JPH0463842B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an adhesive film-forming material that has adhesive properties to biological hard tissue, particularly teeth, and has film-forming ability. (Prior Art) Conventionally, as film-forming materials, various compounds unique to each field are known depending on the field of use. In particular, film-forming materials used for dental treatment have to withstand the complexity of the forces applied in the oral cavity, the variety of adherends, the harsh environments that are difficult to predict, such as humid conditions, and the fact that they are toxic. There are strict requirements that must be met. On the other hand, current film-forming materials for dental treatment improve the margin sealing properties after filling by applying them before filling with amalgam. It is often used for purposes such as blocking phosphoric acid used in advance etching and unpolymerized monomers remaining after filling from the dental pulp. For this purpose, natural resins dissolved in organic solvents are used. Also, for this purpose, materials containing calcium hydroxide as a main component or materials in which polystyrene is dissolved in an organic solvent are used. (Problem to be solved by the invention) However, although these materials are effective to some extent in blocking properties such as phosphoric acid, they have little effect on the tooth structure and the filling materials filled on top of these film-forming materials. Since it does not adhere, it has the disadvantage that it is likely to cause the filler to fall off or cause secondary caries. Therefore, the present inventors have conducted extensive research on adhesive film-forming materials that can block etching solutions such as phosphoric acid and have adhesive properties to tooth structure and filling materials, and as a result, have provided the present invention. It has been reached. That is, the present invention provides the following formula (1) in the molecule: [However, Z ₁ and Z ₂ are oxygen atoms or sulfur atoms, and Z ₃ is oxygen atoms, sulfur atoms, or -NR'-
(However, R' represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.) aryl group, or

[Formula] (where R'' and R represent the same or different hydrogen atoms, substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups), and n is 0 or 1.] A dental adhesive film-forming material whose main component is an alkoxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, tin, calcium, and iron. The present invention also provides the following formula (1) in the molecule: [However, Z ₁ and Z ₂ are oxygen atoms or sulfur atoms, and Z ₃ is oxygen atoms, sulfur atoms, or -NR'-
(However, R' represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.) aryl group, or

[Formula] (where R'' and R represent the same or different hydrogen atoms, substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups), and n is 0 or 1.] a polymer having a vinyl monomer unit represented by: () an alkoxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, tin, calcium, and iron; and () a chelating agent for the alkoxide of the metal. Provided is a dental adhesive film-forming material containing as a main component.One of the components of the adhesive film-forming material of the present invention has the following formula (1) in the molecule. [However, Z ₁ and Z ₂ are an oxygen atom or a sulfur atom, and Z ₃ is an oxygen atom, a sulfur atom, or -NR'- (However, R' is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. ), where R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or

