Kit used for adhesion with molded article of aromatic polyether ketone resin

Abstract

To provide a kit that can satisfy both excellent adhesiveness of an aromatic polyether ketone resin to a molded article and excellent operability in performing an adhesion operation.SOLUTION: A kit used for adhesion with a molded article of an aromatic polyether ketone resin contains: (i) a dental adhesive composition coated on an adhesion subject; and (ii) a dental cement composition coated on a coated surface of the dental adhesive composition, where (i) the dental adhesive composition contains (A) polymerizable monomer, (B) photopolymerization initiator and (C) volatile organic solvent, (i) the dental adhesive composition contains (B) the photopolymerization initiator by 2 to 10 pts.mass in 100 pts.mass, (ii) the dental cement composition contains (A) the polymerizable monomer, (B) the photopolymerization initiator, (D1) organic peroxide, (D2) chemical polymerization accelerator and (E) filler.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a kit for use in bonding to a molded article of an aromatic polyether ketone resin.

Background Art

[0002] In the dental field, aromatic polyether ketone resins are sometimes used as metal replacement prosthetic devices because of their high chemical stability and low allergy risks such as metal allergies.

[0003] Adhesives for polyaryl ether ketone resin materials containing a polymerizable monomer having a hydrogen-bonding functional group, a polymerizable monomer having a mercapto group, or a polymerizable monomer having a benzoyl skeleton have been proposed in Patent Documents 1 to 3. In Patent Document 4, an adhesion method in which an adhesive substantially free of a photoinitiator is applied to a polyaryl ether ketone resin and then irradiated with light, and in Patent Document 5, a method in which an adhesive is applied after irradiating a polyaryl ether ketone resin with light have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, there has been room for improvement in the adhesive strength to a molded article of an aromatic polyether ketone resin. [Means for Solving the Problems]

[0006] As a result of intensive studies, the present inventor has found that the above problems can be solved by using a predetermined adhesion kit.

[0007] The following items are provided by the present disclosure. (Item 1) A kit for use in adhering to a molded article of an aromatic polyether ketone resin, the kit comprising (i) a dental adhesive composition to be applied to an object to be adhered, and (ii) a dental cement composition to be applied to the coated surface of the dental adhesive composition. (i) The dental adhesive composition contains (A) a polymerizable monomer, (B) a photoinitiator, and (C) a volatile organic solvent. (i) The dental adhesive composition contains 2 to 10 parts by mass of (B) the photoinitiator per 100 parts by mass. (ii) The dental cement composition contains (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, and (E) a filler, and (ii) The dental cement composition contains 0.1 to 2 parts by mass of (B) the photoinitiator per 100 parts by mass of (A) the polymerizable monomer contained in the dental cement composition. A kit for use in adhering to a molded article of an aromatic polyether ketone resin, characterized in that it contains the above components. (Item 2) A kit for use in adhering a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, the kit comprising (i) a dental adhesive composition, (ii) a dental cement composition, and (iii) a dental adhesive composition to be applied to the dental material and / or the natural tooth. (i) The dental adhesive composition contains (A) a polymerizable monomer, (B) a photoinitiator, and (C) a volatile organic solvent. (i) The dental adhesive composition contains 2 to 10 parts by mass of (B) the photoinitiator per 100 parts by mass. (ii) The dental cement composition contains (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, and (E) a filler, (ii) The dental cement composition contains (B) 0.1 to 2 parts by mass of a photoinitiator with respect to 100 parts by mass of (A) the polymerizable monomer contained in the dental cement composition, and (iii) The dental adhesive composition is a kit for use in adhering a molded article of an aromatic polyether ketone resin, which contains (A1) a polymerizable monomer having an acidic group, (B) a photoinitiator, and (C) a volatile organic solvent and / or (F) water, to a dental material and / or a natural tooth. (Item 3) (i) The dental adhesive composition according to Item 1, which is characterized by containing (D2) a chemical polymerization accelerator. (Item 4) (i) The dental adhesive composition according to Item 2, which is characterized by containing (D2) a chemical polymerization accelerator. (Item 5) (i) The kit according to Item 3, wherein the dental adhesive composition contains methyl methacrylate as (A) the polymerizable monomer and substantially does not contain (A1) a polymerizable monomer having an acidic group. (Item 6) (i) The kit according to Item 4, wherein the dental adhesive composition contains methyl methacrylate as (A) the polymerizable monomer and substantially does not contain (A1) a polymerizable monomer having an acidic group. (Item 7) A kit for use in adhering to a molded article of an aromatic polyether ketone resin, The kit is a kit containing (i) a dental adhesive composition and (ii) a dental cement composition, (i) In 100 parts by mass of the dental adhesive composition (A) 30 to 85 parts by mass of a polymerizable monomer, (B) 2 to 10 parts by mass of a photoinitiator, (C) 10 to 60 parts by mass of a volatile organic solvent, and (D2) 0.01 to 5 parts by mass of a chemical polymerization accelerator, and (ii) The dental cement composition contains, with respect to 100 parts by mass of the (A) polymerizable monomer contained in the (ii) cement composition, (B) 0.1 to 2 parts by mass of a photoinitiator, (D1) 0.5 to 5 parts by mass of an organic peroxide, (D2) 0.5 to 5 parts by mass of a chemical polymerization accelerator, and (E) 50 to 400 parts by mass of a filler The kit according to item 5, characterized by comprising the above. (Item 8) A kit for use in the adhesion of a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, The kit is a kit comprising (i) a dental adhesive composition, (ii) a dental cement composition, and (iii) a dental adhesive composition, (i) In 100 parts by mass of the dental adhesive composition (A) 30 to 85 parts by mass of a polymerizable monomer, (B) 2 to 10 parts by mass of a photoinitiator, (C) 10 to 60 parts by mass of a volatile organic solvent, and (D2) 0.01 to 5 parts by mass of a chemical polymerization accelerator are contained (ii) The dental cement composition contains, with respect to 100 parts by mass of the (A) polymerizable monomer contained in the (ii) dental cement composition, (B) 0.1 to 2 parts by mass of a photoinitiator, (D1) 0.5 to 5 parts by mass of an organic peroxide, (D2) 0.5 to 5 parts by mass of a chemical polymerization accelerator, and (E) 50 to 400 parts by mass of a filler are contained, and (iii) In 100 parts by mass of the dental adhesive composition (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, (B) 0.5 to 10 parts by mass of a photoinitiator, (C) 0 to 50 parts by mass of a volatile organic solvent, and (E) 0 to 50 parts by mass of water The kit according to item 6, characterized by comprising the above. (Item 9) A kit for use in adhering a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, (1-1) A step of sandblasting the adherend surface of the molded article of the aromatic polyether ketone resin, (1-2) (i) A step of applying a dental adhesive composition to the adherend surface of the molded article of the aromatic polyether ketone resin, irradiating with light, and obtaining a laminate (X), (1-3) A step of applying (iii) the dental adhesive composition to the adherend surface of the dental material and / or the natural tooth, irradiating with light, and obtaining a laminate (Y), (1-4) A step of applying (ii) a dental cement composition to the coated surface of the dental adhesive composition of the laminate (X) and / or the laminate (Y), (1-5) A step of pressing the adherend surfaces of the laminate (X) and the laminate (Y) together, (1-6) A step of removing excess cement from the connecting portion between the laminate (X) and the laminate (Y), and (1-7) A step of irradiating the connecting portion between the laminate (X) and the laminate (Y) with light The kit according to item 8 for use in an adhesion method including the above. (Item 10) A method for manufacturing a laminate (X) for use in adhering to a laminate (Y) obtained by applying the (iii) dental adhesive composition according to item 8 to the adherend surface of a dental material and / or a natural tooth, (2-1) A step of sandblasting the adherend surface of the molded article of the aromatic polyether ketone resin, and (2-2) A step of applying the (i) dental adhesive composition according to item 8 to the adherend surface of the molded article of the aromatic polyether ketone resin, irradiating with light, and obtaining a laminate (X), Manufacturing method.

Effect of the Invention

[0008] An object of the present invention is to provide a kit containing a dental adhesive composition that exhibits good adhesive strength to a molded article of an aromatic polyether ketone resin and also has good operability.

Embodiment for Carrying Out the Invention

[0009] A kit containing the dental adhesive composition of the present invention is a material that can be used for restoring the anatomical form of dental caries or tooth defects, or for improving tooth alignment and occlusion. The kit containing the dental adhesive composition is used in combination with a liquid dental adhesive composition and a paste-like dental cement composition. Among the dental cement compositions, there are cements having self-adhesiveness. Although such dental cement compositions may be used alone, in cases where it is difficult to exhibit sufficient adhesive strength, it is generally used in combination with a dental adhesive composition. In recent years, a molded body of an aromatic polyether ketone resin may be used as a prosthetic device. Polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK), which are molded bodies of aromatic polyether ketone resins, have high chemical stability, so it has been difficult to adhere them with conventional dental adhesive compositions.

[0010] For this reason, as shown in Patent Documents 1 to 5, studies have been conducted on adhesives and adhesion methods for polyaryl ether ketone resins. However, sufficient studies have not been made on the combination of the dental cement composition and the dental adhesive composition.

[0011] It is difficult to incorporate a large amount of a photoinitiator into the dental cement composition in order to achieve good removability of excess cement. On the other hand, since sufficient curing of the adhesive composition by light irradiation leads to the exhibition of good adhesive strength to the aromatic polyether ketone resin, it is preferable to incorporate a large amount of a photoinitiator.

[0012] The present invention has found that by making the blending amount of the photoinitiator in the dental adhesive composition for applying to the molded body of the aromatic polyether ketone resin larger than the blending amount of the photoinitiator in the dental cement composition, it is possible to achieve both the exhibition of good adhesive strength due to sufficient curing in the adhesive layer and the good workability of the dental cement composition, and thus the present invention has been completed.

