JP2006225350A - Adhesive composition for partially repeated restoration in dental treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for partially repeated restoration in dental treatment, capable of exhibiting excellent adhesive force to dentin and a dental restorative material for a long period, to say nothing of an initial stage after adhesion, and to provide an adhesive of two-pack type. <P>SOLUTION: This adhesive composition for the partially repeated repair in the dental treatment comprises a mixture of an agent I into which a hydrophobic acidic group-containing polymerizable monomer (a), an aromatic tertiary amine (e) having an electron-attracting group, and a basic compound (g) for forming a water-soluble salt by reacting with a part of the hydrophobic acidic group-containing polymerizable monomer (a) are mixed as essential mixing ingredients and an agent II into which a silane coupling agent (h) is mixed as an essential mixing ingredient, wherein a water-soluble polymerizable monomer (b), water (c), a photopolymerization initiator (d), and a crosslinkable polymerizable monomer (f) are independently mixed into the agent I, the agent II, or both of the agents. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive composition for partial restorative dental treatment, and more specifically, a restoration site of a hard tissue (dental material) of a tooth restored with dental ceramics, dental hard resin, dental composite resin or the like. The present invention relates to an adhesive composition for partial restorative dental treatment, which is suitable for use in repairing a part of a dental restorative with a filling restorative material such as a dental composite resin.

  For restoration of dental materials damaged by caries, etc. (enamel, dentin and cementum), filling restoration materials such as filling composite resins and filling compomers, and teeth such as metal alloys, porcelain and resin materials are usually used. A crown repair material is used. In recent years, restoration to a more natural color tone has been demanded. Therefore, a filling restoration material and a crown restoration material having a color tone close to natural teeth (in this specification, both are collectively referred to as “aesthetic restoration material”). Is commonly used.

  Restoring with aesthetic restorative materials restores the function of the tooth, as well as restoring the oral appearance of a healthy and natural color. However, after the repair, a part of the repaired part may be worn out or a part of the repaired part may be broken due to an occlusal pressure during food intake or an unexpected impact. In such a case, as a method of redevelopment, after removing all the existing restorations, the complete redevelopment method that starts over from the beginning, and the worn or broken part such as a composite resin for filling, a compomer for filling, etc. There is a partial re-restoration method in which a filling repair material is filled and only the portion is repaired. In addition, as a method of re-restoration when a site close to the repaired site newly suffers from caries, after removing all existing restorations, the new and old caries sites are repaired together with new restorations. There is a complete restorative method and a partial restorative method that repairs only a new carious site. The partial restorative method has a narrower tooth cutting range compared to the full restorative method, in which all the restoratives are re-executed. There are advantages such as less economic burden.

  By the way, in partial restorative dental treatment, because of re-restoration, there are many cases where a tooth and an aesthetic restorative material are mixed in the restorative part, and either the tooth of the filling restorative material or the aesthetic restorative material It is rare that treatment should be performed considering only adhesiveness.

  However, the adhesive for the tooth and the adhesive for the aesthetic restorative material are each designed to exhibit excellent adhesive strength with respect to the tooth and the aesthetic restorative material, respectively. Since there are many cases where the desired adhesive strength is not exhibited when the change is made, it is necessary to use different adhesives for each adherend when such an adherend is used.

  However, when multiple types of adherends exist adjacent to each other, it is practically difficult to use different adhesives for each adherend. An adhesive that exhibits excellent adhesiveness to both is extremely useful.

  Examples of dental adhesives that can be used for dental materials and various aesthetic restorative materials include, for example, radical polymerizable monomers having an acidic group in the molecule, photosensitizers and / or peroxides, and water-solubility. A dental adhesive kit comprising an organic solvent and water has been proposed (Patent Document 1 below).

  Examples of dental primers that can be used for dental materials and various aesthetic restoration materials include, for example, a polymerizable compound having at least one radical polymerizable group and a sulfur atom in the molecule, a coupling agent, and an acidic group. A dental primer composition containing a predetermined amount of each of a polymerizable monomer containing a polymerizable monomer, a volatile organic solvent, and water has been proposed (Patent Document 2 below).

JP 2000-178111 A (Claim 1, [0001]) Japanese Patent Laying-Open No. 2002-265312 (Claim 1, [0006])

  As mentioned above, the restoration site in partial restorative dental treatment often contains a mixture of tooth quality and aesthetic restoration material, so the dental adhesive used in this application has a filling restoration material. Is required to have a strong adhesion to both the tooth and the aesthetic restorative material.

  Moreover, since the oral cavity is always in a moist state, and the dental adhesive is normally subjected to mechanical stress such as occlusion, water resistance and durability are also required.

  Furthermore, the adhesive for partial restorative dental treatment is also required to have an equal adhesive strength to the tooth and adhesive strength to the aesthetic restorative material. The reason for this is as follows. That is, the filling / restoring material is hardened, that is, shrinks in volume (so-called polymerization shrinkage) as the polymerization reaction proceeds. This volumetric shrinkage stress acts as a stress (strain) on the adhesive interface between the adhesive and the tooth or aesthetic restorative material. In partial re-restoration, if the adhesive strength of the adhesive to either the tooth or the aesthetic restorative material is extremely strong, the stress is concentrated at the interface between the adhesive and the adherend with the weaker adhesive strength. Then, interfacial peeling occurs. When peeling occurs at the interface between the adhesive and the tooth, caries bacteria enter the gap, which causes secondary caries. In addition, when peeling occurs at the interface between the adhesive and the aesthetic restorative material, food pigment or the like is deposited in the gap, which significantly impairs the aesthetics of the teeth. In the case where the adhesive strength of the adhesive to the tooth quality and the aesthetic restorative material is uniform, the stress due to the volume shrinkage of the filling restorative material is evenly dispersed, and therefore, interface peeling is unlikely to occur.

  However, even if the adhesive strength of the adhesive immediately after re-restoration is equal to the adhesive strength to the aesthetic restorative material, the deterioration over time of the adhesive strength with respect to one is compared with that of the adhesive strength with respect to the other. In the case of remarkable, the stress due to volume shrinkage that was initially dispersed gradually concentrates as a peeling stress at a place where the deterioration of the adhesive force with time is significant, and interface peeling occurs there. Therefore, it is necessary to maintain that the adhesive strength of the dental adhesive used for partial re-restoration with respect to the tooth and the adhesive strength with respect to the aesthetic restorative material is maintained not only immediately after the re-restoration but also over a long period of time.

  According to Patent Document 1 [0063] Table 1 and Patent Document 2 [0100] Table 1, the kits and compositions described therein are used in the initial stage after bonding (after 24 hours of bonding) and in the tooth quality and various dental restorative materials. In addition, the adhesive strength is excellent, and the variation in the adhesive strength based on the difference in adherend is not large.

  However, as a result of studies by the present inventors, the above-described kits and compositions have a large variation in adhesive strength over time due to the difference in adherends, and therefore, a plurality of kinds of adherends are mixed. When these were used for partial restorative dental treatment, it was found that there was a problem that sufficient adhesion durability (durability of adhesive force) could not be obtained.

  The present invention has been made to solve the above-mentioned problems of the prior art, and the object of the present invention is to provide an excellent adhesive force to the tooth quality and various dental restorative materials not only in the initial stage after bonding but also in the long term. An object of the present invention is to provide an adhesive composition for partial restorative dental treatment and a two-part adhesive.

  The adhesive composition for partial restorative dental treatment according to claim 1, which is provided to achieve the above object, comprises a hydrophobic acidic group-containing polymerizable monomer (a) and a water-soluble polymerizable compound. Monomer (b), water (c), photopolymerization initiator (d), aromatic tertiary amine (e) having an electron-withdrawing group, and crosslinkable polymerizable monomer (f) A basic compound (g) that should react with a part of the hydrophobic acidic group-containing polymerizable monomer (a) to form a water-soluble salt, and a silane coupling agent (h), It is blended as an essential compounding agent.