[Formula] (where R'' and R represent the same or different hydrogen atoms, substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups), and n is 0 or 1.] It is a polymer having a vinyl monomer unit represented by the above formula (1).The need for this polymer to have a phosphorus-containing group represented by the above general formula (1) is due to the fact that the adhesive film forming material of the present invention is This is to provide sufficient adhesive strength and make it durable even when used in wet conditions such as adhesives.In addition, the phosphorus-containing group is not a monomer but a polymer. Therefore, even when the adhesive film-forming material of the present invention is used for dental treatment and restoration, it has the advantage that it is not harmful to the dental pulp and does not cause problems such as polymerization shrinkage. When the adhesive film-forming material of the present invention is used in a wet state, sufficient adhesive strength can be imparted to the adhesive film-forming material of the present invention as long as it has a phosphorus-containing group represented by the above general formula (1). In formula (1), the substituents of the substituted alkyl group or substituted aryl group represented by R, R', R'' and R are not particularly limited, but generally include a halogen atom, an amino group, a hydroxyl group, and an alkoxycarbonyl group. , a carboxyl group or a metal salt thereof, an acryloyl group, a methacryloyl group, etc. are suitable. Also. Among the phosphorus-containing groups represented by the above general formula (1), Z ₁ and Z ₂ are both oxygen atoms, which improves the adhesive strength of the adhesive film forming material of the present invention, and also improves the adhesive strength of the adhesive film forming material of the present invention. This is preferable for reasons such as ease of obtaining raw materials. Furthermore, among the phosphorus-containing groups represented by the general formula (1), Z ₃ is an oxygen atom, R is a hydrogen atom or a substituted or unsubstituted alkyl group, and n is 1. preferable. Further, from the viewpoint of ease of crosslinking reaction with an alkoxide, which will be described later, it is most preferable that R is a hydrogen atom. Moreover, it is preferable that the phosphorus-containing group is directly bonded to any one of C, O, S, and N atoms. Furthermore, from the viewpoint of stability against hydrolysis, bonding with C is more preferable. The polymer of the present invention preferably has a hydrophobic group in addition to the above-mentioned phosphorus-containing group. By using a polymer with hydrophobic groups,
The polymer can have both hydrophilic properties due to phosphorus-containing groups and hydrophobic properties due to hydrophobic groups. In this case, the performance can be particularly improved in adhesion of dissimilar materials, such as a material with a hydrophilic surface and a material with a hydrophobic surface. The hydrophobic group bonded to the polymer used in the present invention is not particularly limited, and known ones can be used. Typical examples of the hydrophobic groups that are generally suitably used are as follows. (1) Aryl groups such as phenyl and naphthyl groups (2) Alkyl groups such as methyl, ethyl, propyl and butyl groups (3) Alkoxy groups such as ethoxy, propoxy and butoxy groups (4) Acetyloxy Acyloxy groups such as groups (5) Alkoxycarbonyl groups such as ethoxycarbonyl groups and butoxycarbonyl groups In addition, the hydrophobic groups shown in (1) to (5) above may be substituted with other substituents as long as the hydrophobic properties are not impaired. May be replaced. These substituents generally include, for example, halogen atoms such as chlorine, bromine, iodine, and fluorine, alkyl groups, alkoxy groups, and phenoxy groups. Further, as will be described in detail later, these hydrophobic groups are generally provided based on the raw materials used when producing the above-mentioned polymer in many cases. Further, the polymer having a phosphorus-containing group used in the present invention may have a carboxyl group or an anhydride group thereof. Suitable polymers having phosphorus-containing groups for use in the present invention are as follows. (b) The following formula [In the formula, R ¹ is a hydrogen atom or an alkyl group,
R ² is an aryl group, an alkyl group, an alkoxy group,
It is an acyloxy group or an alkoxycarbonyl group. ] At least one unit represented by (b) the following formula R ³ and R ⁴ are the same or different hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxyalkyl groups, or alkoxycarbonyl groups. R ⁵ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkenyl group, an acyloxy group,
It is an alkoxycarbonyl group or a cyano group. A is an oxygen atom or a sulfur atom. B is (-X ₁ ) _e --- (-R ⁶ ) _f --- (-X ₂ ) _g --
- is a group represented by. [However, X ₁ and X ₂ are -O-, -S-, -NR〓
-,

【formula】 or

[Formula], and R ⁶ is −R〓−, (−OR〓) _h --R〓OR〓−

[Formula] or (However, R〓 is a hydrogen atom or a substituted or unsubstituted alkyl group, R〓 and R〓 are the same or different substituted or unsubstituted alkylene groups, substituted or unsubstituted alkenylene groups, or alkynylene groups, R〓 is the same or different hydrogen atom, halogen atom, hydroxyl group, alkoxy group, carboxyl group, or phosphonic group, and T
teeth

[Formula] −CH ₂ −,

[Formula] -S- or

[However, R] is a substituted or unsubstituted alkylene group, phenylene group, or benzylene group. ]

Z ₁ and Z ₂ are oxygen atoms or sulfur atoms.
Y is a group represented by (-Z ₃ ) _o --R, or

[Formula] is. [However, Z ₃ is an oxygen atom, a sulfur atom, or -
NR'- (wherein R' represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), R is a hydrogen atom,
a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or

[Formula] (wherein R'' and R represent the same or different hydrogen atoms, substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups), m is an integer of 1 to 5, and m is an integer of 1 to 5. , l and n are 0 or 1.] a, b, c and d are 0 or 1. Consisting of at least one type of unit represented by: General of (a) and (b) above In the formula, a substituted alkyl group,
The substituents of the substituted alkylene group, substituted alkenylene group, or substituted aryl group are not particularly limited and various types may be employed, but generally, halogen atoms, hydroxyl groups, alkyl groups, aryl groups, aryloxy groups, alkylthio groups, alkoxyl groups, etc. group, carboxyl group, amino group, (meth)acryloyl group,
(meth)acryloyloxy group, acyloxy group,
Alkoxycarbonyl group, benzylthio group or