[0013] Furthermore, since the kit used for adhesion to the molded article of the aromatic polyether ketone resin of the present invention can adhere to resins with difficult adhesion such as molded articles of aromatic polyether ketone resins, it can also be used for adhesion of 3D printer material compositions made of resin and glass fiber reinforced resin materials.

[0014] [(A) Polymerizable monomer] The (i) dental adhesive composition and (ii) dental cement composition contained in the kit used for adhesion to the molded article of the aromatic polyether ketone resin of the present invention contain (A) a polymerizable monomer. Any known (A) polymerizable monomer can be used without limitation. Examples of the (A) polymerizable monomer include one or more selected from (A1) a polymerizable monomer having an acidic group and (A2) a polymerizable monomer not having an acidic group. In the polymerizable monomer described in the present invention, the polymerizable group preferably exhibits radical polymerizability. Specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In the present specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylamide" means acrylamide and / or methacrylamide. A polymerizable monomer having a substituent at the α-position of the (meth)acrylic group and / or the (meth)acrylamide group can also be preferably used.

[0015] [(A1) Polymerizable monomer having an acidic group] The (iii) dental adhesive composition that may be contained in the kit used for adhesion to the molded article of the aromatic polyether ketone resin of the present invention contains (A1) a polymerizable monomer having an acidic group. Any (A1) polymerizable monomer having one or more polymerizable groups and at least one or more acidic groups such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group can be used without limitation. By containing a polymerizable monomer having an acidic group, adhesiveness to dental tissues and prosthetic devices can be imparted.

[0016] Specific examples of the polymerizable monomer having a phosphate group include 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)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)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[4-(meth)acryloyloxybutyl] hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl] hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl] hydrogen phosphate, bis[9-(meth)acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0017] Specific examples of the polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0018] Specific examples of the polymerizable monomer having a thiophosphate group include 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, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0019] Specific examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 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; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0020] Specific examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, and the like.

[0021] The polymerizable monomer having a carboxylic acid group is classified into a (meth)acrylic compound having one carboxyl group in the molecule and a (meth)acrylic compound having a plurality of carboxyl groups in the molecule. Specific examples of the (meth)acrylic compound having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, etc.Specific examples of the (meth)acrylic compound having a plurality of carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytetradecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxybutyl trimellitic acid, 4-(meth)acryloyloxyhexyl trimellitic acid, 4-(meth)acryloyloxydecyl trimellitic acid, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; acid anhydrides and acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, etc.

[0022] It is preferable that the (i) dental adhesive composition of the present invention substantially does not contain a polymerizable monomer having an (A1) acidic group. Substantially not containing means a trace amount of addition that does not affect the composition, such as impurities in the raw materials contained in the (i) dental adhesive composition or impurities in the working process. It is preferable that the polymerizable monomer having an (A1) acidic group is 1 part by mass or less, more preferably 0.1 part by mass or less, per 100 parts by mass of the (i) dental adhesive composition. In such a case, good adhesive strength to the molded body of the aromatic polyether ketone resin tends to be exhibited.

[0023] The polymerizable monomer (A1) having an acidic group contained in the (iii) dental adhesive composition of the present invention is at least one selected from a polymerizable monomer having a phosphate group, a polymerizable monomer having a phosphonic acid group, and a polymerizable monomer having a carboxylic acid group, and more preferably 10-methacryloyloxydecyl dihydrogen phosphate, 6-methacryloyloxyhexyl-3-phosphonoacetate, 4-methacryloyloxyethyl trimellitic acid, 4-methacryloxyethyl trimellitic anhydride. It is preferable that the polymerizable monomer (A1) having an acidic group in 100 parts by mass of the (iii) dental adhesive composition of the present invention contains 1 to 30 parts by mass. When it is 1 part by mass or more, good adhesive strength to natural teeth, metals, ceramics, etc. tends to be exhibited, and when it is 30 parts by mass or less, the storage stability tends to be good.

[0024] [(A2) Polymerizable monomer having no acidic group] The (i) dental adhesive composition, (ii) dental cement composition, and (iii) dental adhesive composition of the present invention may contain a polymerizable monomer (A2) having no acidic group. The polymerizable monomer (A2) having no acidic group can be used without limitation as long as it has one or more polymerizable groups and no acidic group. Examples of the polymerizable monomer (A2) having no acidic group include those having one radical polymerizable group, those having two radical polymerizable groups, and those having three or more radical polymerizable groups. The polymerizable monomer (A2) having no acidic group may have a functional group (such as at least one selected from an alkoxysilyl group, urethane, and ether).

[0025] (A2) Among the polymerizable monomers having no acidic group, specific examples of the polymerizable monomer having one radical polymerizable group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-(dihydroxyethyl)(meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, (meth)acrylamide, and the like.

[0026] Among the polymerizable monomers having no acidic group, specific examples of the polymerizable monomer having two radical polymerizable groups include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)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)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditrioethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytrioethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,Examples include 2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, etc.

[0027] (A2) Among the polymerizable monomers having no acidic group, specific examples of the polymerizable monomer having three radical polymerizable groups include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

[0028] Among the polymerizable monomers having no acidic group, specific examples of the polymerizable monomer having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic compounds and (meth)acrylamide compounds having a plurality of alkoxysilyl groups in the molecule. Examples thereof include 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane.Furthermore, examples of those having a urethane group or an ether group include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecan-19-yl)amino)-2-methylpropane-1,3-diyl di(meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosan-22-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18,23-hexaoxa-7,20-diaza-3-silapentacosan-25-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecan-19-yl)amino)-2-methylpropane-1,3-diyl di(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21,24-tetraoxa-18-aza-4-silahexacosane-26-yl (meth)acrylate, 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-silanonadecane-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silicosane-20-yl (meth)acrylate, 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

[0029] There is no restriction whatsoever even if an oligomer or prepolymer having at least one or more polymerizable groups in the molecule is used in addition to these polymerizable monomers. Also, there is no problem even if a substituent such as a fluoro group is present in the same molecule. The polymerizable monomers described above can be used not only alone but also in combination of two or more.

[0030] It is preferable that (A) the polymerizable monomer is contained in an amount of 30 to 85 parts by mass in 100 parts by mass of the dental adhesive composition (i) of the present invention. When the amount is 30 to 85 parts by mass, good adhesive strength to a molded article of an aromatic polyether ketone resin tends to be exhibited. As the (A) polymerizable monomer in (i), it is particularly preferable to contain a (meth)acrylate containing an alkyl group having 1 to 5 carbon atoms, more preferably to contain methyl methacrylate or ethyl methacrylate. When such a compound is contained, good adhesive strength to a molded article of an aromatic polyether ketone resin can be expected.

[0031] <(B) Photoinitiator> The dental adhesive composition (i) and the dental cement composition (ii) contained in the kit used for adhesion to the molded article of the aromatic polyether ketone resin of the present invention contain a (B) photoinitiator. A photoinitiator is a polymerization initiator capable of initiating polymerization by irradiation with light. Photoinitiators that can be used in the dental adhesive composition of the present invention include photosensitizers, photoacid generators, photopolymerization accelerators, and the like. These are known compounds that are generally used and can be used without any limitation.

[0032] Specific examples of the photosensitizers contained in the (B) photopolymerization initiator that can be used in the composition of the present invention include α-diketones such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid; benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; thioxanthones such as 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone; acylphosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and acylgermanium compounds such as bisbenzoyldiethylgermanium and bisbenzoyldimethylgermanium, etc.

[0033] Examples of the photoacid generators contained in the (B) photopolymerization initiator that can be used in the composition of the present invention include triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, etc. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Specific examples of preferred iodonium salt compounds include 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)gallate, bis(4-tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)gallate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyliodonium-2-carboxylate monohydrate, etc.

[0034] As the photo-polymerization accelerator contained in the (B) photo-polymerization initiator that can be used in the composition of the present invention, an amine compound can be used. Examples of the amine compound include p-dimethylaminobenzoic acid ethyl ester, triethanolamine, triisopropanolamine, tribenzylamine, dibenzyl glycine ethyl ester, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, and the like.

[0035] As the photo-polymerization initiator that can be preferably used in the composition of the present invention, there are acylphosphine oxides such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, a combination of α-diketones and an amine compound, and a combination of α-diketones, a photoacid generator, and an amine compound. Regarding the combination of α-diketones and an amine compound, more specifically, the α-diketone compound is preferably camphorquinone, and the amine compound is preferably a combination of a dialkylbenzoic acid ester compound containing p-dimethylaminobenzoic acid ethyl ester. In addition to these, it is preferable to contain triethanolamine, triisopropanolamine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, which are amine compounds containing a hydroxyl group, and a photo-polymerization accelerator such as N,N-dimethylaminoethyl acrylate and N,N-diethylaminoethyl acrylate.

[0036] The (i) dental adhesive composition of the present invention preferably contains 2 to 10 parts by mass of the (B) photo-polymerization initiator per 100 parts by mass. When containing 2 parts by mass or more, there is a tendency to exhibit good adhesive strength to the molded body of the aromatic polyetherketone resin. When containing 10 parts by mass or less, the (i) dental adhesive composition tends to have a sufficient operation margin time from collection to use.

[0037] (ii) The dental cement composition of the present invention preferably contains 0.1 to 2 parts by mass of (B) a photoinitiator with respect to 100 parts by mass of (A) a polymerizable monomer contained in the (ii) dental cement composition. When the content is 0.1 part by mass or more, good adhesive strength to the molded body of the aromatic polyether ketone resin tends to be exhibited. When the content is 2 parts by mass or less, there is a tendency to have a sufficient operation margin time from discharging the (ii) dental cement composition until use, and the operability is good when partially curing the excess cement by light irradiation and removing the partially cured product with an instrument. In the present disclosure, "partial curing" refers to a state between a state where it is not cured at all and a state where it is completely cured, and preferably has a hardness that does not flow and can be removed using an instrument.