  The adhesive composition for partial restorative dental treatment according to claim 2, comprising a hydrophobic acidic group-containing polymerizable monomer (a), an aromatic tertiary amine (e) having an electron-withdrawing group, and A basic compound (g) which reacts with a part of the hydrophobic acidic group-containing polymerizable monomer (a) to form a water-soluble salt, as an essential compounding agent I A water-soluble polymerizable monomer (b), water (c), and photopolymerization start by blending an agent and a silane coupling agent (h) as an essential compounding agent with a second agent. The agent (d) and the crosslinkable polymerizable monomer (f) are each independently blended with the first agent, the second agent or both agents.

  The adhesive composition for partial restorative dental treatment according to claim 3 is the adhesive composition for partial restorative dental treatment according to claim 2, which is a hydrophobic acidic group-containing polymerizable monomer ( a) 1 to 50% by weight, water-soluble polymerizable monomer (b) 1 to 60% by weight, water (c) 1 to 50% by weight, photopolymerization initiator (d) 0.01 to 10 Wt%, aromatic tertiary amine (e) having an electron withdrawing group (e) 0.01 to 10 wt%, crosslinkable polymerizable monomer (f) 5 to 70 wt%, silane coupling agent ( h) 1 to 70% by weight.

  The adhesive composition for partial restorative dental treatment according to claim 4 is the adhesive composition for partial restorative dental treatment according to claim 3, which is based on 100 parts by weight of the basic compound (g). And 25 to 60000 parts by weight of the crosslinkable polymerizable monomer (f).

  The adhesive composition for partial restorative dental treatment according to claim 5 is the adhesive composition for partial restorative dental treatment according to any one of claims 1 to 4, wherein the hydrophobic acidity The (meth) acrylate polymerizable monomer in which the group-containing polymerizable monomer (a) has at least one monovalent or divalent phosphate group or monovalent or divalent pyrophosphate group in the molecule. And the basic compound (g) is an aromatic secondary amine or an aromatic tertiary amine.

  The adhesive composition for partial restorative dental treatment according to claim 6 is the adhesive composition for partial restorative dental treatment according to any one of claims 1 to 4, wherein the hydrophobic acidity The (meth) acrylate polymerizable monomer in which the group-containing polymerizable monomer (a) has at least one monovalent or divalent phosphate group or monovalent or divalent pyrophosphate group in the molecule. And the basic compound (g) is an aliphatic secondary amine or an aliphatic tertiary amine.

  The adhesive composition for partial restorative dental treatment according to claim 7 is the adhesive composition for partial restorative dental treatment according to any one of claims 1 to 4, wherein the hydrophobic acidity The (meth) acrylate polymerizable monomer in which the group-containing polymerizable monomer (a) has at least one monovalent or divalent phosphate group or monovalent or divalent pyrophosphate group in the molecule. And the basic compound (g) is an aliphatic secondary amine having a hydroxyl group or an aliphatic tertiary amine having a hydroxyl group.

  The adhesive composition for partial restorative dental treatment according to claim 8 is the adhesive composition for partial restorative dental treatment according to any one of claims 2 to 7, wherein the first agent or A water-soluble volatile organic solvent (i) is further blended with the second agent or both agents.

  The adhesive composition for partial restorative dental treatment according to claim 9 is the adhesive composition for partial restorative dental treatment according to any one of claims 2 to 8, wherein the first agent or A filler (j) is further blended with the second agent or both agents.

  The adhesive composition for partial restorative dental treatment according to claim 10 is the adhesive composition for partial restorative dental treatment according to any one of claims 1 to 9, wherein the silane coupling agent is used. (H) is represented by the following chemical formula 1.

[Wherein R ¹ represents an organic group having at least one functional group selected from the group consisting of a (meth) acryloyl group, a vinyl group, a mercapto group, and an epoxy group, and R ² has 1 to 5 carbon atoms. An alkyl group or an alkoxy group having 1 to 5 carbon atoms is represented, and R ³ and R ⁴ each independently represent an alkoxy group having 1 to 5 carbon atoms. ]

  The two-component adhesive for partial restorative dental treatment according to claim 11 comprises a hydrophobic acidic group-containing polymerizable monomer (a) and an aromatic tertiary amine (e) having an electron-withdrawing group. And a basic compound (g) that reacts with a part of the hydrophobic acidic group-containing polymerizable monomer (a) to form a water-soluble salt as an essential compounding agent. It consists of the II agent which mix | blends I agent and a silane coupling agent (h) as an essential compounding agent, water-soluble polymerizable monomer (b), water (c), photoinitiator ( d) and the crosslinkable polymerizable monomer (f) are each independently blended with the first agent or the second agent or both agents.

  Provided are an adhesive composition and a two-part adhesive for partial restorative dental treatment that exhibit an excellent adhesive force with respect to a tooth and a dental restorative material for a long period of time from the beginning after adhesion.

The hydrophobic acidic group-containing polymerizable monomer (a) in the present invention has a solubility in water at 25 ° C. of less than 10% by weight. Those having the same solubility of less than 5% by weight are preferred, and those having the same solubility of less than 1% by weight are most preferred. Hydrophobic acidic group-containing polymerizable monomer (a) penetrates into the tooth and binds to it while decalcifying. In the present invention, the hydrophobic acidic group-containing polymerizable monomer (a) is blended in place of the water-soluble acidic group-containing polymerizable monomer. Although the monomer is superior to the hydrophobic acidic group-containing polymerizable monomer (a) in terms of penetrating into the tooth, it is excellent in water resistance after polymerization and curing due to water solubility. This is because the adhesion durability (the durability of the adhesion state) cannot be obtained. The salt which is a reaction product of the hydrophobic acidic group-containing polymerizable monomer (a) and the basic compound (g) in the present invention is also water-soluble, but this salt reacts with the apatite of the tooth. Ultimately, it becomes a water-insoluble Ca salt, so that excellent adhesion durability is obtained. The hydrophobic acidic group-containing polymerizable monomer (a) has a monovalent phosphate group [phosphinico group: = P (═O) OH] and a divalent phosphate group [phosphono group: —P (═O ) (OH) ₂ ], pyrophosphate group [—P (═O) (OH) —OP (═O) (OH) —], carboxylic acid group [carboxyl group: —C (═O) OH, acid Anhydrous group: —C (═O) —O—C (═O) —], sulfonic acid group [sulfo group: —SO ₃ H, —OSO ₃ H] and the like, and acryloyl It is a polymerizable monomer having at least one polymerizable group (polymerizable unsaturated group) such as a group, a methacryloyl group, a vinyl group, and a vinylbenzyl group. Specific examples include the following. In the following, methacryloyl and acryloyl may be collectively referred to as (meth) acryloyl.

  Examples of the hydrophobic phosphate group-containing polymerizable monomer (a-1) include 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meta ) Acrylyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12 -(Meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate Fate, 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- (meth) acryloyloxymethylene] -2- (meth) acryloyloxyethyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2 -(Meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 5-methacryloxypentyl-3-phosphonopropionate, 6-methacryloxyhexyl-3-phosphono Lopionate, 10-methacryloxydecyl-3-phosphonopropionate, 6-methacryloxyhexyl-3-phosphonoacetate, 10-methacryloxydecyl-3-phosphonoacetate, 2-methacryloyloxyethyl (4-methoxyphenyl) ) Hydrogen phosphate, 2-methacryloyloxypropyl (4-methoxyphenyl) hydrogen phosphate.

  Hydrophobic pyrophosphate group-containing polymerizable monomers (a-2) include bis [6- (meth) acryloyloxyhexyl pyrophosphate], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, pyrophosphate Bis [10- (meth) acryloyloxydecyl] is exemplified.

  As the hydrophobic carboxylic acid group-containing polymerizable monomer (a-3), 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) ) Acryloyloxydecyloxycarbonylphthalic acid and their anhydrides, 5- (meth) acryloylaminopentanecarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy Examples include -1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, and 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid.

  Examples of the hydrophobic sulfonic acid group-containing polymerizable monomer (a-4) include styrene sulfonic acid, 6-sulfohexyl (meth) acrylate, and 10-sulfodecyl (meth) acrylate.

