol, isopropanol, and acetone.

[0025] In the dental resin-reinforced glass ionomer cement kit of the present invention, the (F) tri- or higher functional (meth)acrylamide-based polymerizable monomer may be a compound represented by the following formula (2). [ka] (In the formula, R 1 R represents a hydrogen atom or a methyl group, and may be the same or different. 2 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and may be the same or different.

[0026] In the dental resin-reinforced glass ionomer cement kit of the present invention, the dental resin-reinforced glass ionomer cement composition (ii) may further contain (I) an acidic group-containing polymerizable monomer.

[0027] In the dental resin-reinforced glass ionomer cement kit of the present invention, the dental tooth surface treatment composition (i) may further contain (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate in an amount of 0.1% by mass or more and 10% by mass or less.

[0028] In the dental resin-reinforced glass ionomer cement kit of the present invention, the dental tooth surface treatment composition (i) may further contain 0.01% by mass or more and 10% by mass or less of a polymerization initiator (H).

[0029] In the dental resin-reinforced glass ionomer cement kit of the present invention, the dental resin-reinforced glass ionomer cement composition (ii) may contain 0.1% by mass or more and 30% by mass or less of a trifunctional or higher (meth)acrylamide-based polymerizable monomer (F).

[0030] First, each component to be incorporated in the dental tooth surface treatment composition (i) of the present invention will be described.

[0031] The dental tooth surface treatment material composition (i) of the present invention contains (A) a water-soluble organic solvent for the purpose of dissolving (C) a polymerizable monomer having an acid anhydride structure. (A) Water-soluble organic solvents include, but are not limited to, acetone, ethanol, methanol, acetylacetone, methyl ethyl ketone, 1-propanol, isopropanol, 1-butanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol, propylene glycol, phenol, etc. These (A) water-soluble organic solvents may be used alone or in combination of two or more kinds. Among these, ethanol, isopropanol, or acetone may be used in particular from the viewpoint of drying property.

[0032] The (A) water-soluble organic solvent is blended in the dental tooth surface treatment material composition (i) in an amount of 20% by mass to 79% by mass. If the blending amount of the (A) water-soluble organic solvent is less than 20% by mass or more than 79% by mass, sufficient adhesive strength cannot be obtained.

[0033] The dental tooth surface treatment composition (i) of the present invention contains water (B) for the purpose of penetrating the polymerizable monomer having an acid anhydride structure (C) into the tooth structure. The water (B) can be used without any restrictions as long as it does not contain impurities that adversely affect the adhesion of the dental tooth surface treatment composition (i) to the tooth structure and the various properties such as the hardening property and mechanical properties of the dental resin-reinforced glass ionomer cement composition (ii). Specifically, distilled water, purified water, or ion-exchanged water can be used. The water (B) is blended in the dental tooth surface treatment composition (i) in an amount of 20% by mass to 79% by mass. If the amount of water (B) is less than 20% by mass or more than 79% by mass, sufficient adhesive strength cannot be obtained.

[0034] The dental tooth surface treatment material composition (i) of the present invention contains a polymerizable monomer having an acid anhydride structure (C) for the purpose of modifying the hydrophilic tooth surface to be somewhat hydrophobic and improving the affinity with various polymerizable monomers contained in the dental resin-reinforced glass ionomer cement composition (ii). Examples of the acid anhydride structure include, but are not limited to, a succinic anhydride structure, a maleic anhydride structure, and a phthalic anhydride structure. Examples of the polymerizable group include, but are not limited to, a (meth)acryloyloxy group and a (meth)acrylamide group. There is no particular restriction on the number of polymerizable groups, but they can be monofunctional because they easily penetrate into tooth tissue. There is no problem even if the hydrocarbon bonded to the polymerizable group has a hydroxyl group, a halogen atom, an amino group, a glycidyl group, an ether bond, an amide bond, an ester bond, or the like.

[0035] Among them, (C) the polymerizable monomer having an acid anhydride structure can be a compound represented by formula (1). [ka] (In the formula, X represents an ether bond, an amide bond, an ester bond, and / or a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, and A represents a (meth)acryloyloxy group or a (meth)acrylamide group.)

[0036] (C) The polymerizable monomer having an acid anhydride structure may be 4-(meth)acryloyloxyethyl trimellitic anhydride, 4-(meth)acryloylaminoethyl trimellitic anhydride, 4-(meth)acryloyloxyethyl trimellitic amide anhydride, or 4-(meth)acryloylaminoethyl trimellitic amide anhydride.

[0037] The polymerizable monomer having an acid anhydride structure (C) is blended in the dental tooth surface treatment material composition (i) in an amount of 1% by mass to 30% by mass. If the blending amount of the polymerizable monomer having an acid anhydride structure (C) is less than 1% by mass, sufficient adhesive strength cannot be obtained. If the blending amount exceeds 30% by mass, the coating property becomes poor.

[0038] The dental tooth surface treatment composition (i) of the present invention may contain (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate, which is an acidic group-containing polymerizable monomer, in order to further improve adhesion to tooth structure. Unlike other acidic group-containing polymerizable monomers, (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate has the characteristic that it is difficult to reduce storage stability even if it is added to the dental tooth surface treatment composition (i) of the present invention. (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate can be added in an amount of 0.1% by mass to 10% by mass in the dental tooth surface treatment composition (i). If the amount of (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate added is less than 0.1% by mass, sufficient adhesive strength may not be obtained. If it exceeds 10% by mass, the coating property may be deteriorated.

[0039] In the dental tooth surface treatment composition (i) of the present invention, an acidic group-containing polymerizable monomer other than (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate can be optionally contained in order to balance the adhesiveness to enamel and the adhesiveness to dentin, so long as the storage stability is not decreased. Specifically, the same as the acidic group-containing polymerizable monomer (I) that can be blended in the dental resin-reinforced glass ionomer cement composition (ii) described later can be used. However, the blending amount is 1 / 3 or less, 1 / 5 or less, or 1 / 10 or less of the polymerizable monomer having an acid anhydride structure (C) contained in the dental tooth surface treatment composition (i). The dental tooth surface treatment composition (i) of the present invention can be free of an acidic group-containing polymerizable monomer other than (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate.

[0040] The dental tooth surface treatment composition (i) of the present invention may contain a polymerization initiator for the purpose of improving the polymerization activity at the adhesive interface with the dental resin-reinforced glass ionomer cement composition (ii) as long as the storage stability is not decreased. Specifically, the same polymerization initiator (H) as that which can be blended in the dental resin-reinforced glass ionomer cement composition (ii) described later can be used. The blending amount of the polymerization initiator (H) is not particularly limited, but is generally 0.01% by mass or more and 10% by mass or less in the dental tooth surface treatment composition (i). If it is less than 0.01% by mass, the polymerization activity is not improved. Also, if it exceeds 10% by mass, sufficient adhesive strength is not obtained.

[0041] The dental tooth surface treatment composition (i) of the present invention can contain any polymerizable monomer that does not have an acid anhydride structure or an acidic group. Examples of such polymerizable monomers include various polymerizable monomers that can be blended into the dental resin-reinforced glass ionomer cement composition (ii) described below. However, as the blending amount of such polymerizable monomers increases, the dental tooth surface treatment composition (i) becomes difficult to dry after application to the tooth surface, and becomes sticky after drying. Therefore, slippage may occur between the dental resin-reinforced glass ionomer cement composition (ii) to be applied next, making it difficult to perform the filling operation in particular. Therefore, the total blending amount of polymerizable monomers that do not have an acid anhydride structure or an acidic group can be 10% by mass or less, 5% by mass or less, or no blending can be performed in the dental tooth surface treatment composition (i).

[0042] Next, each component to be blended in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention will be described. The dental resin-reinforced glass ionomer cement composition (ii) can be provided in various forms such as a powder-liquid type and a two-paste type.

[0043] The powder-liquid type dental resin-reinforced glass ionomer cement composition (ii) is, for example, composed of (D) a powder material containing an acid-reactive glass powder and (B) a liquid material containing water, (E) a polymer of an acidic group-containing polymerizable monomer, (F) a tri- or higher functional (meth)acrylamide-based polymerizable monomer, and (G) a (meth)acrylate-based polymerizable monomer having a hydroxyl group, and at least one of the powder material and the liquid material can contain (H) a polymerization initiator.

