JPS60135469A - Bondable film-forming material - Google Patents

Abstract

PURPOSE:To provide a bondable film-forming material which can be bonded to ebur dentis or dental fillers without any chemical pretreatments, consisting mainly of a carboxyl group-contg. high-molecular material, an organometallic compd. and proline. CONSTITUTION:A bondable film-forming material consists mainly of a high-molecular material (A) contg. carboxyl groups or its anhydride groups, at least one organometallic compd. (B) selected from an organotitanium compd., an organoaluminum compd., an organosilicon compd., an organozirconium compd. and an organoboron compd. (e.g. tetra-isopropyl titanate and tetraethyl silicate) and at least one proline (C) selected from the compds. of formulas I , II and III (wherein R1 is, H, alkyl, OH, alkylol, NH2; R2 is H, alkyl; R3 is O, methylene). The material can be bonded to ebur dentis or dental fillers which are artificial materials without any chemical pretreatments such as phosphate etching, and hence, it is useful as a restorative dental material.

Description

[Detailed description of the invention] The present invention relates to a novel adhesive film-forming material.

In detail, (1) (i) a polymer having a carboxyl group or its anhydride group, (ii) an organic titanium compound, an organic aluminum compound,
At least one organometallic compound selected from the group consisting of organosilicon compounds, organozirconium compounds, and organoboron compounds, and (iii > General formula (wherein R1 is a group consisting of an alkyl group, a hydroxy group, and an alkylol group) (wherein R2 is a hydrogen atom or an alkyl group, and R3 is an oxygen atom or a methylene group). It is a sexual film forming material.

Conventionally, adhesive film-forming materials such as adhesives have been 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 in biological hard tissue, especially in wet conditions. 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 1 has a bonding point with the tooth structure, it does not have a bonding point with other dental fillings [i+], and has low water resistance, so it has the drawback of being easily dislodged in water. Adhesives using Ic 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-strength phosphoric acid aqueous solution and create a mechanical retention form. However, this method has the disadvantage that it uses highly concentrated phosphoric acid, which can damage even healthy tooth structure.

Furthermore, since adhesives are required to have properties unique to each field of use, it is unlikely that adhesives used in one field can be used industrially in other fields. Therefore, suitable adhesives have been developed depending on the field of use.

Therefore, the present inventors have conducted extensive research on adhesive film-forming materials that adhere to tooth structure without any chemical pretreatment such as phosphoric acid treatment, and that also have adhesive properties with dental filling materials, which are artificial materials. As a result of repeated efforts, we have been able to provide the present invention.

That is, the present invention provides a polymer selected from the group consisting of (i) a polymer having a carboxyl group or its anhydride group, (ii) an organotitanium compound, an organoaluminium compound, an organosilicon compound, an organozirconium compound, and an organoboron compound. at least one organometallic compound, (iii) general formula, (wherein R1 is a group C selected from the group consisting of an alkyl group, a hydroxy group, an alkylol group, and an amino group, and R2 is a hydrogen atom or an alkyl group) (R3 is an oxygen atom or a methylene group).

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. The need for the polymer to have a carboxyl group or its anhydride group is such that it has sufficient adhesive strength even when used in a wet state, such as in dental linings, dental adhesives, etc. This is to make it durable. Particularly effective are polymers in which at least two carboxyl groups or their anhydride 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 polymer having the carboxyl group or its anhydride group is not particularly limited, and any known polymer may be used, but it generally has a molecular weight of 1,000 to 1,000 to 1,000.

A range of O is most preferred. Furthermore, the method for obtaining the polymer is not particularly limited, and any known method can be employed. Generally, a vinyl monomer having a carboxyl group or its anhydride group is homopolymerized, or a copolymerizable vinyl monomer having the functional group and another copolymerizable vinyl monomer, particularly a vinyl monomer having a hydrophobic group, are used. A method of manufacturing by copolymerization is preferred. In addition, a method of copolymerizing a vinyl monomer having a carboxylic acid ester group with another copolymerizable vinyl monomer and hydrolyzing the carboxylic acid ester group of the obtained polymer to convert it into a carboxyl group is also suitable. Adopted.

