JP5483823B2 - Adhesive material for zirconia molded body - Google Patents

Description

  The present invention relates to an adhesive material for a zirconia molded body, and more particularly to an adhesive material for zirconia that exhibits excellent adhesive strength and durability by being used when a resin-based material is bonded to a zirconia molded body.

  In recent years, zirconia has been used in a wide range of fields such as grinding media, mechanical parts, electronic equipment members, bearings, and biomaterials because of its high mechanical strength. In particular, in the dental field, not only mechanical properties such as strength and toughness, but also high aesthetics and biosafety, it has been attracting attention as a material that can be used in place of metals such as gold, silver, and palladium alloys that have been used in the past. Yes. A typical use example is a dental prosthetic material that requires high strength, and zirconia is used not only for a single crown but also for a multi-tooth bridge including a molar portion.

  Although zirconia is generally white and has a color tone that is relatively close to teeth, it is difficult to reproduce the same color tone as teeth alone, so it is used as a core material, that is, the framework part that serves as the foundation A method has been employed in which the (frame) is made of high-strength zirconia and the upper part is made of a ceramic material such as glass porcelain capable of reproducing various color tones (see, for example, Patent Document 1).

  On the other hand, in addition to the ceramic material, a resin-based dental restorative material is generally used as a material that replaces a part or the whole of a natural tooth crown. In particular, a hybrid type hard resin, which is a resin-based dental restorative material containing a large amount of inorganic filler, has high mechanical strength and is actively used in cases of molar jacket crowns. Resin-based dental restorative materials that are not too hard as ceramics, have moderate impact mitigation performance, and are relatively easy to repair even when broken in the oral cavity are highly clinically useful. However, it is not possible to apply the resin-based dental restorative material alone to the bridge case where further strength is required. At present, it is common to use a metal frame together. If a frame can be made with zirconia even for resin-based dental restoration materials, in all clinical cases including multiple tooth bridges, it is opaque to hide metal allergies, discoloration of surrounding tissues and metal color due to the use of metal The aesthetic problems caused by the underlying layer can be solved, and the usefulness of the resin-based dental restorative material as described above can be fully utilized.

  From these backgrounds, development of an excellent adhesive for bonding zirconia and a resin-based dental restorative material has been demanded. For example, an adhesive composition for zirconia has been proposed that contains a phosphonic acid group-containing (meth) acrylate monomer such as 6-methacryloxyhexylphosphonoacetate (see Patent Document 2). In addition, some suggest that it is effective if a resin cement containing 10-methacryloyloxydecyl dihydrogen phosphate (MDP) is applied (see Non-Patent Document 1).

Patent Publication 2005-187436 Patent Publication 2006-45176 “Dental Materials” 1998, Vol. 14, pp. 64-71

  Any of the polymerizable monomers effective for adhering the zirconia and the resin-based dental restorative material as a polymerizable unsaturated group has a (meth) acryloyloxy group as a polymerizable unsaturated group. It is a polymerizable monomer having a (meth) acryloylamino group and having a phosphate group or an acidic group derived from the phosphate as a group exhibiting affinity for zirconia. In the case of an adhesive containing a polymerizable monomer as an active ingredient, although the zirconia frame and the resin-based dental restorative material are bonded to each other at an early stage, they are usefully bonded with considerable strength, but the durability of the adhesive strength However, I was not able to get a satisfactory result.

  The cause is not clear, but zirconia has many Bronsted acid points and Bronsted base points on its surface as compared with metal materials that have been used so far. When a polymerizable monomer is added, the action of these strongly acidic groups is added, and in an environment where water in the oral cavity exists, a methacrylate-based polymerizable monomer used in a resin-based dental restorative material for an adherend. The methacrylic ester portion of the monomer is easily hydrolyzed. From the same environment, even in these phosphoric acid polymerizable monomers themselves, the ester portion is easily hydrolyzed. In addition, phosphoric acid produced by the decomposition of these phosphoric acid-based polymerizable monomers is a strong Lewis base, and adsorbs on the Lewis acid point, which is the surface active site of zirconia, to thereby form a phosphoric acid-based polymerizable monomer. There is also the possibility of inhibiting the adhesive action of the monomer to the zirconia surface. For these reasons, even when zirconia and a resin-based dental restorative material are bonded using the adhesive, it is presumed that the adhesive strength gradually decreases with time.

