JPS6013866A - Adhesive film forming material - Google Patents

Abstract

PURPOSE:To obtain the titled film-forming material having the functions of the dental adhesive, the pulp-protecting lining, and the border-sealing material, and storable for a long period, by using a carboxyl-containing polymer, an organic titanate, and a specific benzoic acid derivative as main components. CONSTITUTION:The objective material is obtained by mixing (A) a carbosyl-containing polymer having a molecular weight of 1,000-100,000 and preferably having a hydrophobic group, (B) 0.02-1.0mol (based on 1 mole of the carboxyl group of the component A) of an organic titanate (e.g. tetra-iso-propyl titanate) and (C) 0.1-4mol (based on 1 mole of the component B) of a benzoic acid derivative of formula [n is 0 or 1-4; X is alkyl, alkoxy, carboxy, etc.; R is (halo) (alkoxy)alkyl, etc.](e.g. 2-methyl-6-methoxybenzoic acid).

Description

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

In detail, (i) a polymer having a carboxyl group, (
11) Organic titanes 1 to (iii) General formula, group, where R is an alkyl group, haloalal, or kyl group.

These include an alkoxyalkyl group, a carboxyalkyl group, a phenoxyalkyl 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. ) is an adhesive film-forming material whose main component is the benzoic acid derivative shown below.

Conventionally, adhesive wave film-forming materials, such as adhesives, are 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 on biological hard tissue, particularly in a wet state. 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 adhesion to tooth tissue, it has no adhesion to other dental filling materials and has low water resistance, so it has the drawback of being easily dislodged in water. Furthermore, adhesives using polymerizable monomers adhere to enamel, but hardly adhere to dentin. For this reason, the tooth substance is treated in advance with a highly concentrated phosphoric acid aqueous solution1.
It was necessary to demineralize the mineral by demineralizing it 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.

Further, since adhesives are required to have properties specific to each field depending on the field of use, 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, it is known that when an organic titanate is mixed into a solvent in which a polymer having a carboxyl group is dissolved, a crosslinking reaction proceeds immediately, resulting in gelation in a short time or precipitation of a crosslinked hard substance. There is. Therefore, it has been considered that it is not possible to mix a polymer having a carboxyl group and an organic titanate and store the mixture in a one-component type.

In order to compensate for such deficiencies, attempts have been made to add organic titanate stabilizers to the above system for liquid-type storage. 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, polymers having carboxyl groups and organic titanium
It has not been possible to completely prevent the crosslinking reaction between the two, and it has not been possible to store both in a one-component state industrially or as a product.

Therefore, the present inventors have conducted repeated research to solve the above drawbacks, and have found that when a compound with a specific groove structure formula among benzoic acid derivatives is used as a stabilizer for organic butanate, The present inventors have discovered that a one-component composition that can be stored can be obtained, and have provided the present invention.

However, the present invention comprises (1) a polymer having a carboxyl group, (ii)
Paid titanate, and (iii) General formula, sen・a/, /l/W r, 8yua/I/ −1=
/l, W.

haloaralkyl group, alkoxy alkyl group, carboxyl alkyl group.

Phenoxyalkyl group, aryl group.

Alkoxyaryl group, acyl group Roxyl group, acyloxyacyl group.

Alkoxycarbonyl, allyl group Or benzyl call. ) is indicated by The main ingredient is benzoic acid derivatives. It is an accommodative film forming material.

One of the main components of the adhesive film forming material of the present invention is a polymer having a carboxyl group or a carboxylic anhydride group. The need for the polymer to have carboxyl groups is such that it has sufficient adhesive strength and can withstand use even when used in wet conditions, such as dental lining materials and dental adhesives. This is to do so. Particularly effective are polymers in which two carboxyl groups are bonded, and moreover, polymers in which two carboxyl groups are bonded to adjacent carbon atoms. Further, in order to impart water resistance to the adhesive film-forming material and impart compatibility with the material to be adhered to, it is more preferable to select a polymer having a hydrophobic group.

