JPS62227957A - Bondable film-forming material - Google Patents

Abstract

PURPOSE:To provide the titled film-forming material having excellent film- forming properties and adhesion to hard tissues of an organism such as inorg. etc., by blending a polymer having carboxyl (anhydride) and hydrophobic groups with Ca(OH)2. CONSTITUTION:A vinyl monomer (a) having carboxyl (anhydride) group and carboxylic ester group attached to neighboring carbon atoms respectively (e.g., maleic anhydride) is copolymerized with 40-90mol% of a vinyl monomer (b) having a hydrophobic group (e.g., styrene) in the presence of a polymn. initiator (e.g., benzoyl peroxide). If desired, the product is hydrolyzed to obtain a polymer (A) having carboxyl (anhydride) and hydrophobic groups, an acid value of 30-700 and an MW of 1,000-100,000. If desired, 1pt.wt. component A is dissolved or suspended in 1-100pts.wt. org. solvent (e.g., ethanol). The component A is blended with Ca (OH)2 in an amount of 0.1-5.0mol per mol of the carboxyl group of the component A or 1/2mol of anhydride group thereof. The components A and B are separately stored and blended with each other when used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an adhesive film-forming material that has adhesive properties to biological hard tissue, particularly teeth, and has film-forming ability.

(Prior Art and Problems to be Solved by the Invention) Conventionally, various compounds unique to IF forming materials are known depending on the field of use. Among these, film-forming materials used for dental treatment are subject to the complexity of the forces applied in the oral cavity, the diversity of adherends, and the need for wet Higashishita and l8-4-? 1k-'?
I/”2&i+lI I T,'Jta l8 1??t SuP )W +self lr N↓
4. Strict properties are required, including that , ^, must not be toxic.

Current film-forming materials for dental treatment can be applied in advance during amalgam filling to improve margin sealing properties after the filling.■ Can be applied in advance when filling with polymeric filling materials. It is often used for the purpose of blocking the phosphoric acid used in etching and the unpolymerized monomer t-pulp remaining after filling.

There are several commercially available products used for this purpose.
These commercially available products still do not fully achieve the above objectives.

On the other hand, JP-A-54-102094 discloses a dental composition comprising a phosphoric acid ester, a reactive polyvalent metal salt, and a resin having a carboxyl group. However, the dental composition shown here is mainly used for root canal filling, temporary filling, or impression, and has adhesive properties that have the adhesive properties and film-forming ability that are the object of the present invention. It could not be used as a film-forming material.

(Means for Solving the Problems) The present inventors have conducted extensive research with the aim of developing an adhesive film-forming material that has both adhesive properties and film-forming ability and can be used satisfactorily for the above-mentioned purposes. I've been piling it up.

As a result, by using a polymer having both a carboxyl group or its anhydride group and a hydrophobic group as a polymer, and using calcium hydroxide as a crosslinking material for the polymer,
The present inventors have discovered that a material can be obtained that exhibits good adhesion and has the ability to form an erodible film, leading to the completion of the present invention.

In the present invention, good adhesion to teeth is achieved only when the polymer has a hydrophobic group in addition to a carboxyl group or its anhydride group. Further, if a compound other than calcium hydroxide is used as a crosslinking material for the polymer, no adhesive property is exhibited at all. It is completely unusual that the adhesive film-forming material targeted by the present invention was obtained for the first time by using calcium hydroxide.

The present invention is an adhesive film-forming material containing (i) a polymer having a carboxyl group or its anhydride group and a hydrophobic group, and (ii) calcium hydroxide gold as a main component.

One of the main components of the adhesive film-forming material of the present invention is a polymer having a carboxyl group or its anhydride group and a hydrophobic group.

The need for the polymer to have a carboxyl group or its anhydride group is for it to have sufficient adhesion to flesh even under moist conditions such as in the oral cavity, and to be durable for use. .

The polymer used in the present invention has a molecular weight of 30 to 700, particularly 4
It is preferable to have an acid value of 0 to 600 in terms of the toughness and water resistance of the resulting coating. In this specification, the acid value refers to the KOf required to neutralize 1 g of resin (
It is defined as the number of da.

