JPH0414030B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a polymer having a carboxyl group or its anhydride group, and at least one compound selected from the group consisting of an organoaluminum compound, an organosilicon compound, an organozirconium compound, and an organoboron compound.
The present invention relates to an adhesive film-forming material for biological hard tissues or skin, which is mainly composed of organic metal compounds of various types. Hitherto, various materials have been proposed for biological hard tissues, such as teeth, such as adhesives, margin sealants, barrier film forming materials such as etching solutions, and several of these materials are commercially available. However, this is not always satisfactory due to the following deficiencies. For example, ionomer cement composed of an aqueous polyacrylic acid solution and an inorganic oxide, and room temperature-curable adhesives using polymerizable monomers are known as adhesives for tooth structure. However, although ionomer cement has adhesive strength with tooth structure, it has the disadvantage that it does not have adhesive strength with other dental filling materials and has low water resistance, so it easily comes off in water. Furthermore, adhesives using polymerizable monomers adhere to enamel, but hardly adhere to dentin. For this reason, it was necessary to demineralize the tooth substance by previously treating it with a high-concentration phosphoric acid aqueous solution and create a mechanical retention form. However, this method has the disadvantage that it uses highly concentrated phosphoric acid, which can damage even healthy tooth structure. Furthermore, since amalgam filled in the dental field has good margin sealing properties immediately after filling, copalite is used as a commercially available margin sealing material. However, its sealing properties are not satisfactory. Furthermore, as a blocking film forming material such as etching solution,
Calcium hydroxide-based lining materials such as Dical are used, but their thick membranes make them difficult to use in shallow cavities, and they also react with phosphoric acid and deteriorate. Furthermore, when dentin is exposed on the tooth surface due to shape defects or gingival recession, when cold water or the outside air comes into contact with the exposed area, the tooth pulp is stimulated and pain is felt. Similarly, cuts and cuts in the skin cause pain. However, there has been no satisfactory material for protecting these patients. Based on the above background, the present inventors have been diligently developing adhesive film-forming materials for biological hard tissue or skin. As a result, at least one organometallic compound selected from the group consisting of a polymer having a hydrophobic group and a carboxyl group or an anhydride group thereof, an organoaluminum compound, an organosilicon compound, an organozirconium compound, and an organoboron compound. The above-mentioned drawbacks have been solved by using an adhesive film-forming material for biological hard tissue or skin which contains as a main component. Furthermore, they discovered that the adhesive film-forming material of the present invention not only forms a strong and transparent film-like material, but also that the formed film surprisingly has a strong antibacterial effect. I have come to propose it here. That is, the present invention provides (i) a polymer having a hydrophobic group and a carboxyl group or an anhydride group thereof, (ii) an organoaluminum compound, an organosilicon compound,
This is an adhesive film-forming material for biological hard tissue or skin, which contains as a main component at least one organic metal compound selected from the group consisting of organic zirconium compounds and organic boron compounds. One of the main components of the adhesive film-forming material of the present invention is a polymer having a hydrophobic group and a carboxyl group or anhydride group thereof. The polymer needs to have a carboxyl group or its anhydride group in order to have sufficient adhesion to, for example, tooth structure and to be usable under moist conditions such as in the oral cavity. It is. The polymer used in the present invention has a molecular weight of 30 to 700,
Particularly suitable are those having an acid value of 40 to 600.
In this specification, the acid value is defined as the number of mg of KOH required to neutralize 1 g of resin. This acid value represents the concentration of carboxyl groups and their anhydride groups in the polymer, and if this oxidation is lower than the above range, the number of crosslinking points with organometallic compounds decreases, resulting in poor toughness of the coating. etc. tend to decrease. On the other hand, if the acid value is larger than the above range, the film formed from the polymer becomes excessively hydrophilic, and the water resistance of the film tends to be lost. The carboxyl group or its anhydride group that the above-mentioned polymer has is often provided based on the raw material used when producing the polymer. As such a raw material, any known vinyl monomer having a carboxyl group or its anhydride group can be used without particular limitation. Examples of those generally suitably used are as follows. That is, acrylic acid-based vinyl monomers such as acrylic acid and methacrylic acid; unsaturated dibasic carboxylic acid monomers such as maleic acid, fumaric acid, itaconic acid, maleic anhydride, and itaconic anhydride; 4-methacryloxyethyl trimellitic acid; Aromatic unsaturated carboxylic acid monomers such as these, or substituted derivatives obtained by substituting these vinyl monomers with substituents are preferably used. The polymer of the present invention preferably has a carboxyl group bonded to each adjacent carbon atom, or has an anhydride group bonded to the carbon atom. Such polymers are generally suitably produced by the following method. That