JPS60135470A - Bondable film-forming material - Google Patents

Abstract

PURPOSE:To provide a bondable film-forming material which can be preserved in the form of one-pack type, can be cured in a proper curing time and is useful as a restorative dental material, consisting mainly of a carboxyl group-contg. high-molecular material, an organometallic compd. and a benzoic acid derivative. 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 organoaluminum conpd., an organosilicon compd., an organozirconium compd. and an organoboron compd. (e.g. aluminum isopropionate and tetraethyl silicate) and a benzoic acid derivative (C) of the formula (wherein n is 0, 1-4; X is alkyl, alkoxyl, carboxyl, etc.; R is alkyl, haloalkyl, alkoxyalkyl, phenoxyalkyl, aryl, benzyl, etc.) (e.g. 2-methyl-6- methoxybenzoic acid). The material can be preserved in one-pack form by using the compd. C as a stabilizer for the compd. B and 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 organoaluminium compound, an organosilicon compound,
selected from the group consisting of organic zirconium compounds and organic boron compounds [at least one type of organometallic compound, and (iii) general formula. (However, n is 0.1.2.3 or 4; Haloalkyl group. Alkoxyalkylalkyl group. Phenoxyalkyl group. Aryl group. Alkoxyaryl group. It is an acyl group, haloacyl group, acyloxyacyl group, alkoxycarbonyl group, allyl group, or benzyl group. ) Adhesive film-forming material whose main component is a benzoic acid derivative. 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 tissues, 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 has adhesive strength with tooth structure, it does not have adhesive strength with other dental filling materials.
Moreover, because of its low water resistance, it has the disadvantage of being easily dislodged in water. Furthermore, adhesives using polymerizable monomers adhere to enamel, but hardly adhere to dentin. For this reason, it was necessary to demineralize the tooth substance by previously treating it with a high-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, adhesives are required to have properties specific to that field depending on the field of use, so adhesives used in one field are rarely able to be used industrially in other fields. Therefore, suitable adhesives have been developed depending on the field of use. On the other hand, when an organometallic compound is mixed into a solvent in which a polymer having a carboxyl group or its anhydride group is dissolved, a crosslinking reaction proceeds immediately, resulting in gelation in a short time or precipitation of a crosslinked cured product. It has been known. Follow゛(,
It has been concluded that it is not possible to mix a polymer having a carboxyl group or its anhydride group and an organometallic compound and store the mixture in a one-component type. In order to compensate for such deficiencies, attempts have been made to add organometallic compound stabilizers to the above system to preserve the liquid type. For example, it has been proposed to use lactic acid, salicylic acid, etc. as the above-mentioned stabilizers, but even if these stabilizers are used, the crosslinking reaction between the polymer having a carboxyl group or its anhydride group and the organometallic compound will not occur. It was not possible to completely prevent this, and it was not possible to preserve both products in a one-component form industrially or as a product. Therefore, the present inventors conducted repeated research to solve the above drawbacks, and found that when a compound with a specific structural formula among benzoic acid derivatives is used as a stabilizer for an organometallic compound, it can be stored in a -liquid state. The present inventors have discovered that a liquid composition can be obtained, and have provided the present invention. That is, the present invention provides: (i) a polymer having a carboxyl group or its anhydride group; (ti) an organoaluminum compound, an organosilicon compound;
at least one organometallic compound selected from the group consisting of organozirconium compounds and organoboron compounds, and (iii) general formula, (where n is o, 1.2.3 or 4, x haalkyl group, an alkoxyl group, a carboxyl group or an acylalkyl group, R is a furkyl group, a haloalkyl group; an alkoxyalkyl group, a carboxyl group, a phenoxyalkyl group, an aryl group, an alkoxyaryl group, an acyl group, a herooacyl group, a 7-syloxyacyl group An adhesive film-forming material whose main component is a benzoic acid derivative represented by the following formulas: , alkoxycarbonyl. One of the main components of the adhesive film forming material H 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 wet conditions, such as dental lining materials and dental adhesives. In particular, polymers in which at least two carboxyl groups or their anhydride groups are bonded to adjacent carbon atoms are effective.They also provide water resistance to the adhesive film forming material. In order to impart compatibility with the adhesive material, it is even more suitable to select a polymer having a hydrophobic group.The polymer having the carboxyl group or its anhydride group is particularly limited. Although any known polymer can be used, in general, those with a molecular weight in the range of 1,000 to 1,000 O. Generally, a vinyl monomer having a carboxyl group or its anhydride group is homopolymerized, or a copolymerizable vinyl monomer having the functional group is copolymerized with another copolymerizable vinyl monomer, especially a vinyl monomer having a hydrophobic group. A preferred method is to copolymerize a vinyl monomer having a carboxylic acid ester group with another copolymerizable vinyl monomer, and produce a copolymer with a carboxylic acid ester group. A method of hydrolyzing and converting into carboxyl groups is also suitably adopted. The polymer used in the present invention has an acid value of 30 to 700. It is also important that it has an acid value of 40 to 600. In this Moe Specification , the acid value is defined as the number of 1llQ of K O+-1 required to neutralize 1g of resin.