  In addition, as a component effective in improving the adhesive force blended into the adhesive material as a dental material, in addition to the polymerizable monomer composed of the phosphoric acid, a carboxylic acid-based component is also known. However, there is no specific example in which such carboxylic acid-based materials are blended with an adhesive for bonding the zirconia and the resin-based dental restorative material, and most of them are actually blended with the adhesive. Even if it is used for the above-mentioned adhesion, even if the initial adhesive strength is low or the initial adhesive strength is high to some extent, as in the case of the phosphoric acid polymerizable monomer, it is not sufficient for its durability. It was a thing.

  In view of the above background, an object of the present invention is to develop an adhesive material for a zirconia molded body having excellent adhesion durability by being used when a resin-based material is bonded to a zirconia molded body.

  The present inventors have intensively studied to solve the above problems. As a result, it is very important to select a polymerizable monomer having an acidic group to be selected, a carboxylic acid type having a lower acidity than that of a phosphoric acid type, and a sufficiently long hydrocarbon in the molecular structure. A specific carboxylic acid group having a structure in which a polymerizable unsaturated group comprising a (meth) acryloyloxy group or a (meth) acryloylamino group and a carboxylic acid group are bonded by this long-chain hydrocarbon group The present inventors have found that the above-mentioned problems can be solved by using the polymerizable monomer, and have completed the present invention.

（式中、Ｒ_１は水素原子または炭素数が１〜１０のアルキル基であり、Ｒ_２は炭素数が６〜１９個の鎖長の二価の脂肪族炭化水素基であり、Ｒ_３は水素原子またはメチル基であり、Ａは酸素原子であり、ｎは２を表す）


That is, the present invention relates to a carboxylic acid group-containing polymerizable monomer represented by the following general formula (1), 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane, triethylene Glycol dimethacrylate, 2,2-bis [(4-methacryloyloxypolyethoxyphenyl) propane, 1,6-bis (methacrylethyloxycarbonylamino) -2,2,4-triethylhexane, 1,6-bis (methacrylic) Ethyloxycarbonylamino) -2,4,4-triethylhexane and one or more polyfunctional polymerizable monomers selected from trimethylolpropane trimethacrylate at least part of the polymerizable monomer component The carboxylic acid group-containing polymerizable monomer is 0 when the total polymerizable monomer component is 100 parts by mass. 1 part by weight or more and 60 parts by weight, the polyfunctional polymerizable monomer is zirconia molded body adhesive material is less than 90 parts by mass or more 20 parts by weight.

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ is a divalent aliphatic hydrocarbon group having a chain length of 6 to 19 carbon atoms, and R ₃ is A hydrogen atom or a methyl group, A is an oxygen atom, and n represents 2)

  The adhesive material for a zirconia molded body of the present invention can be used to adhere these resin materials to a zirconia molded body, thereby making it possible to firmly bond both of them. Strength can be maintained for a long time. Therefore, this adhesive material is used in dental treatment for producing a prosthesis using a high-strength, high-esthetic resin-based dental restorative material on a zirconia frame, and such an adhesive on the zirconia frame. It can be used very well as a pretreatment material applied before coating.

  In the present invention, the zirconia molded body to which the adhesive material is applied may be a molded body containing zirconia as a main component, specifically, a molded body containing at least 60 mol%, preferably at least 80 mol% zirconia. In general, zirconia is often used as a partially stabilized product containing a small amount of rare earth oxides such as yttria and ceria, calcia, magnesia and the like. In addition, hafnia having properties similar to zirconia is generally contained in zirconia. Moreover, it is preferable that a zirconia is a sintered compact.

  The zirconia molded body is generally used with a roughened surface by a method such as sandblasting in order to increase the mechanical fitting force and increase the adhesive force as a pretreatment for bonding. For the zirconia whose surface is roughened, it is preferable to formulate the adhesive material of the present invention in as short a time as possible in order to prevent surface contamination and deactivation.

  The adhesive material of the present invention is an aliphatic hydrocarbon having a chain length of 7 to 20 carbon atoms in a (meth) acryloyloxy group or (meth) acryloylamino group as at least a part of the polymerizable monomer component. It contains a carboxylic acid group-containing polymerizable monomer in which a carboxylic acid group is bonded via a group. The reason why the structure of the polymerizable monomer containing a carboxylic acid group has excellent adhesion strength and durability is not clear, but carboxylic acid is compared with phosphoric acid and acidic groups derived from this acid. Because of its low acidity, the hydrolysis reaction promoting action is weak, the carboxylic acid group has a high affinity for the zirconia surface, and it has a long-chain aliphatic hydrocarbon group so that it is hydrophobic. And the fact that water is difficult to enter the adhesive interface, and that the carboxylic acid group bonded to the hydrocarbon group is highly stable and the acidic group is difficult to desorb, etc. Conceivable.