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.

The following are examples of those that are generally suitably used. That is, α, β of acrylic/I/acid, methacrylic acid, etc.
Unsaturated monocarboxylic acids; alpha, beta unsaturated dicarzenic acids such as maleic acid, hexamaric acid, itaconic acid, maleic anhydride, itaconic anhydride; hydroxy monocarboxylic acids such as lactic acid, beta-hydroxy-n-butyric acid, citric acid, etc. Carboxylic acids; 7-hydroxy-1,1-cundecanedicargenic acid, 11-hydroxy-1,1-u/7' candicargenic acid, 4-hydroxyethyltrimellitic acid, etc. Phosnic acid and the like are preferably used.

The polymers used in the present invention are particularly preferably those having carboxyl groups bonded to adjacent carbon atoms, or those having anhydride groups bonded to the carbon atoms. Such polymers are generally suitably produced by the following method. In other words, there are two CalT atoms in a Charcoal atom treated as one.
For example, the vinyl monomer 1 can be produced by polymerizing the above-mentioned α,β unsaturated dicarboxylic acid as a raw material. In addition, a vinyl monomer having an ester of carboxylic acid or an anhydride group thereof on each of the adjacent carbon atoms, such as maleic anhydride 1
Shun, maleic acid monoester, maleic acid diester,
By producing a copolymer containing fumaric acid monoester and 7-malic acid diester as one component with another copolymerizable vinyl monomer, and then hydrolyzing the anhydride group or cardefic acid ester group. A method of converting part or all of the anhydride group or cargenic acid ester group into a carboxyl group can also be suitably employed.

Furthermore, in the polymer used in the present invention, a carboxyl group bonded to each adjacent carbon atom, or a part of its anhydride group, which is esterified with a hydroxycarboxylic acid, is also preferably used.

It is important that the polymer of the present invention has a hydrophobic group in addition to the above-mentioned carboxyl group or its anhydride group.

By using a polymer having a hydrophobic group, it is possible to impart both hydrophobic properties to the polymer in addition to hydrophilic properties due to the carboxyl group or its anhydride group. In this case, the performance can be particularly improved in adhesion of dissimilar materials, such as a material with a hydrophilic surface and a material 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 group and naphthyl group (2
) Alkyl groups such as methyl, ethyl, propyl and butyl groups (3) Alkoxy groups such as ethoxy, propoxy and butoxy groups (4) Acyloxy groups such as acetyloxy (5)
The alkoxycarbonyl groups such as ethoxycarbonyl group and ptoxycaratnyl group and the hydrophobic groups shown in (1) to (5) above may be substituted with other substituents as long as the hydrophobic properties are not impaired. These substituents generally include, for example, halodane 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 to produce the polymer of the present invention in many cases. 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, those having the hydrophobic group in (1) above include styrene, halodanated styrene, methylstyrene, halodanated methylstyrene, vinylnaphthalene, etc., and those having the hydrophobic group in (2) above include propylene, Isobutine and the like are preferred. Similarly, examples of those having the hydrophobic group in (3) above include ethyl vinyl ether, n-butyl ether, etc., and examples of those having the hydrophobic group in (4) above include vinyl acetate, and the hydrophobic group in (5) above. Those with a functional group are ethyl methacrylate,
Butyl acrylate and the like are preferred.

The vinyl monomer having a hydrophobic group preferably used in the present invention has the following general formula (where R1 is a hydrogen atom or an alkyl group, R2 is an aryl group, an alkyl group, an alkoxy group, an acyloxy group, or an alkoxycarbonyl group). It is expressed as (al).

In the present invention, among the above-mentioned vinyl monomers having a hydrophobic group, it is preferable to use one having a hydrophobic group as described in (1) above in order to improve the adhesiveness of the resulting adhesive film-forming material. Particularly preferred.