is, a polymer can be produced by polymerizing or copolymerizing a vinyl monomer having two carboxyl groups on adjacent carbon atoms, for example, the unsaturated dibasic carboxylic acid monomer described above, as a raw material. In addition, other vinyl monomers having carboxylic acid esters or their anhydride groups on adjacent carbon atoms, such as maleic anhydride, maleic acid monoester, maleic acid diester, fumaric acid monoester, and fumaric acid diester as one component. A copolymer with a copolymerizable vinyl monomer is produced, and then a part or all of the anhydride group or carboxylic acid ester group is converted into a carboxyl group by hydrolyzing the anhydride group or carboxylic acid ester group. A conversion method can also be suitably adopted. The polymer used in the present invention has the hydrophobic group described below and the carboxyl group or its anhydride group, and in particular, a polymer in which a carboxyl group or its anhydride group is bonded to each adjacent carbon atom can be most preferably used. . The polymer of the present invention needs to have a hydrophobic group. By using a polymer having a hydrophobic group, the polymer can have both hydrophilic and hydrophobic properties due to the carboxyl group or its anhydride group. In this case, a trowel can be created which particularly improves its performance in bonding dissimilar materials, such as materials with a hydrophilic surface and materials with a hydrophobic surface. The hydrophobic group bonded to the polymer used in the present invention is not particularly limited, and known ones can be used. Typical examples of the hydrophobic groups that are generally suitably used are as follows. (1) Aryl groups such as phenyl and naphthyl groups (2) Alkyl groups such as methyl, ethyl, propyl and butyl groups (3) Alkoxy groups such as ethoxy, propoxy and butoxy groups (4) Acetyloxy Acyloxy groups such as groups (5) Alkoxycarbonyl groups such as ethoxycarbonyl groups and butoxycarbonyl groups In addition, the hydrophobic groups shown in (1) to (5) above may be substituted with other substituents as long as the hydrophobic properties are not impaired. May be replaced. These substituents generally include, for example, halogen atoms such as chlorine, bromine, iodine, and fluorine, alkyl groups, alkoxy groups, and phenoxy groups. Further, as will be described in detail later, these hydrophobic groups are generally provided based on the raw materials used when producing the polymer of the present invention. The raw material for imparting such a hydrophobic group is not particularly limited, and known vinyl monomers are preferably used. Examples of known vinyl monomers that are particularly preferably used are as follows. That is, as those having a hydrophobic group in (1) above, styrene, halogenated styrene,
Among methylstyrene, halogenated methylstyrene, vinylnaphthalene, etc., propylene, isobutene, etc. are preferable as those having the hydrophobic group described in (2) above. Similarly, ethyl vinyl ether, n-butyl ether, etc. have the hydrophobic group in (3) above, and vinyl acetate, etc. have the hydrophobic group in (4) above, and the hydrophobic group in (5) above. Ethyl methacrylate, phthyl acrylate, etc. are suitable for those having a functional group. The vinyl monomer having a hydrophobic group preferably used in the present invention has the following general formula: (In the formula, R ¹ is a hydrogen atom or an alkyl group,
R ² is an aryl group, an alkyl group, an alkoxy group,
It is an acyloxy group or an alkoxycarbonyl group). Generally speaking, the polymer of the present invention preferably has a molecular weight of about 1,000 to 100,000, preferably about 2,000 to 50,000, for reasons such as ease of availability and handling. The method for obtaining the above-mentioned polymer is not particularly limited, but industrially it is possible to use a vinyl monomer having a hydrophobic group and a vinyl monomer having a carboxyl group as described above, in particular,
A method of obtaining the vinyl monomer by copolymerizing a vinyl monomer having a carboxyl group, its anhydride group, or a carboxylic acid ester group bonded to adjacent carbon atoms, or by subsequent hydrolysis is preferably employed. Therefore, a suitable polymer is (A) represented by the following formula: In the formula, R ¹ is a hydrogen atom or an alkyl group,
R ² is an aryl group, an alkyl group, an alkoxy group,
It is an acyloxy group or an alkoxycarbonyl group. At least one type of unit represented by and (B) the following formula In the formula, R ³ is hydrogen, an alkyl group, or a carboxymethyl group, n and m are zero or 1, and when m is zero, m is 1 and R ³ is a hydrogen atom, and n is 1. In the case of , m is zero and R ³ is hydrogen, an alkyl group or a carboxymethyl group, and the two carboxyl groups may form an anhydride group. It consists of at least one type of unit represented by Further, when carrying out the above-mentioned copolymerization, there are no particular limitations, and in general, polymerization carried out using the following polymerization initiator is suitably employed. For example, radical polymerization using an organic peroxide such as benzoyl peroxide or lauroyl peroxide, an azo compound such as azobisisobutyronitrile, an organometallic compound such as tributylboron, or a redox initiator can be suitably used. The unit having a hydrophobic group represented by formula (A) is present in the polymer having a carboxyl group in an amount of 40 mol% to