llilli represents the concentration of carboxyl groups and their anhydride groups in the polymer, and if this acid value is lower than the above range, the adhesion to hard tissue, especially tooth structure, will decrease,
In addition, by reducing the number of crosslinking points with organometallic compounds,
There is a tendency for the toughness of the film to decrease. On the other hand, if the acid value is larger than the above range, the film formed from the polymer becomes excessively hydrophilic, and the water resistance of the film tends to be lost. Polymers having acid values in the above-mentioned range 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. Namely, acrylic acids such as acrylic acid and methacrylic acid, and maleic acid. Unsaturated dibasic carboxylic acid monomers such as fumaric acid, itaconic acid, maleic anhydride, and itaconic anhydride; aromatic unsaturated carboxylic acid monomers such as 4-methacryloxyethyl trimeritz 1-hexyl acid. Alternatively, substituted derivatives obtained by substituting these vinyl monomers with substituents 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, divinylbenzene, and vinylnaphthalene; vinyl ester compounds such as donyl acetate; methyl diacrylate; Acrylic acid and methacrylic acid derivatives such as ethyl methacrylate, 2- and droxyethyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, acrylamide, methacrylic acid amide; unsaturated nitrile compounds such as acrylonitrile;
Examples include vinyl needle compounds such as methylvinylnythyl. Furthermore, as mentioned above, among the copolymerizable vinyl monomers used as raw materials in the present invention, vinyl monomers having a hydrophobic group are preferably used. By using a vinyl monomer having a hydrophobic group, the polymer can have both hydrophobic properties and hydrophilic properties due to carboxyl groups or their anhydride groups. In this case, as will be described later, it is possible to particularly improve the performance of bonding dissimilar materials such as a material having a hydrophilic surface and a material having a hydrophobic surface. The hydrophobic group is not particularly limited and any known one may be used, but a typical example of a hydrophobic group that is generally used suitably is a phenyl group. Aryl groups such as naphthyl groups; alkyl groups such as methyl, ethyl, and propyl groups; ethoxy groups. Butoxy M! Alkoxy groups such as; acyloxy groups such as acedeloxy groups; 1-toxy carbonyl groups; These include alkoxycarbonyl groups such as butoxycarbonyl groups. Known vinyl monomers having these functional groups can be used without particular restriction. Specific examples of generally preferred vinyl monomers include styrene, methylstyrene, vinylnaphthalene, propylene, butene, and ethyl vinyl ether. These include butyl vinyl ether, vinyl acetate, ethyl methacrylate, and acrylic acid. 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. Also, 90 t%
If it exceeds this amount, there is a tendency that adhesive strength with the tooth structure cannot be obtained. It is also possible to copolymerize one or more of the above vinyl monomers with a carboxyl group or its anhydride group by mixing them together. The method for carrying out the above polymerization is not particularly limited and any known method may be used, but radical polymerization is particularly suitably used. Generally known polymerization initiators used in radical polymerization are also employed. For example, organic peroxides such as benzoyl peroxide and lau [1-yl peroxide; per-A xo-disulfate potassium such as per-A xo-di-sulfate and am7nium per-oxo-disulfate; azo compounds such as azobisisobutyronitrile; ; Polymerization carried out using an organometallic compound such as tributylboron or a redox initiator can be suitably used. These polymerization initiators are added in a range of 0.01 to 3% by weight when added to a 7-mer component such as an unsaturated carboxylic acid, an unsaturated carboxylic ester or an acid anhydride, or a copolymerizable vinyl monomer. It is sufficient to use it. Another main component of the adhesive film-forming material of the present invention is at least one type of organic metal selected from the group consisting of organoaluminum compounds, organosilicon compounds, organozirconium compounds, and organoboron compounds. It is a compound. The organometallic compound used in the present invention is not particularly limited as long as it is listed above, and any known organic compounds can be used, and they can be used alone or in combination. As the organoaluminum compound, aluminum alkylates such as 7-fluminium isobrobylate, aluminum ``)-butyrate, aluminum 5ec-butyrate, aluminum isobutyrate, aluminum t-butyrate, etc. are suitable alone or in combination. Examples of organic silicon compounds include furkyl silicates such as tetraethyl silicate and tetrabutyl silicate; vinyl]-lime-1-4-disilane 7healtrini-l-xysilane, γ-aminopropyl 1-lyl-toxysilane, Alkyl silicates partially substituted with other substituents, such as γ-methacrylic[14, dipropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane, are used alone or in combination. In particular, when furkyl silicates are used, the effects of the present invention are significantly exhibited. The organic zirconium compound C is tetramethylzirconate 1 to .tetraethylzirconate. Tetra-1-propylzirconate, tetra-5ec −
Bujiru Zircone 1-. Alkyl zirconates such as tetra-n-butyl zirconate and tetra-n-butyl zirconate are preferably used alone or in combination. Examples of organic boron compounds include alkylnisdale borates such as phosphoric acid trimethyl ester, boric acid trimethyl ester, boric acid tri-1-propyl ester, boric acid tri-n-butyl ester, and boric acid tri-stearyl ester; boric acid (-Boric acid aryl esters such as -rifhenyl ester and 1-ly-0-tolylnisder boric acid are preferably used singly or in combination.) Amount of organometallic compound used in the adhesive film forming material of the present invention is not particularly limited, but is generally added at a ratio of 0.02 mol to 1.0-11 nyl per 1 mol of carboxyl group or its anhydride group of the molecule having a carboxyl group or its anhydride group. 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. If the amount of the compound added exceeds 1.0 mol, the curing time becomes too short during curing, which may reduce operability and may limit the field of use.
