JPH0348882B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesive material having water resistance, and particularly to an adhesive material having good adhesive strength to biological hard tissues such as teeth and bones that are constantly kept in a moist state. Conventionally, various compounds have been known as adhesives, although there are some differences depending on the field of use. Particularly demanding properties are required for dental adhesives used for biological hard tissues that are constantly kept in a moist state.
As the dental adhesive, a room temperature curing adhesive using an ionomer cement or a polymerizable monomer is known. In particular, adhesives of the latter type that cure polymerizable monomers are often used because of their ease of operation. The type of adhesive that cures the polymerizable monomer generally uses a two-element catalyst consisting of an organic peroxide and an amine in addition to the polymerizable monomer. However, among these polymerizable monomer systems, polymerizable vinyl compounds having carboxylic acid groups and/or carboxylic anhydride groups, or polymerizable vinyl compounds containing polymers having carboxylic acid groups and/or carboxylic anhydride groups, When vinyl compounds are polymerized at relatively low temperatures, there is a drawback that the polymerization rate is extremely slow. In order to compensate for the above drawbacks, the present inventors have already discovered and proposed adding a ternary catalyst of an organic peroxide, an amine, and a carboxylic acid salt to the above polymerizable monomer. As a result of further research, various statistical experiments were conducted regarding the problem of product deterioration that occurs when the adhesive of the type that cures the polymerizable monomer is stored as a product. Complete the
I have come to propose it here. That is, the present invention comprises (1) (a) a polymerizable vinyl compound having a carboxylic acid group and/or an anhydride carboxylic acid group, (b) an organic peroxide, (c) an amine, and (d) a carboxylic acid salt as the main components. This is an adhesive that is stored separately so that at least (b) and (c) are not packaged in the same package. The invention also provides: (2)(a)' A polymer having a carboxylic acid group and/or anhydrous carboxylic acid group, (b) an organic peroxide, (c) an amine, (d) a carboxylic acid salt, and (e) a polymerizable vinyl The present invention also provides an adhesive containing a compound as a main component and at least (b) and (c) stored separately so that they are not contained in the same package. As the polymerizable vinyl compound used in the present invention, conventionally known compounds can be used without any restriction.
Specific examples of those which are particularly preferably used are as follows. For example, olefins such as ethylene, propylene, butene-1; vinyl chloride,
Vinyl halides such as vinyl bromide; vinyl esters such as vinyl acetate and vinyl propionate;
Methyl vinyl ether, ethyl vinyl ether,
Vinyl ethers such as isobutyl vinyl ether; alkenylbenzenes such as styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, and stilbene; methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate,
Alkyl esters or glycidyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol,
Diacrylic esters and dimethacrylic esters such as butylene glycol; triacrylic esters and trimethacrylic esters such as trimethylolpropane and trimethylolethane;
Triacrylic acid ester and trimethacrylic acid ester of tetramethylolethane; Tetraacrylic acid ester and tetramethacrylic acid ester of tetramethylolethane; Bisphenol-A-dimethacrylate, Bisphenol-A
- diglycidyl methacrylate, 2,2-bis(4-methacryloxyethoxyphenyl)propane; acrylic acid, methacrylic acid, methacrylic anhydride, itaconic acid, maleic acid, maleic anhydride,
Acids or acid anhydrides such as P-methacryloxybenzoic acid, N-2-hydroxy-3-methacryloxypropyl-N-phenylglycine, 4-methacryloxyethyl trimellitic acid, 4-methacryloxyethyl trimellitic anhydride, etc. etc. are preferably used. Among the polymerizable vinyl compounds used in the present invention, the polymerizable vinyl compounds having a carboxylic acid group and/or carboxylic anhydride group include other monomers in which the above acid or acid anhydride can be polymerized alone or copolymerized. It is preferably used in combination with The other copolymerizable monomer has a molecular weight of 70 to 70 to the acid or acid anhydride.
It can be used in a range of 99.99wt%, preferably 80 to 99.9wt%. As other copolymerizable monomers, the polymerizable vinyl compounds described above can be used without any restrictions. Furthermore, the polymer having a carboxylic acid group and/or a carboxylic anhydride group in the present invention is a polymer obtained by independently polymerizing the above-mentioned polymerizable vinyl compound having a carboxylic acid group and/or a carboxylic anhydride group. Alternatively, it may be copolymerized with other copolymerizable monomers described above.
Further, after copolymerizing a polymerizable vinyl compound having a group that can be converted into a carboxylic acid and/or anhydride carboxylic acid group, such as a carboxylic acid ester group, alone or with other copolymerizable monomers, It may also be a polymer converted into a carboxylic acid group and/or a carboxylic anhydride group. Specific examples of polymers having carboxylic acid groups and/or carboxylic anhydride groups include polyacrylic acid, polymethacrylic acid, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, and vinylnaphthalene. -fumaric acid copolymer, vinyl acetate-maleic acid copolymer, vinyl acetate-maleic anhydride copolymer, and the like. The catalyst in the present invention consists of an organic peroxide, an amine and a carboxylate. As the above-mentioned organic peroxide, any organic peroxide that is normally used as a polymerization initiator can be used without particular limitation. For example, dibenzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl hydroperoxide, tert-butyl peroxybenzoate and the like are preferably used. Also, as an amine,
Tertiary amines are preferably used. For example, triethylamine, tributylamine, pyridine,
N,N-dimethylaniline, N,N-dimethyl-