It is preferable that the content is 90 mol%. If the hydrophobic group exceeds 90 mol%, it will not be possible to form a film with biological hard tissue. Although the reason for this is not clear at present, it is presumed that the hydrophobicity of the polymer increases, resulting in a decrease in affinity with biological hard tissue. In addition, polymers containing less than 40 mol% of hydrophobic groups are generally difficult to produce industrially because there is no good industrial method for imparting carboxyl groups or their anhydride groups, which will be described later. However, the resulting coating using the polymer tends to have insufficient water resistance. The method for hydrolyzing the ester group or anhydride group of the carboxylic acid is not particularly limited, but generally, a copolymer containing the ester group or anhydride group is dissolved in a suitable organic solvent, and water and A suitable method is to add a small amount of an acid or alkali component as a promoter of the hydrolysis reaction and react at room temperature or under heating. Another component of the adhesive film forming material of the present invention is at least one organometallic compound selected from the group consisting of organoaluminum compounds, organosilicon compounds, organozirconium compounds, and organoboron compounds. The organometallic compounds used in the present invention are not particularly limited as long as they are listed above, and known compounds can be used, and they can be used alone or in combination. As the organic aluminum compound, aluminum alkylates such as aluminum isopropylate, aluminum n-butyrate, aluminum sec-butyrate, aluminum isobutyrate, and aluminum t-butyrate are preferably used alone or in combination. Examples of organic silicon compounds include alkyl silicates such as tetraethyl silicate and tetrabutyl silicate; vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Alkyl silicates such as methoxysilane partially substituted with other substituents are used alone or in combination. The effects of the present invention are particularly noticeable when alkyl silicates are used. Examples of organic zirconium compounds include tetramethylzirconate, tetraethylzirconate, tetra-i-propylzirconate,
Tetra-sec-butylzirconate tetra-n-
Alkyl zirconates such as butyl zirconate and tetra-i-butyl zirconate are preferably used alone or in combination. Examples of organic boron compounds include boric acid trimethyl ester, boric acid triethyl ester, boric acid tri-i-propyl ester,
Boric acid tri-n-butyl ester, boric acid tri-n-butyl ester
Boric acid alkyl esters such as stearyl ester, boric acid triphenyl ester, and boric acid aryl esters such as boric acid tri-o-triester are preferably used alone or in combination. The amount of the organometallic compound used in the adhesive film-forming material of the present invention is not particularly limited, but generally 0.02 mol to 1 mol of the carboxyl group or anhydride group of the polymer having a carboxyl group or anhydride group. It is preferable to add it in a proportion of 1.0 mol.
If the amount of the organic titanate added is less than 0.02 mol, the water resistance of the adhesive film forming material may decrease, and the field of use may be restricted. Furthermore, if the amount of the organometallic compound added exceeds 1.0 mol, the curing time may become too short during curing, resulting in a decrease in operability, which may limit the field of use. Therefore, in the present invention, each addition ratio is preferably determined in advance depending on the physical properties required in the field of use. Furthermore, in order to use the organometallic compound used as a component of the adhesive film-forming material of the present invention in a more stable state, it is often preferable to use a stabilizer for the organometallic compound. In particular, when a solvent is used in the form of use of the adhesive film-forming material of the present invention, it is recommended to use the organometallic compound stabilizer when using the solvent without removing water content, although it depends on the type of the solvent. preferable. The manner in which the adhesive film-forming material of the present invention is used can be changed depending on the type of stabilizer. For example, o-alkoxybenzoic acids such as o-methoxybenzoic acid, o-ethoxybenzoic acid, o-propoxybenzoic acid; β-hydroacrylic acid, β-hydroxybutyric acid, β-hydroxyisovaleric acid, etc.
When hydroxycarboxylic acid is used as a stabilizer, it can be a one-component type product in which the polymer and organometallic compound are dissolved in a solvent in one packaging container. In addition, as the stabilizer, lactic acid, α
α-hydroxycarboxylic acids such as -hydroxy-n-butyric acid and mandelic acid; β-hydroxyalkyl (meth)acrylates such as β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, and glycerin dimethacrylate; catechol, guaiacol, eugenol, etc. Catechol derivatives; proline, 4-methylene-proline, 4
-Proline derivatives such as methyl-proline; When using cyclic esters such as β-butyrolactone, γ-butyrolactone, β-caprolactone, etc., the organic metal compound dissolved in the same solvent as the above-mentioned polymer dissolved in the solvent and It is preferable to prepare a two-component type product in which the stabilizer and the stabilizer are stored in separate containers, and the two are mixed to form an adhesive film-forming material at the time of use. The solvent used in each of the one-component type and two-component type products is not particularly limited and may be appropriately selected from known solvents, but generally alcohols such as ethyl alcohol and isopropyl alcohol; acetic acid; Ethyl; dioxane; tetrahydrofuran and the like are preferred. The concentration of the adhesive film forming material in the solvent is not particularly limited, but is generally 1 to 1.
A content in the range of 30% by weight is preferable because the adhesive film-forming material can be used as a film. Even when used together with the above solvents, the curing reaction starts by evaporating the solvent after coating, so it is easy to use at room temperature. The amount of the stabilizer added to the organometallic compound varies depending on the type of the stabilizer and cannot be absolutely limited, but it is generally 0.1 mol to 4 mol based on the organometallic compound.