Therefore, it is preferable that each addition ratio in the present invention is determined in advance according to 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 l (where n is O, 1, 2, 3, or 4, and X is an alkyl group. An alkoxyl group, a carboxyl group, or an acylfurkyl group) , R is an alkyl group, a haloalkyl group, an alkoxyalkyl group, a carboxyalkyl group, a phenoxyalkyl group, an aryl group, an alkoxyazyl group, an acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a benzyl group. ) is a benzoic acid derivative represented by What is the reaction mechanism of the benzoic acid derivative represented by the above general formula of the present invention, and why can a polymer having a carboxyl group or its anhydride group and an organometallic compound be treated as a one-component type? is still not clear at present. However, the following conclusions can be deduced from the results of statistical experiments. That is, the -OR group and the 1000H group in the above general formula must be positioned at the ortho position of the benzene ring. This is presumably because the metal component of the organometallic compound creates a coordinate bond between the -OR group and the oxygen atom of the -COO+- group, thereby maintaining a stable state of the six-membered ring. However, even if the above -OR group is a 10H group, it is also a 1COO group.
Even if the hydrogen atom of the H group is substituted at another position, or even if the compound satisfies both of these requirements at the same time, such as salicylic acid, the effects of the present invention cannot be exhibited. however,
As long as the 1000HM and 10R groups are present in the ortho position as in the above general formula, even if the hydrogen of the benzene ring is substituted with another substituent (X in the above general formula) or the number of substituents Regardless of the circumstances, the effects of the present invention can be fully exhibited. From the above results, the effect of the present invention is selected when the carboxyl group (-COOH) and the -OR group present in the benzene ring are located at the ortho position, and R of the -OR group is not a hydrogen atom. It is presumed that it acts to stably hold the metal components of the organometallic compound. The benzoic acid derivative used in the present invention is not particularly limited as long as it is represented by the above general formula, and any known compound can be used. In general, from the viewpoint of industrial availability and ease of handling, alkyl groups such as alkyl groups, alkoxy groups, haloalkyl groups, phenoxyalkyl groups, etc. of Atom 1~
Four halogen atoms are preferred, and chlorine, bromine, iodine, and fluorine are preferably used as the halogen atoms in the haloalkyl group and haloacyl group, and chlorine and bromine are particularly preferably used. Furthermore, the phenoxyalkyl group represented by R in the above general formula is preferably a nitrophenoxy group or a carboxyphenoxy group in which the hydrogen atom of the phenoxy group is substituted with a nitro group. Furthermore, the benzoic acid derivative represented by the above general formula that is industrially easily available is the following compound. That is, benzoic acid derivatives represented by the general formula (where n is an integer of 1 to 4, X is an alkyl group, an alkoxyl group, a carboxyl group, or an acylalkyl group, and R' is an alkyl group), or a general Formula, (However, R" is an alkyl group, a haloalkyl group. j A phenoxyalkyl group, a carboxyfulkyl group. A phenoxyalkylsiazyl group. An acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group. j1 A lyl group or a benzyl group. It is a benzoic acid derivative represented by the above general formula (I).More specific examples of representative compounds of the present invention represented by the above general formula are as follows.That is, representative compounds shown by the above general formula (I) Examples of compounds include 2-methyl-6-methoxybenzoic acid M: 2.4-dimethyl-6-methoxybenzoic acid; 2.3.5-trimethyl-6-methoxybenzoic acid: 2, 4.5-1-ridge-3.6-dimethoxybenzoic 1; 3.4-dimethyl-
2,6-dimethoxybenzoic acid: orcinol dicarboxylic acid dimethyl needle; olivetonic acid dimethyl ether, etc. Further, typical compounds represented by the general formula (n) include 2-methoxybenzoic acid, 2-ethoxybenzoic acid, 2-propoxybenzoic acid, 2-isopropoxybenzoic acid, 2-[β-bromoethoxy] Benzoic acid, 2-methoxymethoxybenzoic acid, phenoxyacetic acid-〇-carboxylic acid, α-phenoxypropionic acid-〇-carboxylic acid,
α-Phenoxybutanoic acid-〇-carboxylic acid, α-phenoxyisobutanoic acid-〇-carboxylic acid, α-phenoxyvaleric acid-〇-carboxylic acid, 2-(β-(2-nitrophenoxy)-1toxy)benzoic acid acids, 2[β-(4-nitrophenoxy)-ethoxy]benzoic acid, ethylenedisalicylic acid, 2-pheno”-cybenzoic acid. 2-0-flexoxybenzoic flf, 2-m-flexoxybenzoic acid, 2-p-cresoxybenzoic acid. 2-(2,4-dimethyl-phenoxy)benzoic acid, 2
-β-Naphthyloxybenzoic acid, 2(2-methoxyphenoxy)benzoic acid, 2-acetoxybenzoic acid, 2-benzoyloxybenzoic acid, 2-trichloroalethoxybenzoic acid, 2-prohyacetoxybenzoic acid, 2-tribromoacetate xybenzoic acid, succinyldisalicylic acid, carbomethoxysalicylic acid, carboe] xysalicylic acid, 2-