P-toluidine, N,N-dimethyl-P-xylidine, N,N-dihydroethyl-P-toluidine and the like are preferably used. Furthermore, as the carboxylic acid salt, conventionally known metal salts, ammonium salts, or amine salts of carboxylic acids can be used without any restriction. The carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid such as dicarboxylic acid or tricarboxylic acid. When the carboxylic acid is a polyvalent carboxylic acid, the salt thereof is preferably a polyvalent carboxylic acid salt such as a dicarboxylic acid salt rather than a monocarboxylic acid salt. Specific examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid,
Aliphatic carboxylic acids such as valeric acid, lauric acid, stearic acid, pyruvic acid, methoxyacetic acid, and acetoacetic acid; aromatic carboxylic acids such as benzoic acid, phenylacetic acid, salicylic acid, toluic acid, anisic acid, ethoxybenzoic acid, anthranilic acid, etc. ; Glycolic acid,
Hydroxycarboxylic acids such as lactic acid; Dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, tartaric acid, maleic acid, fumaric acid, and phthalic acid; Vinyl carboxylic acids such as acrylic acid, methacrylic acid, vinyl acetic acid, and methacryloxybenzoic acid. It can be opened. The carboxylic acid salts used in the present invention include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts and calcium salts, iron salts, copper salts, zinc salts, and silver salts of the above-mentioned carboxylic acids. Metal salts such as salts, ammonium salts, or amine salts such as m-butylamine salts and stearylamine salts are preferably used. The mixing ratio of each component of the adhesive of the present invention explained above is as follows. carboxylic acid group and/or
Or, the ratio of polymers having carboxylic anhydride groups to polymerizable vinyl compounds is generally
Selected from the range of 0.01 to 30wt%, preferably 0.1
Selected from the range of ~20wt%. When the polymer having a carboxylic acid group and/or a carboxylic anhydride group is within the above range, good adhesive strength can be obtained when the resulting polymerization composition is used as an adhesive. In addition, organic peroxides, amines, and carboxylic acid salts have a ratio of 0.01 to
It is sufficient to use 10wt%, preferably in the range of 0.1 to 5wt%. If the amount of carboxylate added is less than the above range, the effects of the present invention may not be obtained, and if it is more than the above range, adhesive strength may be reduced. When using the adhesive of the present invention, polymer compounds such as polymethyl methacrylate, unsaturated polyester resin, and epoxy resin; spiro-orthoesters, bicyclo-orthoesters, etc. Addition is effective.
Moreover, an organic solvent can also be added to adjust the viscosity. Among organic solvents, it is preferable to use a low boiling point solvent such as acetone, chloroform, ethanol, methylene chloride, etc. because polymerization and curing can be carried out by evaporating the solvent. In addition, polymerization inhibitors such as hydroquinone and butylated hydroxytoluene; 2-hydroxy-4-
Methoxybenzophenone, 2(2'-hydroxy-
Ultraviolet absorbers such as 5'-methylphenyl)benzotriazole can be added. The adhesive of the present invention comprises a catalyst component consisting of an organic peroxide, an amine and a carboxylic acid salt, and a polymerizable vinyl compound having a carboxylic acid and/or carboxylic anhydride group, or the catalyst component and a carboxylic acid and/or carboxylic anhydride group. Consists of a polymer with acid groups and a polymerizable vinyl compound. When organic peroxide and amine are mixed among these components, a polymerization reaction starts. Therefore, from the viewpoint of storage stability, the adhesive of the present invention is designed to contain at least organic peroxide and amine in the same package. It is divided and stored to prevent it from entering, and is mixed and used only when it is used. Any storage method may be used as long as at least the organic peroxide and the amine are not placed in the same package. When the adhesive of the present invention contains a polymer having a carboxylic acid group and/or a carboxylic anhydride group as a component, the adhesive strength is maintained well by not putting the polymer and the amine in the same package. preferred above. Furthermore, from the viewpoint of storage stability of the adhesive of the present invention, it is a preferred embodiment that the above-mentioned polymer and carboxylic acid salt are not packaged together in the same package. Therefore, examples of preferred embodiments in which a polymer having carboxylic acid groups and/or carboxylic anhydride groups is included as a component of the adhesive of the present invention are as follows. A direction ●Organic peroxide ●Polymer with carboxylic acid and/or carboxylic anhydride groups ●Polymerizable vinyl compound B packaging ●Amine ●Carboxylate A packaging ●Organic peroxide ●Carboxylic acid and/or carboxylic anhydride Polymer having an acid group ●Polymerizable vinyl compound Packaging B ●Amine ●Carboxylate ●Polymerizable vinyl compound Above, the adhesive of the present invention was exemplified in two parts and packaged, but It is also possible to adopt a method of dividing the package into more parts and packaging them. As is clear from the above explanation, when the adhesive material of the present invention is used, for example, in the dental field, it is possible to firmly bond the tooth structure and the filling material even under moist conditions without pre-etching the tooth structure with phosphoric acid. I can do it. Moreover, as described above, the adhesive of the present invention also has the advantage of good storage stability because at least the organic peroxide and the amine are stored separately. Therefore, when using the adhesive of the present invention, it is only necessary to mix the required amount of the adhesive stored separately. Note that the adhesive material of the present invention is not limited to dental adhesive materials, but exhibits a suitable adhesive effect particularly when used in a humid environment. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. In addition, in the following examples and comparative examples, the following compounds are abbreviated as follows.