[0038] (iii) The dental adhesive composition of the present invention preferably contains 0.5 to 10 parts by mass of (B) a photoinitiator in 100 parts by mass. When the content is 0.5 part by mass or more, good adhesive strength tends to be exhibited. When the content is 10 parts by mass or less, the (iii) dental adhesive composition tends to have a sufficient operation margin time from collection until use.

[0039] The (i) dental adhesive composition and (ii) dental cement composition contained in the kit for adhesion to the molded article of the aromatic polyether ketone resin of the present invention, and further (iii) the dental adhesive composition which may be contained in the kit contains a (B) photoinitiator. The molded article of the aromatic polyether ketone resin is a material that is difficult to adhere compared to metals, ceramics such as zirconia, denture base resins, glass fiber reinforced resins, and 3D printer materials used as dental materials. When attempting to adhere to the molded article of the aromatic polyether ketone resin, it tended to be important that the curability of the adhesive material kit used was sufficiently high. Therefore, in the present invention, when the blending amount of the photoinitiator in the (i) dental adhesive composition and (ii) dental cement composition applied to the molded article of the aromatic polyether ketone resin was increased more than usual, although the adhesiveness was improved, it was confirmed that the operating margin time of the (ii) dental cement composition under ambient light and the removability of excess cement during light irradiation decreased. Therefore, when the blending amount of the photoinitiator in the (ii) dental cement composition was made less than the amount contained in the (i) dental adhesive composition, it had little effect on the adhesive strength to the molded article of the aromatic polyether ketone resin, and it was confirmed that good operating margin time of the (ii) dental cement composition under ambient light and removability of excess cement during light irradiation were obtained, leading to the invention. Furthermore, it was confirmed that strong adhesion between the molded article of the aromatic polyether ketone resin and dental materials and / or natural teeth was achieved by using the (iii) dental adhesive composition containing a (B) photoinitiator.

[0040] <(C) Volatile organic solvent> (i) The dental adhesive composition contains (C) a volatile organic solvent. As the (C) volatile organic solvent, an organic solvent that usually has a boiling point of 150°C or lower under normal pressure and a solubility in water at 25°C of 5% by mass or more, more preferably 30% by mass or more, and most preferably is soluble in water at any ratio is used. Among them, a water-soluble volatile organic solvent having a boiling point of 100°C or lower under normal pressure is preferable, and specific examples thereof include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran. Further, among the above-mentioned volatile organic solvents, ethanol, isopropyl alcohol, acetone, and methyl ethyl ketone are more preferable.

[0041] The (i) dental adhesive composition of the present invention preferably contains 10 to 60 parts by mass of the (C) volatile organic solvent in 100 parts by mass. When it contains 10 to 60 parts by mass, good coatability tends to be realized.

[0042] The (iii) dental adhesive composition of the present invention preferably contains 0 to 50 parts by mass of the (C) volatile organic solvent in 100 parts by mass. When it contains 0 to 50 parts by mass, good coatability tends to be realized.

[0043] <(D) Chemical polymerization initiator> The (ii) dental cement composition of the present invention contains (D1) an organic peroxide and (D2) a chemical polymerization accelerator as the (D) chemical polymerization initiator. Chemical polymerization is a polymerization method that cures without requiring a special device such as a light irradiator, and a chemical polymerization initiator is a polymerization initiator that can initiate chemical polymerization.

[0044] [(D1) Organic peroxide] (ii) The dental cement composition of the present invention contains (D1) an organic peroxide. Examples of the (D1) organic peroxide that can be preferably used in the present invention include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, decanoyl peroxide, and the like. Specific examples of peroxy esters include α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and the like. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and the like. Specific examples of peroxy ketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, and the like. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide, and the like. Specific examples of peroxydicarbonates include di-3-methoxy peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, and the like. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, tert-amyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. These may be used in combination of two or more kinds as necessary.

[0045] The dental cement composition (ii) of the present invention contains (D1) an organic peroxide, and preferably contains 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A) contained in the dental cement composition (ii). When the content is 0.5 parts by mass or more, good adhesive strength tends to be exhibited, and when it is 5 parts by mass or less, the storage stability is good.

[0046] [(D2) Chemical polymerization accelerator] The dental cement composition (ii) of the present invention contains (D2) a chemical polymerization accelerator. Examples of the chemical polymerization accelerator include transition metal compounds of the fourth period, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acids and their salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and the like.

[0047] The transition metal compounds of the fourth period as chemical polymerization accelerators refer to metal compounds of Groups 3-12 in the fourth period of the periodic table. Specifically, any metal compounds of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without limitation. Each of the above transition metal elements can take multiple valences, but as long as it is a valence in which it can stably exist, it can be added to the composition of the present invention. For example, Sc (trivalent), Ti (tetravalent), V (trivalent, tetravalent or pentavalent), Cr (divalent, trivalent or hexavalent), Mn (divalent to heptavalent), Fe (divalent or trivalent), Co (divalent or trivalent), Ni (divalent), Cu (monovalent or divalent), Zn (divalent). Specific examples of transition metal compounds include scandium iodide (trivalent) as a scandium compound, titanium chloride (tetravalent), titanium (tetravalent) tetraisopropoxide, etc. as titanium compounds, acetylacetone vanadium (trivalent), vanadium dioxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadium stearate (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedionate) vanadium (tetravalent), bis(maltolate) oxovanadium (tetravalent), vanadium pentoxide (pentavalent), sodium metavanadate (pentavalent), etc. as vanadium compounds, manganese acetate (divalent), manganese naphthenate (divalent), etc. as manganese compounds, iron acetate (divalent), iron chloride (divalent), iron acetate (trivalent), iron chloride (trivalent), etc. as iron compounds, cobalt acetate (divalent), cobalt naphthenate (divalent), etc. as cobalt compounds, nickel chloride (divalent), etc. as nickel compounds, copper chloride (monovalent), copper bromide (monovalent), copper chloride (divalent), copper acetate (divalent), etc. as copper compounds, zinc chloride (divalent), zinc acetate (divalent), etc. as zinc compounds. Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred.

[0048] As the thiourea derivative as a chemical polymerization accelerator, any known thiourea derivative can be used without limitation. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea and the like. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred.

[0049] Examples of sulfinic acids and their salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. Sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

[0050] As borate compounds, specific examples of borate compounds having one aryl group in one molecule include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl(3,5-bistrifluoromethyl)phenylboron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butyloxyphenyl)boron, trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, and n-dodecyl group, etc.).Specific examples of the borate compound having two aryl groups in the molecule include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methyquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl)phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of the borate compound having three aryl groups in the molecule include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, etc. of monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri(3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p-butyloxyphenyl)boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of the borate compound having four aryl groups in one molecule include, for example, tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(3,5-bistrifluoromethyl)phenylboron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts. Among these aryl borate compounds, from the viewpoint of storage stability, it is more preferable to use a borate compound having three or four aryl groups in one molecule.

[0051] Examples of the sulfur-containing reducing inorganic compound include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, etc. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid, etc.

[0052] Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, ammonium nitrite, and the like.

[0053] Examples of the barbituric acid derivative 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, 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-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and salts of thiobarbituric acids (preferably alkali metals or alkaline earth metals). Specific examples of these salts of barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0054] Specific examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide, and the like.

[0055] The (i) dental adhesive composition of the present invention preferably contains a (D2) chemical polymerization accelerator. It is preferably contained in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the (i) dental adhesive composition. When it is contained in an amount of 0.01 part by mass or more, good adhesive strength tends to be exhibited, and when it is 5 parts by mass or less, good storage stability is achieved.

[0056] The (ii) dental cement composition of the present invention contains a (D2) chemical polymerization accelerator, and is preferably contained in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer contained in the (ii) dental cement composition. When it is contained in an amount of 0.5 part by mass or more, good adhesive strength tends to be exhibited, and when it is 5 parts by mass or less, good storage stability is achieved.

[0057] [(E) Filler] The (ii) dental cement composition of the present invention contains an (E) filler. The type of the (E) filler is not limited as long as it is a known filler, and a filler suitable for its use can be blended. It is preferable to blend fillers such as inorganic fillers, organic fillers, and organic-inorganic composite fillers. Examples of the inorganic filler include ion-releasing glass. The (ii) dental cement composition of the present invention may use the exemplified fillers alone or in combination of two or more.

[0058] As the inorganic filler, their chemical compositions are not particularly limited. Specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium borosilicate aluminosilicate glass, strontium borosilicate aluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc. used in dental glass ionomer cements, resin-reinforced glass ionomer cements, resin cements, etc. can also be preferably used. The fluoroaluminosilicate glass mentioned here has silicon dioxide and aluminum oxide as the basic skeleton and contains an alkali metal for introducing non-bridging oxygen. Furthermore, it has an alkaline earth metal containing strontium and fluorine as modified / coordinated ions. Also, it is a composition in which an element of the lanthanoid series is incorporated into the skeleton to impart further radiopacity. This lanthanoid series element is incorporated into the composition as a modified / coordinated ion depending on the composition range.

[0059] The inorganic filler may contain hydrophobized inorganic fine particles. The hydrophobized inorganic fine particles preferably have an average particle diameter of primary particles of 0.1 to 50 nm, and the hydrophobization is preferably carried out with a silane coupling agent and / or a modified silicone oil. By blending the hydrophobized inorganic fine particles, in addition to improving the flexural strength, suppression of sedimentation of the inorganic filler and imparting rheological properties can be expected.