[0044] In addition, the two-paste type dental resin-reinforced glass ionomer cement composition (ii) may contain, for example, (D) an acid-reactive glass powder, (E) a polymer of an acidic group-containing polymerizable monomer, (B) water, (G) a (meth)acrylate-based polymerizable monomer having a hydroxyl group, (F) a (meth)acrylamide-based polymerizable monomer having three or more functional groups, and (H) a polymerization initiator in at least one of the two pastes. In this case, the paste containing (B) water may not contain at least one of (D) an acid-reactive glass powder and (E) a polymer of an acidic group-containing polymerizable monomer. In addition, at least one of the two pastes may further contain (I) an acidic group-containing polymerizable monomer, and the paste containing (B) water may not contain at least one of (D) an acid-reactive glass powder and (I) an acidic group-containing polymerizable monomer.

[0045] The (D) acid-reactive glass powder that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention must contain an acid-reactive element and fluorine. The (D) acid-reactive glass powder contains an acid-reactive element, and in the presence of (B) water, an acid-base reaction with the acidic group of the polymer of the acidic group-containing polymerizable monomer (E), which will be described later, proceeds. Specific examples of the acid-reactive element include, but are not limited to, sodium, potassium, calcium, strontium, barium, lanthanum, aluminum, zinc, etc. These acid-reactive elements may be contained in one or more types, and the content of these elements is not particularly limited.

[0046] Furthermore, in order to impart X-ray contrast to the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, it is desirable to include an element that is X-ray opaque in the acid-reactive glass powder (D). 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. In addition, there is no particular restriction on other elements contained in the acid-reactive glass powder (D), and the acid-reactive glass powder (D) of the present invention can include various elements.

[0047] Examples of (D) acid-reactive glass powder include aluminosilicate glass, borosilicate glass, aluminoborate glass, boroaluminosilicate glass, phosphate glass, borate glass, and silica glass, which contain the above-mentioned acid-reactive elements, fluorine, and X-ray opaque elements, but are not limited to these.

[0048] Furthermore, the shape of the (D) acid-reactive glass powder is not particularly limited, and any particle shape such as spherical, needle-like, plate-like, crushed, and scaly can be used without any restrictions. These (D) acid-reactive glass powders can be used alone or in combination of several kinds.

[0049] The method for producing these (D) acid-reactive glass powders is not particularly limited, and any method such as a melting method, a gas phase method, a sol-gel method, etc. can be used without any problem. Among these, the (D) acid-reactive glass powders produced by the melting method or the sol-gel method, which are easy to control the types and contents of elements contained in the (D) acid-reactive glass powder, can be used.

[0050] (D) The acid-reactive glass powder may be a filler that is generally sold in the market and used without processing such as grinding, but may be adjusted to a desired average particle size by grinding appropriately according to the use or purpose of the dental resin-reinforced glass ionomer cement composition (ii) of the present invention. The grinding method is not particularly limited, and grinding using either a wet method or a dry method may be used. Specifically, grinding may be performed using a high-speed rotating mill such as a hammer mill or a turbo mill, a container-driven medium mill such as a ball mill or a vibration mill, a medium-agitating mill such as a sand grinder or an attritor, a jet mill, or the like.

[0051] For example, when the dental resin-reinforced glass ionomer cement composition (ii) of the present invention is used as a material for filling or core construction, high mechanical properties are required, so the average particle size of the acid-reactive glass powder (D) can be in the range of 0.01 μm or more and 30.0 μm or less, or in the range of 0.01 μm or more and 10.0 μm or less.

[0052] In addition, when the dental resin-reinforced glass ionomer cement composition (ii) of the present invention is used for bonding, a thin coating thickness is required, so the average particle size of the acid-reactive glass powder (D) can be in the range of 0.01 μm or more and 10.0 μm or less, or in the range of 0.01 μm or more and 5.0 μm or less.

[0053] (D) If the average particle size of the acid-reactive glass powder is less than 0.01 μm, the surface area increases and it becomes impossible to include a large amount of the powder in the composition, which may cause a decrease in mechanical properties. Also, the viscosity of the kneaded product increases, which may cause poor operability.

[0054] When used as a filling or core material, if the average particle size of the (D) acid-reactive glass powder exceeds 30.0 μm, the surface of the material after polishing becomes rough, which may cause discoloration. Also, when used as a cementing material, if the average particle size of the (D) acid-reactive glass powder exceeds 10.0 μm, the coating becomes too thick, which may cause the cemented dental prosthesis to lift up, preventing the intended fit.

[0055] For the purpose of adjusting the operability, hardening characteristics, mechanical characteristics, etc. of the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, the acid-reactive glass powder (D) can be subjected to various surface treatments, heat treatments, aggregation treatments in a liquid phase or a gas phase, etc., microencapsulation treatments in which the surface is encapsulated with an organic substance, or grafting treatments in which the surface is functionalized with an organic substance, within the scope of not adversely affecting the acid-base reaction with the polymer of the acidic group-containing polymerizable monomer (E) described below. Moreover, there is no problem even if these treatments are performed alone or in combination of several kinds. Among these, surface treatments or heat treatments can be performed because they are easy to control various properties and have excellent productivity.

[0056] Specific examples of the surface treatment method for the (D) acid-reactive glass powder include washing 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, surface treatment with a silane compound such as γ-methacryloyloxypropyltrimethoxysilane or tetramethoxysilane, etc. The surface treatment methods that can be used in the present invention are not limited to those mentioned above, and these surface treatment methods can be used alone or in combination.

[0057] Specific examples of the heat treatment method for (D) the acid-reactive glass powder include a treatment method in which the powder is heated in an electric furnace or the like at a temperature in the range of 100° C. to 800° C. for 1 hour to 72 hours. The heat treatment method that can be used in the present invention is not limited to the above, and there is no problem whether the heat treatment is performed at a single temperature or at multiple temperatures.

[0058] The water (B) that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention is as described in the dental tooth surface treatment material composition (i). In the two-paste type dental resin-reinforced glass ionomer cement composition (ii), the paste containing water (B) can contain a polymer of an acidic group-containing polymerizable monomer (E).

[0059] The polymer of the acidic group-containing polymerizable monomer (E) that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention can be any polymer obtained by polymerizing a polymerizable monomer that contains at least one acidic group in the molecule. In the case of the powder-liquid type dental resin-reinforced glass ionomer cement composition (ii), the polymer of the acidic group-containing polymerizable monomer (E) can be blended into the liquid material, but there is no problem if a part of it is blended into the powder material.

[0060] (E) 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 the acidic group, and any polymerizable monomer having an acidic group can be used. In addition, the number (monofunctional or polyfunctional) and the type of radically polymerizable unsaturated groups that the acidic group-containing polymerizable monomer has can be used without any limitation.

[0061] Specific examples of the acidic group contained in the acidic group-containing polymerizable monomer include, but are not limited to, a phosphate group, a pyrophosphate group, a phosphonic acid group, a carboxyl group, a sulfonic acid group, a thiophosphate group, etc. The dental resin-reinforced glass ionomer cement composition (ii) of the present invention may not contain a polymer of an acidic group-containing polymerizable monomer other than an acidic group-containing polymerizable monomer having a phosphate group, a pyrophosphate group, a phosphonic acid group, a carboxyl group, a sulfonic acid group, or a thiophosphate group.

[0062] Specific examples of the polymerizable unsaturated group possessed by the acidic group-containing polymerizable monomer include, but are not limited to, a (meth)acryloyloxy group, a (meth)acrylamide group, a styryl group, a vinyl group, an allyl group, etc. Among these unsaturated groups, a (meth)acryloyloxy group or a (meth)acrylamide group can be used, and a (meth)acryloyloxy group can be used.

[0063] Furthermore, these acidic group-containing polymerizable monomers may 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.

[0064] Specific examples of the acidic group-containing polymerizable monomer (E) that can be used to obtain a polymer of the acidic group-containing polymerizable monomer and that has a (meth)acryloyloxy group as the unsaturated group are given below.

[0065] Examples of the acidic group-containing polymerizable monomer having a phosphoric acid group include (meth)acryloyloxymethyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyhexyl dihydrogen phosphate, and 8-(meth)acryloyloxyhexyl dihydrogen phosphate. -(Meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecane Sil 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]hydride Hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl 2'-bromoethyl hydrogen phosphate and the like, but are not limited thereto.