Among the hydrophobic acidic group-containing polymerizable monomers (a-1) to (a-4), at least one monovalent phosphate group [phosphinico group: -P (= O ) (OH)-], divalent phosphoric acid group [phosphono group: -P (= O) (OH) ₂ ] or pyrophosphoric acid group [-P (= O) (OH) -OP (= O) A (meth) acrylate polymerizable monomer having (OH)-] is preferable because it exhibits excellent adhesion to teeth, and in particular, a divalent phosphate group [phosphono group: -P (= O). A (meth) acrylate polymerizable monomer having (OH) ₂ ] is preferred. Among these, a divalent phosphate group-containing polymerizable monomer having an alkyl group or alkylene group having 2 to 40 carbon atoms in the main chain is more preferable, and a molecule such as 10-methacryloyloxydecyl dihydrogen phosphate. A divalent phosphate group-containing polymerizable monomer having an alkylene group having 8 to 12 carbon atoms in the main chain is most preferable.

  The hydrophobic acidic group-containing polymerizable monomer (a) may be used alone or in combination of two or more. Adhesive strength may be reduced when the amount of the hydrophobic acidic group-containing polymerizable monomer (a) is too large or too small. The blending amount of the hydrophobic acidic group-containing polymerizable monomer (a) is preferably in the range of 1 to 40% by weight, more preferably in the range of 1 to 30% by weight, based on the total weight of the adhesive composition. The range of 2 to 20% by weight is most preferable.

  The water-soluble polymerizable monomer (b) in the present invention has a solubility in water at 25 ° C. of 10% by weight or more. Those having a solubility of 30% by weight or more are preferred, and those having solubility in water at an arbitrary ratio at 25 ° C. are more preferred. The water-soluble polymerizable monomer (b) includes a hydrophobic acidic group-containing polymerizable monomer (a), a photopolymerization initiator (d), and an aromatic tertiary amine (e ), And promote the penetration of the crosslinkable polymerizable monomer (f) and the basic compound (g) into the tooth, and also penetrate into the tooth and adhere to the organic component (collagen) in the tooth. . Examples of the water-soluble polymerizable monomer (b) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2,3-dihydroxypropyl (meth). Examples include acrylate, [2- (meth) acryloyloxy] triethylammonium chloride, and polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups).

  One type of water-soluble polymerizable monomer (b) may be blended, or a plurality of types may be blended. Adhesive strength may be reduced when the amount of the water-soluble polymerizable monomer (b) is too much or too little. The amount of the water-soluble polymerizable monomer (b) is preferably in the range of 1 to 60% by weight, more preferably in the range of 2 to 50% by weight, based on the total weight of the adhesive composition. A range of 40% by weight is most preferred.

  Water (c) in the present invention promotes the decalcification action of the hydrophobic acidic group-containing polymerizable monomer (a) on the tooth. It is preferable to use one that does not substantially contain impurities that adversely affect adhesiveness, and distilled water or ion-exchanged water is preferred in that sense. Adhesive strength may be lowered when the amount of water (c) is too large or too small. The amount of water (c) is preferably in the range of 1 to 50% by weight, more preferably in the range of 1 to 30% by weight, and most preferably in the range of 2 to 20% by weight, based on the total weight of the adhesive composition. preferable.

  A known photopolymerization initiator can be used as the photopolymerization initiator (d) in the present invention. Specific examples include α-diketones (d-1), ketals (d-2), thioxanthones (d-3), acylphosphine oxides (d-4), and coumarins (d-5). It is done. Among these, acylphosphine oxides (d-4) are preferable because they give excellent adhesive strength to the composition. When the adhesive composition according to the present invention is cured using a light irradiator equipped with a blue LED, α-diketone (d-1) such as camphorquinone is excellent as a photopolymerization initiator. This is preferable because it imparts curability to the adhesive composition.

  Examples of the α-diketone (d-1) include camphorquinone, benzyl, and 2,3-pentanedione.

  Examples of ketals (d-2) include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of thioxanthones (d-3) include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  Acylphosphine oxides (d-4) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) phenylphosphine oxide, tris (2,4-dimethylbenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethyl Reuben benzoyl ethoxyphenyl phosphine oxide are exemplified.

  Examples of the coumarins (d-5) include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, and 3-chenoylcoumarin.

  A photoinitiator (d) may mix | blend 1 type individually, and may mix | blend multiple types in combination. The blending amount of the photopolymerization initiator (d) is preferably in the range of 0.01 to 10% by weight, more preferably in the range of 0.1 to 7% by weight, based on the total weight of the adhesive composition. A range of 5 to 5% by weight is most preferred.

  The aromatic tertiary amine (e) having an electron withdrawing group in the present invention promotes the curing action by the photopolymerization initiator (d). As the aromatic tertiary amine (e) having an electron withdrawing group, the hydrogen atom of the aromatic ring of the aromatic tertiary amine is an electron such as a carboxylic acid group, a carboxylic acid ester group, a nitrile group, or a halogen group. Examples are compounds substituted with an attractive group. Among these, compounds represented by the following chemical formula 2 are preferable. Among the compounds represented by the chemical formula 2 below, ethyl 4-N, N-dimethylaminobenzoate, methyl 4-N, N-dimethylaminobenzoate, 4- Propyl N, N-dimethylaminobenzoate, n-butoxyethyl 4-N, N-dimethylaminobenzoate, 2- (methacryloyloxy) ethyl 4-N, N-dimethylaminobenzoate, 4-N, N-dimethyl Aminobenzophenone is more preferred.

  The aromatic tertiary amine (e) having an electron-withdrawing group may be used alone or in combination of two or more. The amount of the aromatic tertiary amine (e) having an electron-withdrawing group is preferably in the range of 0.01 to 10% by weight, based on the total weight of the adhesive composition, and 0.05 to 5% by weight. Is more preferable, and the range of 0.1 to 2.5% by weight is most preferable. If the amount of the aromatic tertiary amine (e) having an electron-withdrawing group is less than 0.01% by weight or more than 10% by weight based on the total weight of the dental adhesive composition, The power may be reduced.

  The crosslinkable polymerizable monomer (f) in the present invention has at least two polymerizable groups in the molecule, does not have an acidic group, and is hydrophobic, that is, has a solubility in water of 10 at 25 ° C. It is less than% by weight of polymerizable monomer. The crosslinkable polymerizable monomer (f) was polymerized with a hydrophobic acidic group-containing polymerizable monomer (a) and a water-soluble polymerizable monomer (b) having poor polymerization curability, and was excellent. Curability (especially mechanical strength and water resistance) is imparted to the cured product. Specific examples of the crosslinkable polymerizable monomer (f) include bisphenol A diglycidyl (meth) acrylate (hereinafter referred to as “Bis-GMA”), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl. ] Propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane represented by the following chemical formula 3, propane, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate (Hereinafter referred to as “UDMA”), ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,10-decanediol di Meth) acrylates and, of below 4, Formula 5, Formula 6, Formula 7, a compound represented by the formula 8 or Formula 9, and the like. Among them, in order to obtain excellent curability, it has at least 3 polymerizable groups in the molecule and has a hydrocarbon group in which at least 6 carbon atoms are continuously bonded in a cyclic or linear form. Compounds are preferred.

  The crosslinkable polymerizable monomer (f) may be blended alone or in combination of two or more. When the amount of the crosslinkable polymerizable monomer (f) is excessive, the penetrability of the hydrophobic acidic group-containing polymerizable monomer (a) into the tooth is lowered and the adhesive strength is lowered. On the other hand, if the blending amount is too small, the curability of the composition may be lowered and high adhesive strength may not be exhibited. The amount of the crosslinkable polymerizable monomer (f) is preferably in the range of 5 to 70% by weight, more preferably in the range of 5 to 60% by weight, based on the total weight of the adhesive composition. A weight percent range is most preferred.

  In order to improve the hydrophilic / hydrophobic balance, viscosity, mechanical strength or adhesive strength of the composition, a hydrophobic acidic group-containing polymerizable monomer (a), a water-soluble polymerizable monomer ( You may mix | blend polymerizable monomers other than b) and a crosslinkable polymerizable monomer (f).

  Examples of the polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, and 2,3-dibromo. Examples include propyl (meth) acrylate and 10-hydroxydecyl (meth) acrylate.