[0060] Specific examples of the organic filler include polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0061] Examples of the organic-inorganic composite filler include those obtained by polymer coating the surface of an inorganic filler with a polymerizable monomer, those obtained by mixing and polymerizing an inorganic filler and a polymerizable monomer and then grinding them to an appropriate particle size, those obtained by previously dispersing an inorganic filler in a polymerizable monomer and subjecting them to emulsion polymerization or suspension polymerization, those obtained by previously dispersing an inorganic filler in a polymerizable monomer and a solvent, spray-drying them, and then polymerizing them, those obtained by previously dispersing an inorganic filler in a solvent, spray-drying them, impregnating them with a polymerizable monomer, and then polymerizing them, etc., but are not limited thereto.

[0062] The ion-sustained release glass is characterized by sustaining the release of at least one of fluoride ions, strontium ions, borate ions, and aluminum ions. Among these ions, it is preferable that a plurality of them are simultaneously sustainedly released.

[0063] Any ion-releasing glass can be used without any limitation as long as it contains one or more glass framework-forming elements that form the glass framework and one or more glass-modifying elements that modify the glass framework. These ion-releasing glasses can be used not only alone but also in combination of a plurality of ion-releasing glasses. In the present invention, glass amphoteric elements that have any role of either glass framework-forming elements or glass-modifying elements depending on the glass composition are included in the category of glass framework-forming elements. Specific examples of the glass framework-forming elements contained in the ion-releasing glass include silica, aluminum, boron, phosphorus, etc., and these can be used not only alone but also in combination of a plurality. Specific examples of the glass-modifying elements include halogen elements such as fluorine, bromine, iodine, etc., alkali metal elements such as sodium, lithium, etc., alkaline earth metal elements such as calcium, strontium, etc., and these can be used not only alone but also in combination of a plurality. Among these, it is preferable to contain silica, aluminum, and boron as glass framework-forming elements and fluorine, sodium, and strontium as glass-modifying elements. Specifically, examples include strontium- and sodium-containing silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, fluoroaluminoborosilicate glass, etc. Further, from the viewpoint of releasing fluoride ions, strontium ions, borate ions, and aluminum ions, fluoroaluminoborosilicate glass containing strontium is more preferable. Specific examples of a more preferable glass composition range are as follows: SiO 2 : 10 to 40% by mass, Al 2 O 3 : 10 to 35% by mass, B 2 O 3 : 2.5 to 30% by mass, SrO: 15 to 50% by mass, F: 2.5 to 20% by mass, Na 2 O: 0 to 15% by mass. This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectrum, and fluorescent X-ray analysis, etc. However, as long as the measured values match these composition ranges in any of the analysis methods, there is no problem at all.

[0064] The manufacturing method of these ion-releasing glasses is not particularly limited, and it can be manufactured by a manufacturing method such as a melting method or a sol-gel method. Among them, the manufacturing method using a melting method with a melting furnace is preferable from the viewpoint of the ease of glass composition design including the selection of raw materials. The ion-releasing glass used in the present invention has an amorphous structure, but there is no problem even if it includes a partially crystalline structure, and there is no problem even if it is a mixture of a glass having an amorphous structure and a glass having a crystalline structure. Whether the glass structure is amorphous or not can be confirmed using an analytical instrument such as X-ray diffraction analysis or a transmission electron microscope. Among them, since the ion-releasing glass used in the present invention releases various ions due to the equilibrium relationship with the ion concentration in the external environment, it is preferably an amorphous structure having a homogeneous structure.

[0065] Furthermore, in order to enhance the ion-releasing property from the ion-releasing glass, it is a preferable embodiment to functionalize the glass surface by surface treatment to improve the ion-releasing property. Specific examples of the surface treatment material used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

[0066] This composite surface treatment is a method in which after coating the surface of the ion-releasing glass with a silane compound, the surface is treated using an acidic polymer, and will be specifically described below. A silane compound is mixed into an aqueous dispersion containing ion-releasing glass finely pulverized to a desired average particle size by pulverization or the like, and this is hydrolyzed or partially hydrolyzed in the system to pass through a silanol compound, and then this is condensed to form a polysiloxane, and then the surface of the ion-releasing glass is coated to obtain a polysiloxane-coated ion-releasing glass.

[0067] Specific examples of silane compounds that can be used for polysiloxane coating include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), etc. More preferably, they are tetramethoxysilane and tetraethoxysilane.

[0068] Furthermore, it is more preferable that the silane compound used for polysiloxane coating is a low condensate. For example, they are low condensate silane compounds obtained by subjecting tetramethoxysilane and tetraethoxysilane to partial hydrolysis and condensation. These compounds can be used alone or in combination.

[0069] The polysiloxane-coated ion-releasing glass obtained in the previous step can be made into an ion-releasing glass by subjecting it to an acidic polymer treatment in which it is reacted with an acidic polymer. For the acidic polymer treatment, equipment generally used in the industry can be used as long as it is a dry-flow type stirrer, and examples include a Henschel mixer, a super mixer, a high-speed mixer, etc. The reaction of the acidic polymer with the ion-releasing glass having a polysiloxane film formed thereon can be carried out by bringing them into contact with each other by impregnation, spraying, etc. For example, the polysiloxane-coated ion-releasing glass can be made to flow dry, and in the flowing state, the acidic polymer solution can be dispersed from above and sufficiently stirred. At this time, the method of dispersing the acidic polymer solution is not particularly limited, but the dropping or spraying method that can disperse it uniformly is more preferable. Also, the reaction is preferably carried out near room temperature. When the temperature rises, the reaction between the acid-reactive element and the acidic polymer becomes faster, and the formation of the cement phase becomes non-uniform.

[0070] It is preferable to remove the moisture in the cement reaction phase by performing post-reaction heat treatment. If moisture remains in the cement reaction phase, it is disadvantageous in terms of strength, but the filler of the present invention has its mechanical strength reduction suppressed by polysiloxane coating. The heat treatment method after the acidic polymer treatment is not particularly limited and can be performed by known general methods. Equipment used for heat treatment is preferably a box-type hot air dryer or a rotary heat treatment apparatus capable of uniform heating. The heat treatment temperature ranges from room temperature to 200°C, more preferably from 40 to 150°C. When the temperature is lower than this range, the removal of the aqueous medium is insufficient, and when it is higher than this range, the organic layer of the acidic polymer may decompose or discolor. The heat treatment time depends on the capacity of the dryer, etc., and there is no problem as long as the aqueous medium can be sufficiently removed. After heat treatment, the heat-treated product can be easily crushed by applying a shearing force or an impact force, and the crushing method can be performed using the equipment used in the above reaction, etc.

[0071] The solvent used for preparing the acidic polymer solution used in the reaction is not a problem as long as it is a solvent in which the acidic polymer dissolves, and examples include water, ethanol, isopropanol, acetone, etc. Among these, water is particularly preferred because the acidic groups of the acidic polymer can dissociate and react uniformly with the surface of the basic filler that is the core.

[0072] The weight average molecular weight of the acidic polymer ranges from 2000 to 50000, preferably from 5000 to 40000. When treated with an acidic polymer having a weight average molecular weight of less than 2000, an acidic polymer reaction phase is not formed in the polysiloxane-coated ion-releasing glass, and as a result, the ion-releasing property tends to be low. On the other hand, when treated with an acidic polymer having a weight average molecular weight exceeding 50000, the viscosity of the acidic polymer solution becomes high, making it difficult to uniformly treat the polysiloxane-coated ion-releasing glass. The concentration of the acidic polymer in 100 parts by mass in the acidic polymer solution preferably ranges from 3 to 25 parts by mass, more preferably from 8 to 20 parts by mass. When the acidic polymer concentration is less than 3 parts by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving ion release cannot be obtained. When the acidic polymer concentration exceeds 25 parts by mass, it is difficult to diffuse the polysiloxane layer (porous) in a uniform state, and a homogeneous acidic polymer reaction phase cannot be obtained. Also, when it comes into contact with the ion-releasing glass coated with polysiloxane, a reaction occurs immediately, resulting in problems such as the formation of strongly reacted aggregates. The addition amount of the acidic polymer solution to the polysiloxane-coated ion-releasing glass preferably ranges from 6 to 40 parts by mass, more preferably from 10 to 30 parts by mass. In terms of this addition amount, the amount of the acidic polymer relative to the polysiloxane-coated ion-releasing glass is optimally in the range of 1 to 7 parts by mass, and the amount of water is in the range of 10 to 25 parts by mass.

[0073] The acidic polymers that can be used to form an acidic polymer reaction phase on the surface of the polysiloxane-coated ion-releasing glass by the above method can be copolymer or homopolymer of polymerizable monomers having acidic groups such as phosphate residue, pyrophosphate residue, thiophosphate residue, carboxylic acid residue, sulfonic acid residue, etc. as acidic groups without any problem. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic anhydride, 5-(meth)acryloylaminopentyl carboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethyl phenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogen dithiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, etc. Among the polymers (co)polymerized using these polymerizable monomers, it is preferable to use a homopolymer or copolymer of α-β unsaturated carboxylic acid in which the acid-base reaction with the acid-reactive element contained in the polysiloxane-coated ion-releasing glass is relatively slow. Specific examples include acrylic acid polymer, acrylic acid-maleic acid copolymer, acrylic acid-itaconic acid copolymer, etc.

[0074] The above-mentioned (E) filler can be treated with a surface treatment material typified by a silane coupling agent for the purpose of improving the affinity with the polymerizable monomer, the dispersibility in the polymerizable monomer, the mechanical strength and water resistance of the cured body. Such surface treatment materials and surface treatment methods are not particularly limited, and known methods such as a method of spraying the surface treatment material while stirring the powdery filler, a method of dispersing and mixing the filler and the surface treatment material in a solvent, and a method of supplying a silane coupling agent in a vapor or gaseous state to the filler surface can be adopted without limitation. Examples of the silane coupling agent used for the surface treatment of the filler include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, or hexamethyldisilazane, etc. are preferable. Further, in addition to the silane coupling agent, the surface treatment of the filler can be performed by a method using a titanate-based coupling material or an aluminate-based coupling material. The treatment amount of the surface treatment material in the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the filler before treatment.

