JPS6316432B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel adhesive film-forming material. Specifically, (i) a polymer having a carboxyl group, (ii)
organic titanate and (iii) general formula,

[Formula] (where n is 0, 1, 2, 3 or 4, X is an alkyl group, an alkoxy group,
A carboxyl group or an acylalkyl group, R is an alkyl group, a haloaralkyl group, an alkoxyalkyl group, a carboxyalkyl group, a phenoxyalkyl group, an aryl group, an alkoxyaryl group, an acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group , allyl group or benzyl group. ) is an adhesive film-forming material whose main component is the benzoic acid derivative shown below. Conventionally, adhesive film-forming materials, such as adhesives, are known as various compounds specific to the field of use, depending on the field of use. Particularly demanding properties are required for dental adhesives that are used on biological hard tissue, particularly in a wet state. As the dental adhesive, for example, an ionomer cement composed of an aqueous polyacrylic acid solution and an inorganic oxide, and a room temperature curable adhesive using a polymerizable monomer are known. 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. Further, since adhesives are required to have properties specific to each field depending on the field of use, adhesives used in one field are rarely able to be used industrially in other fields. Therefore, suitable adhesives have been developed depending on the field of use. On the other hand, it is known that when an organic titanate is mixed into a solvent in which a polymer having a carboxyl group is dissolved, a crosslinking reaction immediately proceeds, resulting in gelation in a short time or precipitation of a crosslinked cured product. Therefore, it has been considered impossible to mix a polymer having a carboxyl group and an organic titanate and store the mixture in a one-component type. In order to compensate for such deficiencies, attempts have been made to add organic titanate stabilizers to the above system for one-component storage. For example, it has been proposed to use lactic acid, salicylic acid, etc. as the above-mentioned stabilizers, but even if these stabilizers are used, the crosslinking reaction between the polymer having a carboxyl group and the organic titanate cannot be completely prevented. Therefore, it was not possible to store both in a one-component state industrially or as a product. Therefore, the present inventors have conducted repeated research to solve the above drawbacks, and have found that when a compound with a specific structural formula among benzoic acid derivatives is used as a stabilizer for organic titanates, it is possible to store them as a single solution. The present inventors have discovered that a one-component composition can be obtained and have provided the present invention. That is, the present invention provides (i) a polymer having a carboxyl group, (ii) an organic titanate, and (iii) a general formula,