[0066] 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, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[5-(meth)acryloyloxypentyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, and bis[7-(meth)acryloyloxyheptyl] pyrophosphate. , bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[9-(meth)acryloyloxynonyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, bis[12-(meth)acryloyloxydodecyl] pyrophosphate, tris[2-(meth)acryloyloxyethyl] pyrophosphate, tetra[2-(meth)acryloyloxyethyl] pyrophosphate, and the like, but are not limited to these.

[0067] Furthermore, examples of the acidic group-containing polymerizable monomer having a phosphonic acid group include, but are not limited to, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate, and (meth)acryloyloxyethyl phenylphosphonate.

[0068] Examples of the acidic group-containing polymerizable monomer having a carboxy 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, and 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)acryloyloxyethyl trimellitic acid and its anhydride, 4-(meth)acryloyloxybutyl trimellitic acid and its anhydride, 2-(meth)acryloyloxybenzoic acid, β-(meth)acryloyloxyethyl hydrogen succinate, β -(Meth)acryloyloxyethyl hydrogen maleate, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, p-vinyl benzoic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic acid, 4-(meth)acryloyloxybutyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyoctyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyethyl Examples of the acryloyloxycarbonyl phthalic acid include, but are not limited to, acryloyloxydecyloxycarbonylphthalic acid and its acid anhydrides, 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, and 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid.

[0069] Examples of the acidic group-containing polymerizable monomer having a sulfonic acid group include, but are not limited to, 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth)acrylate, 4-(meth)acryloyloxybenzenesulfonic acid, and 3-(meth)acryloyloxypropanesulfonic acid.

[0070] Examples of the acidic group-containing polymerizable monomer having a thiophosphate group include, but are not limited to, 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0071] The above-mentioned acidic group-containing polymerizable monomers may be used alone or in combination to synthesize a polymer of the acidic group-containing polymerizable monomer (E) without any problem. In addition, the acidic group-containing polymerizable monomer having at least one acidic group in the molecule and a polymerizable monomer having no acidic group may be copolymerized to synthesize a polymer of the acidic group-containing polymerizable monomer (E).

[0072] Among these acidic group-containing polymerizable monomers, an α,β-unsaturated carboxylic acid-based acidic group-containing polymerizable monomer can be used. The α,β-unsaturated carboxylic acid-based acidic group-containing polymerizable monomer that can be used in this case is not particularly limited, and can be used regardless of the number of carboxy groups in the molecule or the presence or absence of carboxylic anhydride or other substituents. The dental resin-reinforced glass ionomer cement composition of the present invention may not contain a polymer of an acidic group-containing polymerizable monomer other than the α,β-unsaturated carboxylic acid-based acidic group-containing polymerizable monomer.

[0073] Specific examples of these α,β-unsaturated carboxylic acid-based acidic group-containing polymerizable monomers include, but are not limited to, (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, tiglic acid, 1-butene-1,2,4-tricarboxylic acid, and 3-butene-1,2,3-tricarboxylic acid.

[0074] The method for 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 restrictions. In addition, the polymerization initiator and chain transfer agent that can be used during the synthesis of the polymer may be appropriately selected to obtain a desired polymer. The polymer of the acidic group-containing polymerizable monomer (E) thus obtained can be used alone or in combination of several kinds.

[0075] The obtained polymer of the acidic group-containing polymerizable monomer (E) may be used after a part of its acidic groups is neutralized using an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., an alkali metal carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc., or an alkali metal hydrogen carbonate such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, etc., for the purpose of adjusting the working time or the curing time, or for the purpose of improving the storage stability. The compound used for this neutralization is not limited to these, and there is no problem in using one or several kinds in combination.

[0076] Furthermore, there is no problem even if the polymer of the acidic group-containing polymerizable monomer (E) has a radically polymerizable unsaturated group. However, the polymer of the acidic group-containing polymerizable monomer (E) having an unsaturated group has a relatively low solubility in water (B) and tends to be low in the amount of the unsaturated group added, which may cause a decrease in the mechanical properties of the cured product. Therefore, the polymer of the acidic group-containing polymerizable monomer (E) may not have an unsaturated group.

[0077] Among these, a polymer (E) of an acidic group-containing polymerizable monomer (polyacrylic acid) synthesized using only acrylic acid as a starting material, or a copolymer (E) of an acidic group-containing polymerizable monomer synthesized using two or more kinds of starting materials, such as acrylic acid and maleic acid, acrylic acid and maleic anhydride, acrylic acid and itaconic acid, or acrylic acid and 3-butene-1,2,3-tricarboxylic acid, can be used.

[0078] The weight average molecular weight of the polymer of the acidic group-containing polymerizable monomer (E) can be in the range of 10,000 to 500,000, in the range of 20,000 to 300,000, or 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 (E) is less than 10,000, the mechanical properties of the cured product become too low, and durability problems may occur. On the other hand, if the weight average molecular weight exceeds 500,000, the viscosity of the kneaded product becomes high when the dental resin-reinforced glass ionomer cement composition (ii) is kneaded, and problems with operability may occur.

[0079] The (F) trifunctional or higher (meth)acrylamide polymerizable monomer that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention can be used without any restrictions as long as it is a polymerizable monomer having three or more (meth)acrylamide groups in the molecule. Note that the (F) trifunctional or higher (meth)acrylamide polymerizable monomer that does not have an acidic group and / or a hydroxyl group is more likely to be effective in improving surface hardening properties and coloring resistance, and reducing water absorption expansion.

[0080] Specific examples of the (F) trifunctional or higher (meth)acrylamide polymerizable monomer include those represented by the following formulas (2) and (3): The dental resin-reinforced glass ionomer cement composition (2) of the present invention may not contain any trifunctional or higher (meth)acrylamide polymerizable monomer other than the trifunctional or higher (meth)acrylamide polymerizable monomer represented by the following formulas (2) and (3).

[0081] [ka]

[0082] (In the formula, R 1 R represents a hydrogen atom or a methyl group, and may be the same or different. 2represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and may be the same or different.

[0083] [ka]

[0084] (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. 1 , m may be the same or different.)

[0085] More specific examples of the (F) tri- or higher functional (meth)acrylamide polymerizable monomer include those represented by the following formulas (4) and (5) to (8).

[0086] [ka]

[0087] (In the formula, R 1 represents a hydrogen atom or a methyl group, and may be the same or different.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Among these, the polymerizable monomer may be a (meth)acrylamide-based monomer having 4 or more functional groups, may be a polymerizable monomer represented by the above formula (2), may be a polymerizable monomer represented by the above formula (4), and may be a polymerizable monomer represented by the above formula (4). 1 may be a polymerizable monomer in which all of R are hydrogen atoms. In the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, it may not contain a trifunctional or higher (meth)acrylamide polymerizable monomer other than a tetrafunctional or higher (meth)acrylamide polymerizable monomer. In the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, it may not contain a trifunctional or higher (meth)acrylamide polymerizable monomer other than the polymerizable monomer represented by the above formula (2). In the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, it may not contain a trifunctional or higher (meth)acrylamide polymerizable monomer other than the polymerizable monomer represented by the above formula (4). In the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, it may not contain a trifunctional or higher (meth)acrylamide polymerizable monomer other than the polymerizable monomer represented by the above formula (4). 1 The copolymer may not contain any tri- or higher functional (meth)acrylamide polymerizable monomer other than a polymerizable monomer in which all of the monomer units are hydrogen atoms.

[0093] The (G) (meth)acrylate-based polymerizable monomer having a hydroxyl group that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention can be any polymerizable monomer having at least one hydroxyl group and at least one (meth)acryloyloxy group as a radically polymerizable unsaturated group in the molecule without any restrictions.