[0075] (E) The shape of the filler is not particularly limited, and fillers having any shape such as spherical, needle-like, plate-like, crushed, or flaky can be used. Also, the average particle diameter of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0076] The (ii) dental cement composition of the present invention contains (E) a filler, and preferably contains 50 to 400 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer contained in the (ii) dental cement composition. When it contains 50 parts by mass or more, good workability and adhesive strength tend to be exhibited, and when it is 400 parts by mass or less, the paste properties are particularly good and it tends to be easy to use.

[0077] [(F) Water] The (iii) dental adhesive composition of the present invention may contain (F) water. (F) Water is not limited as long as it is general water such as distilled water or ion-exchanged water. With respect to 100 parts by mass of the (iii) dental adhesive composition of the present invention, (F) water preferably contains 0 to 50 parts by mass.

[0078] <Other components> In addition, the composition of the present invention may contain components other than the components (A) to (F) above as long as the effects of the present invention are not inhibited. For example, excipients represented by fumed silica, ultraviolet absorbers such as benzophenone-based and benzotriazole-based, α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, chain transfer agents such as terpene-based compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal scavengers such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration preventives, antibacterial agents, coloring pigments, and other conventionally known additives and other components can be arbitrarily added as needed.

[0079] The aromatic polyether ketone resin in the present invention refers to a polymer composed of functional groups containing aryl groups, ether groups, and ketone groups. Specifically, examples include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), etc. Among these, PEEK is widely used. The molded article of the aromatic polyether ketone resin refers to an article obtained by processing the aromatic polyether ketone resin. For example, it refers to an article molded into an arbitrary shape by an injection molding machine or an article molded by cutting with a milling machine. The molded article of the aromatic polyether ketone resin may contain components other than the aromatic polyether ketone resin. Preferably, 50% or more, preferably 70% or more, based on 100 parts by mass of the molded article of the aromatic polyether ketone resin, is the aromatic polyether ketone resin. In such a case, the excellent mechanical properties of the aromatic polyether ketone resin tend to be reflected in the molded article of the aromatic polyether ketone resin. Examples of components other than the aromatic polyether ketone resin contained in the molded article of the aromatic polyether ketone resin include inorganic fillers and pigments. Preferably, only titanium oxide and pigments are included as components other than the aromatic polyether ketone resin.

[0080] The method for producing the composition of the present invention is not particularly limited and can be produced by known methods. For example, (i) the dental adhesive composition can be produced by mixing (A) a polymerizable monomer, (B) a photoinitiator, (C) a volatile organic solvent, etc. by a known method such as a planetary mixer, a tumbler mixer, a mix rotor, a dissolver, a planetary mixer. (iii) The dental adhesive composition can be produced by mixing (A1) a polymerizable monomer having an acidic group, (B) a photoinitiator, (C) a volatile organic solvent and / or (F) water, etc. by a known method such as a planetary mixer, a tumbler mixer, a mix rotor, a dissolver, a planetary mixer. (ii) The dental cement composition is prepared by first preparing a matrix by mixing (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, etc. (excluding (E) a filler) by a known method such as a planetary mixer, a tumbler mixer, a mix rotor, a dissolver, a planetary mixer, and then kneading this matrix and (E) a filler by a known method such as a planetary mixer, a tumbler mixer, a mix rotor, a dissolver, a planetary mixer, and removing bubbles under reduced pressure to prepare a uniform paste. In the present invention, the matrix refers to a mixed solution prepared by mixing components excluding (E) a filler, specifically, a mixed solution prepared by previously mixing (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, etc. When any of (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator is not uniformly dissolved in the matrix, a matrix not containing one or more of these can also be used. As a method for blending (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator not contained in the matrix into the (ii) dental cement composition, it is preferably blended when the matrix and (E) a filler are mixed. Components that do not dissolve in the matrix include those that do not dissolve even when mixed for 48 hours at 100 rpm using a mix rotor. At this time, those that can be mixed at a high temperature are preferably mixed at a temperature of 50°C.On the other hand, for those that may deteriorate by heating, such as (D) chemical polymerization initiators, it is preferable to mix them under the condition of 25 ± 5°C. The most preferable production method is to prepare a uniform matrix by premixing (A) polymerizable monomer, (B) photoinitiator, (D1) organic peroxide, (D2) chemical polymerization accelerator, etc., and then mix (E) filler to produce (ii) the dental cement composition. Also in the present invention, it can be produced without any problem by the above production method.

[0081] The (ii) dental cement composition of the present invention is a composition that is sub-packaged into two or more parts for use by mixing a first paste and a second paste. As a preferred example, the first paste and the second paste each contain (A) polymerizable monomer, (B) photoinitiator, (D) chemical polymerization initiator, and (E) filler, and the (D) chemical polymerization initiator in the first paste and the second paste is one or more selected from (D1) organic peroxide and (D2) chemical polymerization accelerator. As the mixing method, a method of discharging equal amounts of the first paste and the second paste filled in a double syringe and mixing them with a spatula, a method of mixing the first paste and the second paste by attaching a static mixer to the double syringe and pushing the plunger, any known mixing method such as a method of mixing powder and liquid can be used. For example, in the case of a composition sub-packaged into two pastes, the mixing ratio of the first paste and the second paste is preferably 1:0.8 to 1.2 by volume ratio, and more preferably 1:1. Preferably, it is 1:0.7 to 1.3 by mass ratio, and more preferably 1:1.

[0082] The dental adhesive composition applied to the (i) object to be adhered of the present invention (also referred to as “(i) dental adhesive composition” in the present disclosure) may contain only (A) polymerizable monomer, (B) photoinitiator, and (C) volatile organic solvent. Further, as components other than (A) to (C), only one or more of the above-described components may be contained.

[0083] The dental cement composition (also referred to as "(ii) dental cement composition" in the present disclosure) applied to the application surface of the (ii) dental adhesive composition of the present invention may contain only (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, and (E) a filler. Further, as components other than (A) to (E), only one or more of the above-described components may be contained.

[0084] The dental adhesive composition (also referred to as "(iii) dental adhesive composition" in the present disclosure) applied to the (iii) dental material and / or natural tooth of the present invention may contain only (A1) a polymerizable monomer having an acidic group, (B) a photoinitiator, and (C) a volatile organic solvent and / or (F) water. Further, as components other than (A1), (B), and (C) and / or (F), only one or more of the above-described components may be contained.

[0085] <Object to be adhered> (i) The dental adhesive composition of the present disclosure can adhere to a molded article of an aromatic polyetherketone resin, which is generally considered to be a difficult-to-adhere material. Therefore, it can adhere to many objects, including other common difficult-to-adhere materials. From this, as the object to which the (i) dental adhesive composition adheres (also referred to as the "adhesion target object" in the present disclosure), one or more selected from aromatic polyetherketone resin, dental metal, dental ceramics, dental cutting resin materials composed of (meth)acrylate resins, glass fiber reinforced resins, and stereolithography resin materials are exemplified. Among these, the (i) dental adhesive composition can be preferably used for one or more dental resin compositions selected from aromatic polyetherketone resin, dental cutting resin materials composed of (meth)acrylate resins, glass fiber reinforced resin materials, hard resin materials for crowns, and stereolithography resin materials. Further, as the adhesion target object of the (iii) dental adhesive composition, dental materials and / or natural teeth are exemplified. Examples of dental materials include materials for constructing dental abutments, dental metals, dental ceramics, etc. That is, as the adhesion target object to the molded article of the aromatic polyetherketone resin of the present disclosure, one or more selected from dental metal, dental ceramics, dental cutting resin materials composed of (meth)acrylate resins, glass fiber reinforced resins, stereolithography resin materials, dental materials, and natural teeth are exemplified.

[0086] <Laminates (X) and (Y)> In the present disclosure, there are also provided a laminate (X) (also simply referred to as "laminate (X)" in the present disclosure) including a molded article of an aromatic polyetherketone resin and a layer of the (i) dental adhesive composition, and a laminate (Y) (also simply referred to as "laminate (Y)" in the present disclosure) including an adhesion target object other than the aromatic polyetherketone resin and a layer of the (i) dental adhesive composition or a layer of the (iii) dental adhesive composition. In the present disclosure, it is assumed that the adhesive kit of the present disclosure is used in a form in which the (ii) dental cement composition is applied between the laminates (X) and (Y). That is, examples of the final product produced using the adhesive kit of the present disclosure include the following (α) and (β). (α) Molded article of aromatic polyether ketone resin - (i) Dental adhesive composition - (ii) Dental cement composition - (i) Dental adhesive composition - Adhesion target other than the molded article of aromatic polyether ketone resin (β) Molded article of aromatic polyether ketone resin - (i) Dental adhesive composition - (ii) Dental cement composition - (iii) Dental adhesive composition - Adhesion target other than the molded article of aromatic polyether ketone resin

[0087] <Method of using the kit> The kit of the present disclosure is a kit for use in adhering a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, and is assumed to be used in the following method. · (1-1) Step of sandblasting the adherend surface of the molded article of aromatic polyether ketone resin · (1-2) Step of applying a dental adhesive composition to the adherend surface of the molded article of aromatic polyether ketone resin, irradiating with light, and obtaining laminate (X) · (1-3) Step of applying a dental adhesive composition (iii) to the adherend surface of the dental material and / or natural tooth, irradiating with light, and obtaining laminate (Y) · (1-4) Step of applying a dental cement composition (ii) to the coated surface of the dental adhesive composition of laminate (X) and / or laminate (Y) · (1-5) Step of pressing the adherend surfaces of laminate (X) and laminate (Y) together · (1-6) Step of removing excess cement from the connecting portion between laminate (X) and laminate (Y), and · (1-7) Step of irradiating light to the connecting portion between laminate (X) and laminate (Y).