[Formula] (However, Z ₄ is an oxygen atom or a sulfur atom,
R ⁷ is a hydroxyl group, an alkyl group, or an aryl group. ) Groups represented by these are preferred. The above-mentioned hydrophobic group derived from the vinyl monomer having a hydrophobic group is added to the polymer having a phosphorus-containing group in order to impart water resistance and adhesive strength to the tooth substance to the resulting adhesive film-forming material. 40 mol%
It is preferable that the content is ~90 mol%. Furthermore, (c) the following formula [In the formula, R ₁ ' is a hydrogen atom, an alkyl group, or a group in which part of the hydrogen atoms of an alkyl group is substituted with a carboxyl group. x and y are 0 or 1, and x is 0
, y is 1 and R ₁ ′ is a hydrogen atom, and when x is 1, y is 0 and R ₁ ′ is a hydrogen atom, an alkyl group, or a hydrogen atom of a part of an alkyl group is a carboxyl group. It was replaced with . Furthermore, the two carboxyl groups may form an acid anhydride group. ] At least one of the units represented by may be contained in the obtained polymer in a proportion of 20 mol% or less. Also, among the general formulas shown in (b) above, If the number of carbon atoms in the group represented by is in the range of 6 to 40,
Because of its increased hydrophobicity, even polymers that do not contain the units shown in (a) and are composed only of the units shown in (b) and (c) can be suitably used. The polymer used in the present invention generally has a molecular weight of 1,000 to 100,000, preferably 2,000 to 50,000, for reasons of ease of availability and handling.
It is preferable that the The method for obtaining the above polymer is not particularly limited, but generally, a vinyl monomer having a phosphorus-containing group represented by the above general formula (1) is homopolymerized, or a vinyl monomer having the phosphorus-containing group is A preferred method is to copolymerize the monomer with another copolymerizable vinyl monomer, particularly a vinyl monomer having a hydrophobic group. Also suitable is a method in which a vinyl monomer having a phosphate ester group is copolymerized with another copolymerizable vinyl monomer, and the phosphate ester group in the resulting copolymer is hydrolyzed to convert it into the above-mentioned phosphorus-containing group. will be adopted. Examples of vinyl monomers having a phosphorus-containing group that are preferably used for producing the polymer having a phosphorus-containing group represented by the general formula (1) are as follows.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