  In the present invention, the carboxylic acid group-containing polymerizable monomer is not particularly limited as long as it is a compound satisfying the characteristic structure, and a known monomer can be used. The (meth) acryloyloxy group or the (meth) acryloylamino group is preferable among the polymerizable unsaturated groups because of its good polymerizability and relatively little harm for the living body. It is preferably a (meth) acryloyloxy group.

  The aliphatic hydrocarbon group intervening between the ((meth) acryloyloxy group or (meth) acryloylamino group and the carboxylic acid group has a chain length of 7 to 20, preferably 8 to 12 carbon atoms. Here, the chain length of the aliphatic hydrocarbon group is the number of carbon atoms in the chain portion connecting the polymerizable group and the carboxylic acid group in the aliphatic hydrocarbon group, and the aliphatic hydrocarbon group Even if the group has a side chain, the number of carbon atoms is not counted.The aliphatic hydrocarbon group has a chain length of less than 7 or a carboxylic acid group-containing polymerizable monomer greater than 20. In such a case, any of the obtained adhesive materials has low adhesion durability.

  Such a long-chain aliphatic hydrocarbon group may be unsaturated, but is preferably saturated from the viewpoint of chemical stability, and may be either linear or branched. Particularly preferred as such a long-chain aliphatic hydrocarbon group is an alkylene group having a chain length of the above-mentioned carbon number because of its relatively easy synthesis. Examples of such an alkylene group include a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, and an octadecylene group.

  The carboxylic acid group-containing polymerizable monomer is more preferably a polyvalent carboxylic acid compound having a plurality of carboxylic acid groups from the viewpoint of adhesion durability. Of course, in this case, each carboxylic acid group is bonded to a (meth) acryloyloxy group or a (meth) acryloylamino group via an aliphatic hydrocarbon group having 7 to 20 carbon atoms. Is preferred. In the case of a polyvalent carboxylic acid compound, the number of carboxylic acid groups is more preferably 2 to 6 and most preferably 2 because it is relatively easy to synthesize.

  As the carboxylic acid group-containing polymerizable monomer, one having one polymerizable unsaturated group consisting of the (meth) acryloyloxy group or (meth) acryloylamino group is usually used. Those having a plurality of sex groups may be used. Also in this case, it is preferable that each of the polymerizable groups is bonded to a carboxylic acid group via an aliphatic hydrocarbon group having 7 to 20 carbon atoms. There may be a compound having a plurality of both a carboxylic acid group and a polymerizable unsaturated group. In this case, the chain length of the polymerizable unsaturated group and the carboxylic acid group is the other group at the farthest position with respect to one group. Count the number of carbon atoms in the chain portion between them.

  The carboxylic acid group-containing polymerizable monomer of the present invention is preferably a compound represented by the following general formula (1).

In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms of R ₁ may be either linear or branched, and specifically includes methyl, ethyl, propyl, isopropyl, pentyl, heptyl Group, decyl group, etc. Among them, those having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group are preferable. Of these R ₁ , hydrogen atom is particularly preferable.

R ₂ is a divalent aliphatic hydrocarbon group having a chain length of 6 to 19 carbon atoms. More preferably, it has a chain length of 7 to 11 carbon atoms. The long-chain divalent aliphatic hydrocarbon group may be unsaturated, but is preferably saturated in terms of chemical stability. Furthermore, these may be either linear or branched. good. Particularly preferred as such a divalent aliphatic hydrocarbon group is an alkylene group having a chain length of the above-mentioned carbon number because of its relatively easy synthesis. Specific examples of such an alkylene group include a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, and an octadecylene group.

R ₃ is a hydrogen atom or a methyl group, preferably a methyl group.

A is an oxygen atom, n is 2.

  Specific examples of the carboxylic acid group-containing polymerizable monomer represented by the general formula (1) include the following.