The molar amount is preferably selected from the range of 0.5 mol to 2 mol. Further, the stabilizer may be added by being mixed with the organometallic compound in advance, or may be added to the organometallic compound together with other components. In the adhesive film forming material of the present invention, a sufficient cured film forming material can be obtained using only the two components of the above-mentioned hydrophobic group and a polymer having a carboxyl group or its anhydride group, and an organometallic compound. It is also possible to improve the strength or adhesive strength of the cured product by curing it in the coexistence of a polymerizable vinyl monomer and an initiator. As the above-mentioned polymerizable vinyl monomer, the vinyl monomer having a hydrophobic group as described above can be used as is. Among the copolymerizable vinyl monomers, acrylic acid and methacrylic acid derivatives are particularly preferably used because they can be polymerized at room temperature. The initiator is not particularly limited, but it is generally preferable to use a mixed system of peroxide and amine. The peroxide may be any peroxide commonly used as a curing agent, and dibenzoyl peroxide, dilauroyl peroxide, etc. are particularly preferably used. In addition, as amines, N,NI-dimethylaniline, N,NI-dimethyl-P-toluidine, N,NI-dimethylaniline, N,NI-dimethyl-P-toluidine,
-methyl, NI-β-hydroxyethyl-aniline, N,NI-dimethyl-P-(β-hydroxyethyl)-aniline, N,NI-di(β-hydroxyethyl)-P-toluidine, etc. are preferably used. Ru.
Furthermore, it is often a preferred embodiment to use co-catalysts, such as metal salts of sulfinic acids or carboxylic acids, in addition to the initiators. The adhesive film forming material of the present invention can be used as a one-component type curing composition, and moreover, since the curing time during curing is appropriate, operability is improved. The resulting film also has excellent weather resistance,
The result is a tough coating that exhibits chemical resistance, solvent resistance, and adhesion, as well as gloss. The adhesive film-forming material of the present invention is useful, for example, as a coating material for the skin, a therapeutic and restorative material for biological hard tissues, and especially for dentistry. A skin dressing is something that is applied over an affected area, such as a wound or stomatitis, to block air and moisture, thereby blocking irritation. In this case, in conjunction with the antibacterial action described below, it is possible to protect affected areas such as cuts or stomatitis. In addition, the above-mentioned dental treatment and restoration material refers to a material that is used during treatment and restoration of a tooth and is applied to the surface of a tooth or a cavity provided in a tooth, and is a material that is applied to the surface of a tooth or a cavity provided in a tooth. This is the most important use of wood. Examples of such materials include tooth adhesives, barrier film forming materials, and materials for sealing the edges of teeth and filling materials. The case where the adhesive film-forming material of the present invention is used as a dental treatment and restorative material will be described below. BACKGROUND ART Conventionally, in dental treatment and restoration, when a tooth cavity is filled with a filling material such as a composite restorative resin, an adhesive is used to bond the tooth substance and the filling material. However, since conventional adhesives exhibit almost no adhesion to the tooth structure, it is necessary to demineralize the tooth structure by pre-treating the tooth structure with a highly concentrated phosphoric acid aqueous solution and create a mechanical retention form. Ta. However, this method uses a highly concentrated phosphoric acid aqueous solution, which has the disadvantage of damaging even the healthy tooth structure.Especially when etching dentin, not only is the adhesive strength less than expected, but also the dental pulp is passed through the dentinal tubules. The effects of the phosphoric acid aqueous solution may even be felt. Furthermore, since the above method inevitably leaves unreacted monomers, there is a risk that these monomers may cause damage to the dental pulp. However, when the adhesive film-forming material of the present invention is used as an adhesive, it can be directly adhered to dentin without being pretreated with the phosphoric acid aqueous solution, and since the cured product itself is originally a polymer, it is free from unreacted monomers. It has an excellent effect of being non-toxic to the pulp. Next, conventional barrier film-forming materials include calcium hydroxide-based materials and cement, which are used to protect dentin from phosphoric acid etching when filling with composite restorative resins and other filling materials. It is used in However, these materials inevitably form a thick film and do not have adhesive properties with the filling material, making it almost impossible to fill shallow cavities. Therefore, by dissolving the adhesive film-forming material of the present invention in an organic solvent and using it as the barrier film-forming material,
Although it is a thin film, it can protect the tooth structure from phosphoric acid etching solution, and it also has an excellent ability to bond with filling materials. Furthermore, zinc phosphate cement, which is still commonly used for adhesion between metal and tooth structure, contains a large amount of phosphoric acid in its composition, which may cause damage to the pulp. It has been desired to use a barrier film-forming material for protection. However, it has been impossible to use conventional film-forming materials with thick films because their own compressive strength poses a problem. Therefore, when the adhesive film-forming material of the present invention is used as a barrier film-forming material, since it is a thin film, its own strength is not necessary, and moreover, it exhibits the ideal effect of not allowing phosphoric acid to pass through. That's what I do. Furthermore, a third function of the adhesive film-forming material of the present invention is edge sealing properties. As a known substance that is expected to have the above function, for example, a resin such as copalite dissolved in an organic solvent, which is used in amalgam filling, is known. Although this material does form a thin film, it has no adhesive strength with tooth structure or amalgam, and is not very effective in sealing the margins. By using the adhesive film-forming material of the present invention as the edge sealing material, remarkable effects are exhibited in terms of