JPH032121B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a novel tooth covering material. For details, (i) Eq.

[Formula] (However, R ¹ is a hydrogen atom or an alkyl group, R ² is an aryl group, an alkyl group, an alkoxy group, an acyloxy group, or an alkoxycarbonyl group) and the formula;

[Formula] (However, R ³ is hydrogen or a carboxymethyl group, n and m are zero or 1, and when n is zero, m is 1 and R ³ is a hydrogen atom, and n is 1 When , m is zero and R ³ is a carboxymethyl group,
This is a tooth covering material whose main components are a polymer containing a polymer unit represented by (two carboxyl groups may form a carboxylic anhydride group) and (ii) an organic titanate compound. In the following description, the following terms will be used to explain the tooth covering material in an easy-to-understand manner. That is, the term "sealing material" refers to a covering material used to seal between a tooth and a restorative alloy, and the term "blocking covering material" refers to a covering material used to seal between a tooth and a solution such as saliva or an etching agent. Alternatively, it refers to a covering material used to block air. Various types of dressings for living body hard tissue or skin have been proposed, and several types of these are commercially available. However, there are not always satisfactory coating materials due to the following deficiencies. For example, amalgam filled in the dental field does not have good margin sealing properties immediately after filling, so copalite is used as a sealing material. However, its sealing properties are not satisfactory. Conventionally, various materials have been known to form a barrier film between hard biological tissues, such as teeth, and etching agents, such as phosphoric acid aqueous solution, citric acid aqueous solution, etc., as proposed in Japanese Patent Publication No. 15519/1983. . However, it is said that an adhesive strength of 100 kg/cm ² or more is required for teeth, especially enamel, and currently, in order to satisfy the above requirements, the enamel is demineralized with an etching agent and the anchor effect is used. There are circumstances that would not be possible without it. For this reason, for example, in the dental field, it has been necessary to pre-treat tooth structure with a highly concentrated etching agent, such as an aqueous phosphoric acid solution, to mechanically create a retention form. Therefore, it has been desired to develop a barrier film forming material that can withstand high concentrations of etching agents. Furthermore, when dentin is exposed on the tooth surface due to a wedge-shaped defect or gingival recession, when cold water or outside air comes into contact with the exposed area, the tooth pulp is stimulated and pain is felt. Similarly, pain occurs when the skin is cut or cut. However, there have been no satisfactory dressings to protect against these pains. The present inventors have been diligently developing tooth covering materials based on the above-mentioned background. As a result, a polymer having a hydrophobic group and at least two carboxyl groups or one carboxylic anhydride group bonded to each other, and the carboxyl group or carboxylic anhydride group is bonded to an adjacent carbon atom, and an organic It was discovered that the coating material made of titanate compounds not only forms a strong and transparent film, but surprisingly, the formed film also has a strong antibacterial effect, and the present invention was completed and proposed here. I came to the conclusion. That is, the present invention provides formula (i),

[Formula] (However, R ¹ is a hydrogen atom or an alkyl group, R ² is an aryl group, an alkyl group, an alkoxy group, an acyloxy group, or an alkoxycarbonyl group) and the formula;