[0094] (G) Examples of (meth)acrylate polymerizable monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate (2-HEMA), 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)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, Examples of the polymerizable monomer include monofunctional (meth)acrylate polymerizable monomers such as 2,3-dihydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, erythritol mono(meth)acrylate, addition products of phenols and glycidyl (meth)acrylate, for example, 2-hydroxy-3-phenoxypropyl (meth)acrylate and 2-hydroxy-3-naphthoxypropyl (meth)acrylate, and polyfunctional (meth)acrylate polymerizable monomers such as 2-hydroxypropyl-1,3-di(meth)acrylate (GDMA), 3-hydroxypropyl-1,2-di(meth)acrylate, bisphenol A diglycidyl (meth)acrylate (Bis-GMA), and 2-hydroxy-3-acryloyloxypropyl methacrylate (GDA). In addition, polyfunctional (meth)acrylate polymerizable monomers in which two or more of the hydroxyl groups of 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 trisaccharides (maltotriose, raffinose, etc.) are substituted with substituents having a polymerizable unsaturated group can also be suitably used, but are not limited to these.

[0095] Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 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 suitable. Note that, as for these (G) hydroxyl group-containing (meth)acrylate polymerizable monomers, two or more kinds may be appropriately used in combination, if desired. The dental resin-reinforced glass ionomer cement composition (ii) of the present invention may not contain any (meth)acrylate polymerizable monomer having a hydroxyl group other than 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 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).

[0096] In the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, the (G) hydroxyl-containing (meth)acrylate-based polymerizable monomer includes both a monofunctional (meth)acrylate-based polymerizable monomer having a hydroxyl group and a di- to tetrafunctional (meth)acrylate-based polymerizable monomer having a hydroxyl group, and the blending ratio of the monofunctional (meth)acrylate-based polymerizable monomer having a hydroxyl group to the di- to tetrafunctional (meth)acrylate-based polymerizable monomer having a hydroxyl group can be 1:2 to 4:1 by mass ratio. By using the (G) hydroxyl-containing (meth)acrylate-based polymerizable monomer in such a combination and blending ratio, the (B) water, the (E) polymer of the acidic group-containing polymerizable monomer, and the (F) trifunctional or higher (meth)acrylamide-based polymerizable monomer can be easily and uniformly dissolved, thereby improving the mechanical properties and transparency after curing. Furthermore, the di- to tetrafunctional (meth)acrylate polymerizable monomer having a hydroxyl group may be a difunctional (meth)acrylate polymerizable monomer having a hydroxyl group.

[0097] The polymerization initiator (H) that can be used in the dental tooth surface treatment composition (i) and the dental resin-reinforced glass ionomer cement composition (ii) of the present invention may be any known photopolymerization initiator and / or chemical polymerization initiator without any restriction. In the case of the powder-liquid type dental resin-reinforced glass ionomer cement composition (ii), the polymerization initiator (H) 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 can be used.

[0098] Examples of the photopolymerization initiator include those made of a photosensitizer, photosensitizer / photopolymerization promoter, etc. Specific examples of the photosensitizer include α-diketones such as benzil, camphorquinone, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone, benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methylthioxanthone. Thioxanthones such as thioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, and other benzophenones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and other benzophenones; acylphosphine oxides such as bis(2,6-dimethoxybenzoyl)phenylphosphine oxide; α-aminoacetophenones such as 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1; ketals such as benzyl dimethyl ketal, benzyl diethyl ketal, and benzyl (2-methoxyethyl ketal); 3-(4-methoxybenzoyl)coumarin and 3-benzoyl-5,7-dimeth- coumarins such as 3,3'-oxycoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), and 3,3'-carbonylbis(7-dibutylaminocoumarin); titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium, but are not limited thereto.

[0099] Specific examples of the photopolymerization accelerator include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, and isopropyl p-dimethylaminobenzoate. amyl, N,N-dimethyl anthranilic 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 tertiary amines such as N-phenylglycine, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3,5-trimethylbarbituric acid, sodium 1,3,5-trimethylbarbiturate, 1,3,5-trimethylbarbituric acid phosphate ... Examples of suitable sulfur-containing compounds include, but are not limited to, barbiturates such as tin, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversatate, dioctyltin bis(mercaptoacetic acid isooctyl ester) salt, and tetramethyl-1,3-diacetoxydistannoxane, aldehyde compounds such as lauryl aldehyde and terephthalaldehyde, and sulfur-containing compounds such as dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanethiol, and thiosalicylic acid.

[0100] Furthermore, in order to improve the photopolymerization promoting ability, in addition to the above photopolymerization promoters, it is effective to add oxycarboxylic acids such as citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, and dimethylolpropionic acid, but the addition is not limited to these.

[0101] Examples of chemical polymerization initiators include redox-type polymerization initiator systems consisting of peroxide / amine compound, peroxide / amine compound / aromatic sulfinic acid or its salt, or aromatic sulfonyl compound, peroxide / amine compound / (thio)barbituric acid compound or (thio)barbiturate compound, peroxide / amine compound / borate compound, peroxide / ascorbic acid compound, peroxide / thiourea / vanadium compound, or copper compound, and organometallic polymerization initiator systems that react with oxygen or water to initiate polymerization. Furthermore, aromatic sulfinates, borate compounds, and (thio)barbiturates can be polymerized by reacting them with an acidic compound, but are not limited thereto.

[0102] 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, and t-butyl hydroperoxide. Examples of peroxides include, but are not limited to, 1,1,3,3-tetramethylbutyl hydroperoxide, t-amyl hydroperoxide, isopropylbenzene hydroperoxide, 5-phenyl-4-pentenyl hydroperoxide, t-butylperoxyisopropyl carbonate, methyl ethyl ketone peroxide, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, and t-butylperoxybenzoate.

[0103] The amine compound is preferably an aromatic secondary or aromatic tertiary amine, and specific examples thereof include N-methyl-p-toluidine, N-(2-hydroxyethyl)-p-toluidine, ethyl p-methylaminobenzoate, 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, and N,N-bis(2-hydroxyethyl)aniline, but are not limited to these.

[0104] 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-triisopropylbenzenesulfinic acid, and sodium salts, potassium salts, lithium salts, or ammonium salts thereof, 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 thereto.

[0105] Examples of (thio)barbituric acid compounds or (thio)barbiturate compounds 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, and the like. Examples of barbituric acid include, but are not limited to, sylbarbituric 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 salts, and tetraethylammonium salts.

[0106] Examples of borate compounds include trialkylphenyl boron, trialkyl(p-chlorophenyl) boron, trialkyl(p-fluorophenyl) boron, trialkyl(p-butylphenyl) boron, trialkyl(p-butyloxyphenyl) boron, monoalkyltriphenyl boron, monoalkyltris(p-chlorophenyl) boron, monoalkyltris(p-fluorophenyl) boron, monoalkyltris(p-butylphenyl) boron, monoalkyltris(p-butyloxyphenyl) boron, tetraphenyl boron, and tetrakis Examples of the salt include, but are not limited to, sodium salts, potassium salts, lithium salts, magnesium salts, tetramethylammonium salts, tetraethylammonium salts, tetrabutylammonium salts, methylpyridinium salts, ethylpyridinium salts, methylquinolinium salts, and ethylquinolinium salts of (p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(p-butylphenyl)boron, and tetrakis(p-butyloxyphenyl)boron (wherein the alkyl group is an n-butyl group, an n-octyl group, an n-dodecyl group, or the like).

[0107] Examples of ascorbic acid compounds include, but are not limited to, L(+)-ascorbic acid, isoascorbic acid, sodium L(+)-ascorbate, potassium L(+)-ascorbate, calcium L(+)-ascorbate, sodium isoascorbate, and the like.

[0108] Examples of thiourea compounds include, but are not limited to, 1,3-dimethylthiourea, tetramethylthiourea, 1,1-diethylthiourea, 1,1,3,3-tetraethylthiourea, 1-allyl-2-thiourea, 1,3-diallylthiourea, 1,3-dibutylthiourea, 1,3-diphenyl-2-thiourea, 1,3-dicyclohexylthiourea, ethylenethiourea, N-methylthiourea, N-phenylthiourea, N-benzoylthiourea, and N-acetylthiourea.

[0109] Examples of vanadium compounds include, but are not limited to, vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, and the like.

[0110] Examples of 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, and the like.

[0111] Examples of organometallic polymerization initiators include, but are not limited to, organoboron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide.

[0112] These polymerization initiators (H) can be used alone or in combination of two or more, regardless of the polymerization mode or polymerization method. In addition, these polymerization initiators (H) can be subjected to secondary treatment such as encapsulation in microcapsules, if necessary, without any problems.