The polymer of the present invention is generally used industrially with a molecular bone of 1.000 to 1 for reasons such as ease of availability or ease of handling.
00,000, preferably 2,000 to 50,000. The method for obtaining the above polymer is not particularly limited, but industrially it is possible to use a vinyl monomer having a hydrophobic group as described above and a vinyl monomer having a Cal I xyl group, especially adjacent carbon atoms. Cal is a xyl group, its anhydride group, Cal? A method of obtaining K by copolymerizing it with a vinyl monomer bonded with a phosphoric acid ester group or by subsequent hydrolysis is preferably employed.

Therefore, suitable polymers include (A) the following formula (wherein R1 is a hydrogen atom or an alkyl group, EL2 is an aryl group,
It is an alkyl group, an alkoxy group, an acyloxy group, or an alkoxycarbonyl group. ) and (B) the following formula (
In the formula, R3 is hydrogen, an alkyl group, or a carboxyl group? It is a oxymethyl group, n and m are numbers of zero or 1, when n is zero, m is 1 and R is a hydrogen atom, and when n is 1, m
is zero, R is hydrogen, 7/I/kyl group or calgeximethyl group, and the two carboxyl groups may form an anhydride group. ) 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, lanocal polymerization carried out using organic peroxides such as benzoyl peroxide and lauroyl peroxide, azo compounds such as azobisisobutyronitrile, organometallic compounds such as tributylboron, or redox initiators can be suitably used. .

Considering the adhesiveness of the resulting adhesive film-forming material, the monoisomer unit having a hydrophobic group represented by formula (A) is found to be contained in the polymer in an amount of 40 mol tf6 to 90 mol t. preferable.

The method for hydrolyzing the ester group or anhydride group of 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 is added to the copolymer containing the ester group or anhydride group. Also suitable is a method in which a small amount of an acid or alkali component is added as a promoter of the hydrolysis reaction and the reaction is carried out at room temperature or under heating.

Another component of the adhesive film forming material of the present invention is calcium hydroxide.

The amount of calcium hydroxide used in the adhesive film-forming material of the present invention is not particularly limited, but considering the adhesiveness and water resistance of the resulting A1-adhesive film-forming material, carboxyl groups or their anhydride groups and hydrophobic groups are Carboxyl group of polymer having 1
It is preferably added in an amount of 0.02 to 10.0 mol, more preferably 0.1 to 5.0 mol, per mol or 1/2 mol of the anhydride group.

Calcium hydroxide, which is one of the components of the present invention, is essential for maintaining the adhesion of the adhesive film-forming material to teeth and water resistance.

Instead of calcium hydroxide, metal hydroxides such as magnesium, strontium, barium, zinc, and aluminum, or calcium oxide, calcium carbonate, calcium sulfate, and calcium acetate.

Calcium compounds such as calcium chloride, calcium phosphate, and calcium methacrylate were used, but none of them showed adhesiveness to tooth structure.

In order to create a uniform and durable film, the adhesive film-forming material of the present invention uses a polymer having a carboxyl group or its anhydride group and a hydrophobic group and calcium hydroxide in separate packages, and at least It is preferable to use the combination by dissolving or suspending it in an organic solvent.

Generally known organic solvents can be used, but ethanol, isopropyl alcohol, acetone, ethyl acetate and the like are preferably used as they are relatively less toxic.

Banzai solvent is 1 to 100 parts by weight per 1 part by weight of the polymer having a carboxyl group or its anhydride group and a hydrophobic group,
Furthermore, it is preferable to use it in a range of 3 to 60 parts.

The adhesive film-forming material of the present invention has extremely good storage stability when stored in separate packaging as described above. Almost no decrease in strength was observed.

In the adhesive film-forming material of the present invention, a sufficient cured film-forming material can be obtained with only two components, calcium hydroxide and a polymer in which Cal has a Φ-sil group or its anhydride group and a hydrophobic group. If necessary, the strength or adhesive force of the cured product can be improved 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 core copolymerizable vinyl monomers, especially acrylic acid and methacrylic acid? The υ conductor is preferably used because it 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 dipenzoi AI peroxide, zolauroyl oxide, and the like are particularly preferably used. The amines include N,N-dimethylaniline, N,N-dimethyl-P-toluidine, N-methyl-N-β-hydroxyethylaniline, N,N-dimethyl-P-(β-
Hydroxyethyl)-aniline, N,N-di(β-hydroxyethyl)-P-)luizone, and the like are preferably used. Furthermore, it is often a preferred embodiment to use co-catalysts, such as metal salts, such as sulfinates or caldates, in addition to the initiators.