edge sealing properties. Considering the fact that the adhesive film-forming material adheres to tooth structure but not to amalgam, the above function is thought to be due to properties other than adhesiveness, such as adhesion and hydrophobicity. . In addition to amalgam filling, it is also possible to improve the margin sealing properties by using the above-mentioned adhesive film forming material in composite repair resin, cement filling, rubber capping, etc. It may also be used to seal teeth and restorative alloys such as gold, gold-palladium alloys, platinum-gold alloys, silver-gold alloys, platinum-palladium alloys, nickel-chromium alloys, etc. It is possible to use the adhesive film forming material of the present invention for purposes other than those described above. For example, by applying the adhesive film-forming material of the present invention to areas where dentin is exposed on the tooth surface due to a wedge-shaped defect in the tooth cavity, etc., when the material filling the tooth cavity is removed. It can also be used as a shield against external stimuli. Above, the functions as a tooth adhesive, a barrier film forming material, and a margin sealing material have been explained individually, but the adhesive film forming material of the present invention has all of these functions, so it can be used as a single function. In certain cases, all of the above functions can be achieved simply by using the adhesive film-forming material of the present invention. Therefore, in the past, in one case, it was necessary to use multiple materials in combination, which made the operation extremely complicated, and the use of multiple materials in combination resulted in deterioration of each other's functions. In view of this, the adhesive film-forming material of the present invention is an extremely useful composition as a dental treatment and restorative material. When the adhesive film-forming material of the present invention is used as a dental treatment and restorative material, the polymer having a carboxyl group, which is one of the components of the present invention, must also have a hydrophobic group. It is preferred in order to further improve its function as a therapeutic and restorative material. This is effective in imparting water resistance since the oral cavity is under harsh conditions of 100% humidity. Furthermore, when the adhesive film-forming material of the present invention is used as an adhesive between the tooth substance and the composite restoration resin, the carboxyl group has an affinity for the tooth substance, while the hydrophobic group has an affinity for the composite restoration resin. Because it has an affinity for repair resins, it has significantly improved adhesive strength compared to conventional adhesives. Furthermore, the adhesive film-forming material of the present invention has an antibacterial effect, and its effect is seen against anaerobic bacteria. The adhesive film forming material of the present invention has an antibacterial effect against, for example, the following bacteria. Bacteroides gingivalis 381 Actinomyces naeslundii ATCC 12104 Actinomyces visccosus ATCC 15987 Propionibacterium acnes EXC-1 Actinomyces israeli ATCC 12102 Furthermore, the adhesive film forming material of the present invention may include, for example,
Compounds having pharmacological activity such as fluorine compounds and chlorhexidine can also be added and used. 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. Production example 1 Put 200ml of cyclohexane into a 500ml separable glass flask, add 5.2g of styrene,
4.9 g of maleic anhydride and 0.05 g of benzoyl peroxide (hereinafter abbreviated as BPO) were added and thoroughly stirred. Next, after reducing the pressure in the container and purging it with nitrogen, heating polymerization was carried out at 80°C for 4 hours with stirring, and after cooling to room temperature, the formed precipitate was filtered off. The obtained solid was further thoroughly washed with 300 ml of benzene and then dried to obtain 8.7 g of a white polymer. As a result of determining the composition of the produced copolymer from elemental analysis of this material, it was found that styrene
48.4 mol% and maleic anhydride 51.6 mol%. Next, dissolve this product in 80 ml of dioxane, add it to a 500 ml flask, and while stirring thoroughly, add 5% by weight aqueous potassium hydroxide solution.
100 ml was added and allowed to react at room temperature for 10 hours. Next, concentrated hydrochloric acid was added to neutralize the mixture, and then an excess of hydrochloric acid was added to obtain a white solid precipitate. This solid was filtered off, washed with water repeatedly until it became neutral, and further dried to obtain 8.0 g of a copolymer. As a result of measuring the infrared absorption spectrum of this product, the characteristic absorption derived from the carbonyl group of maleic anhydride (1850 cm
^-1 , 1775 cm ^-1 ) completely disappeared, and a new characteristic absorption derived from the carbonyl group of maleic acid appeared at 1720 cm ^-1 , confirming that the hydrolysis reaction was progressing almost quantitatively. . That is, the white solid obtained above contains 48.4 mol% styrene and maleic acid.
It was confirmed that the copolymer contained 51.6 mol%. The acid value of this polymer was 370. Production Example 2 A commercially available styrene-maleic anhydride copolymer with a molecular weight of 50,000 (Monsanto)
Company product) Dissolve 10g in 200ml of dioxin and add 500
10 g of distilled water was added to the flask with sufficient stirring, and the mixture was heated and stirred at 100° C. for 4 hours. Next, this solution was cooled to room temperature and then poured into the distilled water described in step 2 to precipitate a flocculent white polymer. This polymer was washed with water and dried to obtain 9.8 g of a white solid. From the results of elemental analysis and infrared absorption spectrum of this product, it was confirmed that a styrene-maleic acid copolymer was obtained. The acid value of this polymer is 367
It was hot. Production Examples 3 to 4 Two types of commercially available styrene-maleic anhydride copolymers (manufactured by Arco Chemical) with different compositions shown in Table 1 were used in the same manner as in Production Example 1. Hydrolysis was carried out, and a styrene-maleic acid copolymer having the same composition shown in Table 1 was obtained from the elemental analysis results of the raw material copolymer and the measurement results of the infrared absorption spectrum after hydrolysis. The molecular weights were 1700 and 1900, and the acid values were 251 and 184, respectively.