The carboxyl group-containing polymer is not particularly limited and any known polymer can be used, but it generally has a molecular weight of 1.000 to 1.000.
A range of 100.000 is most preferred. Furthermore, the method for obtaining the polymer is not particularly limited, and any known method can be employed. Generally, it is produced by homopolymerizing a vinyl monomer having a carboxyl group or by copolymerizing a copolymerizable vinyl monomer having the functional group with another copolymerizable vinyl monomer, especially a vinyl monomer having a hydrophobic group. The method is suitable.

Also suitable is a method in which a vinyl monomer having a carboxylic acid ester group is copolymerized with another copolymerizable vinyl monomer, and the carboxylic acid ester group in the resulting copolymer is hydrolyzed to convert it into a carboxyl group. Adopted.

In order to impart adhesive properties to the adhesive film-forming material of the present invention, the amount of carboxyl groups in the polymer is preferably 0.001 mol or more per 1 g of the polymer.

The carboxyl group-containing vinyl monomer is not particularly limited and can be used, but the following are examples of those that are generally suitably used. Namely, acrylic acid-based vinyl monomers such as acrylic acid and methacrylic acid, unsaturated dibasic carboxylic acid monomers such as maleic acid, fumaric acid, itafonic acid, maleic anhydride, and itaconic anhydride; Aromatic unsaturated carboxylic acid monomers or 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 carboxylic acid anhydride is not particularly limited, and known ones can be used. Typical examples that are generally preferably used include, for example, ethylene,
Olefin compounds such as propylene and butene and halogen derivatives of olefin compounds such as vinyl chloride and hexafluoropropylene: Diolefin compounds such as butadiene and pentadiene and their halogen derivatives: styrene,
Divinylbenzene.

Aromatic vinyl compounds such as vinylnaphthalene; vinyl ester compounds such as vinyl acetate; methyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate,
Acrylic acid and methacrylic Ilu derivatives such as ethylene glycol diacrylate, diethylene glycol dimethacrylate, acrylamide, and methacrylic acid amide;
Examples include unsaturated nitrile compounds such as acrylonitrile; vinyl ether compounds such as methyl vinyl ether.

Generally speaking, as described above, among the copolymerizable vinyl monomers used as raw materials in the present invention, vinyl monomers having a hydrophobic group are preferably used. By using a vinyl monomer having a hydrophobic group, the polymer can have the properties of both a hydrophilic group and a hydrophobic group due to carboxyl groups. In this case, as will be described later, the performance can be particularly improved in 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 can be used, but representative hydrophobic groups that are generally preferably used include, for example, a phenyl group.

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

Alco-thousand groups such as butoxy group; 7 such as acetyloxy group
Syloxy base; ethoxycarbonyl group.

These include a butoxy group, an alkoxycarbonyl group such as a rubonyl group, and the like.

Known vinyl monomers having these functional groups can be used without particular restriction. Specific examples of generally suitable vinyl monomers include styrene, methylstyrene, vinylnaphthalene, propylene, butene, and ethyl vinyl ether.

These include butyl vinyl ether, vinyl acetate, ethyl methacrylate, butyl acrylate, etc.

Furthermore, 4-methacryloxyethyl trimellitic acid or its acid anhydride is preferably used as a compound having a carboxyl group and a hydrophobic group in the same molecule.

The hydrophobic group derived from the vinyl monomer having a hydrophobic group is 40 mol% in the polymer having a carboxyl group.
It is preferable that the content is 90 mol%. 4 hydrophobic groups
When the amount is less than 0 mol %, water resistance tends to be insufficient, especially when the adhesive film forming material of the present invention is used as a dental adhesive. Moreover, if it exceeds 90 mol%, there is a tendency that adhesive strength with the tooth structure cannot be obtained.

It is also possible to copolymerize one or more of the above vinyl monomers having a carboxyl group or carpolic anhydride group by mixing them. 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; peroxo-sulfates such as potassium peroxo sulfate and ammonium sulfate;
Polymerization carried out using an azo compound such as azobisin butyronitrile; a metal compound such as tributyl boron, or a redox initiator can be suitably used.

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

The main component of the adhesive film-forming material of the present invention is an organic titanate.