[0088] In addition, a method for manufacturing laminate (X) for use in adhesion to laminate (Y) obtained by applying a dental adhesive composition (iii) to the adherend surface of a dental material and / or a natural tooth is assumed to include the following steps. · Step of sandblasting the adherend surface of the molded article of aromatic polyether ketone resin, and · (2-2) Step of applying a dental adhesive composition to the adherend surface of the molded article of aromatic polyether ketone resin, irradiating with light, and obtaining laminate (X). As a method for manufacturing laminate (X) for use in adhesion to laminate (Y) obtained by applying (iii) a dental adhesive composition to the adherend surface of a dental material and / or natural tooth, the following step (2-3) may further be included. · (2-3) Step of applying (ii) a dental cement composition to the surface of laminate (X) coated with the (i) dental adhesive composition. The step of (2-3) may be omitted when applying (ii) a dental cement composition to the surface of (iii) the dental adhesive composition of a dental material and / or natural tooth.

[0089] When (ii) the dental cement composition is a composition having self-adhesiveness to a dental material and / or natural tooth, the step of (1-3) can be omitted, but it is preferable to perform the step of (1-3) because the adhesive strength decreases. A method of omitting the step of (1-3) is shown below. The kit of the present disclosure is a kit for use in adhesion between a molded article of aromatic polyether ketone resin and a dental material and / or natural tooth, and is assumed to be used by the following method. · (3-1) Step of sandblasting the adherend surface of the molded article of aromatic polyether ketone resin, · (3-2) Step of applying (i) a dental adhesive composition to the adherend surface of the molded article of aromatic polyether ketone resin, irradiating with light, and obtaining laminate (X), · (3-3) Step of applying (ii) a dental cement composition to the surface of laminate (X) coated with the dental adhesive composition, · (3-4) Step of pressing the surface of laminate (X) coated with (ii) the dental cement composition against a dental material and / or natural tooth, · (3-5) Step of removing excess cement from the connecting portion between laminate (X) and a dental material and / or natural tooth, and ·Step of irradiating light on the connecting part between the (3 - 6) laminate (X) and the dental material and / or natural tooth.

[0090] In the step of (1 - 3), although the step of irradiating light on the coating surface of the dental adhesive composition can be omitted, it is preferable to irradiate light because the adhesive strength decreases. Also, although a dental adhesive composition that does not contain a photoinitiator can be used, a composition containing a photoinitiator is preferable because the adhesive strength is higher when assuming all adherends.

Examples

[0091] The materials used in the examples and comparative examples and their abbreviations are shown below. [(A) Polymerizable monomer] <(A1) Polymerizable monomer having an acidic group> ·MDP: 10 - Methacryloyloxydecyl dihydrogen phosphate ·MET: 4 - Methacryloxyethyl trimellitic acid ·MHPA: (6 - Methacryloyloxy)hexyl phosphonoacetate ·META: 4 - Methacryloyloxyethoxycarbonyl phthalic anhydride <(A2) Polymerizable monomer having no acidic group> ·BisGMA: 2,2 - Bis[4 - (3 - Methacryloyloxy - 2 - hydroxypropoxy)phenyl]propane ·D2.6E: 2,2 - Bis(4 - (meth)acryloyloxypolyethoxyphenyl)propane with an average addition mole number of 2.6 of ethoxy groups ·UDMA: N,N - (2,2,4 - Trimethylhexamethylene)bis[2 - (aminocarboxy)ethanol] methacrylate ·TEGDMA: Triethylene glycol dimethacrylate ·GDMA: Glycerol dimethacrylate ·HEMA: Hydroxyethyl methacrylate ·MOTMS: Methacryloyloctyltrimethoxysilane ·MPTMS: 3-Methacryloxypropyltrimethoxysilane ·MDDT: 10-Methacryloxydodecyl-6,8-dithiaoctanoate ·NPG: Neopentyl glycol dimethacrylate

[0092] [(B) Photoinitiator] ·CQ: Camphorquinone ·DMBE: Ethyl dimethylbenzoate ·BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide ·CTIPFB: 4-Isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate ·MDEOA: Methyldiethanolamine

[0093] (C) Volatile organic solvent ·Ac: Acetone ·EtOH: Ethanol

[0094] [(D) Chemical initiator] <(D1) Organic peroxide> ·CHP: Cumene hydroperoxide ·TMBH: 1,1,3,3-Tetramethylbutyl hydroperoxide ·TBB: tert-Butyl peroxybenzoate ·BPO: Benzoyl peroxide <(D2) Chemical polymerization accelerator> ·CAc: Copper(II) acetate monohydrate ·VOA: Vanadyl acetylacetonate ·DMPT: N,N-Dimethyl-p-toluidine ·BTU: Benzoylthiourea ·DEPT: N,N-Dihydroxyethyl-p-toluidine ·PTU: Pyridylthiourea ·PA: L-Ascorbyl 6-palmitate

[0095] [(E) Filler] (Filler E1) To 100 g of a zirconium silicate filler (average particle diameter: 1.5 μm; zirconia: 20 wt%, silica: 80 wt%), 20 g of water, 35 g of ethanol, and a silane coupling treatment liquid containing 3 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. Thereafter, heat treatment was performed at 90 °C for 15 hours, and then a sieving step was carried out to obtain Filler E1.

[0096] (Filler E2) To 100 g of a barium silicate filler (average particle diameter: 1 μm, Al 2 O 3 : 10 wt%, B 2 O 3 : 10 wt%, BaO: 25 wt%, SiO 2 : 55 wt%), 20 g of water, 35 g of ethanol, and a silane coupling treatment liquid containing 6 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. Thereafter, heat treatment was performed at 90 °C for 15 hours, and then a sieving step was carried out to obtain Filler E2.

[0097] (Filler E3) To 100 g of a fluoroaluminoborosilicate glass (average particle diameter: 1 μm, SiO 2 : 22.5 wt%, Al 2 O 3 : 20.0 wt%, B 2 O 3 : 12.3 wt%, SrO: 35.7 wt%, Na 2 O: 2.5 wt%, F: 7.0 wt%), 20 g of water, 35 g of ethanol, and a silane coupling treatment liquid containing 6 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. Thereafter, heat treatment was performed at 90 °C for 15 hours, and then a sieving step was carried out to obtain Filler E3.

[0098] (Filler E4) Fluoroaluminoborosilicate glass (average particle size 1 μm, SiO 2 : 22.5 wt%, Al 2 O 3 : 20.0 wt%, B 2 O 3 : 12.3 wt%, SrO: 35.7 wt%, Na 2 O: 2.5 wt%, F: 7.0 wt%) For 100 g, 4.5 g of the low condensate of the silane compound "MKC Silicate MS56S" (SiO 2 content 56.0 mass%, degree of polymerization 2 - 100, manufactured by Mitsubishi Chemical Corporation) was added and stirred and mixed for about 90 minutes. After mixing for a predetermined time, the obtained treated slurry was aged in a hot air dryer at 50 °C for 40 hours, then heated to 150 °C and held for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was put into a Henschel mixer and crushed at 1800 rpm for 5 minutes. For 100 g of the produced filler, 100 g of water, 80 g of ethanol, and 6 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the obtained silane coupling treatment liquid was added and stirred and mixed for 30 minutes. Then, heat treatment was carried out at 90 °C for 15 hours to obtain filler E4.

[0099] (Filler E5) Fluoroaluminoborosilicate glass (average particle size 1 μm, SiO 2 : 22.5 wt%, Al 2 O 3 : 20.0 wt%, B 2 O 3 : 12.3 wt%, SrO: 35.7 wt%, Na 2 O: 2.5 wt%, F: 7.0 wt%) For 100 g, 4.5 g of the low condensate of the silane compound "MKC Silicate MS56S" (SiO 24.5 g of a substance with a content of 56.0% by mass and a degree of polymerization of 2 to 100 (manufactured by Mitsubishi Chemical Corporation) was added and stirred and mixed for about 90 minutes. After mixing for a predetermined time, the obtained treated slurry was aged in a hot air dryer at 50 °C for 40 hours, then heated to 150 °C and retained for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was put into a Henschel mixer and crushed at 1800 rpm for 5 minutes. Subsequently, 16.0 g of an aqueous polyacrylic acid solution (polymer concentration 13% by mass, weight average molecular weight 10,000; manufactured by Nacalai Tesque, Inc.) was sprayed from above. After spraying, the powder taken out from the mixer was heated in a hot air dryer at 100 °C for 3 hours. To 100 g of the manufactured filler, 100 g of water, 80 g of ethanol, and 9 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added and stirred at room temperature for 2 hours to obtain a silane coupling treatment liquid, which was then stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 90 °C for 15 hours to obtain filler E5.

[0100] (Filler E6) · Titanium oxide (average particle diameter 0.25 μm) (Filler E7) · Aerosil R-8200 (manufactured by Evonik) (Filler E8) · Aerosil R-711 (manufactured by Evonik)

[0101] [(F) Water] · DW: Distilled water

[0102] [Polymerization inhibitor] · MeHQ: p-Methoxyphenol · BHT: Dibutylhydroxytoluene [UV absorber] · OB: 2-Hydroxy-4-(octyloxy)benzophenone · BT: 2-(2H-Benzotriazol-2-yl)-4-methylphenol [Fluorescent agent] · FA: Diethyl 2,5-dihydroxyterephthalate

[0103] <Production Example (i)-1: Method for Producing (i) Dental Adhesive Composition-1> All of the compositions shown in row (i)-1 of Table 1 were put into a wide-mouth poly container and mixed for 48 hours under the condition of 100 rpm using a mixing rotor (product name "VMRC-5", manufactured by AS ONE Corporation) to prepare (i) dental adhesive composition-1. The prepared (i) dental adhesive composition-1 was filled into a bottle container of the product name "Beauty Bond Xtreme" (manufactured by Shofu Inc.) for use. In the tables of the present disclosure, the mass parts of each component are described in parentheses after the abbreviations of each component.