[Formula] (where R ³ is hydrogen or carboxymethyl group,
n and m are numbers of zero or 1, when n is zero, m is 1, R ³ is a hydrogen atom, and n is 1
(in which case m is zero and R ³ is a carboxymethyl group, and the two carboxyl groups may form a carboxylic anhydride group); and (ii) an organic titanate. This is a tooth covering material whose main component is a compound. One of the main components of the tooth covering material of the present invention is a polymer composed of the above-mentioned specific polymer units. It is necessary that the polymer has at least two carboxyl groups or one carboxylic anhydride group bonded to it, and that the carboxyl group or carboxylic anhydride group is bonded to an adjacent carbon atom, such as in the oral cavity. This is to ensure that the adhesive has sufficient adhesion to, for example, tooth structure even under extremely humid conditions and can withstand use. The polymer having a carboxyl group or a carboxylic anhydride group and a hydrophobic group is not particularly limited, and known polymers can be used, but in general, polymers having a molecular weight of 1000 to 1000 are used.
A range of 100,000 is most preferred. Furthermore, the method for obtaining the polymer is not particularly limited, and any known method can be employed. The polymer used in the present invention preferably has an acid value of 30 to 700, particularly 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 carboxylic anhydride groups in the polymer, and if this acid value is lower than the above range, the number of crosslinking points with the organic titanate decreases, resulting in a decrease in the 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 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. That is, (1) Aryl groups such as phenyl group and naphthyl group (2) Alkyl groups such as methyl group, ethyl group, propyl group and butyl group (3) Alkoxy groups such as ethoxy group, propoxy group and butoxy group (4) Acyloxy groups such as acetyloxy groups (5) Alkoxycarbonyl groups such as ethoxycarbonyl groups and butoxycarbonyl groups In addition, hydrophobic groups shown in (1) to (5) above may be substituted with other substitutions as long as the hydrophobic properties are not impaired. It may be substituted with a group. 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, butyl acrylate, etc. are suitable for those having a functional group. The hydrophobic group-introducing monomer preferably used in the present invention has the following general formula: (In the formula, R ¹ is a hydrogen atom or an alkyl group, and R ²
is an aryl group, an alkyl group, an alkoxy group, an acyloxy group or an alkoxycarbonyl group). Further, the carboxyl group or carboxylic anhydride group bonded to the polymer used in the present invention only needs to be bonded to adjacent carbon atoms, regardless of the manufacturing method. Generally, it is suitably produced by the following method. That is, vinyl compounds having two carboxyl groups or carboxylic anhydride groups on adjacent carbon atoms, such as maleic acid, fumaric acid,
itaconic acid, maleic anhydride, itaconic anhydride,
There is a method of producing a polymer by polymerizing or copolymerizing 4-methacryloxyethyl trimellitic acid or its anhydride as a raw material. In addition, other monomers containing as one component a vinyl monomer having an ester of carboxylic acid or a carboxylic acid anhydride on the adjacent carbon atoms, such as maleic anhydride, maleic acid monoester, maleic acid diester, fumaric acid monoester, and fumaric acid diester, may also be used. A copolymer with a polymerizable vinyl monomer is produced, and then a part or all of the carboxylic anhydride group or carboxylic ester group is removed by hydrolyzing the carboxylic anhydride group or carboxylic ester group. A method of converting into a carboxyl group can also be suitably employed. The polymer used in the present invention is generally preferably one having 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. Although the method for obtaining the above-mentioned polymer is not particularly limited, industrially it is possible to obtain a vinyl monomer having a hydrophobic group as described above and a carboxyl group, a carboxylic acid ester group, or an anhydride group on the adjacent carbon atom, respectively. Preferably, a method is employed in which the material is obtained by copolymerizing with a vinyl monomer to which a carboxylic acid group is bonded, or by subsequent hydrolysis. Therefore, the polymer constituting the present invention has (A) the following formula:

[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 or a carboxymethyl group, n and m are zero or 1, and when n 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 a carboxymethyl group, and the two carboxyl groups may form a carboxylic 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. In the polymer, the hydrophobic groups contained in the polymer are present in the molecule at a ratio of 0.7 to 9.0 moles when two carboxyl groups or one carboxylic acid anhydride group are 1 mole. preferable. If the amount of the hydrophobic group exceeds 9.0 moles, it will not be possible to form a film with the tooth. 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 teeth. In addition, polymers containing less than 0.7 moles of hydrophobic groups are generally difficult to produce industrially because there is no good industrial method for imparting carboxyl groups or carboxylic acid anhydride groups, which will be described later. However, the water resistance of the resulting film using the polymer tends to be insufficient. In addition, the method of hydrolyzing the carboxylic acid ester group and carboxylic anhydride group is not particularly limited, but
Generally, a copolymer containing maleic anhydride groups, maleic diesters, fumaric diesters, or itaconic diesters is dissolved in a suitable organic solvent, and water and an acid or alkali component are added as accelerators for the hydrolysis reaction. A preferred method is to add a small amount and react at room temperature or under heating. Another component of the coating material of the present invention is an organic titanate compound. The organic titanate compound is not particularly limited, and known ones can be used.
For example, tetra-iso-propyl titanate, tetra-n-butyl titanate, tetrakis(2-
ethylhexyl) titanate, tetrastearyl titanate, di-iso-propoxy bis(acetylacetone) titanate, di-n-butoxy
Bis(triethanolamine) titanate, dihydroxy bis(lacteiacide) titanate, tetraoctylene glycol titanate, tri-n-butoxymonostearyl titanate, isopropyl tri-iso-stearoyl titanate,
Isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, tetra-iso-propyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl) -1-Butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, and the like are particularly preferably used alone or in combination. Further, polymers of the titanate compounds mentioned above may also be used. In the present invention, the formula In the formula, R ⁴ is an alkyl group, and p is zero or
The number is up to 20. Preference is given to using titanates of the formula, especially tetraalkyl titanates. The coating material of the present invention contains the above polymer and an organic titanate compound as constituent components. The mixing ratio of these main components is not particularly limited as long as the object of the present invention is achieved. In general, it is preferable to select the organic titanate compound so that the amount of the organic titanate compound is in the range of 0.02 mol to 2 mol per mol of the unit having the carboxyl group or carboxylic anhydride group bonded in the polymer. be. Furthermore, in order to use the organic titanate compound used as a component of the coating material of the present invention in a more stable state, it is often preferable to use a stabilizer for the organic titanate compound. In particular, when a solvent is used in the usage form of the coating material of the present invention, it is preferable to use the organic titanate compound stabilizer when using the solvent without removing water content, although it depends on the type of the solvent. The manner in which the coating material of the present invention is used may vary depending on the type of stabilizer. For example, o-alkoxybenzoic acids such as o-methoxybenzoic acid, o-ethoxybenzoic acid, and o-propoxybenzoic acid; β-hydroxycarboxylic acids such as hydroacrylic acid, β-hydroxybutyric acid, and β-hydroxyisovaleric acid are stabilized. When used as an agent, it can be a one-component type product in which the polymer and organic titanate compound are dissolved in a solvent in one packaging container. In addition, as the stabilizer, α-hydroxycarboxylic acids such as lactic acid, α-hydroxy-n-butyric acid, and mandelic acid; α-hydroxyethyl methacrylate,
β-hydroxyalkyl (meth)acrylates such as β-hydroxypropyl acrylate and glycenedimethacrylate; Catechol derivatives such as catechol, guaiacol, and eugenol; Proline derivatives such as proline, 4-methylene-proline, and 4-methyl-proline; β- butyrolactone,
When using cyclic esters such as γ-butyrolactone and β-caprolactone, store the polymer dissolved in the solvent, the organic titanate compound dissolved in the same solvent, and the stabilizer in separate containers, and use. It is preferable to use a two-component type product in which the two are sometimes mixed to form a coating material. 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. Further, the amount of the stabilizer added to the organic titanate compound varies depending on the type of the stabilizer and cannot be absolutely limited, but it is generally in the range of 0.1 mol to 4 mol, preferably 0.5 mol to 2 mol, based on the organic titanate compound. It is suitable if you choose. Further, the stabilizer may be added by being mixed with the organic titanate compound in advance, or may be added to the organic titanate compound together with other components. The coating material of the present invention may use the polymer and the organic titanate compound as a one-component or two-component type. Generally, it may be used by dissolving it in the above-mentioned solvent to a suitable concentration, for example, 1 to 30% by weight. The coating material of the present invention may be used by applying a solution of the above concentration to the tooth to form a film. Since the thickness of the coating varies depending on the field of use, the thickness of the coating may be adjusted as necessary. If a thicker coating is required, the coating material may be applied multiple times. By applying the coating material of the present invention to the tooth surface to form a film, it can completely block etching agents such as phosphoric acid and citric acid at a concentration of 10 to 90%. Of course, it is completely isolated from saliva, cold water, and air.
It is possible to prevent pulp stimulation through the exposed dentin of the tooth due to wedge-shaped defects or gingival recession. Further, the coating material of the present invention can be applied to the tooth to form a coating, and then a restorative alloy such as gold, silver, amalgam, metal alloy, dental inorganic cement, etc. can be further laminated. Although the coating material of the present invention does not have adhesive properties with the restorative alloy or inorganic cement in the above-mentioned usage mode, it exhibits sufficient sealing properties between the tooth and the restorative alloy or inorganic cement. Although the coating material of the present invention can be used in various forms as described above, the coating film and the coating material themselves exhibit excellent antibacterial properties. In particular, the antibacterial action is effective against anaerobic bacteria. Because such an effect is exerted, the coating material of the present invention is suitably used for biological hard tissues (particularly in the field of dentistry). In particular, typical examples of bacteria that have antibacterial effects are as follows. Bacteroides gingivalis 381 Actinomyces naeslundii ATCC 12104 Actinomyces viscosus ATCC 15987 Propionibacterium acnes EXC-1 Actinomyces israeli ATCC 12102 In order to explain the present invention more specifically, the present invention will be described below with reference to Examples. It is not limited. 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 bayzoyl peroxide (hereinafter abbreviated as BPO) were added and thoroughly stirred. Next, the inside of the container was depressurized and replaced with nitrogen, and then heating polymerization was carried out at 80° C. for 4 hours with stirring. After cooling to room temperature, the formed precipitate was filtered. 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, this product was dissolved in 80 ml of dioxane, put into a 500 ml flask, and while stirring thoroughly, a 5% by weight aqueous potassium hydroxide solution was added.
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 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)
Dissolve 10g of (manufactured by) in 200ml of dioxane and 500ml
Pour distilled water into a large capacity flask and stir thoroughly.
10 g was added, 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 was 367. Production Examples 3 to 4 Two types of commercially available styrene-maleic anhydride copolymers with different compositions shown in Table 1 (Alco
Using chemical (manufactured by Arco Chemical),
Hydrolysis was carried out in the same manner as in Production Example 1, 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. Obtained. The molecular weights are 1700 and 1900, respectively, and the acid value is 251.
It was 184.