  Most of the carboxylic acid group-containing polymerizable monomers are liquid at room temperature (23 ° C.) and may be used alone as an adhesive material, but are composed of (meth) acryloyloxy groups or (meth) acryloylamino groups. Some of the aliphatic hydrocarbon groups with a large chain length of the aliphatic hydrocarbon group interposed between the polymerizable unsaturated group and the carboxylic acid group are highly viscous or solid at room temperature. In such a case, it may be mixed with another polymerizable monomer that is liquid at room temperature, dissolved in an appropriate viscosity, and used as at least a part of the polymerizable monomer component. In this case, the content is not particularly limited, but in order to exhibit sufficient adhesive strength and durability, when the total polymerizable monomer component is 100 parts by mass, it is preferably 0. .1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more. Since the carboxylic acid group-containing polymerizable monomer has a high viscosity even if the content is too high and it is difficult to obtain good operability, the content is preferably 60 parts by mass or less, more preferably 30 parts by mass or less. The amount is preferably 20 parts by mass or less.

  As said other polymerizable monomer, the well-known thing currently used as a polymerizable monomer of a curable composition can be used without a restriction | limiting. The polymerizable unsaturated group is not particularly limited, and may be a styryl group, an allyl group, a (meth) acryloylthio group, a thio (meth) acryloyloxy group, etc., but the carboxylic acid group-containing polymerization. Like the polymerizable monomer, a (meth) acryloyloxy group or a (meth) acryloylamino group is preferable. Specific examples of these other polymerizable monomers include methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates; Examples include acetoacetoxyethyl methacrylate and 2-acetoacetoxypropyl methacrylate.

  Moreover, as such other polymerizable monomer, it is more preferable to use a polyfunctional polymerizable monomer. Here, the polyfunctional polymerizable monomer has at least two polymerizable groups in the molecule, and by blending such a polyfunctional polymerizable monomer, a uniform polymer film can be obtained. The compatibility with the resin-based material formed on the zirconia surface and later built up is further improved. Further, it is considered that the durability is further improved by the polymer film formed on the surface imparting an effect of mitigating thermal shock and mechanical shock.

  Such a polyfunctional polymerizable monomer is not particularly limited, and a known compound can be used. Specifically, the following are mentioned.

  2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2, 2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) )propane, (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2- Bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane; and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3- Methacrylates such as chloro-2-hydroxypropyl methacrylate or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and diisocyanates Diadducts obtained by addition with diisocyanate compounds having aromatic groups such as methylbenzene and 4,4′-diphenylmethane diisocyanate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neo Pentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate; and acrylates corresponding to these methacrylates; 2-hydroxyethyl Such as methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, etc. Vinyl monomers having —OH groups such as acrylates corresponding to tacrylates or methacrylates, and diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, and methylenebis (4-cyclohexyl isocyanate) Diaducts obtained from the addition of acrylonitrile, acrylic anhydride, methacrylic anhydride, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) phosphate, etc., trimethylolpropane tri Methacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethanate Methacrylates such as methacrylate, and acrylates corresponding to these methacrylates, such as pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4 Cyclohexyl isocyanate), 4,4-diphenylmethane diisocyanate, diadducts obtained from the addition of diisocyanate compounds such as tolylene-2,4-diisocyanate and glycidol dimethacrylate, and the like.

  These other polymerizable monomers may be used alone, or a plurality of them may be used in combination according to the required physical properties.

  The content of these other polymerizable monomers is preferably 99.9 parts by mass or less, more preferably 95 parts by mass or less, when the total polymerizable monomer component is 100 parts by mass. More preferably, it is 90 mass parts or less. Further, from the viewpoint of improving the viscosity, the other polymerizable monomer is preferably contained in an amount of 40 parts by mass or more, more preferably 70 parts by mass or more, and 80 parts by mass or more. More preferably, it is contained.

  It is more preferable that the adhesive material for zirconia shaped bodies of the present invention further contains a polymerization initiator. By including the polymerization initiator, the adhesive layer formed on the surface of the zirconia becomes stronger and works advantageously on the adhesion durability. Such a polymerization initiator is not particularly limited, and a chemical polymerization initiator can also be used satisfactorily. However, heating or redox packaging is divided into two or more materials and used. It is preferable to use a photopolymerization initiator from the viewpoint of operability, such as not requiring the complexity of mixing immediately before.