The film obtained using the adhesive film-forming material of the present invention is a strong film that exhibits excellent weather resistance, chemical resistance, solvent resistance, and adhesiveness, and also has 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 canker sore, to block air and moisture, thereby blocking irritation. In this case, together with the anti-seedling effect 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 the treatment and restoration of teeth, when filling a tooth cavity with a filling material such as composite repair Lennon, an adhesive is used to bond the tooth substance and the filling material. However, since conventional adhesive materials exhibit almost no adhesion to the tooth structure, it is necessary to demineralize the tooth structure by previously treating the tooth structure with a highly concentrated phosphoric acid aqueous solution and create a mechanical retention form. However, this method uses a highly concentrated phosphoric acid aqueous solution, which has the disadvantage of damaging even healthy tooth structure.Especially when etching dentin, not only is it difficult to expect good adhesion, but also mucous membranes pass through 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. The excellent effect of not causing pulp damage is demonstrated.

Next, as conventional barrier film forming materials, calcium hydroxide-based materials and cement are used.
I) It is used to protect dentin from phosphoric acid etching performed during filling with filling materials such as resin. 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, it is possible to protect the tooth structure from the phosphoric acid etching solution even though it is a thin film, and it can be used as a filling material. It exhibits an excellent adhesion function.

Furthermore, zinc phosphate cement, which is still commonly used to bond 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 m'lfr film formers for protection. However, conventional film-forming materials with thick films cannot be used 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 fillings, composite restorative resins,
It is also possible to improve the edge sealing properties in cement filling, rubber capping, etc. by using the above-mentioned adhesive film forming material.

In addition, tooth and restorative alloys such as gold, gold-palladium alloy,
Platinum-gold alloy, silver-gold alloy, platinum-no J? It can also be used to seal lanoum 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, external stimulation can be caused 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 is also possible to use it as an R@ material.

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, conventionally, it has been necessary to use multiple materials in combination for a single case, which has the disadvantage that the operations become extremely complicated, and that using multiple materials in combination can actually reduce the functions of each other. Considering this, the adhesive film-forming material of the present invention is an extremely useful composition as a dental treatment and restorative material. In particular, when the adhesive film-forming material of the present invention is used as an adhesive for composite restoration and thinning with tooth substance, the xyl group has an affinity for the tooth substance, while the aqueous group has an affinity for the tooth substance. Because it has an affinity for composite repair renon, it shows a remarkable improvement in 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.

Bacteroidea gingivalis
381 Actinomyces naeslun
diI ATCC12104 Actinomyce
s v%5cosus ATCC15987Pr
opionibactarium aenes EX
C-1Actinomyces 1sra*li
ATCC 12102 Furthermore, a compound having pharmacological activity such as a fluorine compound or chlorhexidine can be added to the adhesive film forming material of the present invention.

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 Cyclohexane 200Fnl was placed in a paraple flask with a glass top of 500M capacity, and 5.2 g of styrene was placed in it.
, anhydrous maleic l'124.9. ! i+ and benzoyl peroxide (hereinafter abbreviated as BPO) 0.0
5I was 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, and after cooling to room temperature, the formed precipitate was separated by filtration. The obtained solid is further diluted with benzene 3QQ.
After thoroughly washing with FILJ and drying, a white polymer 8.7
I got 1. The composition of the produced copolymer was determined from elemental analysis of this product, and it was found to be 48.4 mo1% of styrene and 51.6 mo1% of anhydrous maleic GL.