[0113] The dental resin-reinforced glass ionomer cement composition (ii) of the present invention may contain an acidic group-containing polymerizable monomer (I) if desired in order to improve adhesion to dentin, base metals, alumina, zirconia, etc. The acidic group-containing polymerizable monomer (I) may be the same as the acidic group-containing polymerizable monomer that can be used to obtain a polymer of the acidic group-containing polymerizable monomer (E). The acidic group-containing polymerizable monomer (I) may be used alone or in combination with several kinds of monomers without any problem. In the case of the powder-liquid type dental resin-reinforced glass ionomer cement composition (ii), the acidic group-containing polymerizable monomer (I) may be blended in at least one of the powder material and / or the liquid material. In the present invention, the acidic group-containing polymerizable monomer (I) means an acidic group-containing polymerizable monomer other than the polymerizable monomer having an acid anhydride structure (C) and the 10-(meth)acryloyloxydecyl dihydrogen phosphate (J).

[0114] Among them, (I) the acidic group-containing polymerizable monomer is preferably a carboxyl group-containing polymerizable monomer, which may have two or more carboxyl groups. By including a carboxyl group-containing polymerizable monomer, it becomes easier to obtain a dental resin-reinforced glass ionomer cement composition (ii) having an excellent balance between adhesion to tooth structure and mechanical properties.

[0115] The main components used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention are the above-mentioned (D) acid-reactive glass powder, (B) water, (E) polymer of acidic group-containing polymerizable monomer, (F) tri- or higher functional (meth)acrylamide-based polymerizable monomer, (G) hydroxyl group-containing (meth)acrylate-based polymerizable monomer, (H) polymerization initiator, and (I) acidic group-containing polymerizable monomer, and the suitable contents thereof are as follows:

[0116] The (D) acid-reactive glass powder can be contained in an amount of 20% by mass or more and 85% by mass or less in 100% by mass of the total mass of the dental resin-reinforced glass ionomer cement composition (ii) excluding the (H) polymerization initiator. If the content of the (D) acid-reactive glass powder is less than 20% by mass, the mechanical strength of the cured product may be too low, resulting in problems with durability. If the content exceeds 85% by mass, the viscosity of the kneaded product may increase when kneaded, resulting in problems with operability. In addition, the curing may become too fast, resulting in insufficient time for operation.

[0117] In the case of the powder-liquid type dental resin-reinforced glass ionomer cement composition (ii), the water (B) can be contained in an amount of 1% by mass or more and 55% by mass or less based on 100% by mass of the total mass of the liquid material excluding the polymerization initiator (H). If the water (B) content is less than 1% by mass, the acid-base reaction is difficult to occur, which may cause poor curing. If it exceeds 55% by mass, the mechanical strength of the cured product may be too low, which may cause durability problems.

[0118] In the case of the two-paste type dental resin-reinforced glass ionomer cement composition (ii), the water (B) is preferably contained in an amount of 1 to 30% by mass, and can be contained in an amount of 5 to 25% by mass, based on the total weight (100% by mass) of the dental resin-reinforced glass ionomer cement composition (ii). If the water content is less than 1% by mass, the acid-base reaction is unlikely to occur, which may cause poor curing. If the water content exceeds 30% by mass, the mechanical strength of the cured product may be too low, which may cause problems with durability.

[0119] The polymer of the acidic group-containing polymerizable monomer (E) may be contained in an amount of 0.1% by mass or more and 40% by mass or less in 100% by mass of the total mass of the dental resin-reinforced glass ionomer cement composition (ii) excluding the polymerization initiator (H). If the content of the polymer of the acidic group-containing polymerizable monomer (E) is less than 0.1% by mass, the acid-base reaction is unlikely to occur, which may cause poor hardening. If the content exceeds 40% by mass, the viscosity of the kneaded product increases when kneaded, which may cause problems in operability. In addition, the hardening may be too fast to provide sufficient time for operation.

[0120] The (F) trifunctional or higher (meth)acrylamide polymerizable monomer may be contained in an amount of 1% by mass or more and 30% by mass or less in 100% by mass of the total mass of the polymer of all polymerizable monomers, (B) water, and (E) acidic group-containing polymerizable monomer in the dental resin-reinforced glass ionomer cement composition (ii). If the content of the (F) trifunctional or higher (meth)acrylamide polymerizable monomer is less than 1% by mass, the curing property of the polymerizable monomer mixture may be deteriorated, and the mechanical properties may be deteriorated. In addition, the storage stability may also be deteriorated. If the content exceeds 30% by mass, the compatibility of each polymerizable monomer, (B) water, and (E) acidic group-containing polymerizable monomer may be deteriorated, and the cured product may become nonuniform, resulting in deterioration of the mechanical properties and transparency.

[0121] The (G) hydroxyl group-containing (meth)acrylate polymerizable monomer may be contained in an amount of 3% by mass or more and 60% by mass or less in 100% by mass of the total mass of the polymer of all polymerizable monomers, (B) water, and (E) acidic group-containing polymerizable monomer in the dental resin-reinforced glass ionomer cement composition (ii). If the content of the (G) hydroxyl group-containing (meth)acrylate polymerizable monomer is less than 3% by mass, the compatibility of each polymerizable monomer, (B) water, and (E) acidic group-containing polymerizable monomer may be poor, and the cured product may become nonuniform, resulting in reduced mechanical properties and transparency. If the content exceeds 60% by mass, the curability of the polymerizable monomer mixture may be poor, resulting in reduced mechanical properties.

[0122] The polymerization initiator (H) may be added in a proportion of 0.01% by mass or more and 10% by mass or less relative to 100% by mass of the total mass of all polymerizable monomers in the dental resin-reinforced glass ionomer cement composition (ii). If the content of the polymerization initiator (H) is less than 0.01% by mass, the hardening property may deteriorate and the mechanical properties may decrease. If the content exceeds 10% by mass, the storage stability may deteriorate.

[0123] The acidic group-containing polymerizable monomer (I) may be contained in an amount of 1% by mass or more and 20% by mass or less, based on 100% by mass of the total mass of all polymerizable monomers in the dental resin-reinforced glass ionomer cement composition (ii), (B) water, and (E) the polymer of the acidic group-containing polymerizable monomer. If the content of the acidic group-containing polymerizable monomer (I) is less than 1% by mass, the adhesion to tooth structure may decrease. If it exceeds 20% by mass, the hardening property may become poor, and the mechanical properties may decrease. In addition, the storage stability may decrease.

[0124] Furthermore, when the dental resin-reinforced glass ionomer cement composition (ii) of the present invention is of a two-paste type, a thickener can be added for the purpose of adjusting the paste properties, so long as it does not adversely affect various characteristics. The thickener that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention in the case of the two-paste type can be either an inorganic thickener or an organic thickener.

[0125] Inorganic thickeners include, but are not limited to, fumed silica, calcium carbonate, calcium silicate, magnesium silicate, and clay minerals such as saponite, montmorillonite, beidellite, vermiculite, sauconite, stevensite, hectorite, smectite, tietite, and sepiolite.

[0126] Examples of organic thickeners include, but are not limited to, methylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, calcium carboxymethylcellulose, carboxypolymethylene, sodium alginate, propylene glycol alginate, sodium polyacrylate, starch, sodium starch glycolate, starch phosphate, polyvinylpyrrolidone, carboxyvinyl polymer, khaya gum, gum arabic, karaya gum, guar gum, etc. These thickeners can be used alone or in combination of two or more.

[0127] The thickener can be contained in each paste in the range of 0.1 to 20.0% by weight.

[0128] The dental resin-reinforced glass ionomer cement composition (ii) of the present invention may contain a polymerizable monomer other than (F) trifunctional or higher (meth)acrylamide polymerizable monomer, (G) hydroxyl group-containing (meth)acrylate polymerizable monomer, and (I) acidic group-containing polymerizable monomer, for the purpose of improving mechanical properties, as long as it does not adversely affect various properties. As such a polymerizable monomer, there is no restriction on the number (monofunctional or polyfunctional) of radically polymerizable unsaturated groups or their types, and known polymerizable monomers can be used. Below, the polymerizable monomer having a (meth)acryloyloxy group as an unsaturated group is specifically shown as a representative example.