Moreover, the vinyl monomer that can be copolymerized with the vinyl monomer having a phosphorus-containing 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 halogen derivatives of olefin compounds such as vinyl chloride and hexafluoropropylene; diolefin compounds such as butadiene and pentadiene. and its halogen derivatives; aromatic vinyl compounds such as styrene, divinylbenzene, vinylnaphthalene;
Vinyl ester compounds such as vinyl acetate; acrylic acid and methacrylic acid derivatives such as methyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, acrylamide, and methacrylic acid amide; acrylonitrile, etc. Unsaturated nitrile compounds: Vinyl ether compounds such as methyl vinyl ether; Acrylic acid vinyl monomers such as acrylic acid and methacrylic acid; Unsaturated dibasic carboxylic acids such as maleic acid, fumaric acid, itaconic acid, maleic anhydride, and itaconic anhydride. Monomers include aromatic unsaturated carboxylic acid monomers such as 4-methacryloxyethyl trimellitic acid, and substituted derivatives obtained by substituting these vinyl monomers with substituents. 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. Any known vinyl monomer having a hydrophobic group can be used without particular limitation. Specific examples of generally suitable vinyl monomers include styrene, methylstyrene, vinylnaphthalene, propylene, butene, ethyl vinyl ether, butyl vinyl ether, vinyl acetate, ethyl methacrylate, butyl acrylate, and the like. The above-mentioned vinyl monomers can also be copolymerized singly or in combination of two or more of the above-mentioned vinyl monomers having a phosphorus-containing group. The method for carrying out the above polymerization is not particularly limited, and any known method may be used, but radical polymerization is particularly preferably used. Generally known polymerization initiators used in radical polymerization are also employed. For example, organic peroxides such as benzoyl peroxide and lauroyl peroxide; peroxodisulfates such as potassium peroxodisulfate and ammonium peroxodisulfate; azo compounds such as azobisisobutyronitrile; organometallic compounds such as tributylboron; Polymerization using a redox initiator can be suitably used. It is sufficient to use these polymerization initiators in an amount of 0.01 to 3% by weight based on the monomer components such as the vinyl monomer having a phosphorus-containing group and the copolymerizable vinyl monomer. The other main component of the adhesive film forming material of the present invention is at least one metal alkoxide selected from the group consisting of titanium, zirconium, aluminum, tin, calcium and iron. The alkoxide used in the present invention is not particularly limited as long as it is listed above, and any known alkoxide can be used, and can be used alone or in combination. As titanium alkoxide, tetra-
iso-propyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexyl)
Alkyl titanates such as titanate, tetrastearyl titanate, tri-n-butoxymonostearyl titanate: di-iso-propoxy bis(acetylacetone) titanate, di-
n-Butoxy bis(triethanolamine) titanate, dihydroxy bislacteiacid) titanate, tetraoctylene glycol titanate; isopropyl tri-iso-stearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate,
Tetra-iso-propyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)
Bis(di-tridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, and the like are used alone or in combination. As the titanium alkoxide used in the present invention, alkyl titanates represented by the following general formula are particularly preferably used. (However, R is an alkyl group, and n is a number up to 0 or 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 zirconium alkoxides include alkyl zirconates such as tetramethyl zirconate, tetraethyl zirconate, tetra-iso-propyl zirconate, tetra-sec-butyl zirconate, tetra-n-butyl zirconate, and tetra-iso-butyl zirconate. Nates are preferably used alone or in combination. Examples of aluminum alkoxide include aluminum-iso-propoxide, aluminum-n-butoxide, aluminum-sec-butoxide, aluminum-iso-butoxide,
Aluminum-t-butoxide and the like are preferably used alone or in combination. Examples of tin alkoxide include chintetraethoxide, chintetra-iso-propoxide,
chintetra-iso-butoxide, chintetra-
Chin alkoxides such as n-butoxide and chintetra-t-butoxide are preferably used alone or in combination. Calcium alkoxides include calcium-isopropoxide, calcium-n-butoxide, calcium-iso-butoxide,
Calcium-t-butoxide and the like are preferably used alone or in combination. Examples of iron alkoxides include ferrite-iso-propoxide and ferrite-n-propoxide.
Ferrite alkoxides such as butoxide, ferrite-iso-butoxide, ferrite-tert-butoxide and the like are preferably used alone or in combination. The amount of alkoxide used in the adhesive film-forming material of the present invention is not particularly limited, but it is generally added at a ratio of 0.02 mol to 1.0 mol per 1 mol of phosphorus-containing groups of the polymer having phosphorus-containing groups. is preferred. If the amount of the alkoxide added is less than 0.02 mol, the water resistance of the adhesive film-forming material may decrease, and the field of use may be restricted. Furthermore, if the amount of the alkoxide added exceeds 1.0 mol, the curing time may become too short during curing, resulting in a decrease in operability, which may limit the field of use. Therefore, in the present invention, each addition ratio is preferably determined in advance depending on the physical properties required in the field of use. The method of mixing the polymer having a phosphorus-containing group and the alkoxide in the present invention is not particularly limited, but a method of mixing in the presence of an organic solvent is most preferably used. The organic solvent is not particularly limited, but ethanol, ethyl acetate, acetone, etc., which generally have a low boiling point and can be easily removed, are preferably used. The adhesive film forming material of the present invention has the above-mentioned general formula (1).
The two components, a polymer having a phosphorus-containing group shown in
Furthermore, by using a chelating agent for the metal alkoxide, the adhesive film forming material of the present invention can be stored for a long period of time. The chelating agent is not particularly limited as long as it is generally known, and can be used alone or in combination of two or more. Specifically, triethanolamine, diethanolamine,
Alkanolamines such as monoethanolamine and dimethylaminoethanol; Acetoacetic acid esters such as methyl acetoacetate and acetoacetic acid; β- such as acetylacetone and benzoylacetone
Diketones; malonic acid esters such as dimethyl malonate and diethyl malonate; salicylic acid esters such as methyl salicylate and ethyl salicylate; ethylene glycol, 1,3-propanediol, 1,3-butanediol, octylene glycol, etc. Glycols; α-hydroxycarboxylic acids such as lactic acid and tartaric acid are used. In addition, among the chelating agents, the following (a)
The compounds listed in (e) to (e) are preferably used from the viewpoint of storage stability. (a) General formula (However, n is 0, 1, 2, 3, or 4, X is an alkyl group, alkoxyl group, carboxyl group, or acylalkyl group, and R is an alkyl group, haloalkyl group, alkoxyalkyl group, carboxyalkyl group, phenolic A benzoic acid derivative represented by a sialkyl group, an aryl group, an alkoxyaryl group, an acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a benzyl group. (b) General formula (However, R is a hydrogen atom, an alkyl group, or an acyl group.) A carboxylic acid compound having a unit bonded within the molecule. (c) General formula (However, R is an alkyl group or an aryl group, X is a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and an alkenyl group, and n is an integer of 1 to 4.) Catechols shown in (d) General formula