This product was then dissolved in 39 m dioxane and 50 m
The mixture was placed in a flask of 0 m/volume, and while stirring thoroughly, an aqueous potassium hydroxide solution roomJ of 5 weight i4-cents was added, and the mixture was allowed to react at room temperature for 10 hours. Next, concentrated hydrochloric acid was added to neutralize the mixture, and an excess of hydrochloric acid was further 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 a copolymer of 8.09. As a result of measuring the infrared absorption spectrum of this product,
Cal of maleic anhydride has a characteristic absorption (1
850cW1-', 1775m-') completely disappeared, and a new characteristic absorption derived from the nyl group of maleic acid appeared at 1720cW1-1, indicating that the hydrolysis reaction was proceeding almost quantitatively. It could be confirmed. That is,
It was confirmed that the white solid obtained above was a copolymer containing 48.4 mol% of styrene and 51.6 mol% of maleic tR.

Note that the acid value of this polymer was 370.

Production Example 2 Molecule-15 as a styrene-maleic anhydride copolymer
Dissolve 10g of 0000 commercially available product (Mon5ant product) in 200d dioxine,
Pour distilled water into a flask with sufficient capacity and stir thoroughly.
g was added thereto, 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 2 tons of distilled water to precipitate a flocculent white polymer. By washing and drying this polymer, a white solid of 9.81% was obtained.
I got it. 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 3
It was 67.

Production Examples 3 to 4 Two types of commercially available products (alcochemicals (Are
Hydrolysis was carried out in the same manner as in Production Example 1 using the same method as in Production Example 1, and from the elemental analysis results of the raw material copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, the results are shown in Table 1. A styrene-maleic acid copolymer having the following composition was obtained. The molecular weights were 1700 and 1900, respectively, and the phosphoric acid number was 251.184.

Table 1 Production Example 5 35 g of maleic anhydride and 50 M of benzene containing azobisin butyronitrile (hereinafter abbreviated as AIBN) of 90 to 90% were added to a 300 ml pressure-resistant glass container, and the mixture was cooled in a dry ice-methanol bath. While doing so, the contents were purged with nitrogen under reduced pressure, and then purified propylene 129 was added by distillation through a liquefaction meter. Next, at 60℃
After stirring for 6 hours, copolymerization was carried out. 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 shows 55.6 mol of maleic anhydride to 44.6 mol of propylene.
It was 4 mol.

Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain propylene-maleic acid copolymer 2421. 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 Benzene 5 containing 35.7.9 maleic anhydride and 90 m9 AIBN in a pressure-resistant glass container with contents 3Q□++/
Add 0rnl. Isobutyne (12.5.9) was added thereto by distillation through a liquefaction needle, followed by copolymerization 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 isobutyne and 52.9 mol of maleic anhydride.

Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain inbutene-maleic acid copolymer 20.59.

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 was 470. Production Example 7 2001d of benzene was placed in a 5001717 volume λ glass set T4 Rubble 7 flask, and 5.3 Ii of n-butyl vinyl ether, 4.91 Ii of maleic anhydride and AIBN O were added to it. ,051i were added and stirred thoroughly.

Next, after reducing the pressure in the container and purging it with nitrogen, heating polymerization was carried out at 60° C. for 6 hours, and the precipitate formed was filtered off. The composition of the produced copolymer was determined from elemental analysis of this product and was found to be 49.8 mol% of n-butyl vinyl ether and 50.2 mol% of maleic anhydride.

Next, this product was dissolved in 20017+7 dioxane, placed in a 500 M 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 10.19 white solid. By measuring the infrared absorption spectrum of this product, it was found that most of the maleic anhydride groups were maleic 9. It was confirmed that the base had changed. The acid value of the polymer was 375.

Production Example 8 As a copolymer of n-octadecyl vinyl ether-maleic anhydride, Polyscience
Production Example 2 using a product manufactured by Es, Inc.
Hydrolysis was carried out in the same manner as above, and the same n-octadecyl vinyl ether-maleic acid copolymer was obtained from the elemental analysis results of the raw material copolymer and the measurement results of the infrared absorption spectrum after hydrolysis.

The acid value of this polymer was 196.

Production example 9 Itaconic acid 30,9. Styrene 20.9 to dioxa 72
00g, BPO to monomer 0,1
% and polymerization was carried out at 10°C for 5 hours. The obtained primer was added to 1 t of hexane to precipitate it, filtered and dried, and then washed with distilled water to remove unreacted itaconic acid. The yield was 4.2 inches. As a result of elemental analysis, it was found that it was 49.0 mol of itaconic acid and 51.0 mol of styrene.