The polymer used in the present invention is 30 to 7O0°, especially 4O
It is also important to have an acid value of between 600 and 600. In this specification, the acid value is KO required to neutralize 1 g of resin.
It is defined as the ll1g number of I. This acid value represents the concentration of carboxyl groups and their anhydride groups in the polymer, and if this acid value is lower than the above range, hard tissue,
In particular, there is a tendency for the toughness of the coating to decrease due to a decrease in adhesion to the tooth structure and a decrease in the number of crosslinking points with the organometallic compound. On the other hand, if this acid value is larger than the above range, the film formed from the polymer will become excessively hydrophilic,
The coating tends to lose its water resistance. Polymers having acid values within the above-mentioned ranges are particularly suitable for use as dental adhesive film-forming materials.

The vinyl monomer having a carboxyl group or its anhydride group is not particularly limited and can be used, but the following are examples of those that are generally preferably used. That is, acrylic acid-based vinyl monomers such as acrylic acid and methacrylic acid, and maleic acid.

Unsaturated dibasic carboxylic acid monomers such as fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride; Aromatic unsaturated carboxylic acid monomers such as 4-methacryloxyethyl trimellitic acid.

Alternatively, substituted derivatives obtained by substituting Mk groups on these vinyl monomers are preferably used.

Furthermore, the vinyl monomer that can be copolymerized with the vinyl monomer having a carboxyl group or its anhydride group 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 vinyl chloride.

Halogen derivatives of olefin compounds such as hexafluoropropylene; diolefin compounds and their halogen derivatives such as butadiene and pentadiene; aromatic vinyl compounds such as styrene-2-divinylbenzene and vinylnaphthalene; vinyl ester compounds such as donyl acetate; acrylic acid Acrylic acid and methacrylic acid derivatives such as methyl, ethyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, acrylamide, methacrylic acid amide; unsaturated nitrile compounds such as acrylonitrile;
Examples include 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 monomer having a hydrophobic group, the polymer can have both hydrophobic properties and hydrophilic properties due to carboxyl groups or their anhydride groups. In this case, as will be described later, the performance of -C 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 is not particularly limited and any known hydrophobic group can be used, but representative examples of hydrophobic groups that are generally preferably used include, for example, a nor-J-ol group.

Aryl groups such as naphthyl groups; alkyl groups such as methyl, ethyl and propyl groups; ethoxy groups.

Alkoxy groups such as butoxy groups; acyl A-goxy groups such as acetyloxy groups; ethoxycarbonyl groups.

There are alkoxycarbonyl groups such as butoxycarbonyl group.

As the vinyl monomers forming these functional groups, known ones can be used without particular restriction. Specific examples of generally suitable vinyl monomers include styrene, methylstyrene, vinylnaphthalene, propylene, butene, and ethyl vinyl ether.

These include butyl vinyl ether, vinyl acetate, ethyl methacrylate, butyl acrylic liquor, etc.

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 or its anhydride 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 also be copolymerized singly or in combination of two or more vinyl monomers having a carboxyl group or anhydride group thereof. 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 peroxodisulfate, peroxo2
Polymerization carried out using a beroxodisulfate such as ammonium sulfate; an azo compound such as azobisisobutyronitrile; an organometallic compound such as tributyl tributene, or a redox initiator can be suitably used.

These polymerization initiators should be used in an amount of 0.01 to 3% by weight based on monomer components such as unsaturated carboxylic acids, unsaturated carboxylic esters or acid anhydrides, and copolymerizable vinyl monomers. It is sufficient.

Another main component of the adhesive film forming material of the present invention is at least one organic compound selected from the group consisting of an organic titanium compound, an organic aluminum compound, an organic silicon compound, an organic zirconium compound, and an organic boron compound. It is a metal compound.

The organometallic compounds used in the present invention are not particularly limited as long as they are listed above, and known compounds can be used, and they can be used alone or in combination.

Examples of organic titanium compounds include alkyl titanates such as tetra-1so-propyl titanate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetrastearyl titanate, and tri-n-butoxymonostearyl titanate. −
1] Boxy bis(acetylacetone) titanate.