[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%. By elemental analysis, maleic anhydride 55.6 mol%, propylene 44.4 mol%,
It was hot. 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. 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%.
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. The acid value of this copolymer was 470. 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 resulting precipitate was filtered off. 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 heating and 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. A copolymer of n-octadecyl vinyl ether-maleic acid was similarly obtained from the results of elemental analysis and the measurement results of infrared absorption spectrum after hydrolysis. 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 diethyl fumarate.
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 p-chlorostyrene and maleic anhydride,
Polymerization was carried out under the same conditions as in Production Example 1 using BPO 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,
A vinyl acetate-maleic acid copolymer was obtained from the elemental analysis results of the produced polymer and the measurement results of the infrared absorption spectrum after hydrolysis. The acid value of this polymer is
It 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 resulting copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, a p-chloromethylstyrene-maleic acid copolymer was obtained. I got it. The acid value of this polymer was 301. Example 1 In order to confirm that the barrier film forming material of the present invention has the ability to block phosphoric acid and citric acid aqueous solutions, 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 barrier film forming materials shown in Table 1 were applied to the back surface as barrier materials (backing materials), and nitrogen gas was again blown to remove the solvent. As etching materials, 37% orthophosphoric acid aqueous solution and 10% citric acid aqueous solution were used.
A drop was placed on the barrier material and left alone. In order to detect phosphoric acid and citric 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 phosphoric acid and citric acid aqueous solutions was 15% when no barrier material was used.
The time was 1 minute 10 seconds for the one using Copalite (trade name), and over 10 minutes for the one using Dycal (trade name). 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.

【table】

[Table] 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 sealing materials shown in Table 2 No. 1 to No. 13 and the conventionally used copalite were each thinly applied to the cavity walls, and then the alloys shown in Table 3 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 3 was directly filled without using the above composition, or when Copalite was applied and then filled with the alloy shown in Table 3, intrusion of pigment was observed in all samples. Ta. On the other hand, with respect to the sealing materials No. 1 to No. 13 in Table 2, no penetration of the dye was observed, and good sealing results were obtained.

[Table] Example 3 In order to confirm that the barrier film forming material of the present invention has the ability to block unreacted phosphoric acid in 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, a barrier film forming material shown in Table 4 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 that passes through the above barrier material,
A PH test paper was placed under the membrane filter, and the time when the color changed was determined as the passing 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, whereas it was 10 minutes or more in all cases using the barrier material of the present invention.

【table】

[Table] 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 an ethanol solution of the copolymer obtained in Production Examples 1 to 13 was placed in the cavity as shown in Table 5. After mixing equal amounts of Solution A consisting of the following and Solution B consisting of an ethanol solution of an organic titanate, the mixture was applied. 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 coating 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, staining due to fuchsin was observed on the tooth substance of the blanks to which the coating material of the present invention was not applied, but the teeth to which the coating material of the present invention was applied showed
Good results were obtained in all cases, with no dye penetration observed.

[Table] Example 5 No. 5 in Table 5 was applied to a patient who has a wedge-shaped defect in the tooth neck and feels 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. 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 liquids (A) and (B) of No. 1 in Table 2 of Example 1 well, soak a paper disk in this, evaporate the ethanol, place it on a flat plate, and heat it anaerobically for 48 hours. Culture was carried out. After 48 hours, an antibacterial zone several millimeters wide had formed at the edge of the paper for all bacteria. Bacteria used Bacteroides gingivalis 381 Actinomyces naeslundii ATCC 12104 Actinomyces viscosus ATCC 15987 Propionibacterium acnes EXC-1 Actinomyces israeli ATCC 12102

Claims (1)

[Claims] 1(i) Formula, [Formula] (wherein R ¹ is a hydrogen atom or an alkyl group, and R ² is an aryl group, an alkyl group, an alkoxy group, an acyloxy group, or an alkoxycarbonyl group) A polymerized unit represented by the formula [Formula] (where R ³ is hydrogen or a carboxymethyl group,
n and m are numbers of zero or 1, when n is zero, m is 1, R ³ is a hydrogen atom, and n is 1
(when m is zero, R ³ is a carboxymethyl group, and the two carboxyl groups may form a carboxylic anhydride group), and (ii) an organic titanate. A tooth covering material whose main component is a compound.