  Any known photopolymerization initiator can be used without limitation. Specifically, camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, Α-diketones such as 3,4-phenanthrenequinone and 9,10-phenanthrenequinone; thioxanthones such as 2,4-diethylthioxanthone; 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone 1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1, 2-benzyl-diethylamino-1 -(4-morpholinophenyl) -propanone-1,2-benzyl- Α-aminoacetophenones such as methylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1; 2,4,6- Acylphosphine oxide derivatives such as trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are suitable. Used for.

  In addition, when using a chemical polymerization initiator as a polymerization initiator, the thing of the redox type | system | group which generates a radical combining 2 or more types of this compound can use it conveniently. Typical redox chemical polymerization initiators include organic oxides and amines, organic peroxides and amines and organic sulfinic acids, organic peroxides and amines and aryl borates. A system comprising an aryl borate and an acidic compound, a system comprising a barbituric acid derivative, a copper compound and a halogen compound.

  These polymerization initiators can be used not only independently but also in combination of two or more as required.

  In the present invention, when the polymerization initiator is used in this way, the content is 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total polymerizable monomer component. It is desirable to do.

  Moreover, you may mix | blend the hardening accelerator according to each polymerization initiator together with a polymerization initiator. If a photopolymerization initiator is used, such curing accelerators include N, N-dimethyl-p-toluidine, N, N′-dimethylbenzylamine, N-methyldibutylamine, dimethylaminoethyl methacrylate, N, Amine compounds such as N-dimethyl-m-anisidine and ethyl p-dimethylaminobenzoate; thiourea compounds such as allylthiourea and o-tolylthiourea; phosphite compounds such as dimethylphosphite and dioctylphosphite; .

  The addition amount of these curing accelerators is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total polymerizable monomer component.

  Furthermore, an organic solvent, a thickener, a polymerization inhibitor and the like can be added to the adhesive material of the present invention as long as the performance is not deteriorated. The organic solvent is used to improve the viscosity of the adhesive material in combination with the other polymerizable monomer or the like, or in combination with this, and preferably uses a volatile solvent. Is done. Specifically, alcohols such as ethanol, methanol, 1-propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, pentanone and hexanone, esters such as ethyl acetate, methyl acetate and ethyl propionate, , 2-dimethoxyethane, 1,2-diethoxyethane, ethers such as tetrahydrofuran, hydrocarbons such as heptane, hexane, octane and toluene, and halogenated hydrocarbons such as chloroform and dichloromethane are preferably used. . Of these, acetone, ethanol, isopropyl alcohol and the like are preferably used. These organic solvents may be used alone or in combination of two or more compounds. Thickeners are also used to adjust the viscosity. Cellulose compounds, polyacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyacrylamide, polyvinyl alcohol, etc. as organic systems, colloidal silica, fumed silica, There are fine particle calcium carbonate, fine particle alumina, silicate and the like. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene and the like. Various additives such as ultraviolet absorbers, dyes, antistatic agents, pigments, and fragrances can be selected and used as necessary.

  The method for producing the adhesive material of the present invention is not particularly limited, and any known method for producing an adhesive material such as a dental pretreatment material or a dental adhesive may be followed. In general, all components to be blended may be weighed under inert light such as red light and mixed well until a uniform solution is obtained.

  Since the adhesive material of the present invention has a high affinity for both zirconia and resin, it is particularly suitable as an adhesive material for bonding a zirconia molded body and a resin-based material. This makes it possible to produce a structure that takes advantage of the high degree of freedom of form and color, which are characteristic of resin materials, while having excellent mechanical strength and durability due to zirconia.

  The resin material in the present invention is a polymerizable composition comprising a polymerizable monomer and a polymerization initiator. A known compound having a polymerizable unsaturated group is used as the polymerizable monomer. Specifically, polymerizable monomers similar to those described above can be used as the polymerizable composition used as the adhesive material of the present invention. In particular, a polyfunctional polymerizable monomer is preferable because a high-strength structure can be obtained by a crosslinked structure. Examples of suitable polyfunctional polymerizable monomers include 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl A polymerizable monomer composition mainly composed of propane or urethane dimethacrylate is exemplified. Moreover, it does not specifically limit about the polymerization initiator used for this resin material, The thing similar to what was mentioned above can be used as a polymerization initiator used as an adhesive material of this invention. In particular, it is preferable to use a photopolymerization initiator from the viewpoint of operability such as not requiring the complexity of mixing immediately before use. Examples of suitable photopolymerization initiators include camphorquinone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. Furthermore, an inorganic filler is generally added to the resin-based material from the viewpoint of operability such as mechanical strength and durability improvement and viscosity adjustment. Inorganic fillers are generally particles having a particle size of less than 10 microns. Examples of suitable inorganic fillers include metal oxides such as silica, alumina, zirconia, and titania, and powders such as these metal composite oxides. These inorganic fillers are coated with a silane coupling agent or the like for the purpose of improving the mechanical strength and durability of the resin-based material and improving the operability by improving the compatibility with the polymerizable monomer. Generally, it is processed and used. The blending amount of the inorganic filler is 75 parts by mass or more, more preferably 80 parts by mass or more, and still more preferably 85 parts by mass or more when the entire resin material is 100 parts by mass. Above preferred. The resin material may further contain pigments, dyes, polymerization inhibitors, antioxidants, ultraviolet absorbers, fluorescent agents, fragrances and the like.