【formula】

【formula】

〔effect〕

The adhesive film-forming material of the present invention is useful, for example, as a paint base, a coating material for resin or glass, a dental treatment restorative material, and the like. The above-mentioned dental treatment and restorative material refers to a material that is used in tooth treatment and restoration and is applied to the surface of a tooth or a cavity provided in a tooth, and is the most preferred adhesive film-forming material of the present invention. This is an important use. Examples of such materials include tooth adhesives,
Examples include lining materials for protecting the dental pulp, and materials for sealing the edges of teeth and filling materials. The case where the adhesive film-forming material of the present invention is used as a dental treatment and restorative material will be described below. BACKGROUND ART Conventionally, in dental treatment and restoration, when a tooth cavity is filled with a filling material such as a composite restorative resin, an adhesive is used to bond the tooth substance and the filling material. However, since conventional adhesives exhibit almost no adhesion to the tooth structure, it is necessary to demineralize the tooth structure by pre-treating the tooth structure with a highly concentrated phosphoric acid aqueous solution and create a mechanical retention form. Ta. However, this method uses a highly concentrated phosphoric acid aqueous solution, which has the disadvantage of damaging even the healthy tooth structure.Especially when etching dentin, not only is the adhesive strength less than expected, but also the dental pulp is passed through the dentinal tubules. The effects of the phosphoric acid aqueous solution may even be felt. Furthermore, since the above method inevitably leaves unreacted monomers, there is a risk that these monomers may cause damage to the dental pulp. However, when the adhesive film-forming material of the present invention is used as an adhesive, it can be directly adhered to dentin without pre-treatment with the phosphoric acid aqueous solution, and since the adhesive film-forming material itself is originally a polymer, it can be bonded directly to dentin. It exhibits excellent effects in that it does not cause any damage to the dental pulp due to the reactive monomer, and also does not cause problems such as polymerization shrinkage. Next, conventional lining materials for pulp protection include calcium hydroxide-based materials and cement, and the dentin is removed from the phosphoric acid etching performed when filling with composite restorative resins and other filling materials. It is used for protection, etc. However, these materials inevitably form a thick film and do not have adhesive properties with the filling material, making it almost impossible to fill shallow cavities. Therefore, by dissolving the adhesive film-forming material of the present invention in an organic solvent and using it as the lining material, it is possible to protect the tooth structure from the phosphoric acid etching solution even though it is a thin film, and it also adheres to the filling material. Demonstrates excellent functionality. In addition, zinc phosphate cement, which is still commonly used to bond metal teeth, contains a large amount of phosphoric acid in its composition, which may cause damage to the pulp. It was desired to use a backing material for protection. However, conventional lining materials with thick coatings could not be used because their own compressive strength was a problem. Therefore, when the adhesive film-forming material of the present invention is used as the backing material, since it is a thin film, it does not require much strength on its own, and moreover, it exhibits the ideal effect of not allowing phosphoric acid to pass through. I'm going to do it. Furthermore, a third function of the adhesive film-forming material of the present invention is edge sealing properties. As a known substance that is expected to have the above function, for example, a resin such as copalite dissolved in an organic solvent, which is used in amalgam filling, is known. Although this material does form a thin film, it has no adhesive strength with tooth structure or amalgam, and is not very effective in sealing the margins. By using the adhesive film-forming material of the present invention as the edge sealing material, remarkable effects are exhibited in terms of edge sealing properties. Considering the fact that the adhesive film-forming material adheres to tooth structure but not to amalgam, the above function is thought to be due to properties other than adhesiveness, such as adhesion and hydrophobicity. . In addition to amalgam filling, it is also possible to improve the margin sealing properties by using the adhesive film forming material in composite restoration ranges, cement filling, rubber capping, and the like. It is possible to use the adhesive film forming material of the present invention for purposes other than those described above. For example, by applying the adhesive film-forming material of the present invention to areas where dentin is exposed on the tooth surface due to a wedge-shaped defect in the tooth cavity, etc., when the material filling the ivory cavity is removed. It can also be used as a shield against external stimuli. Above, the functions as a tooth adhesive material, a lining material for protecting the pulp, and a margin sealing material have been explained individually, but since the adhesive film forming material of the present invention has all of these functions, In one case, all of the above functions can be achieved by simply using the adhesive film-forming material of the present invention. Therefore, in the past, in one case, it was necessary to use multiple materials in combination, which made the operation extremely complicated, and the use of multiple materials in combination resulted in deterioration of each other's functions. Considering what I was doing,
The adhesive film-forming material of the present invention is an extremely useful composition as a dental treatment and restorative material. When the adhesive film-forming material of the present invention is used as a dental treatment restorative material, the polymer having a phosphorus-containing group, which is one of the components of the present invention, must also have a hydrophobic group. It is preferred in order to further improve its function as a therapeutic and restorative material. This is effective in imparting water resistance since the oral cavity is under harsh conditions of 100% humidity. Furthermore, when the adhesive film-forming material of the present invention is used to bond tooth structure and composite restorative resin, the phosphorus-containing group has an affinity for the tooth structure, while the hydrophobic group has an affinity for the tooth structure. Because it has an affinity for composite repair resins, it has significantly improved adhesive strength compared to conventional adhesives. In addition, by using a chelating agent, it is not only possible to preserve alkoxides that easily react with moisture in the air or solvent for a long period of time, but also to prevent chelation during mixing. By adjusting the amount of the agent added, it became possible to control the operation time according to the conditions. 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 381
(Bacteroides gingivalis 381) Actinomyces naesrundeii ATCC
12104 (Actinomyces naeslundii ATCC 12104) Actinomyces viscosus ATCC 15987
(Actinomyces viscosus ATCC 15987) Propionibacterium acnes EXC-1
(Propionibacterium acnes EXC-1) Actinomyces israeli ATCC 12102
(Actinomyces israeli ATCC 12102) Furthermore, since the adhesive film-forming material of the present invention has the property of adhering to the skin and mucous membranes, it has the above-mentioned antibacterial effect, and when applied to the cut site, The affected area can be sterilized and protected. Further, 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, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Production example of a polymer having a phosphorus-containing group (1) A vinyl monomer having a phosphorus-containing group shown in Table 1, a copolymerizable vinyl monomer, an initiator, and a solvent were placed in a glass container, and while stirring, N ₂
Polymerization was carried out in an air stream at a constant temperature for a certain period of time.
After polymerization, the polymer was taken out, and residual monomers were removed by dialysis or polymer precipitation separation.
Analysis is confirmed by infrared absorption or BC-NMR,
Molecular weight was confirmed by GPC.