Allyloxybenzoic acid, 2-benzyloxybenzoic acid, and the like. One or more of the benzoic acid derivatives used in the present invention may be used together with an organic solvent if necessary. The organic solvent is particularly limited and any known one can be used, but in general it is preferable to use one that has a low boiling point and can be easily removed later, for example, organic solvents such as methanol, ethanol, and ethyl acetate are preferably used. Further, the amount of the benzoic acid derivative 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. Generally, it is suitable to use it in an amount of 0.1 mol to 4 mol, preferably 0.5 mol to 2 mol, per 1 mol of the organometallic compound which is one component of the present invention. If the benzoic acid derivative is used in a large amount relative to the organometallic compound, the operation time when mixing the adhesive film forming material with other mixtures will generally become longer, or the cured product will deteriorate. The production rate tends to be slow. In the present invention, the polymer having a carboxyl group or its anhydride group, the organometallic compound, and the benzoic acid derivative can be stored in a one-component type and will not harden for a long period of time. The storage method is not particularly limited, but a storage method in the presence of an organic solvent is most preferably used. As described above, the organic solvent is not particularly limited, but methanol, ethanol, isopropyl alcohol, ethyl acetate, etc., which generally have a low boiling point and can be easily removed, are preferably used. Further, when the adhesive film forming material of the present invention is dissolved in an organic solvent and used, the concentration of the forming material is not particularly limited, but generally it is in the range of 1 to 30% by weight. C can be used, which is preferable. Even when used together with the above solvents, the curing reaction starts by evaporating the solvent after application, so it is easy to use at room temperature. In addition to the above-mentioned method of storing the adhesive film-forming material in one solution, it is of course possible to store each of the three components of the adhesive film-forming material of the present invention separately and mix and cover the three components during curing, or to store the organometallic compound and benzoic acid derivative. It is also possible to adopt a method in which the materials are mixed in advance and stored, and then a polymer having a carboxyl group or anhydride group thereof is mixed therein at the time of curing. In the adhesive film-forming material of the present invention, a sufficient cured product can be obtained using only the three components of the polymer having a carboxyl group or its anhydride group, the organometallic compound, and the benzoic acid derivative. It is also possible to improve the strength or adhesion of the cured product by curing it in the coexistence of a polymerizable vinyl polymer and an initiator. As the above-mentioned polymerizable OL vinyl monomer, the copolymerizable vinyl heptamers described above 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 combination 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. N1-dimethylaniline, N
, Nl-dimethyl-P-toluidine. N-methyl Nl-β-hydroxyethyl-aniline,
N,Nl-dimedyru-P-(β-hydroxyethyl)-
Aniline, N, Nl-di(β~hydroxyethyln-P
-1-/Reizin etc. are preferably used. Furthermore, it is often a preferred embodiment to use co-catalysts, such as metal salts, such as sultuic acids or carboxylic acids, in addition to the initiators. The adhesive film-forming material of the present invention can be used as a -liquid type curing composition, and moreover, since the curing time during curing is appropriate, operability is improved. 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 two-in-one ink material for resin or glass, 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 the treatment and restoration of teeth and is applied to the surface of the tooth or the surface of a cavity formed on the tooth, and the adhesive film forming material of the present invention This is the most important use of ff2. Such materials include, for example, tooth sockets, pulp protector linings, tooth and filling material margin seals, and the like. A case in which the adhesive film forming material of the present invention is used as a dental treatment and restoration material will be explained below.In the treatment and restoration of a tooth, the cavity of the tooth is filled with a filling material such as a composite restorative resin. At this time, adhesives are used to bond the tooth structure and the filling material.However, since conventional adhesives show little adhesion to the image quality, the tooth structure is preliminarily coated with a high-strength phosphoric acid aqueous solution. It was necessary to mechanically create a form of retention.However, this method has the disadvantage that even healthy quality is damaged because it uses a highly concentrated phosphoric acid aqueous solution. In particular, when applying a single layer to dentin, adhesive strength cannot be expected to be very strong.