[Table] Production Example 5 50 ml of benzene containing 35 g of maleic anhydride and 90 mg of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added to a 300 ml pressure-resistant glass container, and the mixture was cooled in a dry ice-methanol bath. At the same time, the contents were purged with nitrogen under reduced pressure, and then 12 g of purified propylene was added by distillation through a liquefaction meter. Next, stirring was continued for 36 hours at 60°C to carry out copolymerization. After the polymerization was completed, the contents were poured into a large amount of anhydrous ether to precipitate the resulting copolymer, thoroughly washed by a decanting method, and immediately dried in a vacuum dryer. The yield was 60%. Elemental analysis revealed that maleic anhydride was 55.6 mol% and propylene was 44.4 mol%. Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain a propylene-maleic acid copolymer.
Obtained 24.2g. As a result of measuring the infrared absorption spectrum of this copolymer, it was confirmed that the maleic anhydride groups in the raw material were almost quantitatively converted to maleic acid. The acid value of this polymer was 508. Production Example 6 Add 50 ml of benzene containing 35.7 g of maleic anhydride and 90 mg of AIBN to a 300 ml pressure-resistant glass container. To this, 12.5 g of isobutene was charged by distillation through a liquefaction meter, and then copolymerization was carried out at 60° C. for 15 minutes. After the polymerization is completed, the contents are poured into a large amount of anhydrous ether to precipitate the resulting copolymer, and the supernatant is discarded by a decanting method, thoroughly washed with anhydrous ether, and then dried under reduced pressure. The yield was 43.3%. Elemental analysis revealed that this copolymer contained 47.1 mol% of isobutene and 52.9 mol% of maleic anhydride. Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain an isobutene-maleic acid copolymer.
Obtained 20.5g. As a result of measuring the infrared absorption spectrum of this copolymer, it was confirmed that the maleic anhydride groups in the raw material were almost quantitatively converted to maleic acid. The acid value of this copolymer is 470.
It was hot. Production example 7 In a 500ml glass separable flask,
Add 200ml of benzene, add 5.3g of n-butyl vinyl ether, 4.9g of maleic anhydride and
0.05 g of AIBN was added and thoroughly stirred. Next, after depressurizing the container and replacing it with nitrogen, the container was heated to 60℃ for 6 hours.
Polymerization was carried out by heating for a period of time, and the generated precipitate was separated by filtration. As a result of determining the composition of the produced copolymer from elemental analysis of this material, it was found that n-butyl vinyl ether
49.8 mol% and maleic anhydride 50.2 mol%. Next, this product was dissolved in 200 ml of dioxane, placed in a 500 ml flask, and 10 g of distilled water was added with thorough stirring, followed by stirring at 60° C. for 2 hours. The obtained polymer solution was solidified with dry ice-methanol and then freeze-dried to obtain 10.1 g of white solid. By measuring the infrared absorption spectrum of this product, it was confirmed that most of the maleic anhydride groups were converted to maleic acid groups. The acid value of the polymer was 375. Production Example 8 A copolymer of n-octadecyl vinyl ether-maleic anhydride manufactured by Polysciences Inc. was used and hydrolyzed in the same manner as in Production Example 2 to obtain a raw material copolymer. From the elemental analysis results and the measurement results of the infrared absorption spectrum after hydrolysis, a copolymer of n-octadecyl vinyl ether-maleic acid was similarly obtained. The acid value of this polymer was 196. Production example 9 30g of itaconic acid and 20g of styrene were mixed with dioxane.
The mixture was dissolved in 200 g, BPO was added in an amount of 0.1% based on the monomer, and polymerization was carried out at 10°C for 5 hours. The obtained polymer was poured into hexane 1, precipitated, filtered and dried, and unreacted itaconic acid was removed by washing with distilled water. The yield was 4.2%.
The results of elemental analysis revealed that itaconic acid was 49.0 mol% and styrene was 51.0 mol%. The acid value of this polymer was 340. Production example 10 Styrene and fumaric acid diethyl ester are made into AIBN
was used as an initiator and polymerized at 60°C for 20 hours to obtain a polymer. The composition of the copolymer was determined by elemental analysis to be 56.5 mol% styrene and fumaric acid diethyl ester.
It was 43.5 mol%. Next, add 100ml of this polymer.
30 ml of concentrated sulfuric acid was added to 0.5 g of the solution in an Erlenmeyer flask, and the mixture was left at room temperature. In 2 days, the polymer was completely dissolved and a yellow solution was obtained.