【table】

[Table] (2) Put the vinyl monomer having a phosphorus-containing group and the copolymerizable vinyl monomer shown in Table 2, an initiator, and a solvent into a dropping funnel, and drop them into a flask containing the same solvent and initiator. Polymerization was carried out while The polymerization method was carried out under stirring and a constant temperature in a N ₂ stream, and the reaction was continued at the same temperature for 3 hours after the dropwise addition. To determine the degree of polymerization, the contents were taken out and residual monomers were separated by dialysis or precipitation.

【table】

[Table] (3) Put the vinyl monomer having a phosphorus-containing group shown in Table 3, an initiator, and benzene into a glass autoclave, exchange the gas inside the container with _N2 , and then immerse the autoclave in a dry ice-methanol bath. A certain amount of copolymerizable vinyl monomer gas was charged while the inside of the container was kept at a low temperature. Next, the mixture was heated to a constant temperature and polymerized while stirring. After polymerization, the contents were taken out and residual monomers were removed by dialysis or precipitation.
Analysis was confirmed by infrared absorption or C- ¹³ NMR, and molecular weight was confirmed by GPC.

[Table] (4) Vinyl monomers having phosphorus-containing groups shown in Table 4, copolymerizable vinyl monomers, BPO
Then, benzene was placed in a dropping funnel, and polymerization was carried out while dropping the mixture into a flask containing benzene in advance. After reacting in N ₂ at 70° C. for 6 hours, the contents were taken out and concentrated to obtain each polymer.

【table】

[Table] Example 1 Solutions of polymers having phosphorus-containing groups shown in Table 5
The following tests were conducted using adhesive film-forming materials consisting of (A) and an alkoxide-containing solution (B). (1) Adhesion to dentin (2) Marginal sealing to cavities (3) Barrier to phosphoric acid aqueous solution The above tests were evaluated in the following manner. First, paste () and paste () were prepared according to the following formulation. () Bisglycidyl methacrylate triethylene glycol dimethacrylate dimethyl p-toluidine silane-treated quartz powder (particle size 80 μm or less) 11.0 parts by weight 10.5 〃 0.5 〃 78.0 〃 () bisglycidyl methacrylate triethylene glycol dimethacrylate benzoyl peroxide silane-treated quartz powder ( Particle size: 80 μm or less) 11.0 parts by weight 10.5 〃 0.5 〃 78.0 〃 (1) Adhesion to dentin The labial surface of a freshly extracted bovine tooth was polished with emery paper (#320) to expose the smooth dentin, and then polished. After washing the surface with water for 30 seconds, the surface was dried by blowing nitrogen gas. A 2 mm thick wax plate with 4 mm diameter holes was attached to the 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 bitten with plate-shaped wax, and nitrogen gas is blown to remove the excess ethanol. The adhesive film forming material was removed. The above pastes () and (2) were mixed at a ratio of 1:1 and filled thereon.
After being left for one hour, the wax plate was removed, and the sample was immersed in water at 37°C for a day and night, and then its tensile strength was measured. Tensilon manufactured by Toyo Bald Wind Co., Ltd. was used for the measurement, and the tensile speed was 10 mm/min. The results obtained are shown in Table 5.