Di-n-butoxy bis(triethanolamine) titanate, dihydroxy bis(raftiquacid) titanate, tetraoctylene glycol titanate,; isopropyl 1-so 1s0-stearoyl titanate,
Isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetra-1so-propyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2
,2-diallyloxymethyl-1-butyl)bis(di-
1-lysosyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) dilentitanate, etc. are used alone or in combination. Further, as the organic titanium compound of the present invention, alkyl titanates represented by the following general formula are particularly preferably used.

OROR (where R is an alkyl group and n is O or a number up to 20). In particular, when a tetraalkyl titanate is used, the storage stability effect of the adhesive film forming material of the present invention is remarkable.

Examples of organic silicon compounds include alkyl silicates such as tetra-1-tyl silicate and tetrabutyl silicate; vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercap Alkyl silicates partially substituted with other substituents, such as 1-hepropyltrimethoxysilane, are used alone or in combination. In particular, when alkyl silicates are used, the effects of the present invention are significantly exhibited.

Examples of organoaluminum compounds include aluminum isopropylate, aluminum butyrate, and aluminum 5ec-butyrate.

Aluminum alkylates such as aluminum isobutyrate and aluminum-t-butyrate are preferably used alone or in combination.

Examples of organic zirconium compounds include tetramethylzirconate and tetraethylzirconate.

Tetra-1-propyl zirconate, tetra-5ea-
Alkyl zirconates such as butyl zirconate, tetra-n-butyl zirconate, and tetra-1-butyl zirconate are preferably used alone or in combination.

As organic boron compounds, boric acid alkyl esters such as boric acid trimethyl ester, boric acid triethyl ester, boric acid tri-i-propyl ester, boric acid tri-butyl ester, boric acid tri-stearyl ester; boric acid triphenyl ester , boric acid tree 0-
Boric acid aryl esters such as tolyl ester are preferably used alone or in combination.

The amount of the organometallic compound used in the adhesive film-forming material of the present invention is not particularly limited, but is generally 0.00000000000 per 1 mole of the carboxyl group or anhydrous group of the polymer having a carboxyl group or its anhydride group. It is preferable to add it in a proportion of 0.02 to 1.0 mol. If the amount of the organometallic compound added is less than 0.102 moles, the water resistance of the adhesive film-forming material may decrease, and the field of use may be restricted.

Furthermore, if the amount of the organometallic compound added exceeds 1.0 mol, the length of 1 m during curing may become too short, resulting in a decrease in operability, which may limit the field of use.

Therefore, it is preferable that each addition ratio in the present invention is 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 (wherein R1 is a group selected from the group consisting of an alkyl group, a hydroxyl group, an alkylol group, and an amino group, and R2
is a hydrogen atom or an alkyl group, and R1 is an oxygen atom or a methylene group. This is an adhesive film-forming material whose main component is at least one type of proline selected from the group consisting of: .

The prolines used in the present invention are not particularly limited as long as they are represented by the above general formula, and known compounds can be used.

Particularly, the alkyl group and 7-fluoryl group in the above formula preferably have 1 to 8 carbon atoms because of easy availability. In particular, alkyl groups include those having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl groups; 1 to 2 are preferred.

More specific examples of typical compounds represented by the above general formula of the present invention are as follows.

Proline, cis-3-aminoproline, 4-ke1~prolJ7. l-, d-, dl-allo-hydroxyproline, 3-hydroxyproline, 4-hydroxymethylproline, 4-human I]xyN-methylproline, exo-3,4-methanoproline, 4-methylbroline, N~ Examples include methylproline, 4-methyleneproline, 4-ke1-5-methylproline, and the like.

One or more of the prolines 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 in general it is preferable to use one that has a low boiling point and can be easily removed later, such as methanol.

Organic solvents such as ethanol and ethyl acetate are preferably used. Further, the amount of the prolines represented by the general formula used in the present invention is not particularly limited, and may be appropriately determined depending on the field of use in which the adhesive film forming material obtained in the present invention is used. In general, it is suitable if the amount is used in the range of 0.1 mol to 4 mol, preferably 0.5 mol-2'E, per 1 mol of the organometallic compound which is one of the components of the present invention. When using a large amount of prolines relative to the organometallic compound, the operating time when mixing the adhesive film-forming material with other mixtures is generally shortened, and the formation of a cured product is reduced. It tends to be slower. 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. In addition, when the adhesive film forming material of the present invention is dissolved in an organic solvent and used, the 21 degree 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 as a coating. When used together with the above solvent, the curing reaction begins by evaporating the solvent after coating, making it easy to use at room temperature.