[0104] <Production Examples (i)-2 to 18 and Comparative Production Examples (i)-C1 to C3: Methods for Producing (i) Dental Adhesive Compositions-2 to 18 and (i) Dental Adhesive Compositions-C1 to C3> Except for changing to the compositions described in Tables 1 to 2, the same method as in Production Example (i)-1 was carried out to obtain (i) dental adhesive compositions-2 to 18 and (i) dental adhesive compositions-C1 to C3. Note that "C" indicated by C + number such as "C1" is the "C" of "Comparative" and is used in the tables of the present disclosure for the meaning of comparison.

[0105]

Table 1

[0106]

Table 2

[0107] <Production Example (ii)-1: Method for Producing (ii) Dental Cement Composition-1> All except the (E) filler shown in the (ii)-1 row of Table 3 were put into a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a mixing rotor (product name "VMRC-5", manufactured by AS ONE Corporation) to obtain a matrix. Then, the matrix and the (E) filler were put into a kneader, stirred uniformly, and defoamed under vacuum to obtain a first paste and a second paste. After that, the first paste and the second paste were filled into a double syringe (5 mL) manufactured by Mix Pack to prepare (ii) dental cement composition-1. When using (ii) dental cement composition-1 in the examples, it was used by discharging equal amounts from the double syringe manufactured by Mix Pack and kneading with a plastic spatula.

[0108] <Production Example (ii)-2 to 18 and Comparative Production Example (ii)-C1 to C4: Manufacturing methods of (ii) dental cement composition-2 to 18 and (ii) dental cement composition-C1 to C4> Except for changing to the compositions described in Tables 3 to 6, the same method as in Production Example (ii)-1 was carried out to obtain (ii) dental cement composition-2 to 18 and (ii) dental cement composition-C1 to C4.

[0109]

Table 3

[0110]

Table 4

[0111]

Table 5

[0112]

Table 6

[0113] <Production Example (iii)-1: Manufacturing method of (iii) dental adhesive composition-1> All of the compositions shown in the row (iii)-1 of Table 7 were put into a wide-mouth plastic container and mixed for 48 hours under the condition of 100 rpm using a mixing rotor (product name "VMRC-5", manufactured by AS ONE Corporation), whereby (iii) dental adhesive composition-1 was prepared. The prepared (iii) dental adhesive composition-1 was filled into a bottle container of the product name "Beauty Bond Xtreme" (manufactured by Shofu Inc.) and used.

[0114] <Production Examples (iii)-2 to 12 and Comparative Production Examples (iii)-C1 to C3: Methods for Producing (iii) Dental Adhesive Compositions-2 to 12 and (iii) Dental Adhesive Compositions-C1 to C3> Except for changing to the compositions described in Tables 7 to 8, the same method as in Production Example (iii)-1 was carried out to obtain (iii) dental adhesive compositions-2 to 12 and (iii) dental adhesive compositions-C1 to C3.

[0115]

Table 7

[0116]

Table 8

[0117] <Example 1> The (i) dental adhesive composition, (ii) dental cement composition, and (iii) dental adhesive composition described in the row "1" of the leftmost column of Table 9 were used as follows in Evaluations 1 to 3 to evaluate the adhesive kit of the present disclosure. In addition, in the "Light Irradiation" column in the table, "Yes" and "No" indicate that the composition was irradiated with light after applying the (iii) dental adhesive composition and is described as "Yes", and those not irradiated with light are described as "No".

[0118] <Examples 2 to 19 and Comparative Examples C1 to C7> Except for changing to the combinations described in Table 9, the same method as in Example 1 was carried out to evaluate each adhesive kit.

[0119] <Evaluation 1: Adhesive strength to the molded article of aromatic polyether ketone resin (adhesive strength (PEEK))> The adherend surface of a molded article of aromatic polyether ketone resin molded into a plate shape with a thickness of 3 mm (polyether ether ketone: 78%, titanium oxide: 20%, other pigments, etc.: 2%) was polished with waterproof abrasive paper #600, and alumina (50 μm) was used for sandblasting treatment (0.2 MPa) on the adherend surface, followed by water washing and drying. (i) A dental adhesive composition was applied to the adherend surface of the molded article of aromatic polyether ketone resin, and air drying was performed. (i) The coated surface of the dental adhesive composition was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Co., Ltd.) to obtain a laminate (X)-1. Next, the adherend surface of a φ4 mm resin block rod produced from a dental cutting resin block (product name "Matsuura Block HC Super Hard", manufactured by Matsuura Co., Ltd.) was subjected to sandblasting treatment (0.2 MPa) with alumina (50 μm), followed by water washing and drying. (i) A dental adhesive composition was applied and air drying was performed. The coated surface of the (i) dental adhesive composition applied to the resin block rod was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Co., Ltd.) to obtain a laminate (Y)-1. (ii) An equal amount of the first paste and the second paste of a dental cement composition were thoroughly kneaded and an appropriate amount was applied to the coated surface of the (i) dental adhesive composition of the laminate (Y)-1, and the laminate (X)-1 and the laminate (Y)-1 were quickly joined together. A load of 200 g was applied to the joined body of the laminate (X)-1 and the laminate (Y)-1 from the vertical direction, and the excess cement was wiped off with a cloth. Then, it was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Co., Ltd.). After removing the load, the produced adhesion test specimen was immersed in water at 37°C for 24 hours, and then the shear adhesive strength was measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). When the adhesive strength was 20 MPa or more, it was judged as extremely good adhesive strength; when it was 15 to 20 MPa, it was judged as good adhesive strength; when it was 10 to 15 MPa, it was judged as medium adhesive strength; and when it was less than 10 MPa, the adhesive strength was judged to be insufficient. The higher the adhesive strength to the molded article of aromatic polyether ketone resin, the more preferable it is because the risk of detachment and the like decreases.

[0120] <Evaluation 2: Adhesive strength to dentin (adhesive strength (dentin))> The adherend surface of a molded article of aromatic polyether ketone resin (polyether ether ketone: 78%, titanium oxide: 20%, other pigments, etc.: 2%) molded into a columnar shape with a thickness of 2 mm and a diameter of 4 mm was polished with waterproof abrasive paper #600, and the adherend surface was sandblasted with alumina (50 μm) (0.2 MPa) and then washed with water and dried. (i) A dental adhesive composition was applied to the adherend surface of the molded article of aromatic polyether ketone resin, and air drying was performed. (i) The coated surface of the dental adhesive composition was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Co., Ltd.) to obtain a laminate (X)-2. The epoxy-embedded bovine central incisor was polished with waterproof abrasive paper #600 to expose the dentin plane. (iii) A dental adhesive composition was applied to the dentin plane, and air drying was performed. (iii) The coated surface of the dental adhesive composition was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Co., Ltd.) to obtain a laminate (Y)-2. (ii) The first paste and the second paste of the dental cement composition were thoroughly kneaded in equal amounts and an appropriate amount was applied to the coated surface of the dental adhesive composition of the laminate (X)-2, and the laminate (X)-2 and the laminate (Y)-2 were joined together. A load of 200 g was applied from the vertical direction to the joined body of the laminate (X)-2 and the laminate (Y)-2, and the excess cement was wiped off with a cloth. Then, it was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Co., Ltd.). After removing the load, the prepared adhesive test specimen was immersed in water at 37°C for 24 hours, and then the shear adhesive strength was measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). When the adhesive strength was 10 MPa or more, it was judged as good adhesive strength; when it was 5 MPa, it was judged as good adhesive strength; and when it was less than 5 MPa, the adhesive strength was judged to be insufficient. The higher the adhesive strength to dentin, the more preferable it is because the risk of detachment and the like decreases.

[0121] <Evaluation 3: Operability> After thoroughly kneading equal amounts of the first paste and the second paste of each (ii) dental cement composition, apply it to a molded article of aromatic polyether ketone resin that is Φ15 mm in diameter and 5 mm in height (polyether ether ketone: 78%, titanium oxide: 20%, other pigments, etc.: 2%), and immediately press it against another molded article of aromatic polyether ketone resin that is Φ15 mm in diameter and 5 mm in height (polyether ether ketone: 78%, titanium oxide: 20%, other pigments, etc.: 2%). For the excess cement that emerged from the pressing, light irradiation was performed for 5 seconds using a dental polymerization LED light irradiator (product name "Penbright", manufactured by Matsuura Dental Co., Ltd.). Then, the degree of removing the excess cement using a short needle was evaluated. Five evaluators evaluated the removability of the excess cement, and the most frequent judgment was adopted as the evaluation result. When it was moderately cured and the removability of the excess cement with a short needle was good, it was designated as A; when the degree of curing was slightly low or the curing had progressed too far and it was difficult to remove the excess cement with a short needle, it was designated as B; when it was not cured or was over-cured and it was impossible to remove the excess cement with a short needle, it was designated as C. Good removability of the excess cement is preferable because it leads to a reduction in the treatment time of the operator. Furthermore, it is also preferable because there may be no excessive load on the adhesive during curing and good adhesive strength can be expected.

[0122] The results of each test shown in Table 9 will be described.