【table】

【table】

【table】

【table】

[Table] (2) Margin sealing properties for cavities A cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of an extracted human tooth. Next, using the adhesive film-forming material shown in Table 5 and a conventionally used commercial product (copalite) for comparison, each was thinly applied to the wall of the cavity, and then filled with cement or amalgam. After 1 hour of filling, store in water at 37℃,
After a day, a percolation test was conducted in which the sample was immersed in an aqueous solution of fuchsin at 4°C and 6°C for 60 times for 1 minute alternately to test its margin sealing properties. The extracted tooth was then sectioned down the center to examine whether there was any pigment (fuchsin) intruding between the cavity and the filling. The reproducibility of the above tests was confirmed using five samples for each type of experiment. As a result, pigment intrusion was observed in all samples that were filled with linear amalgam or cement without using the above composition, or those that were coated with copalite and then filled with amalgam or cement. On the other hand, regarding the adhesive film forming materials in Table 5,
In all cases, no dye penetration was observed, and good results were obtained. (3) Blocking property against phosphoric acid aqueous solution In order to confirm that the adhesive film-forming material of the present invention has the ability to block phosphoric acid aqueous solution, a test was conducted using the following method. First, a membrane filter with a pore size of 3 μm was soaked in distilled water for 1 hour, then taken out, and the surface was dried by blowing nitrogen gas. Next, commercially available Copalite, Dical, and the adhesive film-forming materials shown in Table 5 were applied to the back surface as barrier materials (backing materials), and nitrogen gas was again blown to remove the solvent. A 37% orythophosphoric acid aqueous solution was used as the phosphoric acid aqueous solution, and one drop was dropped onto the barrier material and left to stand. In order to detect phosphoric acid passing through the above-mentioned blocking material, a PH test paper was placed under the above-mentioned membrane filter, and the time when the color changed was determined as the passage time. As a result, the permeation time of the phosphoric acid aqueous solution was 15 seconds in the case where no barrier material was used, and 1 minute and 10 seconds in the case using Copalite (trade name).
In addition, it took 10 minutes for the product using Dycal (trade name). On the other hand, when the adhesive film forming material of the present invention shown in Table 5 was used as the barrier material, the permeation time of the phosphoric acid aqueous solution was 1 hour or more in all cases. Example 2 Using an adhesive film forming material consisting of a solution (A) of a polymer having a phosphorus-containing group and a solution (B) containing an alkoxide and a chelating agent shown in Table 6, Example 1 and The following test was conducted in a similar manner. (1) Adhesion to dentin (2) Marginal sealing to cavities (3) Barrier to phosphoric acid solution The adhesive strength to dentin is shown in Table 6.
All of the adhesive film-forming materials shown in Table 6 had good margin sealing properties for cavities, and no intrusion of dye was observed. Regarding the barrier properties against phosphoric acid aqueous solution, the 6th
As a result of using the adhesive film-forming materials of the present invention shown in the table as a barrier material, the permeation time of the phosphoric acid aqueous solution was 1 hour or more in all cases.

【table】

【table】

【table】

【table】

【table】

[Table] Example 3 Solutions of polymers with phosphorus-containing groups shown in Table 7
(B) and a solution containing an alkoxide and a chelating agent (B) using an adhesive film forming material,
The following test was conducted in the same manner as in Example 1. (1) Adhesion to dentin (2) Marginal sealing to cavities (3) Barrier to phosphoric acid aqueous solution The adhesive strength to dentin is shown in Table 7. Both the margin sealing properties for the cavity and the adhesive film forming material shown in Table 7 were good, and no intrusion of the dye was observed. Regarding the barrier properties against phosphoric acid aqueous solutions, when the adhesive film forming materials of the present invention shown in Table 7 were used as barrier materials, the permeation time of phosphoric acid aqueous solutions was 1 hour or more in all cases.