  The carboxylic acid group-containing polymerizable monomer contained in the adhesive material of the present invention has high hydrophobicity and good compatibility with not only a zirconia molded body but also a resin material. Therefore, the adhesive material of the present invention having such a component composition has a high filling rate of the inorganic filler in the resin-based material (specifically, the filling rate of the inorganic filler is 75% by mass or more, more preferably 80%. Mass% or more, more preferably 85 mass% or more), even when the amount of the matrix resin component is small (that is, the condition where it is difficult to expect wettability to the zirconia surface), high adhesion durability to the zirconia molded body is obtained. Can be meaningful.

  Examples of the adhesive material described above include a dental adhesive used when a dental prosthesis is manufactured by building up a resin-based dental restorative material on a zirconia frame. For example, the adhesive is applied to a zirconia frame, which is an adherend whose surface is roughened by sandblasting or the like, using a brush or the like, and compressed after being left for about 5 to 60 seconds as necessary. Lightly spray air or the like to make the layer uniform, and if the organic solvent is mixed, volatilize it, then irradiate with visible light using a dental irradiator to polymerize and cure the adhesive, then Then, a known resin-based dental restorative material is built up or coated, and light-irradiated or the like to polymerize and cure, and if necessary, build-up and polymerization operations are repeated to produce a crown shape. When using the above-mentioned dental adhesive containing a photopolymerization initiator, it is common to use light irradiation and cure the dental adhesive, but use it without light irradiation. You may move to the next operation in the state of hardening. In this case, the uncured adhesive layer is also cured at the time of polymerization curing by resin irradiation of the resin-based dental restorative material built or applied thereon.

  Further, the adhesive material of the present invention is an embodiment in which a polymerization initiator is not blended, and after applying to a zirconia molded body, it is applied and built up on the adhesive or resin-based material without being cured, and these are cured together. It may be used as a pretreatment material to be cured. The method of use in this case will be described by taking as an example a pretreatment material for producing a dental prosthesis by adhering a resin-based dental restoration material to the zirconia frame. The adherend whose surface is roughened by sandblasting or the like. The pretreatment material is applied to the zirconia frame to be obtained by using a brush or the like, and left as it is for about 5 to 60 seconds as necessary, and then lightly blown with compressed air or the like to make the layer uniform, and an organic solvent is mixed. In this case, after volatilizing this, build up or apply a known resin-based dental restorative material, polymerize and cure by irradiating light, etc., and repeat the build-up and polymerization operations as necessary to create a crown shape I should do it. Thus, when using as a pre-processing material, it is not necessary to use an adhesive agent together on the application surface of the pre-processing material.

  The amount of application of the adhesive material for zirconia molded body of the present invention to the zirconia molded body surface is not particularly limited, but when the adhesive layer thickness is too thin, it is difficult to obtain stable adhesion durability, and the adhesive layer thickness is too thick. It is difficult to achieve aesthetic satisfaction. More specifically, it is more preferable that the adhesive is applied so as to have a thickness of 10 to 100 microns. Examples of the method for adjusting the thickness include adjustment of the coating amount, strength of air blow, and the like, but from the viewpoint of reducing operational blur, it can be adjusted by the viscosity of the nonvolatile component in the adhesive material. . The non-volatile component here means a component having a boiling point of 200 degrees or more. This viscosity can be adjusted by the viscosity of the carboxylic acid group-containing polymerizable monomer itself, the viscosity of the polyfunctional polymerizable monomer, the addition of a thickener, an organic solvent, or the like. As an example of the viscosity of the non-volatile component in the preferable adhesive material, the measured viscosity under the conditions of 2 ° φ20 mm cone plate, gap 30 microns, shore rate 100 [1 / s] is 100 to 5000 centipoise, more preferably 200 It is more preferable to adjust to ~ 2000 centipoise.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.