[Formula] (where n is 0, 1, 2, 3, or 4, X is an alkyl group, alkoxy group, carboxyl group, or acylalkyl group, and R is an alkyl group, haloaralkyl group, alkoxyalkyl group, carboxyl group) The main component is a benzoic acid derivative represented by an alkyl group, a phenoxyalkyl group, an aryl group, an alkoxyaryl group, an acyl group, a haloxyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a benzyl group. It is an adhesive film forming material. One of the main components of the adhesive film forming material of the present invention is a polymer having a carboxyl group or a carboxylic anhydride group. The need for the polymer to have carboxyl groups is such that it has sufficient adhesive strength and can withstand use even when used in wet conditions, such as in dental lining materials, dental adhesives, etc. This is to do so. Particularly effective are polymers in which two carboxyl groups are bonded, and moreover, polymers in which two carboxyl groups are bonded to adjacent carbon atoms. Further, in order to impart water resistance to the adhesive film-forming material and impart compatibility with the material to be adhered to, it is more preferable to select a polymer having a hydrophobic group. The carboxyl group-containing polymer is not particularly limited and any known polymer may be used, but in general, those having a molecular weight in the range of 1,000 to 100,000 are most suitable.
Furthermore, the method for obtaining the polymer is not particularly limited, and any known method can be employed. Generally, it is produced by homopolymerizing a vinyl monomer having a carboxyl group or by copolymerizing a copolymerizable vinyl monomer having the functional group with another copolymerizable vinyl monomer, especially a vinyl monomer having a hydrophobic group. The method is preferred. Also preferably employed is a method in which a vinyl monomer having a carboxylic acid ester group is copolymerized with another copolymerizable vinyl monomer, and the carboxylic acid ester group in the resulting copolymer is hydrolyzed to convert it into a carboxyl group. be done. In order to impart adhesive properties to the adhesive film-forming material of the present invention, the amount of carboxyl groups in the polymer is preferably 0.001 mol or more per 1 g of the polymer. The carboxyl group-containing vinyl monomer is not particularly limited and can be used, but the following are examples of those that are generally suitably used. That is, acrylic acid-based vinyl monomers such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, itaconic acid,
Unsaturated dibasic carboxylic acid monomers such as maleic anhydride and itaconic anhydride; aromatic unsaturated carboxylic acid monomers such as 4-methacryloxyethyl trimellitic acid, or substituted derivatives of these vinyl monomers with substituents, etc. is preferably used. Furthermore, the vinyl monomer that can be copolymerized with the vinyl monomer having a carboxyl group or carboxylic acid anhydride is not particularly limited, and known ones can be used.
Typical examples that are generally preferably used include, for example, olefin compounds such as ethylene, propylene, butene, and halogen derivatives of olefin compounds such as vinyl chloride and hexafluoropropylene; diolefin compounds such as butadiene and pentadiene. and its halogen derivatives; aromatic vinyl compounds such as styrene, divinylbenzene, and vinylnaphthalene; vinyl ester compounds such as vinyl acetate; methyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, Acrylic acid amide,
Examples include acrylic acid and methacrylic acid derivatives such as methacrylic acid amide; unsaturated nitrile compounds such as acrylonitrile; and vinyl ether compounds such as methyl vinyl ether. Furthermore, as described above, among the copolymerizable vinyl monomers used as raw materials in the present invention, vinyl monomers having a hydrophobic group are preferably used.
By using a vinyl monomer having a hydrophobic group, the polymer can have the properties of both a hydrophilic group and a hydrophobic group due to carboxyl groups. In this case, as will be described later, the performance can be particularly improved in bonding dissimilar materials such as a material having a hydrophilic surface and a material having a hydrophobic surface. The hydrophobic group is not particularly limited and any known one can be used, but typical hydrophobic groups that are generally preferably used include, for example, aryl groups such as phenyl group and naphthyl group; methyl group, ethyl group, Alkyl groups such as propyl groups; alkoxy groups such as ethoxy groups and butoxy groups; acyloxy groups such as acetyloxy groups; alkoxycarbonyl groups such as ethoxycarbonyl groups and butoxycarbonyl groups. Known vinyl monomers having these functional groups can be used without particular restriction. Specific examples of generally suitable vinyl monomers include styrene, methylstyrene, vinylnaphthalene, propylene, butene, ethyl vinyl ether, butyl vinyl ether, vinyl acetate, ethyl methacrylate, butyl acrylate, and the like. Furthermore, 4-methacryloxyethyl trimellitic acid or its acid anhydride is preferably used as a compound having a carboxyl group and a hydrophobic group in the same molecule. The hydrophobic group derived from the vinyl monomer having a hydrophobic group is preferably contained in the polymer having a carboxyl group in an amount of 40 mol % to 90 mol %. When the hydrophobic group content is less than 40 mol %, the adhesive film forming material of the present invention tends to have insufficient water resistance, especially when used as a dental adhesive.
Moreover, if it exceeds 90 mol%, there is a tendency that adhesive strength with the tooth structure cannot be obtained. The above-mentioned vinyl monomers can be copolymerized singly or in combination of two or more vinyl monomers having a carboxyl group or a carboxylic anhydride group. The method for carrying out the above polymerization is not particularly limited, and any known method may be used, but radical polymerization is particularly preferably used. Generally known polymerization initiators used in radical polymerization are also employed.
For example, organic peroxides such as benzoyl peroxide and lauroyl peroxide; potassium sulfate for peroxo,
Polymerization carried out using a peroxo-sulfate such as ammonium sulfate; an azo compound such as azobisisobutyronitrile; an organometallic compound such as tributylboron, or a redox initiator can be suitably used. These polymerization initiators are effective against monomer components such as unsaturated carboxylic acids, unsaturated carboxylic esters or acid anhydrides, and copolymerizable vinyl monomers.