The acid value of this polymer was 340.

Production Example 10 Using styrene and 7-malic acid noethyl ester (AIBN) as an initiator, polymerization was carried out at 60° C. for 20 hours to obtain a polymer. The composition of the copolymer was found to be 56% styrene based on elemental analysis.
5 molti, fumaric acid diethyl ester 43.5 molti. Next, 30 tJ of concentrated sulfuric acid was added to a 1 OOLL+7 Erlenmeyer flask containing 5Ii of this polymer and allowed to stand 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, it was thoroughly washed with water and finally dried to obtain a solid of 0.459. This j? IJ Mama acid value was 93.

Manufacturing example 11 As a vinyl acetate-maleic anhydride copolymer.

Polysciences, In
c. Hydrolysis was carried out in the same manner as in Production Example 7 using a copolymer made by Co., Ltd., and the vinyl acetate-maleic acid copolymer was determined from the elemental analysis results of the copolymer and the measurement results of the infrared absorption spectrum after hydrolysis. A polymer was obtained. The acid value of this polymer was 399.

Production example 12 p-10 rostilent maleic anhydride (Q't BPO
Polymerization was carried out under the same conditions as in Production Example 1 using the compound as an initiator. From the results of elemental analysis of the obtained copolymer, p-10
Rostyrene 47.9rno1%, maleic anhydride 52.
It was 1mo1%. 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 Polymerization was carried out under the same conditions as Production Example 1 using p-chloromethylstyrene and maleic anhydride (BPO) as initiators. From the results of elemental analysis of the obtained copolymer, it was found that 48.9 mol of p-chloromethylstyrene and 1 mol of maleic anhydride were present.
It was 51.1 nol%.

Next, this product was hydrolyzed in the same manner as in Production Example 7, and p-chloromethylstyrene-maleic acid o A co-a combination was obtained.

The acid value of this polymer was 301.

Production Example 14 Zoethyl malonate 33.8, 9. Ethanol 150mJ
was added, and 4.85 g of metallic sodium was added while cooling with ice, followed by stirring until a homogeneous solution was obtained. followed by 10-bromo-1 decanol 50. After dropping OI using a dropping funnel, the mixture was heated at 80° C. for 3 hours.

The above solution was transferred to a 50% (1/2) eggplant flask, and the ethanol was distilled under reduced pressure.Next, the 20 wt% Nao■ solution was
201d and heated at 100° C. for 2 hours, 130M of 6N hydrochloric acid was added dropwise to bring the − of the solution to about 2. The obtained solid was rinsed with water through a glass filter, then dissolved in acetone and dehydrated with anhydrous sodium sulfate and anhydrous magnesium sulfate. Subsequently, acetone was distilled off under reduced pressure at room temperature, and 3
A viscous white solid of 5.6.51 was obtained.

It was confirmed from the infrared absorption spectrum of the product and f(-NMrt) that it was a hydroxycarboxylic acid represented by the following formula.

Next, 10 g of the commercially available styrene-maleic anhydride copolymer shown in Production Example 2 was dissolved in 100 g of pyridine.
13 g of the above hydroxycarboxylic acid was added and refluxed for 10 hours. Then, 10 g of distilled water was added, and the mixture was further refluxed for 5 hours.

The obtained reaction solution was diluted by adding the same amount of acetone, and the polymer was separated by adding it little by little to acetic acid prepared to be slightly acidic.

From the infrared absorption spectrum of the obtained polymer, it was confirmed that 30 moles of acid anhydride groups reacted with the hydroxycarboxylic acid, and the remaining acid anhydride groups reacted with water to become calyjr xyl groups.

The acid value of this polymer was 314.

Production Example 15 The following hydroxycarboxylic acid was obtained by carrying out the same operation as in Production Example 14, except that the following compound was used as a raw material.