[0129] Examples of monofunctional polymerizable monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)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, benzyl (meth)acrylate, and isobornyl (meth)acrylate.

[0130] 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)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2(4-(meth)acryloyloxyethoxyphenyl)-2(4-(meth)acryloyloxydiethoxyphenyl)propane, Examples of the acryloyloxyalkyl group include, but are not limited to, 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, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, and 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene.

[0131] Examples of the aliphatic bifunctional polymerizable monomer include, but are not limited to, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(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, and 1,10-decanediol di(meth)acrylate.

[0132] Examples of the trifunctional polymerizable monomer include, but are not limited to, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolmethane tri(meth)acrylate.

[0133] Examples of the tetrafunctional polymerizable monomer include, but are not limited to, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like.

[0134] Examples of urethane-based polymerizable monomers include di(meth)acrylates having a bifunctional or trifunctional or higher urethane bond derived from an adduct of a polymerizable monomer having a hydroxyl group, such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, or 3-chloro-2-hydroxypropyl(meth)acrylate, with a diisocyanate compound, such as methylcyclohexane diisocyanate, methylenebis(4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylbenzene, or 4,4-diphenylmethane diisocyanate, but are not limited thereto.

[0135] In addition to the above-mentioned (meth)acrylate group-containing polymerizable monomers, polymerizable monomers having a sulfur atom in the molecule, polymerizable monomers having a fluoro group, and oligomers or polymers having at least one polymerizable group may be used. These polymerizable monomers may be used alone or in combination as necessary.

[0136] In addition, there is no problem if a polymerizable monomer having one or two (meth)acrylamide groups in the molecule is contained in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention, so long as the presence of such a polymerizable monomer does not affect the various properties of the composition.

[0137] In the case of the powder-liquid type dental resin-reinforced glass ionomer cement composition (ii), the polymerizable monomers other than (F) tri- or higher functional (meth)acrylamide-based polymerizable monomers, (G) (meth)acrylate-based polymerizable monomers having a hydroxyl group, and (I) acidic group-containing polymerizable monomers may be contained in an amount of up to 5.0% by mass relative to the total mass of the liquid material (100% by mass).

[0138] In the case of the two-paste type dental resin-reinforced glass ionomer cement composition (ii), the polymerizable monomers other than (F) tri- or higher functional (meth)acrylamide-based polymerizable monomers, (G) (meth)acrylate-based polymerizable monomers having a hydroxyl group, and (I) acidic group-containing polymerizable monomers may be contained in an amount of 10% by weight or less based on the total mass (100% by mass) of the dental resin-reinforced glass ionomer cement composition (ii).

[0139] The dental resin-reinforced glass ionomer cement composition (ii) of the present invention may contain, but is not limited to, a polybasic carboxylic acid, phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, or the like, for the purpose of controlling the acid-base reaction between (D) the acid-reactive glass powder and (E) the polymer of the acidic group-containing polymerizable monomer and adjusting the working time and hardening time.

[0140] Specific examples of polybasic carboxylic acids that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention include tartaric acid, citric acid, maleic acid, fumaric acid, malic acid, aconitic acid, tricarballylic acid, itaconic acid, 1-butene-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, etc. The polybasic carboxylic acids described above are not limited to these, and can be used without any restrictions.

[0141] In addition, these polybasic carboxylic acids, phosphoric acids, pyrophosphoric acids, and / or tripolyphosphoric acids can be used alone or in combination of several kinds. The polybasic carboxylic acids, phosphoric acids, pyrophosphoric acids, and / or tripolyphosphoric acids are preferably contained in the range of 0.1% by mass or more and 15.0% by mass or less in 100% by mass of the total mass of the dental resin-reinforced glass ionomer cement composition (ii).

[0142] Furthermore, the dental resin-reinforced glass ionomer cement composition (ii) of the present invention may contain a surfactant for the purpose of improving the mixing property, so long as the surfactant does not affect various properties. The surfactant that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention may be either an ionic surfactant or a nonionic surfactant.

[0143] Specific examples of ionic surfactants include anionic surfactants such as metal salts of aliphatic carboxylates, e.g., sodium stearate; sulfated metal salts of aliphatic carboxylates, e.g., sodium dioctyl sulfosuccinate; and metal salts of higher alcohol sulfates, e.g., sodium stearyl sulfate.

[0144] Examples of cationic surfactants include adducts of higher alkylamines and ethylene oxide, amines prepared from lower amines, alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, etc. Examples of amphoteric surfactants include metal salts of higher alkylaminopropionic acids such as sodium stearylaminopropionate, and betaines such as lauryldimethylbetaine.

[0145] Examples of nonionic surfactants include polyethylene glycol-type or polypropylene glycol-type surfactants in which ethylene oxide or propylene oxide is added to higher alcohols, alkylphenols, fatty acids, higher aliphatic amines, aliphatic amides, or the like, and polyhydric alcohol-type surfactants in which polyhydric alcohols, diethanolamines, sugars, and fatty acids are ester-bonded.

[0146] The surfactants described above are not limited to these, and can be used without any restrictions. These surfactants can be used alone or in combination. The surfactant can be contained in the range of 0.001% by mass or more and 5.0% by mass or less in 100% by mass of the total mass of the dental resin-reinforced glass ionomer cement composition (ii).

[0147] Furthermore, the dental resin-reinforced glass ionomer cement composition (ii) of the present invention may contain a non-acid-reactive powder for the purpose of adjusting the handling properties, mechanical properties, or hardening properties, so long as the properties are not adversely affected.

[0148] The non-acid-reactive powder that can be used in the dental resin-reinforced glass ionomer cement composition (ii) of the present invention is not particularly limited as long as it does not contain an element that reacts with the acidic group possessed by the polymer of the acidic group-containing polymerizable monomer (E).

[0149] Examples of non-acid-reactive powders include known dental fillers, such as inorganic fillers, organic fillers, and organic-inorganic composite fillers, which can be used alone or in combination without any restrictions. Among them, inorganic fillers can be used. The shape of these non-acid-reactive powders is not particularly limited, and they may be any particle shape such as spherical, needle-like, plate-like, crushed, and scaly, or aggregates thereof, but is not limited thereto. The average particle size of these non-acid-reactive powders is not particularly limited, but can be in the range of 0.001 μm to 30 μm.

[0150] Specific examples of inorganic fillers include, but are not limited to, quartz, amorphous silica, ultrafine silica particles, various glasses that do not contain elements that react with acidic groups (including glasses produced by the fusion method, synthetic glasses by the sol-gel method, glasses produced by gas phase reactions, etc.), silicon nitride, silicon carbide, boron carbide, etc.

[0151] The non-acid-reactive powder may be contained in an amount of 0.001% by mass or more and 40% by mass or less, based on 100% by mass of the total mass of the dental resin-reinforced glass ionomer cement composition (ii).

[0152] The dental tooth surface treatment composition (i) and the dental resin-reinforced glass ionomer cement composition (ii) of the present invention may contain various known additives as necessary. Examples of additives that can be used in the present invention include polymerization inhibitors, chain transfer agents, colorants, discoloration prevention agents, fluorescent agents, ultraviolet absorbing agents, antibacterial agents, and preservatives.

[0153] The method for using the dental resin-reinforced glass ionomer cement kit of the present invention is as follows, but the present invention is not limited to these procedures. The method includes the following steps: a first step of applying the dental tooth surface treatment composition (i) of the present invention to a tooth surface that has been subjected to caries removal, cavity formation, etc., followed by washing with water and drying; a second step of immediately drying the applied surface without washing with water; a third step of applying the dental resin-reinforced glass ionomer cement composition (ii) of the present invention to the dried surface without irradiating it with light; and a fourth step of irradiating the applied dental resin-reinforced glass ionomer cement composition (ii) with light to harden it. Thus, the dental resin-reinforced glass ionomer cement kit of the present invention does not require polymerization of the dental tooth surface treatment composition (i) applied to the tooth surface by washing with water or irradiating it with light.