It is sufficient to use it in a range of 0.01 to 3% by weight. The main component of the adhesive film-forming material of the present invention is an organic titanate. The organic titanate used in the present invention is not particularly limited, and any known organic titanate can be used. For example, tetra-iso-propyl titanate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetrastearyl titanate,
Alkyl titanates such as tri-n-butoxy monostearyl titanate; di-iso-propoxy bis(acetylacetone) titanate, di-n-butoxy bis(triethanolamine)
Titanate, dihydroxy bis(lacteiacide) titanate, tetraoctylene glycol titanate,; isopropyl tri-iso-stearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate,
Tetra-iso-propyl bis(dioctyl phosphite) titanate, trioctyl bis(ditridecyl phosphite) titanate, tetra(2,
2-Diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, etc. are used alone or in combination. Ru. Furthermore, the organic titanate used in the present invention can be sufficiently stored as a one-component type, especially for alkyl titanates such as those represented by the following general formula. That is, the general formula, which is generally considered to have poor storage stability, (However, R is an alkyl group, and n is a number of 0 or up to 20.) It is also sufficiently effective against organic titanates represented by the following formula. The amount of organic titanate used in the adhesive film-forming material of the present invention is not particularly limited, but it is generally added at a ratio of 0.02 mol to 1.0 mol per 1 mol of carboxyl groups of the polymer having carboxyl groups. preferable. The amount of the organic titanate added is
If the amount 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 organic titanate 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. The third component used in the adhesive film forming material of the present invention has the general formula: (However, n is 0, 1, 2, 3, or 4, X is an alkyl group, alkoxy group, carboxyl group, or acylalkyl group, and R is an alkyl group, haloalkyl group, alkoxyalkyl group, carboxyalkyl group, Enoxyalkyl group, aryl group, alkoxyaryl group, acyl group, haloacyl group, acyloxyacyl group, alkoxycarbonyl group,
It is an allyl group or a benzyl group. ) is a benzoic acid derivative represented by At present, it is not clear what kind of reaction mechanism the benzoic acid derivative shown by the above general formula of the present invention uses, and why a polymer having a carboxyl group and an organic titanate can be treated as a one-component type. do not have. However, the following conclusions can be deduced from the results of statistical experiments. That is, the -OR group and the -COOH group in the above general formula need to be located at the ortho position of the benzene ring. It is speculated that this is because titanium forms a coordinate bond between the oxygen atoms of the -OR group and -COOH group, thereby maintaining a stable state of the six-membered corner. However, the above −OR group is −
Even if it is an OH group, even if the hydrogen atom of the -COOH group is substituted with a group at another position, or even if it is a compound that satisfies both of these at the same time, such as salicylic acid, the effects of the present invention cannot be exhibited. . However, as in the above general formula, as long as the -COOH group and -OR group are present in the ortho position, no matter if the hydrogen of the benzene ring is substituted with another substituent (X in the above general formula) or regardless of the number of substituents. Regardless, the effects of the present invention are fully exhibited. From the above results, the effect of the present invention is that the carboxyl group (-
COOH) and the -OR group are present in the ortho position, and when R of the -OR group is not a hydrogen atom, it is presumed that titanium acts selectively to stably hold the titanium. The benzoic acid derivative used in the present invention is not particularly limited as long as it is represented by the above general formula, and any known compound can be used. Generally easy to obtain industrially,
For ease of handling, the alkyl group represented by X or R, such as an alkyl group, an alkoxy group, a haloalkyl group, or a phenoxyalkyl group, represented by the above general formula is a lower alkyl group, such as one having 1 to 4 carbon atoms. The halogen atom of the haloalkyl group or haloacyl group is preferably chlorine, bromine, iodine or fluorine, particularly chlorine or bromine. Furthermore, the phenoxyalkyl group represented by R in the above general formula is preferably a nitrophenoxy group or a carboxyphenoxy group in which the hydrogen atom of the phenoxy group is substituted with a nitro group. Furthermore, the benzoic acid conductor represented by the above general formula, which is industrially easily available, is the following compound. That is, the general formula, (However, X is an integer of 1 to 4, X is an alkyl group,
a benzoic acid derivative represented by an alkoxy group, a carboxyl group, or an acylalkyl group, in which R' is an alkyl group, or a general formula, (However, R″ is an alkyl group, haloalkyl group, alkoxyalkyl group, carboxyalkyl group, phenoxyalkyl group, aryl group, alkoxyaryl group, acyl group, haloacyl group, allyl group, or benzyl group) It is a benzoic acid derivative. More specifically, representative compounds represented by the above general formula of the present invention are exemplified as follows.
That is, representative compounds represented by the general formula () include 2-methyl-6-methoxybenzoic acid;
2,4-dimethyl-6-ethoxybenzoic acid; 2,
3,5-trimethyl-6-methoxybenzoic acid;
2,4,5-trimethyl-3,6-dimethoxybenzoic acid; 3,4-dimethyl-2,6-dimethoxybenzoic acid; orcinoldicarboxylic acid dimethyl ether; olivetonic acid dimethyl ether, and the like. In addition, typical compounds represented by the above general () include 2-methoxybenzoic acid, 2-ethoxybenzoic acid, 2-propoxybenzoic acid, 2-isopropoxybenzoic acid, 2-[β-bromoethoxy]
Benzoic acid 2-methoxymethoxybenzoic acid, phenoxyacetic acid-O-carboxylic acid, α-phenoxypropionic acid-O-carboxylic acid, α-phenoxybutanoic acid-O-carboxylic acid, α-phenoxyisobutanoic acid-O- Carboxylic acid, α-phenoxyvaleric acid, 2-[β-(2-nitrophenoxy)-ethoxy]benzoic acid, 2[β-(4-nitrophenoxy)]
-Ethoxy]benzoic acid, ethylene disalicylic acid,
2-phenoxybenzoic acid, 2-O-cresoxybenzoic acid, 2-m-cresoxybenzoic acid, 2-p-
Cresoxybenzoic acid, 2-(2,4-dimethyl-