[There is a risk that the phosphoric acid aqueous solution may affect the dental pulp through the dentinal tubules. In addition, since the above method inevitably leaves unreacted monomer,
There is also the possibility that this monomer may cause dental pulp damage. However, when the adhesive film-forming material of the present invention is used as an adhesive, it can be directly adhered to dentin without being pretreated with the phosphoric acid aqueous solution, and since the cured product itself is originally a polymer, it is free from unreacted monomers. It has an excellent effect of being non-toxic to the pulp. Next, conventional lining materials for pulp protection include calcium hydroxide-based materials and cement, and the dentin is removed from the phosphoric acid etching performed when filling with composite restorative resins and other filling materials. It is used for protection, etc. However, these materials inevitably form a thick film.
It was almost impossible to fill shallow cavities because of the fact that it was difficult to adhere to filling materials. Therefore, by dissolving the adhesive film-forming material of the present invention in an organic solvent and using it as the lining material, it is possible to protect the tooth structure from the phosphoric acid etching solution even though it is a thin film, and it also adheres to the filling material. Demonstrates excellent functionality. In addition, 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 a lining material to protect the material. However, conventional lining materials with thick coatings were not usable because their own compressive strength was a problem. Therefore, when the adhesive film-forming material of the present invention is used as the backing material, since it is a thin film, it does not require much strength on its own, and moreover, it exhibits the ideal effect of not allowing phosphoric acid to pass through. Furthermore, the 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) 7).
It is known that resins such as Komulai 1 to 1 are dissolved in organic solvents to be used when filling with malgam. This material is
It is true that a thin film is formed, but there is no bonding point with the tooth substance or amalgam, and it is not very effective in sealing the margins. By using the adhesive film-forming material of the present invention as the edge sealing material, a nice effect is 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 property by using the above-mentioned adhesive film forming material in cement filling, rubber coating 1/tubing, etc. It is possible to use the adhesive film forming material of the present invention for purposes other than those described above. For example, when the tooth cavity has been filled with dentine, or when the adhesive film-forming material of the present invention is applied to a tooth where dentin is exposed on the tooth surface due to a horizontal defect in the tooth cavity, etc. 1i can also be used as a shield against external stimuli.The functions of the tooth adhesive, the lining material for protecting the pulp, and the margin sealing material have been explained individually above, but Since the adhesive film-forming material has both of these functions, it is possible to exhibit all of the above functions in one case by simply using the adhesive film-forming material of the present invention. Therefore, in the past, it was usually necessary to use multiple materials in one case, making the operation extremely complicated, and using multiple materials could result in poor functionality of each other. Considering that it had the disadvantage of descending,
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 carbo-4 syl group or its anhydride group, which is one of the components of the present invention, has a hydrophobic group (jf
It is preferable to have the same function in order to further improve the function as a healing and restoring moon for @lH. This is effective in imparting water resistance since the inside of the oral cavity is under harsh conditions f-1 with 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, while the aqueous 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. B acteroides gingivalis 3
81ACtinOmyCeS naeslundiiΔ
TCC12104 Δctinomyces vrscosus ATCC1
5987 propionibacterium acnes
EX C-1A ctinomyces 1srael
iArCC12102 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 an incision. The affected area can be sterilized and protected. Further, a compound having pharmacological activity such as a fluorine compound or chlorhexidine may be further added to the adhesive film-forming material of the present invention. In order to explain the present invention more specifically, examples are given below (although the present invention is not limited to these examples. Production Example 1 Glass separable flask with a capacity of 500 IllJ! Add cyclohexyl(nan 2001 + 1j!) to this, add styrene 5.2 (], maleic anhydride 1104.9 () and bebenzoyl peroxide (hereinafter abbreviated as BPO)) 0.0'5 (+). The inside of the container was then thoroughly stirred. Next, after reducing the pressure inside the container and purging it with nitrogen, heating polymerization was carried out with stirring at 80° C. for 4 hours, and after cooling to a variable temperature, the formed precipitate was filtered out. The obtained solid was further Benbin 300
8.7 g of white polymer after washing with mJ for 11 minutes and drying
I got it. From the elemental analysis of this product, we determined the composition of the copolymer produced: 48.4 n+oJ% of styrene and 51.6 moJ of maleic anhydride! Met. Next, this product was dissolved in 80 m) of di-A-kizan, and
Pour into a flask with a volume of 0.0 m and stir thoroughly.