  These polymerizable monomers may be blended singly or in combination of two or more. When the compounding amount of these polymerizable monomers is excessive, the penetrability into the tooth may be lowered and the adhesive force may be lowered. Usually, the compounding amount of these polymerizable monomers is preferably 40% by weight or less, more preferably 20% by weight or less, and most preferably 10% by weight or less based on the total weight of the adhesive composition.

  In the present invention, the basic compound (g) is blended in place of the water-soluble acidic group-containing polymerizable monomer, instead of the hydrophobic acidic group-containing polymerizable monomer (a). Because it was decided. That is, the hydrophobic acidic group-containing polymerizable monomer (a) is superior in water resistance after polymerization and curing as compared with the water-soluble acidic group-containing polymerizable monomer, as described above. However, the penetration into the tooth is not good. Therefore, in the present invention, in order to improve the adhesion of the hydrophobic acidic group-containing polymerizable monomer (a) to the tooth and improve the adhesive force, a part thereof is reacted with the basic compound (g). It was decided to make it a water-soluble salt. Moreover, the acidity of a composition falls by mix | blending a basic compound (g), As a result, since hydrolysis of the polymerizable monomer to contain is suppressed, storage stability is also improved significantly. Incidentally, the produced salt is dissociated in an aqueous solution, and is separated into an anion and a cation. The basic compound (g) is reacted with a part rather than all of the hydrophobic acidic group-containing polymerizable monomer (a). If all of the basic compound (g) is made into a water-soluble salt, the pH will increase. This is because the tooth quality cannot be demineralized and the permeability is decreased.

  As the basic compound (g), a salt that dissolves in water at a concentration of 0.016 M (mol / liter) or more at 25 ° C. by reaction with the hydrophobic acidic group-containing polymerizable monomer (a). That generate a salt that dissolves in water at a concentration of 0.16M or more is more preferable, and that that generates a salt that dissolves in water at a concentration of 0.32M or more is most preferable. Specific examples include hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, sodium formate, sodium benzoate, Sodium hydrogen oxalate, sodium acetate, potassium acetate, sodium propionate, sodium borate, sodium dihydrogen phosphite, potassium dihydrogen phosphite, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate , Salts of alkali metals such as dipotassium hydrogen phosphate and weak acids having a pKa of 3 or more (strong basic acids having no aromatic group) and amines. As the amines, any of the primary amines, secondary amines and tertiary amines may be a hydrophobic acidic group-containing polymerizable monomer (a) and a water-soluble salt. If it can form, it will not specifically limit. The aromatic tertiary amine (e) having an electron-withdrawing group is a basic compound in that it does not generate a water-soluble salt by reaction with the hydrophobic acidic group-containing polymerizable monomer (a). Distinguishable from (g). It is preferable to select amines according to the type of the hydrophobic acidic group-containing polymerizable monomer (a) and to adjust the blending amount thereof. Specific examples of amines include triethanolamine, diethanolamine, methyldiethanolamine, 2-dimethylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, and 6-dimethyl. Aminohexyl (meth) acrylate, 10-dimethylaminodecyl (meth) acrylate, 4-dimethylaminophenethyl alcohol, 4-diethylaminophenethyl alcohol, 4-dipropylaminophenethyl alcohol, N, N-bis (2-hydroxyethyl)- p-toluidine, N, N-bis (2-hydroxypropyl) -p-toluidine, N, N-dimethyl-p-toluidine, N, N-dipropyl-p-toluidine, N, N-diethyl-p-toluidine, , N-bis (ethoxyethyl) -p-toluidine, N, N-bis (butoxysiethyl) -p-toluidine, N, N-bis (polyoxyethylene) oxyethyl-p-toluidine, hexamethylenediamine, dimethylamine Aqueous solution, pentamethylenediamine, diethylamine, ethylenediamine, 2-aminoethanol, triethylamine, and 2-dimethylaminoethanol are exemplified.

  Among the above basic compounds, 10-methacryloyloxydecyl dihydrogen phosphate (hereinafter referred to as “MDP”), which is a divalent hydrophobic phosphate group-containing polymerizable monomer (a-1). ) When a basic compound is mixed with a suspension composition similar to soapy water consisting of 0.16 mmol and 1 ml of distilled water, the white turbidity of the suspension composition is reduced. Basic compounds are preferable, and basic compounds are more preferable in which the suspension composition becomes a transparent solution.

  A basic compound (g) may mix | blend 1 type individually, and may mix | blend multiple types in combination. The basic compound (g) is preferably blended so that the pH of the liquid (composition) is in the range of 1.5 to 4.0, so that the pH is in the range of 1.8 to 3.5. It is more preferable to mix, and it is most preferable to mix so that pH may become the range of 2.0-3.0. When the pH of the composition is less than 1.5, that is, when the blending amount of the basic compound (g) is too small, water-solubilization of the hydrophobic acidic group-containing polymerizable monomer (a) becomes insufficient. Therefore, the permeability may decrease. On the other hand, when the pH of the composition exceeds 4.0, that is, when the compounding amount of the basic compound (g) is excessive, the permeability may be lowered due to a decrease in the deashing action. Incidentally, when the basic compound (g) is blended so that the pH of the liquid is 4.0 or less, almost all of the blended basic compound (g) is a hydrophobic acidic group-containing polymerizable monomer ( Since it reacts with a part of a), the basic compound (g) is substantially not contained in the composition, and the hydrophobic acidic group-containing polymerizable monomer (a) of the unreacted portion and the salt And cations and anions generated by the dissociation of.

  Although the water-soluble salt itself produced by the reaction of the basic compound (g) and the acidic group-containing polymerizable monomer (a) is poor in polymerization curability, the crosslinkable polymerizable monomer (f) having high polymerization curability. ) Is added separately, the adhesive composition according to the present invention is excellent in polymerization curability. However, when the amount of the crosslinkable polymerizable monomer (f) is excessive, excellent adhesiveness may not be obtained due to a decrease in permeability to the tooth. That is, the blending ratio of the crosslinkable polymerizable monomer (f) to the acidic group-containing polymerizable monomer (a) may greatly affect the polymerization curability or adhesiveness of the composition. The blending amount of the crosslinkable polymerizable monomer (f) with respect to 100 parts by weight of the basic compound (g) for obtaining a composition excellent in both polymerization curability and adhesiveness is preferably 25 to 60000 parts by weight, 50 to 12000 parts by weight is more preferable, and 100 to 6000 parts by weight is most preferable.

In order to obtain excellent adhesion to the tooth, the salt of the acidic group-containing polymerizable monomer (a) and the basic compound (g) that reacts with the apatite of the tooth sufficiently penetrates the tooth. There is a need to. Therefore, the salt which is a reaction product of (a) and (g) needs to be water-soluble. As a preferred combination of the two, (a) is at least one monovalent phosphate group [phosphinico group: -P (= O) (OH)-] in the molecule, divalent phosphate group [phosphono group: (Meth) acrylate polymerizable monomer having —P (═O) (OH) ₂ ] or pyrophosphate group [—P (═O) (OH) —OP (═O) (OH) —] And (g) is preferably an aromatic secondary amine or an aromatic tertiary amine (i), (a) is the same (meth) acrylate polymerizable monomer, and ( The combination (ii) wherein g) is an aliphatic secondary amine or aliphatic tertiary amine is more preferred, (a) is the same (meth) acrylate polymerizable monomer, and (g) is a hydroxyl group A combination which is an aliphatic secondary amine having an aliphatic group or an aliphatic tertiary amine having a hydroxyl group (iii) The most preferred.

  As the combination (i), 10- (meth) acryloyloxydecyl dihydrogen phosphate and N, N-bis (2-hydroxyethyl) -p-toluidine, 10- (meth) acryloyloxydecyl dihydrogen phosphate and 4 -Dimethylaminophenethyl alcohol, 10- (meth) acryloyloxydecyl dihydrogen phosphate and 4-dimethylaminophenethyl alcohol, 10- (meth) acryloyloxydecyl dihydrogen phosphate, N, N-dipropyl-p-toluidine, bis [6- (Meth) acryloyloxyhexyl] hydrogen phosphate and 4-dimethylaminophenethyl alcohol, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate and 4-diethyla Minophenethyl alcohol, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate and N, N-dipropyl-p-toluidine, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate and N, N-bis ( 2-hydroxyethyl) -p-toluidine, [1- (meth) acryloyloxymethylene] -2- (meth) acryloyloxyethyl dihydrogen phosphate, 4-dimethylaminophenethyl alcohol, bis (6-methacryloyloxyhexyl pyrophosphate) ) And N, N-bis (2-hydroxyethyl) -p-toluidine, bis (8-methacryloyloxyoctyl) pyrophosphate and N, N-bis (2-hydroxyethyl) -p-toluidine.