phenoxy)benzoic acid, 2-β-naphthyloxybenzoic acid, 2-(2-methoxyphenoxy)benzoic acid, 2-acetoxybenzoic acid, 2-benzoyloxybenzoic acid, 2-trichloroacetoxybenzoic acid, 2-bromoacetoxybenzoic acid acids, 2-tribromoacetoxybenzoic acid, succinyldisalicylic acid, carbomethoxysalicylic acid, carboethoxysalicylic acid, 2-allyloxybenzoic acid, 2-benzyloxybenzoic acid, and the like. One or more of the benzoic acid derivatives used in the present invention may be used together with an organic solvent if necessary. The organic solvent is not particularly limited and any known organic solvent can be used, but it is generally preferable to use one that has a low boiling point and is easy to remove afterwards, for example, organic solvents such as methanol, ethanol, and ethyl acetate are preferably used. Furthermore, the amount of the benzoic acid derivative represented by the above general formula used in the present invention is not particularly limited, and may be determined as appropriate depending on the field of application in which the adhesive film forming material obtained in the present invention is used. 0.1 mol to 4 mol, preferably 0.5 mol to 1 mol of the organic titanate, which is one component of the present invention.
It is preferable to use it in a range of 2 moles. If the benzoic acid derivative is used in a large amount relative to the organic titanate, the operation time when mixing the adhesive film forming material with other mixtures will generally become longer, or the formation of a cured product will occur. It tends to be slower. The carboxyl group-containing polymer, organic titanate, and benzoic acid derivative in the present invention can be stored as one-component type and will not harden for a long period of time. The storage method is not particularly limited, but a method of storing in the presence of an organic solvent is most preferably used. As described above, the organic solvent is not particularly limited, but methanol, ethanol, isopropyl alcohol, ethyl acetate, etc., which generally have a low boiling point and can be easily removed, are preferably used. Further, when the adhesive film forming material of the present invention is dissolved in an organic solvent and used, the concentration of the forming material is not particularly limited, but generally it is in the range of 1 to 30% by weight. It is preferable because it can be used. 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. In addition to the above-mentioned method of storing the adhesive film-forming material as a single solution, there is also a method of storing the three components of the adhesive film-forming material of the present invention separately and mixing the three components at the time of curing. It is also possible to adopt a method in which the materials are mixed and stored, and then a polymer having a carboxyl group is mixed therein at the time of curing. In the adhesive film-forming material of the present invention, a sufficient cured product can be obtained using only the three components, the polymer having a carboxyl group, the organic titanate, and the benzoic acid derivative. It is also possible to improve the strength or adhesive strength of the cured product by curing it in the coexistence of a monomer and an initiator. As the above-mentioned polymerizable vinyl monomer, the copolymerizable vinyl monomers already explained can be used as they are. 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. The amines include N,N'-dimethylaniline, N,N'-dimethyl-P-toluidine, N,N'-dimethylaniline, N,N'-dimethyl-P-toluidine,
-methyl, N'-β-hydroxyethyl-aniline, N,N'-dimethyl-P-(β-hydroxyethyl)-aniline, N,N'-di(β-hydroxylethyl)-P-toluidine, etc. are preferred. used for. 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 and
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 paint base, a coating material for resin or glass, a dental treatment restorative material, and the like. The above-mentioned dental treatment and restorative material refers to a material that is used in tooth treatment and restoration and is applied to the surface of a tooth or a cavity provided in a tooth, and is the most preferred adhesive film-forming material of the present invention. This is an important use. Examples of such materials include tooth adhesives,
Examples include lining materials for protecting the dental pulp, 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 lining materials for pulp protection include calcium hydroxide-based materials and cement, and the dentin is removed from the phosphoric acid etching performed when filling with composite restorative resins and other filling materials. It is used for protection, etc. 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 lining material, it is possible to protect the tooth structure from the phosphoric acid etching solution even though it is a thin film, and it also adheres to the filling material. Demonstrates excellent functionality. 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. This included using a backing material for protection. However, conventional lining materials with thick coatings could not be used because their own compressive strength was a problem. Therefore, when the adhesive film-forming material of the present invention is used as the backing material, since it is a thin film, it does not require much strength on its own, 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 is possible to use the adhesive film forming material of the present invention for purposes other than those described above. For example, it can be used as a shield against external stimuli by removing the material that filled the cavity of a tooth or by applying the adhesive film-forming material of the invention to a wedge-shaped defect in the gum region. be. Above, the functions as a tooth adhesive material, a lining material for protecting the pulp, and a margin sealing material have been explained individually, but since the adhesive film forming material of the present invention has all of these functions, In one case, all of the above functions can be achieved by simply 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. Considering what I was doing,
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. 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 200 ml of cyclohexane into a 500 ml separable glass flask, and add 5.2 ml of styrene to it.
g, 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%, 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, we found that the characteristic absorption (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
It was confirmed that the hydrolysis reaction was progressing almost quantitatively. That is, the white solid obtained above contains 48.4 mol% styrene and maleic
It was confirmed that the copolymer contained 51.6 mol%. Production examples 2 to 3 As a styrene-maleic anhydride copolymer
Using two types of commercially available products (manufactured by Arco Chemical) with different compositions shown in Table 1, hydrolysis was carried out in the same manner as in Production Example 1. From the measurement results of absorption spectra, styrene-maleic acid copolymers having the compositions shown in Table 1 were also obtained.