[0154] The dental resin-reinforced glass ionomer cement kit of the present invention can be used for a wide range of purposes in dental treatment, such as as a filling material and adhesive material, as well as a pit and fissure sealant, a lining material, and abutment construction material. EXAMPLES

[0155] 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 (J) and other components used to prepare the dental tooth surface treatment composition (i) and the dental resin-reinforced glass ionomer cement composition (ii) in the examples and comparative examples, as well as their abbreviations, are as follows:

[0156] [(A) Water-soluble organic solvent] ·ethanol ·acetone Propylene glycol

[0157] [(B)Water] Distilled water

[0158] [(C) Polymerizable monomer having an acid anhydride structure] 4-META: 4-Methacryloyloxyethyltrimellitic anhydride 4-AETA: 4-Acryloyloxyethyltrimellitic anhydride

[0159] [(D) Acid-reactive glass powder] ·CK-Si-1: Silane-treated fluoroaluminosilicate glass powder 1 (50% particle size: 4.5μm)

[0160] [(E) Polymer of Acidic Group-Containing Polymerizable Monomer] PCA1: Acrylic acid homopolymer powder (weight average molecular weight: 50,000)

[0161] [(F) Trifunctional or higher (meth)acrylamide polymerizable monomer] Tetrafunctional acrylamide polymerizable monomer FAM-401 (manufactured by Fujifilm Corporation): A compound represented by formula (4) in which all R1s are hydrogen atoms Trifunctional acrylamide polymerizable monomer FAM-302L (manufactured by Fujifilm Corporation): a compound represented by formula (8)

[0162] [(G) (Meth)acrylate-based polymerizable monomer having a hydroxyl group] HEMA: 2-hydroxyethyl methacrylate Bis-GMA: Bisphenol A diglycidyl methacrylate ·GDMA: Glyceryl dimethacrylate

[0163] [(H) Polymerization initiator] CQ: dl-Camphorquinone DMBE: Ethyl p-dimethylaminobenzoate ·DM-3B: Dimethylaminoethyl methacrylate p-TSNa: Sodium p-toluenesulfinate ·KPS: Potassium peroxodisulfate ·AA: Ascorbic acid ·DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine

[0164] [(I) Acidic group-containing polymerizable monomer] 4-MET: 4-methacryloyloxyethyl trimellitic acid 4-AET: 4-Acryloyloxyethyl trimellitic acid

[0165] [(J) 10-(meth)acryloyloxydecyl dihydrogen phosphate] 10-MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0166] [others] 14EG: Polyethylene glycol #600 dimethacrylate ·HEAA: Hydroxyethylacrylamide 2AM: N,N'-methylenebismethacrylamide PEG400: Polyethylene glycol Aerosil R972: Fumed silica average particle size approx. 16 nm

[0167] The method for producing the silane-treated fluoroaluminosilicate glass powder is as follows.

[0168] [Production of silane-treated fluoroaluminosilicate glass powder 1] After mixing various raw materials of silicon dioxide, aluminum oxide, aluminum phosphate, sodium fluoride, and strontium carbonate (glass composition: SiO2 26.4 mass%, Al2O3 29.3 mass%, SrO 20.5 mass%, PO5 10.9 mass%, Na2O 2.5 mass%, F 10.4 mass%), the raw material mixture was melted in a melting furnace at 1400 ° C. The melt was removed from the melting furnace and quenched in water to obtain glass. The obtained glass was pulverized to obtain fluoroaluminosilicate glass powder 1. The 50% particle size of this glass powder was measured by a laser diffraction type particle size measuring device (Microtrac MT3300EXII: manufactured by Nikkiso Co., Ltd.) and found to be 4.5 μm. Furthermore, 200 g of this fluoroaluminosilicate glass powder 1 was dispersed in 500 mL of water, and then 2 g of 3-methacryloyloxypropyltrimethoxysilane was added and stirred at room temperature for 2 hours. The solvent was removed under reduced pressure, and the residue was further dried at 100° C. for 5 hours to obtain silane-treated fluoroaluminosilicate glass powder 1.

[0169] [Preparation of dental tooth surface treatment composition] The components were mixed in the ratios shown in Tables 1 and 2 to prepare dental tooth surface treatment compositions used in the examples and comparative examples.

[0170] [Preparation of powder, liquid and paste materials for dental resin-reinforced glass ionomer cement composition] The powder, liquid and paste materials of the dental resin-reinforced glass ionomer cement compositions used in the Examples and Comparative Examples were prepared by mixing the components in the ratios shown in Tables 3 to 6. The combinations of the dental resin-reinforced glass ionomer cement compositions were as shown in Table 7.

[0171] [Table 1]

[0172] [Table 2]

[0173] [Table 3]

[0174] [Table 4]

[0175] [Table 5]

[0176] [Table 6]

[0177] [Table 7]

[0178] The dental resin-reinforced glass ionomer cement kits, which were prepared by combining these dental tooth surface treatment compositions (C1-23) and dental resin-reinforced glass ionomer cement compositions (R1-R13) as shown in Tables 8 and 9, were evaluated for applicability, drying property, shear bond strength to enamel and dentin, and storage stability. In addition, the shear bond strength to enamel and dentin of a commercially available dental filling composite resin (Lightfill II: manufactured by Matsufu Co., Ltd.) was also evaluated (Comparative Example 11). The test results are shown in Tables 8 and 9. The evaluation methods are as follows:

[0179] <Applicability> The labial surface of a bovine mandibular anterior tooth was polished with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to expose the flat surface of the dentin, which was then polished with #600 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to obtain a smooth surface. The dental tooth surface treatment composition was applied to the smooth surface after rinsing and drying, and the applicability was evaluated. The evaluation criteria are as follows: A: It is easy to apply and produces a uniform coating surface. B: The coating is sticky and difficult to apply, and the coating surface is uneven. In addition, A was determined to have good coatability.

[0180] <Drying> The labial surface of a bovine mandibular anterior tooth was polished with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to expose the flat surface of the dentin, which was then polished with #600 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to obtain a smooth surface. After washing with water and drying, the dental tooth surface treatment composition was applied to the smooth surface, which was then immediately air-dried at a discharge pressure of 0.05 MPa for 5 seconds, and the drying property was evaluated. The evaluation criteria are as follows: A: Almost no stickiness remains on the dried surface. B: Stickiness remains on the dried surface. In addition, A was determined to have good drying properties.

[0181] <Shear bond strength to enamel and dentin> The labial surface of a bovine mandibular anterior tooth was polished with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to expose the flat surface of the enamel or dentin, which was then polished further with #600 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to obtain a smooth surface. After rinsing with water and drying, a 2 mm thick silicone ring with a Φ4 mm cavity was placed on the smooth surface to determine the bonding area. After the dental tooth surface treatment composition was applied to the tooth surface in the cavity, it was immediately air-dried for 5 seconds at a discharge pressure of 0.05 MPa. Next, the dental resin-reinforced glass ionomer cement composition was filled, and then it was irradiated with light for 10 seconds using a light polymerization irradiator (Penbright, manufactured by Matsukaze Co., Ltd.) to harden the composition, thereby preparing an adhesion test specimen. A total of 5 adhesion test specimens were prepared. The adhesive test specimens were left in a thermostatic water bath at 37°C and humidity of 90% or more for 60 minutes, and then immersed in distilled water at 37°C for 24 hours. After removing the silicon ring, the adhesive test specimens were measured for shear bond strength at a crosshead speed of 1 mm / min using a universal testing machine (Shimadzu Corporation). The values ​​in the table show the average values ​​for five adhesive test specimens. Adhesive strengths of 5 MPa or more for both the enamel and the target dentin were judged to indicate good adhesive strength.

[0182] <Storage stability> After storing the dental tooth surface treatment composition in an incubator at 50°C for 2 months, the coating properties were evaluated according to the test method described above for <Coating properties> and compared with the coating properties of the dental tooth surface treatment composition immediately after preparation. The evaluation criteria are as follows: A: There is almost no change in the coating properties. B: The adhesiveness has increased, making application difficult. C: The liquid material has separated or gelled and cannot be used. Incidentally, A was determined to have good storage stability.