[Table] Examples 1 to 8, Comparative Examples 1 to 3 Adhesive solutions (a) and (b) were prepared according to the formulations shown in Table 1, and the adhesive strength with untreated dentin was measured using the following method. It was measured with First, paste (1) and paste () were prepared according to the following formulations. Bis-GMA 11.0 parts by weight TEGDMA 10.5 () N,N-dimethyl-p-toluidine
0.5 〃 Silanized quartz powder (particle size 80μm or less)
78.0 〃 Bis-GMA 11.0 parts by weight TEGDMA 10.5 〃 BPO 0.5 〃 Silanized quartz powder (particle size 80μm or less)
78.0 Next, the labial surface of the freshly extracted bovine tooth was polished with emery paper (#320) to expose the smooth dentin, and the surface was dried by blowing nitrogen gas. Then, a 2 mm thick plate of wax with holes of 4 mm in diameter was attached to the dry surface using double-sided tape. Next, the above solutions (a) and (b) were mixed at a ratio of 1:1, applied to the dentin surface surrounded by plate-shaped wax, and nitrogen gas was blown to remove the ethanol and excess adhesive. .
Paste () and () on it 1:
They were mixed and filled at a ratio of 1:1. After being left for one hour, the wax plate was removed, and the sample was immersed in water at 37°C for a day and night, and then its tensile strength was measured. For the measurement, Tensilon manufactured by Toyo Baldwin was used, and the tensile speed was 10.
mm/min. The results obtained are shown in Table-1.
For comparison, the adhesive strength with untreated dentin was measured in the same manner without the addition of organic peroxide, amine, or carboxylate, and the results are also listed in Table 1. Furthermore, solutions (a) and (b) prepared in Examples 1 to 8 were each placed in a 5 ml glass sample tube, sealed tightly, and stored at 23°C in an atmosphere with relative humidity of 50% to determine storage stability. Examined. As a result, all of them remained stable for a long period of time with no change for more than one year.