Next, the abbreviations or structures of the compounds used in the examples are shown below.
(1) Abbreviation or structure (A) Acid group-containing polymerizable monomer
MAC-I; 7-methacryloyloxy-1,1-heptanedicarboxylic acid (chain length of aliphatic hydrocarbon group interposed between methacryloyloxy group and carboxylic acid group: 7 carbon atoms)
MAC-II; 11-methacryloyloxy-1,1-undecanedicarboxylic acid (chain length of aliphatic hydrocarbon group interposed between methacryloyloxy group and carboxylic acid group: 11 carbon atoms)
MAC-III; 13-methacryloxy-1,1-tridecanedicarboxylic acid (chain length of aliphatic hydrocarbon group interposed between methacryloyloxy group and carboxylic acid group: 13 carbon atoms)
MAA: Methacrylic acid (Chain length of aliphatic hydrocarbon group interposed between methacryloyloxy group and carboxylic acid group: 0 carbon atoms)
MEP: 2-methacryloyloxyethylphthalic acid (Chain length of aliphatic hydrocarbon group interposed between methacryloyloxy group and carboxylic acid group: 0 carbon atoms)
MEM; 2-methacryloyloxyethyl hydrogen maleate (chain length of aliphatic hydrocarbon group interposed between methacryloyloxy group and carboxylic acid group: 0 carbon atoms)
MHPP; 6-methacryloxyhexyl-3-phosphonopropionate
PM: Mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate
MDP: 10-methacryloyloxydecyl dihydrogen phosphate (B) and other polymerizable monomers
bis-GMA; 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane
TEGDMA; triethylene glycol dimethacrylate
bis-MPEPP; 2,2-bis [(4-methacryloyloxypolyethoxyphenyl) propane]
UDMA: Mixture of 1,6-bis (methacrylethyloxycarbonylamino) -2,2,4-triethylhexane and 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-triethylhexane
HEMA; hydroxyethyl methacrylate
TMPT; Trimethylolpropane trimethacrylate
MMA: Methyl methacrylate (C) photopolymerization initiator
CQ: camphorquinone
TPO; 2,4,6-trimethylbenzoyldiphenylphosphine oxide (D) and others
DMBE; ethyl N, N-dimethyl-p-aminobenzoate
PMMA: Polymethylmethacrylate
MT10: Hydrophobized dry silica
BHT: Preparation of dibutylhydroxytoluene (2) resin material 600 g of spherical silica titania with an average particle size of 0.4 micron and 400 g of spherical silica titania with an average particle size of 0.08 micron are mixed in 4 L of pure water. It was dispersed using a circulation type bead mill. A filler composition was obtained by adding γ-methacryloxypropyltrimethoxysilane hydrolyzed in an acetic acid aqueous solution to the dispersion and stirring, followed by spray drying with a spray dryer and further drying under reduced pressure. To 70 g of bis-MPEPP, 25 g of TEGDMA, and 5 g of UDMA, 0.5 mass% CQ, 0.5 mass% DMBE, and 0.1 mass% BHT were added and mixed to prepare a uniform matrix composition. 100 g of the matrix composition and 410 g of the filler composition were charged into a mixer kept at 55 ° C. and stirred and mixed until a uniform paste was formed. The obtained paste was defoamed under reduced pressure to prepare a test resin-based dental restorative material.
(3) Adhesive durability test
An 11 × 11 × 5 mm yttria partially stabilized zirconia sintered compact was polished with # 120 water-resistant abrasive paper and washed with ion-exchanged water. After drying, the polished surface was sandblasted with alumina having a particle size of 50 microns (5 kg / cm ² ), and the alumina powder on the surface was removed by air blow to produce a zirconia frame. A double-sided tape with a hole with a diameter of 3 mm was fixed to this plane, and then paraffin wax with a hole with a thickness of 0.5 mm and a diameter of 6 mm was fixed on the circular hole so as to have the same center.