Potassium hydroxide aqueous solution 10OIllJ
was added and 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. After filtering out this solid, repeat washing with water until it becomes neutral.
Further drying yielded 8.0 g of copolymer. As a result of measuring the infrared absorption spectrum of this product, the characteristic absorption derived from the carbonyl group of maleic anhydride <185
0c1.1775cm'l) completely disappeared, and a new characteristic absorption derived from the carbonyl group of maleic acid appeared at 1720c
It was confirmed that the hydrolysis reaction was progressing almost quantitatively. In other words, the white solid obtained above was styrene 48°4m.
It was confirmed that the copolymer contained 51.6% of maleic acid and 51.6% of maleic acid. The acid value of this polymer was 370c. Production Example 2 Styrene-maleic anhydride copolymer -C molecule 1i
50,000 commercial products (Monsanto product) 10
g2001114! Dissolved in dioxin, 500I
10 g of distilled water was added to the flask with sufficient stirring, and the mixture was heated and stirred at 100° C. for 4 hours. Then, after cooling this solution to room temperature, 2J! By pouring it into distilled water, a flocculent white polymer was precipitated. By washing and drying this polymer, a white solid of 9.8
I got g. 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 Hydrolysis was carried out in the same manner as in Production Example 1 using two types of commercially available styrene-maleic anhydride copolymers having different compositions shown in Table 1 (manufactured by Arc. CIIemiCa1). From the elemental analysis results of the raw material copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, a sulfuric acid copolymer having the composition shown in Table 1 was obtained. The molecules m are respectively 1700.1900 and the acid value is 25.
It was 1.184. Table 1 Production Example 5 Contents Benzene 50+11 containing maleic anhydride 35(] and 90II1g of azobisisobutyronitrile (hereinafter abbreviated as AIBN) in a 300m pressure glass container.
/ was added, and the contents were purged with nitrogen under reduced pressure while cooling 11 L in a dry ice slumethanol bath.
] 12 g of pyrene were 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 Okawa's anhydrous ether to precipitate the resulting copolymer, thoroughly washed by a decanting method, and gently dried in a vacuum drying mold. The yield was 60%. Maleic anhydride 55.61110% by elemental analysis
The propylene content was 44.4 ml'%. 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 constantly converted to maleic acid. Note that the acid value of this polymer was 508. Production Example 6 Benzene 50111J? containing 35.70 ml of maleic anhydride and 90 m () of AIBN is added to a pressure-resistant glass container with contents of 300 ml. To this, 12.5 Cl of isobutyne is charged by distillation through a liquefaction meter. Copolymerization is then carried out at 60°C for 15 minutes.After the polymerization is complete, 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 and covered. The yield was 43.3%.Elemental analysis revealed that this product contained 47.11% of isobutyne and 52% of maleic anhydride.
It was a copolymer containing 9n+o/%. Next, this product was hydrolyzed in the same manner as in Production Example 1 to obtain an isobutyne-maleic acid copolymer with a weight of 20°50. 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 In a glass separable flask with a capacity of 500 rn,
Benzene 200m1! and n-butyl vinyl ether 5.30, maleic anhydride 4.90 and ΔI
BNO, 051J 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 it was found to be 1-butyl vinyl ether 49°8 11o1% and anhydrous maleic 150.2 mo1%.Next, this product was mixed with dioxane of 2OOIIJ! Dissolved, poured into a 500-111J? volume flask, added 10 (I) of distilled water with sufficient stirring, and stirred at 60°C for 2 hours. After solidifying the obtained polymer solution with dry ice-methanol, By freeze-drying, io,
io 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-octadecylvinyl needle-maleic anhydride, Polysciencecs, In
c. Hydrolysis was carried out in the same manner as in Production Example 2 using a commercially available product, and based on the elemental analysis results of the raw material copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, the same n-
An octadecyl vinyl ether-maleic acid copolymer was obtained. The acid value of this polymer was 196. Production Example 9 Itaconic acid 30 (1), styrene 20 (I) were dissolved in 200 g of dioxene, BPO was added to the monomer, and 1 was added to 0.
1% was added and polymerization was carried out at 10°C for 5 hours. The obtained polymer was placed in Hekyrin 1], filtered and dried through a settling valve 1, 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 the content was 49.0 T-nyl itaconic acid and 51.0 mol% sutyrene. The acid value of this polymer was 340C. Production Example 10 Styrene and dimethyl fumarate 1 ster were polymerized at 60°C for 20 hours using AI8N as an initiator (a polymer was obtained. The composition of the copolymer was determined to be 1256% by elemental analysis.