In the adhesive film-forming material of the present invention, a sufficient cured product can be obtained using only the three components of the above-mentioned polymer having a carboxyl group or its anhydride group, the organometallic compound, and the above-mentioned prolines. It is also possible to improve the strength or adhesive strength of the cured product by curing it in the coexistence of a polymerizable vinyl monomer and an initiator.

As the above-mentioned polymerizable vinyl monomer, the copolymerizable vinyl monomers already described 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.

In addition, as amines, N, Nl-dimethyl, phosphorus, N,
Nl-dimethyl-P-toluidine.

N-methyl Nl-β-hydroxyethyl-aniline,
N,Nl-dimethyl-P-(β-hydroxyethyl)-
Aniline, N, Nl-di(β-hydroxyethyl)-P
-t-luidine and the like are preferably used. 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.

By using prolines, the adhesive film-forming material of the present invention not only makes it possible to preserve organic metals that easily react with moisture in the air or solvent for a long period of time, but also By adjusting the amount of prolines added, it became possible to control the operation time according to the conditions. Furthermore, the resulting film is a tough 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 paint base, a resin or glass coating material, a dental treatment and 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 adhesive materials for teeth, lining materials for protecting dental pulp, and materials for sealing the margins of teeth and MA materials.

The case where the adhesive film-forming material of the present invention is used as dental treatment restoration I will be explained below.

BACKGROUND ART Conventionally, in dental treatment and restoration, when filling a tooth cavity 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 adhesive materials exhibit almost no adhesion to the tooth structure, it was necessary to demineralize the tooth structure by pre-treating the tooth structure with a high-il 1 degree 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.In particular, when etching dentin, not only is it not possible to expect much adhesive strength, but it also penetrates into the pulp through the dentinal tubules. There is a possibility that the phosphoric acid aqueous solution will affect the product. In addition, since the above-mentioned method inevitably leaves unreacted monomers, there is a risk that this monomer 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 pre-treatment with the phosphoric acid aqueous solution, and since the cured product itself is originally a polymer, there is no unreacted monomer. It has the excellent effect of not causing any damage to the dental pulp.

Next, as conventional lining materials for protecting the pulp, calcium hydroxide-based materials and cement 1~ have been used. It is used to protect the 2nd quality. 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 can also be bonded to the filling material. It exhibits excellent functions.

Furthermore, zinc monophosphate cement, which is still commonly used for adhesion between metal and tooth structure, contains a large amount of phosphoric acid in its composition, which may cause damage to the pulp. It has been desired to use a lining material to protect /C0.However, conventional lining materials with thick coatings have been unable to be used because their own compressive strength poses problems.

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.

Known substances that are expected to have the above-mentioned functions include, for example, resins such as Tuparite dissolved in organic solvents, which are used in amalgam filling. 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 by using the above-mentioned adhesive film forming material in cement filling, rubber coating, etc.

It is possible to use the adhesive film forming material of the present invention for purposes other than those described above. For example, the adhesive film-forming material of the present invention can be applied to areas where dentin is exposed on the tooth surface due to removal of the material filling the cavity of the tooth or a horizontal defect in the tooth cavity. In some cases, it can also be used as a shielding material against external stimuli.

The functions as a tooth adhesive material, a lining material for protecting the dental pulp, and a marginal chain material have been individually explained above, but 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, conventionally, in a single case, it was necessary to use multiple materials in combination, making the operation extremely complicated, and using multiple materials in combination resulted in a deterioration in 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.

When the adhesive film-forming material of the present invention is used as a dental treatment restorative material, the polymer having a carboxyl group or its anhydride 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 the function as the above-mentioned dental treatment restorative material. This is effective in imparting water resistance because the oral cavity is under severe conditions of 100% humidity. In addition, 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 or its anhydride group has an affinity for the tooth substance, and on the other hand, it has an aqueous property. Because the base has an affinity for composite repair resins, the adhesive strength is significantly improved compared to conventional adhesives.