When this was poured into a large amount of ice water, the styrene-fumaric acid copolymer precipitated out. After filtering this,
After repeated washing with water and finally drying, 0.45 g of solid was obtained. The acid value of this polymer was 93. Production Example 11 A vinyl acetate-maleic anhydride copolymer manufactured by Polysciences Inc. was used and hydrolyzed in the same manner as Production Example 7, and the results of elemental analysis of the copolymer were From the measurement results of the infrared absorption spectrum after hydrolysis, a vinyl acetate-maleic acid copolymer was obtained. The acid value of this polymer was 399. Production example 12 BPO of p-chlorostyrene and maleic anhydride
Polymerization was carried out under the same conditions as in Production Example 1 using as an initiator. The results of elemental analysis of the obtained copolymer revealed that it contained 47.9 mol% of p-chlorostyrene and 52.1 mol% of maleic anhydride. Next, this product was hydrolyzed in the same manner as in Production Example 7, and a vinyl acetate-maleic acid copolymer was determined from the elemental analysis results of the resulting polymer and the measurement results of the infrared absorption spectrum after hydrolysis. Obtained. The acid value of this polymer was 318. Production example 13 p-chloromethylstyrene and maleic anhydride
Polymerization was carried out under the same conditions as in Production Example 1 using BPO as an initiator. From the results of elemental analysis of the obtained copolymer, 48.9 mol of p-chloromethylstyrene
%, maleic anhydride 51.1 mol%. Next, this product was hydrolyzed in the same manner as in Production Example 7, and based on the elemental analysis results of the produced copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, p-chloromethylstyrene-maleic acid was determined. A copolymer was obtained. The acid value of this polymer was 301. Example 1 The following test was conducted using the adhesive film forming materials shown in Table 2. (1) Adhesion to dentin (2) Marginal sealing to cavities (3) Blocking to phosphoric acid aqueous solution The above tests were evaluated in the following manner. First, paste () and paste () were prepared according to the following formulations. () Bisglycidyl dimethacrylate triethylene glycol dimethacrylate dimethyl p-toluidine silane-treated quartz powder (particle size 80 μm or less) 11.0 parts by weight 10.5 〃 0.5 〃 78.0 〃 () Bisglycidyl methacrylate triethylene glycol dimethacrylate benzoyl peroxide silane treatment Quartz powder (particle size 80μm or less) 11.0 parts by weight 10.5 〃 1.0 〃 78.0 〃 (1) Adhesion to dentin The labial surface of a freshly extracted bovine tooth was polished with emery paper (#320) to expose the smooth dentin. After washing the polished surface with water for 30 seconds, the surface was dried by blowing nitrogen gas. A 2 mm thick plate of wax with 4 mm diameter holes was attached to the dry surface using double-sided tape. Next, liquids (A) and (B) of the adhesive film forming materials shown in Table 2 were mixed at a ratio of 1:1, applied to the dentin surface scratched with plate-shaped wax, and nitrogen gas was applied. I sprayed off the ethanol and excess adhesive. The above pastes () and (2) were mixed at a ratio of 1:1 and filled thereon. 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
The speed was set at 10 mm/min. The results obtained are shown in Table 2.

【table】

[Table] (2) Margin sealing properties for cavities A cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of an extracted human tooth. Next, after applying a thin layer of adhesive film-forming materials shown in Table 2 No. 1 to No. 20 and conventionally used copalite to the cavity wall,
Filled with cement or amalgam. Filling 1
After 1 hour, store in water at 37°C, and after 1 day at 4°C and 60°C.
60 times alternately for 1 minute each in fuchsin aqueous solution at ℃.
A immersion percolation test was conducted to test the margin sealing properties. The extracted tooth was then sectioned down the center to examine whether there was any pigment (fuchsin) intruding between the cavity and the filling. The reproducibility of the above tests was confirmed using five samples for each type of experiment. As a result, when the samples were directly filled with amalgam or cement without using the above-mentioned composition, or when the samples were coated with copalite and then filled with amalgam or cement, intrusion of pigment was observed in all samples. On the other hand, with respect to the adhesive film forming materials No. 1 to No. 20 in Table 2, no penetration of the dye was observed, and good results were obtained. (3) Blocking property against phosphoric acid aqueous solution In order to confirm that the adhesive film-forming material of the present invention has the ability to block phosphoric acid aqueous solution, a test was conducted using the following method. First, a membrane filter with a pore size of 3 μm was soaked in distilled water for 1 hour, then taken out, and the surface was dried by blowing nitrogen gas. Next, commercially available Copalite, Dical, and the adhesive film forming material used in Example 1 were applied to the back side as a blocking material (backing material), and nitrogen gas was again blown to remove the solvent. A 37% orthophosphoric acid aqueous solution was used as the phosphoric acid aqueous solution, and one drop was dropped onto the barrier material and left to stand. In order to detect phosphoric acid passing through the adhesive film forming material, a PH test paper was placed under the membrane filter, and the time when the color changed was determined as the passage time. As a result, the permeation time of the phosphoric acid aqueous solution was 15 seconds for the one that did not use any barrier material, the one that used Copalite (trade name) was 1 minute and 10 seconds, and the one that used Daical (trade name) It was hot for over 10 minutes. On the other hand, when the adhesive film forming material of the present invention shown in Table 2 was used as the barrier material, the permeation time of the phosphoric acid aqueous solution was 10 minutes or more in all cases. Comparative Example 1 The same procedure as in Example 1 was carried out except that liquids (A) and (B) having the following compositions were used in place of liquids (A) and (B) in Example 1, respectively. Liquid (A); Polyacrylic acid 8 parts by weight Ethanol 92 parts by weight (B) Liquid: Aluminum-i-propylate
2 parts by weight Ethanol 98 parts by weight As a result, the adhesive strength with untreated dentin was 3.1
Kg/cm ² , which was not a satisfactory strength compared to the results of Example 1. Example 2 A cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of an extracted human tooth. Next, the adhesive film-forming materials shown in Table 2 and the conventionally used copalite were each thinly applied to the cavity walls, and then the alloys shown in Table 4 were respectively filled. One hour after filling, it was stored in water at 37°C, and one day later, it was subjected to a percolation test in which it was immersed in fuchsin aqueous solutions at 4°C and 60°C 60 times for 1 minute alternately to test its margin sealing properties. The extracted tooth was then sectioned down the center to examine whether there was any pigment (fuchsin) intruding between the cavity and the filling. The reproducibility of the above tests was confirmed using five samples for each type of experiment. As a result, when the alloy shown in Table 4 was directly filled without using the above composition, or when the alloy shown in Table 4 was applied after coating with copalite, intrusion of pigment was observed in all samples. Ta. On the other hand, with respect to the adhesive film-forming materials shown in Table 2, no dye penetration was observed, and good sealing results were obtained.