[Table] Production example 4 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. 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 24.2
I got g. 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. Production Example 5 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%.
This substance contains 47.1mol of isobutene according to elemental analysis.
The copolymer contained 52.9 mol% of maleic anhydride. Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain 20.5% of isobutene-maleic acid copolymer.
I got g. 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. Production Example 6 0.5 g of polymethyl methacrylate and 30 ml of concentrated sulfuric acid were added to a 100 ml Erlenmeyer flask and allowed to stand at room temperature. The polymer was completely dissolved in 2 days and a yellow solution was obtained. When this was poured into a large amount of ice water, polymethacrylic acid precipitated out. This was filtered, thoroughly washed with water, and finally dried to obtain 0.45 g of solid. Elemental analysis of the obtained polymer revealed that 32% of the ester groups were converted to carboxyl groups by hydrolysis. Production example 7 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%.
From the results of elemental analysis, it was found that itaconic acid was 49.0 mol% and styrene was 51.0 mol%. Production example 8 Vinyl chloride and itaconic acid dimethyl ester
Polymerization was carried out at 50° C. for 6 hours using AIBN as an initiator. The polymer was dissolved in benzene and poured into methanol to precipitate it, which was filtered and dried under reduced pressure. The composition of the copolymer was determined by elemental analysis to be vinyl chloride.
41 mol%, and methyl itaconate was 59 mol%. This polymer was hydrolyzed in the same manner as in Production Example 6, and elemental analysis revealed that 28% of the ester groups were converted to carboxyl groups. Production example 9 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 43.5 mol% diethyl fumarate. This polymer was hydrolyzed in the same manner as in Production Example 6, and the elemental analysis showed that 35%
It was found that the ester of was changed to a carboxyl group. Example 1 The storage stability of a mixture of a solution (A) of a polymer having a carboxyl group and a solution (B) containing an organic titanate and a benzoic acid derivative shown in Table 2 was investigated. The test method was as follows. That is, (A) and (B) were prepared with the compositions shown in Table 2, mixed in a glass container, immediately capped, and stored in a constant temperature room at 20°C. Storage stability was then compared and studied with the end point being when the solution gelled or lost its transparency. As a result, no precipitation occurred for more than 12 months, no loss of transparency occurred, and no gelation occurred.