Furthermore, the adhesive film-forming material of the present invention has an antibacterial effect, and its effect is seen against anaerobic bacteria.

The adhesive film forming material of the present invention has an antibacterial effect against, for example, the following bacteria.

Bacteroides gingivalis 38
1A ctinoIllyces naeslundi
1ATCC12104 A C1inoC11no viscosusATCC
15987 propionibacterium acnes
E X C-1A ct+nomyces 1srae
liATCC12102 Furthermore, since the adhesive film-forming material of the present invention has the property of adhering to the skin and mucous membranes, in combination with the above-mentioned antibacterial effect, it can be applied to the cut site to sterilize and sterilize the affected area. can be protected. Furthermore, it is also possible to further add a pharmacologically active compound such as a fluorine compound or chlorhexidine to the adhesive film-forming material of the present invention.

EXAMPLES In order to explain the present invention more specifically, examples will be described below, but the present invention is not limited to these examples.

Manufacturing example 1 500n+J! Put 200 m of cyclohexane into a large glass separable flask, and add 5 m of styrene to it.
2 (1, 4.9 g of 7-leic acid anhydride and benzoyl peroxide (hereinafter abbreviated as BPO) O,05!J were added and stirred thoroughly.

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 while stirring, and after cooling to room temperature, the formed precipitate was filtered. The obtained solid was further diluted with 300 ml of benzene.
8.7 g of re-dried white polymer thoroughly washed with
I got it. As a result of elemental analysis of this product, the composition of the produced copolymer was determined to be 48.4 mo% of styrene, anhydrous maleic M.
It was 51.5IIlono.

Next, this product was dissolved in 80 μl of dioxane, placed in a 500 μm flask, and while thoroughly stirred, 700 μl of a 5% by weight aqueous potassium hydroxide solution was added.
1 was added and reacted with 10 FR vortex. Next, S 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 and washed repeatedly with water until it became neutral.
Further drying yielded a copolymer of 8.0(I).

As a result of measuring the infrared absorption spectrum of this product, it was found that the characteristic absorption derived from the carbonyl group of maleic anhydride (185
0clll-', 1775cm') lfi completely disappeared, and a new characteristic absorption derived from the carbonyl group of maleic acid appeared at 172OCIIl'1, confirming that the hydrolysis reaction was progressing almost quantitatively. .

In other words, the white solid obtained above is styrene 48°4m0
J! It was confirmed that the copolymer contained 51.6 mo% of malein'M.

Note that the acid value of this polymer was 370.

Production Example 2 Molecule 150 as a copolymer of styrene-maleic anhydride
000 commercial product (M01SantO product) 1Oa
200 ml (dissolved dioxin, 500+1
17 Pour distilled water into a flask and stir thoroughly.
0(+) 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 distilled water (2) to precipitate a flocculent white polymer. By washing this polymer with water and drying it, a white solid of 9.8 o was obtained. From the results of elemental analysis and infrared absorption spectrum of this product, it was confirmed that a styrene-maic acid copolymer was obtained.

Note that the acid value of this polymer was 367.

Production Examples 3 to 4 Two commercial products with different compositions shown in Table 1 as styrene-maleic anhydride copolymers <A r (0 Chemi
ca1) in the same manner 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 compositions shown in Table 1 were obtained. A styrene-maleic acid copolymer was obtained.

The molecular weight is 1700.1900 and the acid value is 25.
It was 1.184.

Table 1 Production Example 5 Content: 50 m of benzene containing maleic anhydride 35 (+) and azobisisobutyronitrile (hereinafter abbreviated as AIBN) of 90111111 in a 300 m pressure glass container.
1! was added, the contents were purged with nitrogen under reduced pressure while cooling in a dry ice-methanol bath, and then purified propylene 12(+) was added by distillation through a liquefaction meter.

Next, copolymerization was carried out by stirring at 60° C. for 36 hours. 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 gently dried in a vacuum dryer. The yield was 60%. Elemental analysis showed 55.6% maleic anhydride and 44.41110% propylene.

Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain 24.2 g of a propylene-maleic acid copolymer.

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, which was Ic.