【table】

[Table] Examples 9 to 14 Solutions (a) and (b) were prepared according to the formulations shown in Table 2, and the adhesive strength with untreated dentin was determined in the same manner as in Examples 1 to 8. It was measured. The results are also listed in Table-2. Furthermore, the storage stability of solutions (a) and (b) was examined in the same manner as in Examples 1 to 8, and the results showed that they were stable for more than one year.

【table】

[Table] Examples 15 to 21 Solutions (a) and (b) were prepared according to the formulations shown in Table 3, and the adhesive strength with untreated dentin was determined in the same manner as in Examples 1 to 8. It was measured. The results are also listed in Table-3. Furthermore, the storage stability of solutions (a) and (b) was examined in the same manner as in Examples 1 to 8, and the results showed that they were stable for more than one year.

【table】

[Table] Example 22 Using the adhesive solutions (a) and (b) formulated in Examples 6, 8, 11, 20 and 21, an edge sealing property test was conducted in the following manner. First, a cavity with a diameter of 3 mm and a depth of about 2 mm was immediately formed on the labial surface of a freshly extracted bovine tooth. Next, the cavity wall was treated with a 37% orthophosphoric acid aqueous solution for 1 minute, washed with water for 30 seconds, and the surface was dried by blowing nitrogen gas. Next, the adhesive (a) solution and (b) solution are mixed at a ratio of 1:1, applied to the cavity wall, and nitrogen gas is blown to remove the ethanol and excess adhesive, followed by the paste ().
and () were mixed at a ratio of 1:1 and filled.
After leaving it for one hour, it was immersed in water at 37°C for a day and night, excess composite resin was removed, and a percolation test was performed in which it was immersed in fuchsin aqueous solutions at 4°C and 60°C for 60 times for 1 minute alternately. Next, while grinding the filled tooth from the buccal side perpendicular to the labial surface, it was examined whether there was any intrusion of pigment between the cavity wall and the filling. As a result of using the adhesives of Examples 6, 8, 11, 20 and 21, in all cases, no dye penetration was observed and the edge sealing properties were good.

Claims (1)

[Scope of Claims] 1 (a) a polymerizable vinyl compound having a carboxylic acid group and/or an anhydride carboxylic acid group, (b) an organic peroxide, (c) an amine, and (d) a carboxylic acid salt as the main components, A dental adhesive in which at least (b) and (c) are stored separately so that they are not contained in the same package. 2 (a)' A polymer having a carboxylic acid group and/or an anhydride carboxylic acid group (b) an organic peroxide (c) an amine (d) a carboxylic acid salt and (e) a polymerizable vinyl compound as the main components, A dental adhesive that is stored separately so that at least (b) and (c) are not contained in the same package.