【table】

[Table] Example 2 Solution A consisting of 10 parts by weight of the styrene-maleic anhydride copolymer hydrolyzate obtained in Production Example 1 and 90 parts by weight of ethanol was mixed with solution (B) having the composition shown in Table 3. They were mixed and examined for storage stability. As a result, no precipitate was observed in any of them even after 12 months or more, and they remained transparent and did not form a gel. In Table 3, TBT is an abbreviation for tetra-n-butyl titanate.

【table】

[Table] Comparative Example 1 Storage stability was measured in the same manner as in Example 1, except that the benzoic acid derivative shown in the solution composition column of Table 4B was used instead of the benzoic acid derivative used in Example 1. The results are also listed in Table 4.

【table】

[Table] Application examples The following tests were conducted using the adhesive film forming materials shown in Examples 1 and 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 para-toluidine Milan-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 Milan-treated 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, (A) of the adhesive film forming material
The solution and solution (B) were mixed at a ratio of 1:1 and applied to the dentin surface surrounded by the wax plate, and nitrogen gas was blown to remove 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. Tensilon manufactured by Toyo Baldwin was used for the measurement, and the tensile speed was 10 mm/min. The results obtained are shown in Table 5.

[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, Table 2 of Example 1, No. 1~
After applying a thin layer of the adhesive coating material shown in No. 9 and conventionally used copalite to the cavity wall, cement or amalgam was 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 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. 9 in Table 2 of Example 1, 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 above-mentioned blocking material, a PH test paper was placed under the above-mentioned 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 barrier material was used, and 1 minute and 10 seconds in the case using Copalite (trade name).
In addition, the test time using Dycal (trade name) was 10 minutes or more. On the other hand, when the adhesive film-forming material of the present invention shown in Examples 1 and 2 was used as the barrier material, the permeation time of the phosphoric acid aqueous solution was 10 minutes or more in both cases.

Claims (1)

[Claims] 1 (i) a polymer having a carboxyl group, (ii) an organic titanate, and (iii) a general formula (However, n is 0, 1, 2, 3 or 4, X is an alkyl group, alkoxyl group, carboxyl group or acylalkyl group, and R is an alkyl group, haloalkyl group, alkoxyalkyl group, carboxyalkyl group, phenoxy Formation of an adhesive film based on a benzoic acid derivative represented by an alkyl group, an aryl group, an alkoxyaryl group, an acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a pendyl group. Material. 2. The adhesive film forming material according to claim 1, wherein the polymer having a carboxyl group has a hydrophobic group. 3. The adhesive film forming material according to claim 1, wherein the polymer having carboxyl groups is a polymer having two carboxyl groups (-COOH) bonded to adjacent carbon atoms. 4. The adhesive film forming material according to claim 1, wherein the polymer has a molecular weight of 1,000 to 100,000. 5. The adhesive film forming material according to claim 1, wherein the polymer is a copolymer of a copolymerizable vinyl monomer having a hydrophobic group and a vinyl monomer having a carboxyl group. 6. The adhesive film forming material according to claim 1, wherein the organic titanate is a tetraalkyl titanate. 7 The benzoic acid derivative has the general formula (However, n is an integer of 1 to 4, X is an alkyl group,
The adhesive film-forming material according to claim 1, which is a compound represented by an alkoxy group, a carboxyl group, or an acylalkyl group, and R' is an alkyl group. 8 The benzoic acid derivative has the general formula (However, R″ is an alkyl group, a haloalkyl group, an alkoxyalkyl group, a carboxyalkyl group, a phenoxyalkyl group, an aryl group, an alkoxyaryl group, an acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a benzyl group).