Production Example 6 50 m of benzene containing 35.79 m of maleic anhydride and 1 g of AIBN are added to a pressure-resistant glass container with a content of 300 m. To this, 12.5 liters of isobutyne was charged by distillation through a liquefaction meter, and then copolymerization was carried out at 60°C for 15 minutes. After the polymerization was completed, the contents were poured into a large amount of anhydrous ether to precipitate the resulting copolymer. The supernatant was discarded by the decanting method, thoroughly washed with anhydrous ether, and then dried under reduced pressure.

The yield was 43.3%. According to elemental analysis, this product contains 47.11107% isobutyne and 52% maleic anhydride.
It was a copolymer containing 91110%.

Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain 20.5 g of isobutene-maleic acid copolymer.

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. Note that the acid value of this copolymer was 470.

Production example 7 5OOIllI! Put 200 m of benzene into a removable glass flask, and add 5.3 g of n-butyl vinyl 1-thyl, 4.9 g of maleic anhydride, and AI.
BNO, 05o was 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°E311101% n-butyl vinyl ether and 50.2 mo1% anhydrous maleic R.

Next, this product was dissolved in 200111J of di;1-1 diline and 500Illi! 10 g of distilled water was added to the flask with sufficient stirring, and the mixture was stirred at 60° C. for 2 vi. The obtained polymer solution was solidified with dry ice-methanol, and then freeze-dried and covered.
0.1 (l) of white solid was obtained.

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 As a copolymer of n-octadecyl vinyl ether-maleic anhydride, PolyscienceCs, lnc
,.

Hydrolysis was carried out in the same manner as in Production Example 2 using a commercially available amount of n-octadecylvinyl needle. A copolymer of maleic acid was obtained.

The acid value of this polymer was 196.

Production example 9 30g of itaconic acid, 20Q of styrene and 200g of dioxane
(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 11, precipitated and separated, 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%.

The acid value of this polymer was 340.

Production Example 1O Styrene and fumaric acid didel-1 ster were combined at 60° C. for 20 hours using AIBN as an initiator to form a polyester. I got -. The composition of the copolymer was determined from elemental analysis in step 12.
56.5 mol% fumaric acid diethyl ester 43.5-E
%. Next, 0.5 g of this polymer was placed in a 100 m Erlenmeyer flask, and 3.0 g of concentrated sulfuric acid was added.
0m1! was added and 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 filtration, this was thoroughly washed with water and finally dried to obtain a solid having a rating of 0.45 (I). The acid value of this polymer was 93.

Production Example 11 As a vinyl acetate-maleic anhydride copolymer, P o
Hydrolysis was carried out in the same manner as in Production Example 7 using a product manufactured by Lysciences, Inc., and vinyl acetate-malein was determined from the elemental analysis results of the copolymer and the measurement results of the infrared absorption spectrum after hydrolysis. A copolymer of acid was obtained. The oxidation price of this polymer was 399.

Production Example 12 P-chlorostyrene and maleic anhydride were prepared under the same conditions as Production Example 1 using BPO as an initiator. From the results of elemental analysis of the obtained copolymer, it was found that D-chlorostyrene was 47.9 mol% and maleic anhydride was 52.1 mol%.
%Met. Next, this product was hydrolyzed in the same manner as in Production Example 7, and based on the elemental analysis results of the produced polymer and the measurement results of the infrared absorption spectrum after hydrolysis, the copolymerization of p-chlorostyrene-maleic acid was confirmed. Obtained union.

The acid value of this borine was 318.

Production Example 13 Polymerization was carried out under the same conditions as Production Example 1 using p-ri0 romedyl styrene and maleic anhydride using BPO as an initiator. From the results of elemental analysis of the obtained copolymer, 48.9 mo1% of p-chloromethylstyrene and 5% of non-fomaleic acid were found.
It was 1.11101%.

Next, this product was hydrolyzed by the h method similar to Production Example 7, and p-chloromethylstyrene-maleic acid A copolymer was obtained.

The acid value of this polymer was 301.

Example 1 The storage stability of solutions containing organometallic compounds and prolines shown in Table 2 was investigated. The solution was stored in a glass container at 20°C, 37°C, and 45°C. Storage stability was compared and examined with the end point being when the solution gelled or lost its transparency.