  As the combination (ii), 10- (meth) acryloyloxydecyl dihydrogen phosphate and triethylamine, 10- (meth) acryloyloxydecyl dihydrogen phosphate and diethylamine, 10- (meth) acryloyloxydecyl dihydrogen phosphate and 2-diethylaminoethyl (meth) acrylate, 10- (meth) acryloyloxydecyl dihydrogen phosphate and 3-dimethylaminopropyl (meth) acrylate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate and triethylamine, bis [6- (Meth) acryloyloxyhexyl] hydrogen phosphate and diethylamine, bis [6- (meth) acryloyloxyhexyl] hydrogen Sulfate and 2-diethylaminoethyl (meth) acrylate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate and 3-dimethylaminopropyl (meth) acrylate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate And triethylamine, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate and diethylamine, bis (6-methacryloyloxyhexyl) pyrophosphate and triethylamine, bis (8-methacryloyloxyoctyl) pyrophosphate and triethylamine The

  As the combination (iii), 10- (meth) acryloyloxydecyl dihydrogen phosphate and triethanolamine, 10- (meth) acryloyloxydecyl dihydrogen phosphate and methyldiethanolamine, 8- (meth) acryloyloxyoctyl dihydro Examples include gen phosphate and triethanolamine, 6- (meth) acryloyloxyhexyl dihydrogen phosphate and methyl diethanol amine, and 12- (meth) acryloyl oxide decyl dihydrogen phosphate and triethanol amine.

  A known silane coupling agent can be used as the silane coupling agent (h) in the present invention. Specific examples include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (2-methoxy Ethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldichlorosilane, γ-methacryloyloxypropyldimethoxymethylsilane, ω-methacryloyloxydecyltrimethoxysilane, ω-methacryloyloxyundecyltrimethoxysilane, γ-methacryloyloxypropylpentamethyldisiloxane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Rudimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, 3-phenyl-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, 3- (vinylbenzyl) aminopropyltriethoxysilane, 3- (vinylbenzyl) aminopropyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, diphenylethoxyvinylsilane, diphenylchlorosilane, dimethoxydi Phenylsilane is mentioned.

  Among the silane coupling agents described above, the silane coupling agent represented by the following chemical formula 10 is preferable from the viewpoint of adhesiveness and handleability.

[Wherein R ¹ represents an organic group having at least one functional group selected from the group consisting of a (meth) acryloyl group, a vinyl group, a mercapto group, and an epoxy group, and R ² has 1 to 5 carbon atoms. An alkyl group or an alkoxy group having 1 to 5 carbon atoms is represented, and R ³ and R ⁴ each independently represent an alkoxy group having 1 to 5 carbon atoms. ]

  Specific examples of a particularly preferred silane coupling agent having a polymerizable group include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, and ω-methacryloyloxyun. An example is decyltrimethoxysilane.

  A silane coupling agent (h) may mix | blend 1 type individually, and may mix | blend multiple types in combination. If the amount of the silane coupling agent (h) is excessive, the adhesive strength to the tooth may be reduced, while if too low, the adhesive strength to the porcelain may be decreased. The amount of the silane coupling agent (h) is preferably in the range of 1 to 70% by weight, more preferably in the range of 5 to 60% by weight, and in the range of 5 to 50% by weight based on the total weight of the adhesive composition. Is most preferred.

  Adhesive strength, applicability, penetrability to tooth, and water (c) of acidic group-containing polymerizable monomer (a), photopolymerization initiator (d) and crosslinkable polymerizable monomer (f) In order to improve the solubility in water, a water-soluble volatile organic solvent (i) may be blended. As the water-soluble volatile organic solvent (i), the boiling point under normal pressure is usually 150 ° C. or less, and the solubility in water at 25 ° C. is 5% by weight or more, more preferably 30% by weight or more, and most preferably An organic solvent which can be dissolved in water at an arbitrary ratio is used. Among these, a water-soluble volatile organic solvent having a boiling point of 100 ° C. or less under normal pressure is preferable. Specific examples thereof include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran.

  One type of water-soluble volatile organic solvent (i) may be blended, or a plurality of types may be blended. If the amount of the water-soluble volatile organic solvent (i) is excessive, the adhesive strength may be lowered. The blending amount of the water-soluble volatile organic solvent (i) is preferably in the range of 1 to 70% by weight, more preferably in the range of 1 to 50% by weight, based on the total weight of the adhesive composition, and 2 to 30% by weight. The range of is most preferable.

  In order to improve adhesive strength, applicability, fluidity, radiopacity, and mechanical strength, a filler (j) may be blended. A filler (j) may mix | blend 1 type individual, and may mix | blend multiple types in combination. Examples of the filler (j) include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.

As the inorganic filler, silica; minerals based on silica such as kaolin, clay, mica, mica; silica based, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La Examples thereof include ceramics and glasses containing ₂ O ₃ , SrO ₂ , CaO, P ₂ O _{5 and the} like. As the glass, lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferable. Crystal quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferable.

  Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymer, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

  Examples of composite fillers of inorganic fillers and organic fillers include inorganic fillers dispersed in organic fillers and inorganic / organic composite fillers coated with various polymerizable monomers. Is done.

  In order to improve curability, mechanical strength, and coatability, the filler (j) may be used after being surface-treated with a known surface treatment agent such as a silane coupling agent. As the surface treatment agent, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Examples are mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

  The filler (j) is preferably a fine particle filler having a primary particle diameter of 0.001 to 0.1 μm from the viewpoint of adhesive strength and applicability. Specific examples thereof include “Aerosil OX50”, “Aerosil 50”, “Aerosil 200”, “Aerosil 380”, “Aerosil R972”, “Aerosil 130” (all of which are manufactured by Nippon Aerosil Co., Ltd., trade names). It is done.

  The blending amount of the filler (j) is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 0.5 to 20% by weight, based on the total weight of the adhesive composition. The range of is most preferable.

  In order to impart acid resistance to the tooth, a fluorine ion releasing substance may be blended. Fluorine ion-releasing substances include fluorine glasses such as fluoroaluminosilicate glass; metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride; methyl methacrylate and methacryl Fluorine ion releasing polymers such as copolymers with acid fluoride; fluorine ion releasing substances such as cetylamine hydrofluoride are exemplified.

  You may mix | blend a stabilizer (polymerization inhibitor), a coloring agent, a fluorescent agent, and an ultraviolet absorber. Also, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan Good.

  The adhesive composition for partial restorative dental treatment according to the present invention is preferably in a two-pack form from the viewpoint of storage stability. In this case, as the packaging form, the function of the silane coupling agent (h) due to the progress of the condensation reaction of the silane coupling agent (h) due to the hydrophobic acidic group-containing polymerizable monomer (a) For the purpose of avoiding the decrease, a hydrophobic acidic group-containing polymerizable monomer (a), an aromatic tertiary amine (e) having an electron-withdrawing group, and a basic compound (g) are blended. The packaged form of the first agent and the second agent containing the silane coupling agent (h) is preferred. Water-soluble polymerizable monomer (b), water (c), photopolymerization initiator (d), and crosslinkable polymerizable monomer (f) are blended in the first agent, second agent or both agents, respectively. do it. For the purpose of diluting the silane coupling agent (h), the II agent is preferably blended with a polymerizable monomer having low reactivity with the silane coupling agent (h). The monomer is preferably a crosslinkable polymerizable monomer (f). The amount ratio of each component of the adhesive composition obtained by mixing the first agent and the second agent is (a) 1 to 40% by weight, (b) 1 to 60% by weight, and (c) 1 to 50% by weight. %, (D) 0.01 to 10% by weight, (e) 0.01 to 10% by weight, (f) 5 to 70% by weight, and silane coupling agent (h) 1 to 70% by weight.