【table】

【table】

【table】

【table】

[Table] Example 4 The storage stability of the solution (B) containing an alkoxide and a chelating agent shown in Tables 6 and 7 was investigated. Solution (B) was placed in a glass container at 20°C.
It was stored at 37°C and 45°C. Storage stability was then compared and studied with the end point being when the solution gelled or lost its transparency. As a result, No. 1 to No. 81 in Table 6, No. 1 in Table 7
- No. 55 did not cause precipitation, lose transparency, or gelation for more than 12 months. Further, No. 56 to No. 65 in Table 7 did not cause precipitation even after 6 months had passed. Example 5 When an adhesive film-forming material consisting of a solution (A) of a polymer having a phosphorus-containing group shown in Tables 5, 6, and 7 and a solution (B) containing an alkoxide was mixed. The gelation rate was measured. For measurement, drop 0.5 ml of solution (A) and solution (B) into a 5 ml transparent glass container, shake for 10 seconds, and then
The mixture was allowed to stand, and the time at which gelation started was determined visually. As a result, the adhesive film forming materials consisting of solutions (A) and solutions (B) shown in Tables 6 and 7 were both
Gelation started after 30 minutes or more. On the other hand, when using solution (A) and solution (B) shown in Table 5, both
Gelation started within 10 minutes. Example 6 Brain Heart Infusion
Heart Infusion medium (agar and Brain Heart Infusion)
A flat plate was prepared in a shear dish using a medium consisting of
400ml of a diluted solution of the following bacteria cultured on an agar plate.
After dropping it and spreading it evenly over the surface, the surface was dried. No. 1, No. 5, No. 7, No. 10, No. 14, No. of Example 1.
16, No.18, No.19, No.20, No.21, No.29, No.32, No.
33, No.35, No.36, No.37, No.38, No.39, No.40, No.
41, No. 42, No. 43, No. 44 (A) liquid and (B) liquid are mixed,
After soaking a paper disk in this, the ethanol was evaporated, the plate was placed on a plate, and anaerobic culture was performed for 48 hours. After 48 hours, an antibacterial zone several millimeters wide had formed at the edge of the paper for all bacteria. Bacterium used Bacteroides gingivalis 381
(Bacteroides gingivalis 381) Actinomyces naesrundeii ATCC
12104 (Actinomyces naeslundii ATCC 12104) Actinomyces viscosus ATCC 15987
(Actinomyces viscosus ATCC 15987) Propionibacterium acnes EXC-1
(Propionibacterium acnes EXC-1) Actinomyces israeli ATCC 12102
(Actinomyces israeli ATCC 12102) Example 7 Example 1 for a patient who has a wedge-shaped defect in the tooth neck and feels pain when exposed to air or cold water.
When liquids (A) and (B) shown in No. 1, No. 5, No. 7, and No. 18 were mixed and applied to the wedge-shaped defect, the pain caused by contact with air and cold water was relieved. It was done. No. 1, No. 5, No. 7, No. 10, No. 14, No. of Example 1.
16, No.18, No.19, No.20, No.21, No.29, No.32, No.
33, No.35, No.36, No.37, No.38, No.39, No.40, No.
41, No. 42, No. 43, No. 44 (A) liquid and (B) liquid are mixed,
It was applied to the skin incision. As a result, the wound is sealed and the pain is alleviated. Also, when applied to the affected area of stomatitis, it no longer oozed out due to food and drink. Example 8 Brain Heart Infusion
Heart Infusion medium (agar and Brain Heart Infusion)
A flat plate was prepared in a shear dish using a medium consisting of
400ml of a diluted solution of the following bacteria cultured on an agar plate.
After dropping it and spreading it evenly over the surface, the surface was dried. No. 1, No. 5, No. 7, No. 10, No. 14, No. of Example 2.
16, No.18, No.19, No.20, No.21, No.29, No.32, No.
33, No.35, No.36, No.37, No.38, No.39, No.40, No.
41, No.42, No.43, No.44, No.45, No.61, No.67, No.
72, No. 77, solutions (A) and (B) were mixed, a disk of paper was soaked in the mixture, the ethanol was evaporated, the solution was placed on a flat plate, and anaerobic culture was performed for 48 hours. After 48 hours, an antibacterial zone several millimeters wide had formed at the edge of the paper for all bacteria. Bacterium used Bacteroides gingivalis 381
(Bacteroides gingivalis 381) Actinomyces naesrundeii ATCC
12104 (Actinomyces naeslundii ATCC 12104) Actinomyces viscosus ATCC 15987
(Actinomyces viscosus ATCC 15987) Propionibacterium acnes EXC-1
(Propionibacterium acnes EXC-1) Actinomyces israeli ATCC 12102
(Actinomyces israeli ATCC 12102) Example 9 Example 2 for a patient who has a wedge-shaped defect in the tooth neck and feels pain when exposed to air or cold water.
When liquids (A) and (B) shown in No. 1, No. 5, No. 7, and No. 18 were mixed and applied to the wedge-shaped defect, the pain caused by contact with air and cold water was relieved. It was done. No. 1, No. 5, No. 7, No. 10, No. 14, No. of Example 2.
16, No.18, No.19, No.20, No.21, No.29, No.32, No.
33, No.35, No.36, No.37, No.38, No.39, No.40, No.
41, No.42, No.43, No.44, No.45, No.61, No.67, No.
72, No. 77, solutions (A) and (B) were mixed and applied to the skin incision. As a result, the wound is sealed and the pain is alleviated. Also, when applied to the affected area of stomatitis, it no longer oozed out due to food and drink.

Claims (1)

[Claims] 1 () The following formula (1) in the molecule [However, Z ₁ and Z ₂ are oxygen atoms or sulfur atoms, and Z ₃ is oxygen atoms, sulfur atoms, or -NR'-
(However, R' represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.) Aryl group, or [Formula] (where R'' and R represent the same or different hydrogen atoms, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), and n is 0 or 1 ] A polymer having a vinyl monomer unit represented by () and a dental product containing as a main component an alkoxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, tin, calcium and iron. It is an adhesive film forming material. 2 () The following formula (1) is in the molecule. [However, Z ₁ and Z ₂ are oxygen atoms or sulfur atoms, and Z ₃ is oxygen atoms, sulfur atoms, or -NR'-
(However, R' represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.) Aryl group, or [Formula] (where R'' and R represent the same or different hydrogen atoms, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), and n is 0 or 1 ] A polymer having a vinyl monomer unit represented by () an alkoxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, tin, calcium and iron; and () an alkoxide of the metal. A dental adhesive film-forming material whose main ingredient is a chelating agent.