Production Example 1 except that the following K, the above hydroxycarboxylic acid was used
Performing the same operation as in 4, 40 moles of acid anhydride groups react with the above hydroxycarboxylic acid, and the remaining acid anhydride groups react with water to form carboxylic acid. It was confirmed that it became phosphoric acid.

The acid value of this polymer was 332.

Example 1 The following test was conducted using the adhesive film forming materials shown in Table 2.

(1) Adhesion to dentin (2) Marginal sealability for cavities (3) Blocking property against phosphoric acid water bath solution Evaluation of the above tests was conducted in the following manner.

゛First, paste (1) and paste according to the following recipe)
(10 was prepared.

(1) Adhesiveness to dentin Glue the labial surface of a freshly extracted tooth with emery tape (S32
0) to expose the smooth dentin, and then polish the polished surface with 3
After washing with water for 0 seconds, air was blown to dry the surface.

A wax plate with a thickness of 2 cm and a hole of 4 m in diameter 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 surrounded by plate-shaped wax, and air was blown onto the dentin surface. Blow off the ethanol and excess adhesive.

On top of this, the bases (1) and (n) were mixed at a ratio of 1:1 and filled. After being left for one hour, the plate-like wax was removed, and after being immersed in water at 37°C for a day and night, the tensile strength was measured. For the measurement, Tensilon manufactured by Toyo Baldwin was used, and the tensile rate was 101/min. The results obtained are shown in Table 2.

Thereafter, 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 with margin sealing for the white (2) cavity. Next, using the adhesive film-forming materials shown in Table 2 and a conventionally available commercially available product (Kono 4 Light) for comparison, each was applied to the wall of the cavity, and then filled with cement or amalgam. 1 hour after filling, store in water at 37℃,
One day later, a collation test was performed by dipping the sample in an aqueous solution of Tsukusin at 4° C. and 60° C. 60 times for 1 minute each alternately to test the margin sealing property.

The extracted tooth was then cut in the middle and examined for the presence of pigment (7cusin) intrusion 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 composition, or when Kono or Light was applied 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 Todoroki 1620 in Table 2, no penetration of the dye was observed in any of them, 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, as a shielding material (mounting material), commercially available Cor-Glite was used.
Dical and the adhesive film forming material used in Example 1 were applied to the back surface, and air was blown again to remove the solvent. A phosphoric acid aqueous solution (37 thiol) was used, and one drop was dropped on the barrier material and allowed to stand.

In order to detect phosphoric acid passing through the adhesive film-forming material, a 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 a product that did not use any shielding material, and Copalite (trade name)
It took 1 minute and 10 seconds for the one that used DAIKAL (trade name), and more than 10 minutes for the one that used DICAL (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.

Example 2 A cavity with a diameter of 3 m and a depth of 2 m 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 respectively applied to the wet wall, and then the alloys shown in Table 3 were respectively filled. One hour after filling, it was stored in water at 37°C, and after one day it was heated to 4°C and 60°C.
The percolasi W/test was conducted in which the sample was alternately immersed in an aqueous solution of Tsukusin at 1 minute each time 60 times to test the margin sealing property.

The extracted tooth was then sectioned down the center to examine whether there was any pigment (tsuksin) intruding between the cavity and the filling.

The reproducibility of the above tests was confirmed using five samples for each class 18i experiment. As a result, when the alloy shown in Table 3 was directly filled without using the above composition,
Alternatively, for those coated with copalite and then filled with the alloy shown in Table 3, intrusion of the pigment was observed in all samples.

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 3 Example 3 In order to confirm that the adhesive film forming material of the present invention has the ability to block unreacted phosphoric acid of zinc phosphate cement, 1.
The test was conducted using the following method.

First, a membrane filter with a pore size of 3μ was soaked in distilled water for 1 hour, taken out, and dried by blowing air onto the surface.

Next, the adhesive film forming material shown in Table 2 was applied to the surface as a barrier material, and the solvent was removed by blowing air again.

In addition, as a commercially available zinc phosphate cement, Eri) 100
After mixing according to the recipe, place it on top of the barrier material,
A glass plate was placed on it and a load of 100F was applied to it.