43.5 mol%
Met. Next, 0.5 g of this polymer was placed in a '100111 No. 1 Lurenmeyer flask, and 3 Q ml of concentrated sulfuric acid was added thereto, and the mixture was heated to room temperature. The polymer was completely dissolved in 2 days, leaving a yellow solution. 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 with a rating of 0.45 (I). The acid value of this polymer was 93. Production Example 11 Vinyl acetate-maleic anhydride copolymer As a polymer, Po1
ysciences, [nc,, using the product manufactured by
Hydrolysis was carried out in the same manner as in Production Example 7, and a vinyl acetate-maleic acid copolymer was obtained from the elemental analysis results of the copolymer and the measurement results of the infrared absorption spectrum after hydrolysis. 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 [U1-)O as an initiator. From the results of elemental analysis of the obtained copolymer, 47.9 mo1% of p-chlorostyrene and 52.1 mole% of maleic anhydride were found.
The mo was 1%. Next, this product was hydrolyzed in the same manner as in Production Example 7, and p
A copolymer of -chlorostyrene-maleic acid was obtained. The acid value of this polymer was 318. Production Example 13 Polymerization of p-chloromethylstyrene and maleic anhydride was carried out under the same conditions as Production Example 1 using BPO as an initiator. From the results of elemental analysis of the obtained copolymer, 48.9 mo1% of p-chloromethylstyrene and 5% maleic anhydride were found.
It was 1.1 mo1%. Next, this product was hydrolyzed in the same manner as in Production Example 7, and based on the elemental analysis results of the produced copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, p-chloromethylstyrene-maleic acid was determined. A copolymer was obtained. The acid of this polymer (the number was 301.
The storage stability was investigated when mixing 11(Δ) with a solution (13) containing an organoaluminum compound and a benzoic acid derivative. The destination method was as follows. That is, (Δ) and (B) were prepared with the compositions shown in Table 2, placed at -C, mixed in a glass container, immediately capped, and stored in a constant temperature room at 20°C. The storage stability was evaluated using a -C comparison, with the end point being when the solution gelled or lost its transparency. As a result, no precipitation occurred for more than 12 months, no loss of transparency occurred, and no gelation occurred. Example 2 A 10% ethanol solution (Δ) of the hydrolyzate of the styrene-maleic anhydride copolymer of Production Example 1 was used as a polymer having a carboxyl group, and aluminum-n-butyrate and various benzoates were used as organoaluminum compounds. The storage stability when equal amounts of the ethanol solution (B) containing the acid derivative were mixed was examined in the same manner as in Example 1. The composition of (B) is shown in Table 3. As a result, no precipitation occurred for more than 12 months, no loss of transparency occurred, and no gelation occurred. 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 any of an organosilicon compound, an organozirconium compound, and an organoboron compound. The storage stability was examined in the same manner as in Example 1 when equal amounts of ethanol solution (B) containing O-l-oxybenzoic acid and O-l-xybenzoic acid as a benzoic acid derivative were mixed. (
The composition of B) is shown in Table 4. As a result, no precipitation occurred for more than 12 months, no loss of transparency occurred, and no gelation occurred. Comparative Example 1 Storage stability was measured in the same manner as in Example 1, except that the carboxylic acid compound shown in (8) solution composition side of Table 5 was used instead of the carboxylic acid compound used in Example 2. The results are also listed in Table 5. Application Example 1 The following tests were conducted using the adhesive film forming materials shown in Examples 1, 2 and 3. (1) Adhesiveness to dentin (2) Marginal sealing property to cavities (3) Blocking property to phosphoric acid aqueous solution Tests related to the above were evaluated using the methods described above. First, paste <I) a3 and paste (I[) were prepared according to the following formulations. (1) Adhesive adhesive applied to dentin Apply emery paper (#320) to the labial surface of a freshly extracted tooth.
) 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 plate-shaped wax plate with a thickness of 21 mm and a hole of 4 mm in diameter was attached to the dry surface with double-sided tape. Next, the adhesive film forming material was Solution (A) and solution (B) were mixed at a ratio of 1:1 and applied to the dentin surface coated with plate-like wax, and nitrogen gas was blown to remove the ethanol and excess adhesive film-forming material. The above pastes (1) and (n) were mixed at a ratio of 1:1 and filled thereon.After being left for one hour, the wax plate 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 speed was 1.