  The method of using the adhesive composition according to the present invention will be described as follows, taking as an example the case of repairing a broken restoration. That is, first, the adhesive composition according to the present invention is applied to the fracture surface of the restoration and the tooth portion to be restored using a sponge or brush, and in that state, 0 seconds (that is, described later immediately after application). For 120 seconds, preferably 1 to 60 seconds, more preferably 5 to 30 seconds, most preferably 10 to 20 seconds, or 60 using a sponge or the like on the tooth surface. Continue rubbing for no more than a second. Next, after air blowing using a dental air syringe, a filling composite resin (filling restoration material) is applied to the surface on which the adhesive composition is applied, and both are simultaneously cured to complete the bonding. However, since the photopolymerization initiator (d) is blended in the adhesive composition according to the present invention, a dental visible light irradiator or the like is used for the adhesive composition before applying the filling restorative material. It is preferable to irradiate with light to polymerize and cure it, because better adhesiveness can be obtained.

  The adhesive composition according to the present invention exhibits an excellent adhesive force even if it is not pretreated with a phosphoric acid etching agent or a self-etching primer before being applied to the fracture surface or tooth surface of the restoration. However, when it is applied after cleaning the adhesive surface with a phosphoric acid etching agent, hypochlorite preparation, hydrogen peroxide solution, etc., it may exhibit better adhesion to porcelain and enamel.

  The present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. The abbreviations appearing below are as follows.

(Acid group-containing polymerizable monomer)
Among the following acidic group-containing polymerizable monomers, those with (a) added later correspond to the hydrophobic acidic group-containing polymerizable monomer (a) in the present invention.
MDP: 10-methacrylolyloxydecyl dihydrogen phosphate (a)
POP: Bis (8-methacryloyloxyoctyl) pyrophosphate (a)
4-MDT: 4-methacryloyloxydecyloxycarbonylphthalic acid (a)
MA: Maleic acid

[Water-soluble polymerizable monomer (b)]
HEMA: 2-hydroxyethyl methacrylate 9G: Nonaethylene glycol dimethacrylate

[Photopolymerization initiator (d)]
CQ: dl-camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[Aromatic tertiary amine (e) having an electron-withdrawing group]
DABB; 4-N, N-dimethylaminobenzoic acid n-butoxyethyl DABE; 4-N, N-dimethylaminobenzoic acid ethyl DMAI: 4-N, N-dimethylaminobenzoic acid isoamyl DMAB; 4-N, N- Dimethylaminobenzophenone

[Crosslinkable polymerizable monomer (f)]
Bis-GMA: bisphenol A diglycidyl methacrylate 2.6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane represented by the following chemical formula 11

NPG: Neopentyl glycol dimethacrylate UDMA: [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate

[Basic compounds]
Among the following basic compounds, those to which (g) is added later correspond to the basic compound (g) in the present invention.
NaOH: Sodium hydroxide (g)
Ca (OH) ₂ : Calcium hydroxide NaHCO ₃ : Sodium bicarbonate (g)
K ₂ CO ₃ : Potassium carbonate (g)
CH ₃ COONa: Sodium acetate (g)
BSS: Sodium benzenesulfinate TPSS: Sodium 2,4,6-triisopropylbenzenesulfinate TEA: Triethanolamine (g)
MDA: Methyldiethanolamine (g)
DMAEMA: 2-dimethylaminoethyl methacrylate (g)
DEPT: N, N-bis (2-hydroxyethyl) -p-toluidine (g)
DAPA: 4-dimethylaminophenethyl alcohol (g)
DEPA: 4-diethylaminophenethyl alcohol (g)
ED: Ethylenediamine (g)
AE: 2-aminoethanol (g)
TE: Triethylamine (g)

[Silane coupling agent (h)]
MPS: 3-methacryloyloxypropyltrimethoxysilane [filler (j)]
R972: Fine particle silica manufactured by Aerosil

[Others]
BHT: 2,6-di (t-butyl) -4-methylphenol (stabilizer (polymerization inhibitor))

Example 1
MDP (12 parts by weight), NaOH (3 parts by weight), HEMA (30 parts by weight), distilled water (15 parts by weight), Bis-GMA (30 parts by weight), ethanol (10 parts by weight), TMDPO (2 parts by weight), CQ (1 part by weight), DABB (1 part by weight), and BHT (0.05 part by weight) were mixed to prepare the first agent. Moreover, Bis-GMA (50 weight part) and MPS (50 weight part) were mixed and the II agent (No. 1) was prepared. Next, an adhesive composition was prepared by mixing the I agent and the II agent in equal weight. In addition, pH of this adhesive composition was in the range of 1.5-4.

(Examples 2 to 19)
In the preparation of the first agent, 18 kinds of the first agent were prepared in the same manner as in Example 1 except that MDP and / or NaOH were changed. Moreover, the II agent (No. 2-No. 5) which shows a composition in following Table 1 was prepared. Next, an adhesive composition was prepared by mixing the I agent and the II agent in equal weight. In addition, pH of the adhesive composition of Examples 2-19 was in the range of 1.5-4.

(Comparative Example 1)
An adhesive composition was prepared in the same manner as in Example 1 except that NaOH was not added to the first agent.

(Comparative Examples 2-7)
In the preparation of the first agent, it was the same as in Example 1 except that Ca (OH) ₂ , BSS, TPSS, DABE, DMAI or DMAB (all 3 parts by weight) was added instead of NaOH (3 parts by weight). Thus, six types of adhesive compositions were prepared.

(Comparative Example 8)
An adhesive composition was prepared in the same manner as in Example 1 except that MA (12 parts by weight) was added to the first agent instead of MDP (12 parts by weight).

  In Examples 1-19 and Comparative Examples 1-8, the acidic group-containing polymerizable monomer and basic compound blended in the first agent, the solubility of the acidic group-containing polymerizable monomer in water, and the acidic group-containing polymerization Of the salt produced by the reaction of the basic monomer with the basic compound in water, No. II of the second agent Table 2 and Table 3 below collectively show the amount (% by weight) of the silane coupling agent (h) in the total weight of the composition. The solubility of the acidic group-containing polymerizable monomer in water and the solubility of the salt in water were examined by the following test methods, respectively.

[Method for testing solubility of acidic group-containing polymerizable monomer in water]
In a 25 ° C environment, add distilled water (0.9 g) and acidic group-containing polymerizable monomer (0.1 g) to a transparent container with a capacity of 10 ml, and stir with a stirrer bar to make the liquid cloudy. Observe visually. In the case of a clear liquid, it is judged that the solubility of the acidic group-containing polymerizable monomer exceeds 10% by weight and evaluated as x. If the liquid is not clear, add 1 g of distilled water, stir with a stirrer bar, and visually observe the liquid again. When it changed to a clear liquid, it was judged that the solubility of the acidic group-containing polymerizable monomer was in the range of 5 to 10% by weight, and evaluated as △, while when it did not change to a clear liquid, Judgment is made that the solubility of the acidic group-containing polymerizable monomer is less than 5% by weight, and it is evaluated as ◯.

[Method of testing solubility of salt in water]
In an environment of 25 ° C, add distilled water (1 ml) and acidic group-containing polymerizable monomer (0.16 mmol) to a transparent container having a volume of 10 ml, and stir with a stirrer bar. A suspension similar to is prepared. A basic compound (0.16 mmol) is added to the suspension and the change in turbidity of the suspension is visually observed. When it changes to a clear liquid, it judges that the solubility of the salt produced | generated by reaction of an acidic group containing polymeric monomer and a basic compound exceeds 0.16M, and evaluates (circle). If there is no change in the turbidity of the suspension or the turbidity increases, add another 9 ml of distilled water, stir at room temperature for 1 day, and then visually observe the change in turbidity again. When the liquid is changed to a clear liquid, the solubility of the salt of the acidic group-containing polymerizable monomer is judged to be in the range of 0.016 to 0.16M, and evaluated as Δ, while the liquid is not changed to a clear liquid. In such a case, the solubility of the salt of the acidic group-containing polymerizable monomer is judged to be less than 0.016 M, and evaluated as x.