In order to detect phosphoric acid passing through the adhesive film-forming material, a 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, whereas the permeation time for the phosphoric acid solution using the adhesive film-forming material of the present invention was more than 10 minutes. there were.

Example 4 A cavity with a diameter of 3 cm and a depth of 2 tm 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 air, and the cavity was filled with an aqueous solution of 7Xin, and stored in a constant temperature room at 37° C. and 100% humidity for one day. 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 fuchsia/aqueous solution had penetrated into the tooth structure. As a result, when the blank was not coated with the adhesive film-forming material of the present invention, l! 1. Coloration due to tsukushin was observed, but no penetration of pigment was observed in any of the samples coated with the adhesive film-forming material of the present invention, and good results were obtained.

Example 5 For a patient who had a bowl-shaped defect on the tooth neck and felt pain when exposed to air or cold water, solutions A and B shown in AIK in Table 2 were mixed and applied to the wedge-shaped defect. , pain from contact with air and cold water was eliminated.

In addition, the &2 [Co., Ltd.] solution of Example 1 and solution (B) 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 alone.

Example 6 Brain Heart Infection
A flat plate was prepared in a petri dish using Heart Infusion medium (a medium consisting of agar and plain infusion). A diluted solution of the following bacteria cultured on an agar plate was dropped by 400ml and spread uniformly over the surface, and then the surface was dried.

The solid liquid of A1 of Example 1 and the liquid (B) were thoroughly mixed, and a disc of opening paper was soaked in the mixture. After evaporating the ethanol, the mixture was placed on a flat plate and anaerobically cultured for 48 hours.

After 48 hours, an antibacterial zone several inches wide had formed at the edge of the mouthpaper for all bacteria.

Bacteria used: Bacteroides gingivalls
381 Aetinomyeesnaeslundi
i ATCC12104Actlnomies v
iseosus ATCC15987Propio
nibaeterium acnes EXC-
1Actlnomiess 1araeli AT
CC12102 Example 7 Liquid and liquid of the adhesive film forming material of the present invention shown in Table 2
B) Solutions were packaged separately and stored at 37°C.

The storage stability was evaluated using the same method as in Example 1, with the end point being when the adhesive strength to dentin was extremely reduced.

As a result, the adhesive strength of all adhesive film-forming materials after storage for one year or more was only reduced by 1 to 4 k$/cm2.

Comparative Example 1 A 10% ethanol solution of the hydrolyzate of the styrene-maleic anhydride copolymer of Production Example 2 as a polymer having a carboxyl group and a hydrophobic group, and a solution other than calcium hydroxide shown in Table 4 were used. Example 1 about adhesion to dentin when equal amounts of crosslinking agent (ethanol solution) were mixed
It was measured in the same way.

The results are shown in Table 4.

Below is a blank table 4 Comparative Example 2 (Water resistance of coating) Hydrolysis product 1 of styrene-maleic anhydride copolymer of Production Example 2 as a polymer having a xyl group and a hydrophobic group
A 0% ethanol solution (A) and a 6% ethanol solution (B) of the hydroxide, metal oxide, or calcium compound shown in Table 5 were prepared.

Next, the labial surface of the freshly extracted natural tooth was coated with emery (-, 41-
($320) to expose smooth dentin, the polished surface was washed with water for 30 seconds, and then air was blown to dry the surface. Subsequently, the solution (A) and the cutting solution were mixed at a ratio of 1:1 and applied to the dentin surface, and then air was blown to blow off the solvent.

The raw teeth covered with this film were stored in distilled water at 37°C, and the state of the film was observed every 10 minutes.

The results are shown in Table 5.

Comparative Example 3 A polymer having no hydrophobic group was applied to dentin in the same manner as in Example 1, using the ethanol solution mixture of the transverse coalescence shown in Table 6 and a 6% ethanol solution of calcium hydroxide (B). Adhesive strength was measured.

The results are shown in Table 6.

Table 5

Claims (1)

[Claims] (1) An adhesive film-forming material containing (i) a polymer having a carboxyl group or its anhydride group and a hydrophobic group, and (ii) calcium hydroxide as a main component.