[0123]

Table 9

[0124] It was confirmed that the compositions described in the examples achieved both good adhesiveness and good workability with respect to the molded article of aromatic polyether ketone resin.

[0125] (i) In Examples 1 to 6, Example 15, and Example 17 where the dental adhesive composition used Production Examples (i)-1 to 6 containing a polymerizable monomer having an (A1) acidic group or Production Examples (i)-15 and 17 not containing methyl methacrylate, the adhesive strength to the molded article of aromatic polyether ketone resin tended to be low.

[0126] (i) Example 10 using Production Example (i)-10 with a low content of the (B) photoinitiator in the dental adhesive composition and (ii) Example 7 using Production Example (ii)-1 with a low content of the (B) photoinitiator in the dental cement composition showed a tendency of low adhesive strength to the molded article of the aromatic polyether ketone resin.

[0127] Examples 4, 9, and 11 using Production Examples (iii)-11 and (iii)-12 which are (iii) dental adhesive compositions not containing a photoinitiator, or Example 15 using Production Example (iii)-10 containing a photoinitiator and not performing light irradiation on the (iii) dental adhesive composition during the adhesion operation to dentin showed a tendency of slightly low adhesive strength to dentin.

[0128] (ii) Example 8 using Production Example (ii)-2 with a high content of the (B) photoinitiator in the dental cement composition showed a tendency of slightly poor workability. Also, Example 9 using Production Example (ii)-16 with a low content of the (D) chemical initiator in the (ii) dental cement composition showed a tendency of low adhesive strength to the molded article of the aromatic polyether ketone resin and dentin.

[0129] Comparative Example C1 and Comparative Example C2 that adhered to the molded article of the aromatic polyether ketone resin using Comparative Production Example (i)-C1 with an extremely low content of the (B) photoinitiator or Comparative Production Example (i)-C2 not containing the (B) photoinitiator did not have sufficient adhesive strength to the molded article of the aromatic polyether ketone resin. Comparative Example C3 that adhered to the molded article of the aromatic polyether ketone resin using Comparative Production Example (i)-C3 not containing the (A) polymerizable monomer did not have sufficient adhesive strength to the molded article of the aromatic polyether ketone resin.

[0130] Comparative Examples C1 to C3 that adhered to dentin using Comparative Production Examples (iii)-C1 to C3 not containing the (A1) polymerizable monomer having an acidic group did not have sufficient adhesive strength to dentin.

[0131] (B) Photoinitiator-free Comparative Production Example (ii)-C1 or Comparative Example C4 and Comparative Example C5 using a large amount of (B) photoinitiator in Comparative Production Example (ii)-C2 tended to have poor operability.

[0132] (D1) Comparative Example C6 and Comparative Example C7 in which adhesion was performed using Comparative Production Example (ii)-C3 containing no organic peroxide or Comparative Production Example (ii)-C4 containing no chemical polymerization accelerator tended to have low adhesion strength to the molded article of aromatic polyether ketone resin.

[0133] The kit of the present invention evaluated in the examples can be used for adhesion to the molded article of aromatic polyether ketone resin. Furthermore, it can be used for adhesion to dental materials such as dental metals, dental ceramics, dental resin materials, etc. and / or natural teeth with the molded article of aromatic polyether ketone resin. In addition, since it is possible to adhere to the molded article of aromatic polyether ketone resin which is difficult to adhere, it can also be suitably used for known dental resin compositions such as dental cutting resin materials, glass fiber reinforced resins, and stereolithography resin materials composed of (meth)acrylate resins.

Industrial Applicability

[0134] According to the present invention, it is possible to achieve both good adhesiveness to the molded article of aromatic polyether ketone resin and good operability during the adhesion operation.

Claims

1. A kit for use in adhering to a molded article of an aromatic polyether ketone resin, the kit comprising (i) a dental adhesive composition to be applied to an object to be adhered, and (ii) a dental cement composition to be applied to the coated surface of the dental adhesive composition. (i) The dental adhesive composition contains (A) a polymerizable monomer, (B) a photoinitiator, and (C) a volatile organic solvent. (i) The dental adhesive composition contains 2 to 10 parts by mass of (B) the photoinitiator per 100 parts by mass. (ii) The dental cement composition contains (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, and (E) a filler, and (ii) The dental cement composition contains 0.1 to 2 parts by mass of (B) the photoinitiator with respect to 100 parts by mass of (A) the polymerizable monomer contained in the dental cement composition. A kit for use in adhering to a molded article of an aromatic polyether ketone resin, characterized in that it contains the above components.

2. A kit for use in adhering a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, the kit comprising (i) a dental adhesive composition, (ii) a dental cement composition, and (iii) a dental adhesive composition to be applied to the dental material and / or the natural tooth. (i) The dental adhesive composition contains (A) a polymerizable monomer, (B) a photoinitiator, and (C) a volatile organic solvent. (i) The dental adhesive composition contains 2 to 10 parts by mass of (B) the photoinitiator per 100 parts by mass. (ii) The dental cement composition contains (A) a polymerizable monomer, (B) a photoinitiator, (D1) an organic peroxide, (D2) a chemical polymerization accelerator, and (E) a filler. (ii) The dental cement composition contains 0.1 to 2 parts by mass of (B) the photoinitiator with respect to 100 parts by mass of (A) the polymerizable monomer contained in the dental cement composition, and (iii) The dental adhesive composition contains (A1) a polymerizable monomer having an acidic group, (B) a photoinitiator, and (C) a volatile organic solvent and / or (F) water. A kit for use in adhering a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, characterized in that it contains the above components.

3. The kit according to claim 1, wherein (i) the dental adhesive composition contains (D2) a chemical polymerization accelerator.

4. The kit according to claim 2, wherein (i) the dental adhesive composition contains (D2) a chemical polymerization accelerator.

5. The kit according to claim 3, wherein (i) the dental adhesive composition contains methyl methacrylate as the polymerizable monomer (A) and substantially does not contain a polymerizable monomer having an acidic group (A1).

6. The kit according to claim 4, wherein (i) the dental adhesive composition contains methyl methacrylate as the polymerizable monomer (A) and substantially does not contain a polymerizable monomer having an acidic group (A1).

7. A kit for use in bonding to a molded article of an aromatic polyetherketone resin, the kit comprising (i) a dental adhesive composition and (ii) a dental cement composition, wherein in 100 parts by mass of the dental adhesive composition (i), there are contained (A) 30 to 85 parts by mass of a polymerizable monomer, (B) 2 to 10 parts by mass of a photoinitiator, (C) 10 to 60 parts by mass of a volatile organic solvent, and (D2) 0.01 to 5 parts by mass of a chemical polymerization accelerator, and wherein (ii) the dental cement composition contains, based on 100 parts by mass of the polymerizable monomer (A) contained in the cement composition, (B) 0.1 to 2 parts by mass of a photoinitiator, (D1) 0.5 to 5 parts by mass of an organic peroxide, (D2) 0.5 to 5 parts by mass of a chemical polymerization accelerator, and (E) 50 to 400 parts by mass of a filler The kit according to claim 5, characterized in that it contains the above.

8. A kit for use in bonding a molded article of an aromatic polyetherketone resin to a dental material and / or a natural tooth, the kit comprising (i) a dental adhesive composition, (ii) a dental cement composition, and (iii) a dental adhesive composition, wherein in 100 parts by mass of the dental adhesive composition (i), there are contained (A) 30 to 85 parts by mass of a polymerizable monomer, (B) 2 to 10 parts by mass of a photoinitiator, (C) 10 to 60 parts by mass of a volatile organic solvent, and (D2) 0.01 to 5 parts by mass of a chemical polymerization accelerator, wherein (ii) the dental cement composition contains, based on 100 parts by mass of the polymerizable monomer (A) contained in the dental cement composition, (B) 0.1 to 2 parts by mass of a photoinitiator, (D1) 0.5 to 5 parts by mass of an organic peroxide, (D2) 0.5 to 5 parts by mass of a chemical polymerization accelerator, and (E) 50 to 400 parts by mass of a filler, and wherein in 100 parts by mass of the dental adhesive composition (iii), there are contained (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, (B) 0.5 to 10 parts by mass of a photoinitiator, (C) 0 to 50 parts by mass of a volatile organic solvent, and (E) 0 to 50 parts by mass of water The kit according to claim 6, characterized by comprising

9. A kit for use in adhering a molded article of an aromatic polyether ketone resin to a dental material and / or a natural tooth, (1-1) a step of sandblasting the adherend surface of the molded article of the aromatic polyether ketone resin; (1-2) (i) a step of applying a dental adhesive composition to the adherend surface of the molded article of the aromatic polyether ketone resin, irradiating with light, and obtaining a laminate (X); (1-3) a step of applying (iii) a dental adhesive composition to the adherend surface of the dental material and / or the natural tooth, irradiating with light, and obtaining a laminate (Y); (1-4) a step of applying (ii) a dental cement composition to the coated surface of the dental adhesive composition of the laminate (X) and / or the laminate (Y); (1-5) a step of pressing the adherend surfaces of the laminate (X) and the laminate (Y) together; (1-6) a step of removing excess cement at the connecting portion between the laminate (X) and the laminate (Y); and (1-7) a step of irradiating the connecting portion between the laminate (X) and the laminate (Y) with light The kit according to claim 8, which is used in an adhesion method comprising

10. A method for manufacturing a laminate (X) for use in adhering to a laminate (Y) obtained by applying the (iii) dental adhesive composition according to claim 8 to the adherend surface of a dental material and / or a natural tooth, (2-1) a step of sandblasting the adherend surface of the molded article of the aromatic polyether ketone resin; and (2-2) a step of applying the (i) dental adhesive composition according to claim 8 to the adherend surface of the molded article of the aromatic polyether ketone resin, irradiating with light, and obtaining a laminate (X), Manufacturing method.

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