  When the adhesive material of the present invention was used as a dental pretreatment material, the dental pretreatment material was applied to the hole portion, allowed to stand for 20 seconds, and then sprayed with compressed air for about 10 seconds to homogenize and dry. On the other hand, when the adhesive material of the present invention is used as a dental adhesive, it is operated in the same manner as in the case of the dental pretreatment material, applied to the hole portion of the zirconia frame, and then dried. Then, the adhesive was cured by irradiating with a visible light irradiator (Power Light, manufactured by Tokuyama Dental Co., Ltd.) for 10 seconds. Whether used as a dental pretreatment material or a dental adhesive, the thickness of each adhesive material applied on the zirconia frame was adjusted to about 50 microns.

Next, the test resin-based dental restorative material is filled on each of the application surface of the dental pretreatment material or the application / curing surface of the dental adhesive, and the surface is covered with a polyester film. A test piece was prepared by irradiating light for 120 seconds with a vessel (Pearcure Light, manufactured by Tokuyama Dental Co., Ltd.). Each adhesion test piece was immersed in water at 37 ° C. for 24 hours, and then immersed in water at 4 ° C. and 60 ° C. for 1 minute alternately in a thermal shock tester, and this was performed 3000 times. The test piece was taken out, the surface of the cured resin dental restorative material was treated with 1-2 kg / cm 2 of low-pressure alumina sand blast, and the SUS attachment that had been sand blasted in advance was bonded with an instantaneous adhesive. Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), the tensile strength was measured at a crosshead speed of 2 mm / min, and the tensile adhesive strength between the zirconia frame and the cured resin-based dental restoration material was measured. For each test, four tensile bond strengths were measured by the above method, and the average value was defined as the bond strength [MPa] after durability.
Example 1
(A) 15 parts by mass of MAC-10 as an acid group-containing polymerizable monomer, (B) 51 parts by mass of bis-GMA and 34 parts by mass of TEGDMA as other polymerizable monomers A polymerizable monomer composition was prepared, and 100 parts by mass of the polymerizable monomer composition, (C) 0.5 parts by mass of CQ as a photopolymerization initiator, 1.0 parts by mass of DMBE, 0.03 parts by mass of BHT Parts were added and mixed until uniform to produce the adhesive material of the present invention.
An adhesion durability test was performed using this adhesive material. The results are shown in Table 1. Even after 3000 thermal shock tests, sufficient adhesion durability was exhibited.
Examples 2 to 9, 11
Each adhesive material was prepared with the composition shown in Table 1, and the adhesion durability test was conducted in the same manner as in Example 1. The results are shown in Table 1. In any of the examples, sufficient adhesion durability was exhibited even after 3000 thermal shock tests.
Comparative Examples 1-8
Each adhesive material was prepared with the composition shown in Table 1, and the adhesion durability test was conducted in the same manner as in Example 1. The results are shown in Table 1. In any of the comparative examples, sufficient adhesion was not obtained after 3000 thermal shock tests.

Claims (4)

Carboxylic acid group-containing polymerizable monomer represented by the following general formula (1) and 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane, triethylene glycol dimethacrylate, 2, 2-bis [(4-methacryloyloxypolyethoxyphenyl) propane, 1,6-bis (methacrylethyloxycarbonylamino) -2,2,4-triethylhexane, 1,6-bis (methacrylethyloxycarbonylamino)- Zirconia molding comprising one or two or more polyfunctional polymerizable monomers selected from 2,4,4-triethylhexane and trimethylolpropane trimethacrylate as at least a part of the polymerizable monomer component When the total polymerizable monomer component is 100 parts by mass, the carboxylic acid group The adhesive material for zirconia molded bodies, wherein the contained polymerizable monomer is 0.1 part by mass or more and 60 parts by mass or less, and the polyfunctional polymerizable monomer is 20 parts by mass or more and 90 parts by mass or less.

(In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ is a divalent aliphatic hydrocarbon group having a chain length of 6 to 19 carbon atoms, and R ₃ is A hydrogen atom or a methyl group, A is an oxygen atom, and n represents 2) The adhesive material for a zirconia molded article according to claim 1, which is a dental pretreatment material used when a dental prosthesis is produced by bonding a resin-based dental restoration material to a zirconia frame. Furthermore, the adhesive material for zirconia molded bodies according to claim 1 or 2, further comprising a photopolymerization initiator. The adhesive material for a zirconia molded article according to claim 3, which is a dental adhesive used for producing a dental prosthesis by bonding a resin-based dental restorative material to a zirconia frame.