  About each adhesive composition, the adhesive force with respect to a tooth | gear, the adhesive force with respect to porcelain, and edge sealing property were investigated by the following test method, respectively. The results are shown in Tables 4 and 5. The numerical values of the adhesive strength (MPa) shown in the table are average values of the measured values for the eight test pieces. Further, the marginal sealing score is an average score for five test pieces.

[Adhesive strength test method for dentin]
The front teeth of the cow are smoothly wet-polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) to expose the enamel surface or dentin surface, and then the surface water is blown off using a dental air syringe. After applying an adhesive tape with a thickness of about 150 μm with a 3 mm diameter round hole to the exposed enamel surface or dentin surface, applying the adhesive composition to the round hole with a brush and leaving it for 20 seconds The adhesive composition applied using a dental air syringe is dried until the fluidity of the adhesive composition disappears. Next, light irradiation is performed for 10 seconds using a dental light irradiator (Morita, trade name “JETLITE 3000”). Next, a photopolymerization type composite resin (Kuraray Medical, trade name “Clear Fill AP-X”) is placed on the application surface of the adhesive composition, and a release film (Kuraray, trade name “EVAL”) Then, a slide glass is placed on the release film and pressed, and irradiated with light using a dental light irradiator “JETLITE 3000” for 20 seconds to be cured. Next, one end face (circular shape) of a stainless steel cylindrical rod having a diameter of 5 mm and a length of 1.5 cm using dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.) with respect to this hardened surface. Cross section) and let stand for 30 minutes to make a test piece. A total of 32 test pieces (16 with the enamel surface exposed and 16 with the dentin surface exposed) are prepared. Next, the test pieces were immersed in distilled water in a sample container, left in a thermostat set at 37 ° C. for 24 hours, then taken out, and 8 test pieces adhered to enamel, ivory The tensile bond strength is measured for eight test pieces bonded to the quality, and this is taken as the initial value. The tensile bond strength is measured by using a universal testing machine (Instron) and setting the crosshead speed at 2 mm / min. For the 8 test pieces adhered to the remaining enamel and 8 test pieces adhered to the dentin, the test pieces were further immersed 4000 times alternately in a 4 ° C water bath and a 60 ° C water bath for 1 minute each. After applying the thermal cycle load, the tensile adhesive strength is measured. Bond durability is evaluated by the tensile bond strength after this thermal cycle load.

[Adhesion test method for porcelain]
A porcelain block (product name “VITA CELAY” manufactured by VIDEO Corporation) is polished smoothly with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.), and then water on the surface is blown off using a dental air syringe. Adhere an adhesive tape with a thickness of about 150 μm with a 3 mm diameter round hole on the surface of the porcelain block, apply the adhesive composition to the round hole with a brush, leave it for 20 seconds, and then apply dental air Dry until the fluidity of the adhesive composition applied using a syringe is lost. Next, light irradiation is performed for 10 seconds using a dental light irradiator (Morita, trade name “JETLITE 3000”). Next, a photopolymerization type composite resin (Kuraray Medical, trade name “Clear Fill AP-X”) is placed on the application surface of the adhesive composition, and a release film (Kuraray, trade name “EVAL”) Then, a slide glass is placed on the release film and pressed, and irradiated with light using a dental light irradiator “JETLITE 3000” for 20 seconds to be cured. Next, one end face (circular cross section) of a stainless steel cylindrical rod having a diameter of 5 mm and a length of 1.5 cm using a dental resin cement (trade name “Panavia 21” manufactured by Kuraray Co., Ltd.) on the hardened surface. ) And let stand for 30 minutes to obtain a test piece. A total of 16 test pieces are prepared. Next, the test piece is immersed in distilled water in a sample container and left in a thermostat set at 37 ° C. for 24 hours, then taken out, and the tensile adhesive strength is measured for eight pieces. The tensile bond strength is measured by using a universal testing machine (Instron) and setting the crosshead speed at 2 mm / min. For the remaining 8 pieces, in order to measure the adhesion durability, after applying a thermal cycle load of immersing 4000 times alternately in a 4 ° C water bath and a 60 ° C water bath for 1 minute each, the tensile bond strength was measured. taking measurement. Bond durability is evaluated by the tensile bond strength after this thermal cycle load.

(Border sealing test)
A porcelain block (trade name “VITA CELAY”, manufactured by VIDENT) is processed into a size of 10 mm in length, 5 mm in width, and 3 mm in height to produce five pieces of porcelain. Insert a dental cutting tool into a cavity with a depth of 3mm, slightly larger than 10mm in the direction parallel to the tooth axis and slightly larger than 5mm in the direction perpendicular to the tooth axis, so that the porcelain slices fit on the lip of the front teeth of the cow. Use to form. Dental porcelain adhesive (made by Kuraray Medical, trade name “Clear Fill Mega Bond Porcelain Bonding Kit”) and dental resin cement (made by Kuraray Medical, trade name “Panavia F”) 2.0 "). After coalescence, the sample is allowed to stand at room temperature for 30 minutes, and then left in a thermostat set at 37 ° C. for 24 hours in a state immersed in distilled water in a sample container. Then, the fused bovine teeth are taken out, and a half of the porcelain section (length 5 mm, width 5 mm, height 3 mm) is removed using a dental cutting instrument, and a model in which a part of the porcelain restoration is missing. And Water on the surface of the defect part of this model is blown off using a dental air syringe, the adhesive composition is applied using a brush in the defect cavity, and left for 20 seconds, and then the adhesive is used using a dental air syringe. Dry until the composition is no longer fluid. Next, light irradiation is performed for 10 seconds using a dental light irradiator (Morita, trade name “JETLITE 3000”). Next, a photopolymerizable composite resin (manufactured by Kuraray Medical Co., Ltd., trade name “Clearfill AP-X”) was placed on the application surface of the adhesive composition and filled into the cavity, and then a dental light irradiator “JETLITE 3000” was used. Is used for 20 seconds to cure the photopolymerized composite resin. Next, the excess photopolymerized composite resin is removed with a dental polishing tool, and the adhesion margin is exposed to obtain a test piece. Five test pieces are prepared in total. Next, the test piece was immersed in distilled water in a sample container and allowed to stand in a thermostat set at 37 ° C. for 24 hours, and then placed in a 4 ° C. water bath and a 60 ° C. water bath for 1 minute each. A thermal cycle load is applied so as to immerse 4000 times alternately. After that, the hole at the tip of the root of the bovine tooth is sealed with dental wax (product name “Utility Wax”, manufactured by GC Corporation), and nail varnish is applied to areas other than porcelain slices, photopolymerizable composite resin, and adhesive margins. To do. Thereafter, the test piece is immersed in a 0.2% basic fuchsin aqueous solution for 24 hours at room temperature. After removing the test piece from the fuchsin aqueous solution and washing it with water, cut it half along the tooth axis so that it passes through the porcelain slice and the restoration part of the photopolymerizable composite resin, so that the cross section of the restoration part by the photopolymerizable composite resin can be observed. To. If no penetration of fuchsin is observed at the margin of both the tooth and the photopolymerizable composite resin, and the porcelain section and the photopolymerizable composite resin, the score is 0. If the intrusion is within 1 mm, score 1 if it exceeds 1 mm and within 2 mm, score 2 if it exceeds 2 mm and within 3 mm, score 3 and if the intrusion reaches the fossa For example, as the score 4, the average of the scores of the five test pieces is obtained for each of the dentine side and the porcelain side, and the marginal sealing performance is evaluated using this average value.

  As shown in Table 4, the adhesive compositions of Examples 1 to 19 have a high adhesive strength after initial and thermal cycle loading and a low marginal sealing score for both the tooth and the porcelain. . From this, it can be seen that the adhesive composition according to the present invention exhibits an excellent adhesive force and exhibits excellent marginal sealing properties for both tooth and porcelain. On the other hand, as shown in Table 5, the adhesive composition of Comparative Example 1 in which the basic compound was not blended has low initial adhesive strength to the tooth, and extremely low adhesive strength after thermal cycle loading. The adhesive strength of the adhesive composition of Comparative Example 1 on the tooth is low because the basic compound is not blended, and the hydrophobic acidic group-containing polymerizable monomer (MDP) penetrates into the tooth. Because it was not good. The adhesive strength of the adhesive composition of Comparative Example 8 containing a water-soluble acidic group-containing polymerizable monomer (MA) instead of the hydrophobic acidic group-containing polymerizable monomer is also extremely low. This is because the water resistance of the cured product was extremely low.