0111+1/min. The results obtained are shown in Table 6. (2) Marginal sealing of the cavity] - A cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of the extracted tooth. Next, the adhesive film forming materials shown in Example 1 (Table 2), Example 2 (Table 3) and Example 3 (Table 4) C,
For comparison, a conventionally used commercial product (Copalite) was used, and the walls of each cavity were painted with tinge 1, and then filled with cement or amalgam. One hour after filling, it was stored in water at 37°C, and after one day, it was heated to 4°C. A percolation test was conducted in which the sample was alternately immersed in an aqueous solution of Tsukusin at 60° C. for 1 minute each 60 times 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. In addition, for Test 1 above, 5 samples were used for each type of experiment to confirm the two-way property. As a result, in the cases where amalgam or cement was directly filled without using the above composition, or where copalite was painted and then filled with amalgam or cement, pigment intrusion was observed in all I samples. On the other hand, with respect to the adhesive film forming materials of Example 1 (Table 2), Example 2 (Table 3), and Example 3 (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, tests were conducted using the following method. child. 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 barrier material (backing material), commercially available products such as Palite, Dical, and the adhesive film forming material used in Examples 1, 2, and 3 were applied to the back surface, and nitrogen gas was again blown to remove the solvent. was removed. Using a phosphoric acid aqueous solution and a C37%A phosphoric acid aqueous solution, one drop was dropped onto the barrier material and a natural number of drops were placed on the barrier material. In order to detect the phosphoric acid that passes through the above-mentioned blocking material,
The test paper was placed under the membrane filter, and the time when the color changed was determined as the passing time. As a result, the permeation time of the phosphoric acid aqueous solution was 15 seconds in the case of using no barrier material at all, 1 minute and 10 seconds for the case using Copalite (trade name), and 1 minute and 10 seconds for the case using Copalite (trade name).
The time it took was 10 minutes. On the other hand, as shown in Examples 1 and 2.3, when the adhesive film forming material of the present invention (1) was used as the barrier material, the permeation time of the phosphoric acid aqueous solution was 1 hour or more in all cases. Application example 2 Brain Heart lnfusion medium (
Agar and r3rain Heart lnrusion
A flat plate was prepared in a petri dish using a medium consisting of 4.00 ml of a diluted solution of the following bacteria cultured in LM was dropped onto an agar plate, spread uniformly over the C surface, and then the surface was dried. Mix No. 1 of Example 1, <A) solution of 1 and (B)in well, soak the opening paper disk in this, evaporate the ethanol, place it on a flat plate, and perform anaerobic culture for 48 hours. Ta. After 48 hours, an antibacterial zone with a width of several mm had formed at the edge of the mouthpaper for all bacteria. Bacteria used: 3acteroides gingivalis 38
1Acttnomyces naeslundii△Ding CC12104 A CtinomyCeS viscosus ATCC
15987 Propionibacterium acnes
E X C-1 Actinomycesisraeli
ATCC12102 Application Example 3 The (Δ) solution and (B) solution shown in No. 1 of Example 1 were mixed for a patient who has a transverse defect in the tooth neck and feels pain when exposed to air or cold water. When applied to the posterior cuneiform defect, pain caused by contact with air and cold water was demonstrated. No. 1 of Example 1. No, 9. Example 3 No. 1° No. 2. No, 3. No, 4. No, 5. No, 6.
No. Solution (A) and solution (B) in Step 7 were mixed and applied to the skin incision. As a result, the wound was sealed and the pain was relieved. Also, when applied to the affected area of stomatitis, it no longer oozed out due to food and drink. Patent applicant: Tokuyama Kashitatsu Co., Ltd.

Claims (7)

[Claims] (1) (+) A polymer having a carboxyl group or its anhydride group, (ii) an organoaluminum compound, an organosilicon compound,
at least one paid metal compound selected from the group consisting of organic zirconium compounds and organic boron compounds, and (iii) a general formula (% formula % alkylboxyl group or acylalkyl group, R is an alkyl group or a haloalkyl group). Benzoic acid derivatives represented by alkoxyalkyl group, carboxyalkyl group, phenoxyalkyl group; aryl group, alkoxyaryl group; acyl group, herooacyl group, acyloxyacyl group, alkoxycarbonyl group, allyl group, or benzyl group) Adhesive film forming material whose main component is (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 carboxyl groups or their anhydride groups has at least two carboxyl groups (-Cool-1
The adhesive film-forming material according to claim (1), which is a polymer in which the anhydride group or the anhydride group is bonded to adjacent carbon atoms. (4) The molecular weight of the polymer is 1,000 to 10O. The adhesive liquid film forming material according to claim (1), which is 0OO. (5) The polymer has a copolymerizable vinyl monomer having a hydrophobic group and a carboxyl group or its anhydride group.
Claims which are copolymers with vinyl monomers (
1) Adhesive film forming material as described. (6) The benzoic acid derivative is a compound represented by the general formula (n is an integer of 1 to 4, X is an alkyl group, alkoxyl group, carboxyl group, or acylalkyl group, and R' is an alkyl group) An adhesive film forming material according to claim (1). (7) The benzoic acid derivative has the general formula (R" is an alkyl group, H[1 alkyl group, alkoxyalkylphenoxyalkyl group, 7 aryl group, alkoxyaryl group, acyl group, haloacyl group, acyloxyacyllbonyl group, allyl group. or a benzyl group).