[0183] [Table 8]

[0184] [Table 9]

[0185] As shown in Table 8, the dental resin-reinforced glass ionomer cement kits of Examples 1 to 13 exhibited excellent application and drying properties of the dental tooth surface treatment material (i) and high adhesive strength. In addition, even after storage at 50°C for 2 months, the application properties were maintained as they were immediately after preparation. On the other hand, as shown in Table 9, the dental resin-reinforced glass ionomer cement kits of Comparative Examples 1 to 15 and the commercially available dental composite resin (Comparative Example 11) were inferior in any of the properties of application, drying properties, adhesive strength, or storage stability compared to the dental resin-reinforced glass ionomer cement compositions of Examples 1 to 13. [Industrial Applicability]

[0186] The dental resin-reinforced glass ionomer cement kit of the present invention can be used for filling and repairing teeth whose shape has been partially damaged due to caries, fractures, etc., and for attaching dental prosthetic devices to teeth whose shape has been damaged.

Claims

1. A resin-reinforced glass ionomer cement kit for dental use, comprising a dental tooth surface treatment material composition (i) and a resin-reinforced glass ionomer cement composition for dental use (ii), wherein the dental tooth surface treatment material composition (i) is, (A) 20% by mass or more and 79% by mass or less of a water-soluble organic solvent, (B) 20% by mass or more and 79% by mass or less of water, and (C) 1% by mass or more and 30% by mass or less of a polymerizable monomer having an acid anhydride structure, and the resin-reinforced glass ionomer cement composition for dental use (ii) is, (D) an acid-reactive glass powder, (B) water, (E) a polymer of an acidic group-containing polymerizable monomer, (F) a trifunctional or higher-functional (meth)acrylamide-based polymerizable monomer, (G) a (meth)acrylate-based polymerizable monomer having a hydroxyl group, and (H) a polymerization initiator, and the dental tooth surface treatment material composition (i) does not have an acid anhydride structure and does not contain a polymerizable monomer having no acidic group, a resin-reinforced glass ionomer cement kit for dental use.

2. The resin-reinforced glass ionomer cement kit for dental use according to Claim 1, wherein the polymerizable monomer (C) having an acid anhydride structure is a compound represented by the following formula (1). 【Chemical Formula 1】 (In the formula, X represents an ether bond, an amide bond, an ester bond and / or a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, and A represents a (meth)acryloyloxy group or a (meth)acrylamide group.)

3. The resin-reinforced glass ionomer cement kit for dental use according to Claim 1, wherein the polymerizable monomer (C) having an acid anhydride structure is at least one selected from the group consisting of 4-(meth)acryloyloxyethyl trimellitic anhydride, 4-(meth)acryloylaminoethyl trimellitic anhydride, anhydride of 4-(meth)acryloyloxyethyl trimellitic amide, and anhydride of 4-(meth)acryloylaminoethyl trimellitic amide.

4. The resin-reinforced glass ionomer cement kit for dental use according to Claim 1, wherein the water-soluble organic solvent (A) is at least one selected from the group consisting of ethanol, isopropanol and acetone.

5. The resin-reinforced glass ionomer cement kit for dental use according to Claim 1, wherein the trifunctional or higher-functional (meth)acrylamide-based polymerizable monomer (F) is a compound represented by the following formula (2). 【Chemical 2】 (wherein, R １ represents a hydrogen atom or a methyl group, and they may be the same or different from each other. R ２ represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and they may be the same or different from each other.)

6. The dental resin-reinforced glass ionomer cement kit according to claim 1, wherein the dental resin-reinforced glass ionomer cement composition (ii) further contains (I) a polymerizable monomer containing an acidic group.

7. The dental resin-reinforced glass ionomer cement kit according to claim 1, wherein the dental tooth surface treatment material composition (i) further contains (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate in an amount of 0.1% by mass or more and 10% by mass or less.

8. The dental resin-reinforced glass ionomer cement kit according to claim 1, wherein the dental tooth surface treatment material composition (i) further contains (H) a polymerization initiator in an amount of 0.01% by mass or more and 10% by mass or less.

9. The dental resin-reinforced glass ionomer cement kit according to claim 1, wherein the dental resin-reinforced glass ionomer cement composition (ii) contains (F) a trifunctional or higher (meth)acrylamide-based polymerizable monomer in an amount of 0.1% by mass or more and 30% by mass or less.

10. The dental resin-reinforced glass ionomer cement kit according to claim 2, wherein the polymerizable monomer having an acid anhydride structure (C) is at least one selected from the group consisting of 4-(meth)acryloyloxyethyl trimellitic anhydride, 4-(meth)acryloylaminoethyl trimellitic anhydride, the anhydride of 4-(meth)acryloyloxyethyl trimellitic amide, and the anhydride of 4-(meth)acryloylaminoethyl trimellitic amide.

11. The dental resin-reinforced glass ionomer cement kit according to claim 2, wherein the trifunctional or higher (meth)acrylamide-based polymerizable monomer (F) is a compound represented by the following formula (2). [Chemical Formula 3] (wherein R １ represents a hydrogen atom or a methyl group, and they may be the same or different from each other. R ２ represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and they may be the same or different from each other.)

12. The dental resin-reinforced glass ionomer cement kit according to claim 2, further comprising (I) a polymerizable monomer containing an acidic group.

13. The dental resin-reinforced glass ionomer cement kit according to claim 2, wherein the dental tooth surface treatment material composition (i) further contains (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate in an amount of 0.1% by mass or more and 10% by mass or less.

14. The dental resin-reinforced glass ionomer cement composition (ii) is the dental resin-reinforced glass ionomer cement kit according to claim 2, containing 0.1% by mass or more and 30% by mass or less of a (meth)acrylamide-based polymerizable monomer having three or more functional groups (F).

15. The dental resin-reinforced glass ionomer cement kit according to claim 3, wherein the (meth)acrylamide-based polymerizable monomer having three or more functional groups (F) is a compound represented by the following formula (2). [Chemical Formula 4] (wherein, R １ represents a hydrogen atom or a methyl group, and they may be the same or different from each other. R ２ represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and they may be the same or different from each other.)

16. The dental resin-reinforced glass ionomer cement kit according to claim 3, further containing (I) an acidic group-containing polymerizable monomer in the dental resin-reinforced glass ionomer cement kit.

17. The dental resin-reinforced glass ionomer cement kit according to claim 3, further containing (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate in an amount of 0.1% by mass or more and 10% by mass or less in the dental tooth surface treatment material composition (i).

18. The dental resin-reinforced glass ionomer cement composition (ii) is the dental resin-reinforced glass ionomer cement kit according to claim 3, containing 0.1% by mass or more and 30% by mass or less of a (meth)acrylamide-based polymerizable monomer having three or more functional groups (F).

19. The dental resin-reinforced glass ionomer cement kit according to claim 5, further containing (I) an acidic group-containing polymerizable monomer in the dental resin-reinforced glass ionomer cement composition (ii).

20. The dental resin-reinforced glass ionomer cement kit according to claim 5, further containing (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate in an amount of 0.1% by mass or more and 10% by mass or less in the dental tooth surface treatment material composition (i).

21. The dental resin-reinforced glass ionomer cement composition (ii) is the dental resin-reinforced glass ionomer cement kit according to claim 5, containing 0.1% by mass or more and 30% by mass or less of a (meth)acrylamide-based polymerizable monomer having three or more functional groups (F).

22. The dental resin-reinforced glass ionomer cement kit according to claim 6, further containing (J) 10-(meth)acryloyloxydecyl dihydrogen phosphate in an amount of 0.1% by mass or more and 10% by mass or less in the dental tooth surface treatment material composition (i).

23. The dental resin-reinforced glass ionomer cement composition (ii) is the dental resin-reinforced glass ionomer cement kit according to claim 6, containing 0.1% by mass or more and 30% by mass or less of a trifunctional or higher (meth)acrylamide-based polymerizable monomer (F).

24. The dental resin-reinforced glass ionomer cement composition (ii) is the dental resin-reinforced glass ionomer cement kit according to claim 7, containing 0.1% by mass or more and 30% by mass or less of a trifunctional or higher (meth)acrylamide-based polymerizable monomer (F).

25. A method of applying the dental resin-reinforced glass ionomer cement kit according to any one of claims 1 to 24 to dental tissue, comprising: a first step of applying the dental tooth surface treatment material composition (i) to the tooth surface; a second step of immediately drying the coated surface without performing water washing; a third step of applying the dental resin-reinforced glass ionomer cement composition (ii) to the dried surface without performing light irradiation; a fourth step of performing light irradiation on the applied dental resin-reinforced glass ionomer cement composition (ii) to cure it. A method comprising the above steps.

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