(Comparative Example 9)
MDP (12 parts by weight), NaOH (3 parts by weight), HEMA (30 parts by weight), distilled water (15 parts by weight), Bis-GMA (80 parts by weight), ethanol (10 parts by weight), TMDPO (2 parts by weight), CQ (1 part by weight), DABB (1 part by weight), and BHT (0.05 part by weight) were mixed to prepare an adhesive composition. Incidentally, this adhesive composition is a composition obtained by removing the silane coupling agent (h) from the adhesive composition prepared in Example 1.

(Comparative Example 10)
6-[(4-vinylbenzyl) propyl] amino-1,3,5-triazine-2,4-dithione (0.4 parts by weight), MPS (5 parts by weight), and bis (2-methacryloyloxyethyl) ) Hydrogen phosphate (20 parts by weight), 2.6E (5 parts by weight), acetone (38.1 parts by weight), distilled water (30 parts by weight), and sodium p-toluenesulfinate (1.5 Part by weight) was mixed to prepare a primer composition. This primer composition is the primer composition of Example 7 of JP-A-2002-265312 (Patent Document 2).

  With respect to the adhesive composition prepared in Comparative Example 9 and the primer composition prepared in Comparative Example 10, the adhesion to teeth, the adhesion to porcelain, and the edge sealing property were examined by the test methods described above. The results are shown in Table 6.

  The adhesive composition of Comparative Example 9 shown in Table 6 has a lower adhesive strength to porcelain than the adhesive composition of Example 1 shown in Table 4, and the porcelain side score for marginal sealing is also shown. Very bad. From this, when the silane coupling agent (h), which is an essential compounding agent in the present invention, is not compounded, the adhesive composition that exhibits an excellent adhesive force with respect to both tooth and porcelain is It turns out that it cannot be obtained. In addition, the primer composition of Comparative Example 10 shown in Table 6 is comparable to the adhesive compositions of Examples 1 to 13 shown in Table 4 in terms of initial adhesive strength, although both the tooth quality and the porcelain are comparable. The adhesive strength to the tooth after cycle loading is extremely low, and reflecting the result, the score on the tooth side is poor even with marginal sealing. This is because the primer composition of Comparative Example 10 has low penetrability into the tooth and has better curability (mechanical strength and water resistance of the cured product) than the adhesive compositions of Examples 1-13. Because there is no.

(Example 20)
A 40% phosphoric acid aqueous solution (manufactured by Kuraray Medical Co., Ltd., trade name “K Etchant GEL”) was applied as a tooth surface cleaning agent to the surfaces of the tooth and porcelain. After leaving still for 10 seconds, washing with water and drying to wash the surface of the adherend, the adhesive composition of Example 5 was subjected to the above-mentioned test methods to adhere to the tooth and to the porcelain. The force and marginal sealing properties were examined. The results are shown in Table 7. For convenience of comparison, Table 7 shows the results when no tooth surface cleaning agent is applied.

  As shown in Table 7, when the adhesion operation is performed after cleaning the surface of the tooth and porcelain with a tooth surface cleaning agent, the adhesive strength is higher than when the adhesion operation is performed without cleaning. As a result, good results were obtained with respect to marginal sealing. This shows that it is preferable to clean the surface of the adherend in advance before applying the adhesive composition according to the present invention.

Claims (11)

  Hydrophobic acidic group-containing polymerizable monomer (a), water-soluble polymerizable monomer (b), water (c), photopolymerization initiator (d), and electron-withdrawing group The aromatic tertiary amine (e), the crosslinkable polymerizable monomer (f), and a part of the hydrophobic acidic group-containing polymerizable monomer (a) react to form a water-soluble salt. An adhesive composition for partial restorative dental treatment comprising a basic compound (g) to be produced and a silane coupling agent (h) as essential ingredients.   One of the hydrophobic acidic group-containing polymerizable monomer (a), an aromatic tertiary amine (e) having an electron-withdrawing group, and one of the hydrophobic acidic group-containing polymerizable monomer (a) A basic compound (g) that reacts with a part to form a water-soluble salt as an essential compounding agent, and an silane coupling agent (h) as an essential compounding agent. Water-soluble polymerizable monomer (b), water (c), photopolymerization initiator (d) and crosslinkable polymerizable monomer (f) Independently, an adhesive composition for partial restorative dental treatment blended in the first agent, the second agent or both agents.   1 to 50% by weight of a hydrophobic acidic group-containing polymerizable monomer (a), 1 to 60% by weight of a water-soluble polymerizable monomer (b), 1 to 50% by weight of water (c), Photopolymerization initiator (d) 0.01 to 10% by weight, aromatic tertiary amine (e) 0.01 to 10% by weight having an electron-withdrawing group, and crosslinkable polymerizable monomer (f) The adhesive composition for partial restorative dental treatment according to claim 2, comprising 5 to 70% by weight and 1 to 70% by weight of the silane coupling agent (h).   The adhesive composition for partial restorative dental treatment according to claim 3, wherein 25 to 60000 parts by weight of the crosslinkable polymerizable monomer (f) is blended with 100 parts by weight of the basic compound (g). .   The hydrophobic acidic group-containing polymerizable monomer (a) has at least one monovalent or divalent phosphate group or monovalent or divalent pyrophosphate group in the molecule (meth) acrylate system. It is a polymerizable monomer and the basic compound (g) is an aromatic secondary amine or an aromatic tertiary amine, for partial restorative dental treatment according to any one of claims 1 to 4. Adhesive composition.   The hydrophobic acidic group-containing polymerizable monomer (a) has at least one monovalent or divalent phosphate group or monovalent or divalent pyrophosphate group in the molecule (meth) acrylate system. The partial restorative dental treatment according to any one of claims 1 to 4, which is a polymerizable monomer and the basic compound (g) is an aliphatic secondary amine or an aliphatic tertiary amine. Adhesive composition.   The hydrophobic acidic group-containing polymerizable monomer (a) has at least one monovalent or divalent phosphate group or monovalent or divalent pyrophosphate group in the molecule (meth) acrylate system. 5. The polymerizable monomer according to claim 1, which is a polymerizable monomer and the basic compound (g) is an aliphatic secondary amine having a hydroxyl group or an aliphatic tertiary amine having a hydroxyl group. An adhesive composition for partial restorative dental treatment.   The adhesive composition for partial restorative dental treatment according to any one of claims 2 to 7, further comprising a water-soluble volatile organic solvent (i) in addition to the first agent or the second agent or both agents. object.   The adhesive composition for partial restorative dental treatment according to any one of claims 2 to 8, wherein a filler (j) is further blended with the first agent or the second agent or both agents. The adhesive composition for partial restorative dental treatment according to any one of claims 1 to 9, wherein the silane coupling agent (h) is represented by the following chemical formula (1).

[Wherein R ¹ represents an organic group having at least one functional group selected from the group consisting of a (meth) acryloyl group, a vinyl group, a mercapto group, and an epoxy group, and R ² has 1 to 5 carbon atoms. An alkyl group or an alkoxy group having 1 to 5 carbon atoms is represented, and R ³ and R ⁴ each independently represents an alkoxy group having 1 to 5 carbon atoms. ]   One of the hydrophobic acidic group-containing polymerizable monomer (a), an aromatic tertiary amine (e) having an electron-withdrawing group, and one of the hydrophobic acidic group-containing polymerizable monomer (a) A basic compound (g) that reacts with a part to form a water-soluble salt as an essential compounding agent, and an silane coupling agent (h) as an essential compounding agent. A water-soluble polymerizable monomer (b), water (c), a photopolymerization initiator (d) and a crosslinkable polymerizable monomer (f), each independently comprising A two-component adhesive for partial restorative dental treatment, which is blended in the first agent or the second agent or both agents.