As a result, in all cases, 4L of precipitate was not lost for more than 12 months, transparency was not lost, and gelation did not occur.

Comparative Example 1 Except for the pro-1 nones used in Example 1 (1), a stabilizer not shown in Table 3 was used [the storage stability was investigated in Example 1 and Mr. Sho 1]. .

The results are listed in Table 3. Example 2 A solution of a polymer having a carboxyl group shown in Table 4 (
The following test was conducted using an adhesive film-forming material consisting of A> and a solution (B) containing an organometallic compound and pro-1 nones.

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

First, paste (I) and paste (
II) was adjusted.

(1) Adhesiveness to dentin Apply emery paper (#320
) to expose the smooth dentin, and the polished surface was
After washing with water for several seconds, the surface was dried by blowing nitrogen gas ().

A sheet of wax with a thickness of 2111111 mm and a hole of 4 mm in diameter was attached to a dry surface using double-sided tape.

Next, liquids (A) and (B) of the adhesive film forming material are mixed in a ratio of 1=1, applied to the dentin surface surrounded by plate wax, and nitrogen gas is blown to remove the excess ethanol. The adhesive film forming material was removed. The above-mentioned bases (i) and (n) were mixed in a 1:1 ratio and filled thereon.

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, Denjiron manufactured by Toyo Baldwin was used, and the tensile speed was 1.
It was set to 0ml/min. The results obtained are shown in Table 5.

(2) Diameter 3111 IIl, depth 21 + 1 on the labial surface of the marginal sealing human necrosis opposite to the cavity.
111 cavities were created. Next, using the adhesive film-forming materials shown in Table 4 and a conventionally used commercial product (Cobalite) for comparison, each was thinly applied to the wall of the cavity and then filled with cement or amalgam. 3 after 1 hour of filling
It was stored in water at 7°C, and one day later, a percolation test was performed in which it was immersed in an aqueous solution of Tsukusin 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 (tsuksin) 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 composition, or where cobalite 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 shown in Table 4, 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 adhesive film forming materials shown in Table 4 were applied to the back surface 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, P l-
1 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 for the one that did not use any barrier material, the one that used Cobalite (trade name) was 1 minute and 10 seconds, and the time for the penetration time of the phosphoric acid aqueous solution was 1 minute and 10 seconds for the one that did not use any barrier material.
The time it took was 10 minutes.

On the other hand, when the adhesive film forming material of the present invention shown in Table 4 was used as the barrier material, the permeation time of the phosphoric acid aqueous solution was 1 hour or more in all cases.

Example 3 A 10% ethanol solution (A>) of the hydrolyzate of the styrene-maleic anhydride copolymer of Production Example 1 as a polymer having a carboxyl group, and the organoaluminum compound and organosilicon compound shown in Table 2.

Equal amounts of either one of an organic zirconium compound and an organic boron compound and an ethanol solution (B) containing proline as a proline were mixed, and the adhesion to dentin was examined in the same manner as in Example 2. . The results are shown in Table 6.

In addition, tests were conducted in the same manner as in Example 2 for margin sealing properties during amalgam filling and blocking properties against phosphoric acid aqueous solutions, but no invasion of tsuksin was observed in either case.
The phosphoric acid aqueous solution was not allowed to pass through for more than 1 hour.

Table C) Back Example 4 B rain l-1 ear l nfusion medium (agar and 3rail t-+eart II
A flat plate was created in a petri dish using a ion (a rented area made of ion).

A diluted solution of the following bacteria cultured on an agar plate was added to 40011.
After applying 11 drops and spreading it evenly over the surface, the surface was dried.

Solution No. 1 of Example 1 (A) and solution (B) were mixed well, and a disc of opening paper was soaked in this. After evaporating the ethanol, the mixture was placed on a flat plate and air cultured for 48 hours. Ta.

After 48 hours, an antibacterial zone with a width of several m+i had been formed at the edge of the mouthpaper for all bacteria.