[Table] Example 3 In order to confirm that the adhesive film-forming material of the present invention has the ability to block unreacted phosphoric acid from zinc phosphate cement, a test was conducted using the following method. . First, a membrane filter with a pore size of 3 μm was soaked in distilled water for 1 hour, then taken out, and the surface was dried by blowing nitrogen gas. Next, the adhesive film forming material shown in Table 2 was applied as a barrier material to the surface, and nitrogen gas was again blown to remove the solvent. Furthermore, Elite 100 was used as a commercially available zinc phosphate cement, and after kneading it according to the recipe, it was placed on a barrier material, a glass plate was placed on it, and a load of 100 g was applied to it. In order to detect phosphoric acid passing through the adhesive film forming material, a PH test paper was placed under the membrane filter, and the time when the color changed was determined as the passage time. As a result, the permeation time of the phosphoric acid aqueous solution was 15 seconds in the case where no adhesive film-forming material was used, while the permeation time for the phosphoric acid aqueous solution was 10 minutes or more in all cases using the adhesive film-forming material of the present invention. It was hot. Example 4 A cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of an extracted human tooth, and equal amounts of solutions A and B as shown in Table 2 were mixed and applied to the cavity. After application, it was dried with nitrogen gas, the cavity was filled with fuchsin aqueous solution, and it was stored for one day in a constant temperature room at 37°C and 100% humidity. Next, in order to examine the water resistance of the adhesive film-forming material of the present invention, the extracted tooth was cut at the center, and it was examined whether the fuchsin aqueous solution had penetrated into the tooth structure. As a result, coloring due to fuchsin was observed on the tooth substance of the teeth that were not coated with the adhesive film-forming material of the present invention as fuchsin, but in all of the teeth that were coated with the adhesive film-forming material of the present invention, the pigment was not applied. Good results were obtained with no intrusion observed. Example 5 No. 2 in Table 2 was applied to a patient who had a wedge-shaped defect in the tooth neck and felt pain when exposed to air or cold water.
When solutions A and B shown in 1 were mixed and applied to the wedge-shaped defect, the pain caused by contact with air and cold water was resolved. In addition, No. 2, No. 9, No. 14, No. 15, and No. of Example 1.
Solutions (A) and (B) of No. 17, No. 18, No. 19, and No. 20 were mixed and applied to the skin incision. As a result, the wound is sealed and the pain is alleviated. Also, when applied to the affected area of stomatitis, it no longer oozed out due to food and drink. Example 6 Brain Heart Infusion medium (agar and Brain
A plate was prepared in a shear plate using a medium (medium consisting of Heart Infusion). After dropping 400 ml of the diluted solution of the following bacteria cultured on an agar plate and spreading it evenly over the surface,
Let the surface dry. Mix well No. 1 (A) liquid and (B) liquid of Example 1,
After immersing the opening paper disk in this, the ethanol was evaporated, the disk was placed on a plate, and anaerobic culture was performed for 48 hours. After 48 hours, an antibacterial zone several millimeters wide had formed at the edge of the mouthpaper for all bacteria. Bacteria used Bacteroides gingivalis 381 Actinomyces naeslundii ATCC 12104 Actinomyces viscosus ATCC 15987 Propionibacherium acnes EXC-1 Actinomyces israeli ATCC 12102

Claims (1)

[Scope of Claims] 1 () A polymer having a hydrophobic group and a carboxyl group or an anhydride group; () A polymer selected from the group consisting of an organoaluminum compound, an organosilicon compound, an organozirconium compound, and an organoboron compound. An adhesive film-forming material for biological hard tissue or skin, comprising at least one organometallic compound as a main component. 2. The adhesive film forming material according to claim 1, wherein the polymer is a polymer having a carboxyl group bonded to each adjacent carbon atom, or an anhydride group bonded to the carbon atom. . 3. The adhesive film forming material according to claim 1, wherein the polymer has a molecular weight of 1,000 to 100,000. 4 Hydrophobic groups are present in the polymer body at 40 mol% to 90 mol%
The adhesive film-forming material according to claim 1, comprising: 5. The adhesive film-forming material according to claim 1, wherein the hydrophobic group is at least one group selected from the group consisting of an aryl group, an alkyl group, an alkoxyl group, an acyloxy group, and an alkoxycarbonyl group.