The bacteria used were 13acteroides gingivalis,
381AcNnoIRyccs naeslundi
iAl'CC12104 A ctrnomyces viscosus ATCC
15987 Propionibacterium acnes
E X C-1ΔctinoIllyces 1sra
eli A T CC12102 Example 5 Solution (A) and solution I3) shown in No. 001 of Example 1 were mixed for a patient who had a transverse defect in the tooth neck and felt pain when exposed to air or cold water. When applied to the posterior cuneiform defect, the pain caused by contact with air and cold water disappeared.

No. 1, No. 2 of Example 1. No, '9. No,
10°No, 12. Ng, 13. No,'l 4.
No, 15. No.

16, No, 17. Solution (A) and solution (B) were mixed and painted on the skin incision. As a result, the wound L1 is sealed and the pain is relieved.

Also, when applied to the affected area of stomatitis, it no longer oozed out due to food and drink.

Patent Applicant: Tokuyama Soda Co., Ltd. Procedural Amendment Written on January 17, 1980 Commissioner of the Patent Office Kazuo Wakasugi Special Fraud Application (5) filed on December 22, 1988 2 Name of Invention Adhesive Film Forming Material 3 , Relationship with the person making the amendment Patent applicant address: 1-1-4 Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture, "Claims" gutter and "Detailed description of the invention" column of the specification subject to amendment 5. Contents of amendment (1) Akira 1IIi! F1-2: The scope of claims is amended as shown in the attached sheet.

(2) 5th line from the bottom of the 3rd page; 6th page - 7 wa'';
';Lth line;First king rRt is'', then insert ``hydrogen atom,''.

(3) 3rd line from the bottom on page 3; 13th line from the bottom on page 6;
On page 18, lines 16 to 15 from the bottom, insert ``1 cr atom or'' after ``selected''.

6. List of attached documents fi+ One or more attached sheets showing the contents of the amended claims Claims after the amendment r(x)(1) Polymer having a carboxyl group or its anhydride group, (11) at least one organometallic compound selected from the group consisting of organotitanium compounds, organo-aluminum compounds, organosilicon compounds, organozirconium compounds, and organoboron compounds, and (wherein R1 is a hydrogen atom or an alkyl group); , hydroxy group,
It is an atom or group selected from the group consisting of an alkyl group and an amide group, R8 is a water atom or an alkyl group, and R8 is an oxygen atom or a methylene group. ) An adhesive film-forming material whose main component is at least one type selected from the group consisting of:

(2) Claim (1) in which the polymer having a carboxyl group or its anhydride group has a hydrophobic group
The adhesive film forming material described above.

(3) The polymer having a carboxyl group or its anhydride group is a polymer in which at least two carboxyl groups (-COOH) or its anhydride groups are bonded to adjacent carbon atoms! An adhesive film forming material according to claim (1).

(4) The molecular weight of the polymer is l, o o o ~ ioo
,oo.

The adhesive film forming material according to claim (1).

(5) Claim (2) in which the polymer is a copolymer of a copolymerizable vinyl monomer having a hydrophobic group and a vinyl monomer having a carboxyl group or its anhydride group.
The adhesive film forming material described above. ”

Claims (5)

[Claims] (1) At least one selected from the group consisting of (i) a polymer having a carboxyl group or its anhydride group, (ii) an organotitanium compound, an organoaluminium compound, an organosilicon compound, an organozirconium compound, and an organoboron compound. and (where R1 is a group selected from the group consisting of an alkyl group, a hydroxyl group, an alkylol group, and an amino group, R2 is a hydrogen atom or an alkyl group, and R3 is an oxygen atom or An adhesive film-forming material containing as a main component at least one proline selected from the group consisting of a methylene group. (2) Claim (1) in which the polymer having a carboxyl group or its anhydride group has a hydrophobic group
The adhesive film forming material described above. (3) The polymer having a carboxyl group or its anhydride group has at least two carboxyl groups (-C(10H)
The adhesive film-forming material according to claim (1), which is a polymeric material in which the carbon atoms are bonded to adjacent carbon atoms. (4) The molecular weight of the polymer is 1,000 to ioo. The adhesive film forming material according to claim (1), which is Ooo. (5) Claims (2) in which the polymer is a copolymer of a copolymerizable monomer having a hydrophobic group and a monomer having a carboxyl group or its anhydride group.
) The adhesive film forming material described in ).