The organic titanate used in the present invention is not particularly limited, and any known organic titanate can be used. For example, alkyl titanates such as tetra-1so-propyl titanate, tetra-n-butyl titanate, tetrakis(2L ethylhexyl) titanate, tetrastearyl titanate, tri-butoxymonostearyl titanate
so-propoxy bis(acetylacetone) titanate, di-n-butoxy bis(triethanolamine)
Titanate, dihydroxy bis(raftiquacid)
titanate, tetraoctylene glycol titanate,
; Isopropyl tris 1 So-stearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl tris 1-1) titanate 1-. Detler is.

-buD virhis(dioctyl small sulfate l-) ditanate, 1-laoquodi bis(di-1 helidecylbosnoj'ite) ditanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-1 heliacyl) phosphite Seed 1~, Bi's〈JA Kujirupyro Small Sufu I
-1-)-A Kishino 7 Seji 1-Ditane 1~. Jis (
DiA-ctylbairobosuno-1-to) ethylene ditane-1-
etc. may be used alone or in combination. In addition, the liquid titanate 1 used in the present invention can sufficiently store liquid titanates, especially alkyl titanates as shown by the following general formula. That is, it is sufficiently effective against organic titanes 1 to 1 represented by the general formula (wherein R is an alkyl group and n is O or a number up to 20), which are generally considered to have poor storage stability. It is true.

The amount of organic titanate used in the adhesive film-forming material of the present invention is not particularly limited, but is generally based on 1 mole of carboxyl groups of the polymer containing carboxyl groups.
, is preferably added in a proportion of 0.02 to 1.0 mol. If the amount of the organic titanate 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 organic titanate added exceeds 1.0 mol, the curing time may become too short during curing, resulting in decreased operability, and the field of use may be limited.

Therefore, in the present invention, it is preferable that each addition ratio is determined in advance depending on the physical properties required in the field of use.

The third component used in the adhesive film-forming material of the present invention has the general formula:

j) An alkyl group, a carboxyl group, or an acylargyl group, where R is an alkyl group, a haloargyl group, a carboxyalkyl group, a carboxyalkylnoenoxyph group, an aryl group, an alkoxyaryl group, an acyl group, or a haloacyl group. , acyloxyacyl, alkoxycarbonyl group.

It is 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 the reason why it is possible to treat a polymer having a carboxyl group and an organic titanate as a one-component type? It is not yet clear. However, the following conclusions can be deduced from the results of statistical experiments. That is, in the general formula, -OR group and -0 0 0 1-
One unit must be located at the A-root position of Bekinzenza. It is speculated that the reason for this is that titanium forms a coordinate bond between the -OR group and the oxygen atom of the 1000H group, thereby maintaining a stable six-membered corner state. However, even if the above -OR group is 10 R groups, even if the hydrogen atom of one COOH group is not substituted at another position, or even if it is a compound that satisfies both of these at the same time, such as salicylic acid, the present invention is applicable. It is not possible to make the most of the effect. However, regardless of whether it is substituted with the above-mentioned - group (X in the above general formula) or the number of substituents,
However, the effect of the present invention is that the group (-C O OH) and -
It is presumed that when the OR group is located at the 1- to 1-positions and the -0I group [( is not a hydrogen atom), it selectively acts to stably hold titanium.

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. Generally, an alkyl group of X or R represented by the above general formula in terms of industrial availability, ease of handling, etc.
An alkyl group such as an alkoxy group, a haloalkyl group, or a phenoxyalkyl group is a lower alkyl group, e.g. 1 to 4 carbon atoms.
Preferred are haloalkyl groups 9. The halogen atoms in the heroacyl group are chlorine and bromine.

Iodine and fluorine, particularly chlorine and bromine, are 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.

Further, the benzoic acid derivative represented by the above general formula which is industrially easily available is the following compound. That is, (however, X is 1 to 4
is an integer, and X is an alkyl group.

Alkoxy group: a carboxyl group or an acylalkyl group, R' is an alkyl group), or a benzoic acid derivative represented by the general formula (wherein, Rn is an alkyl group or a haloalkyl group).

Alkoxyalkyl group, carboxyalkyl group.

It is a benzoic acid derivative represented by a phenoxyalkyl group, an aryl group, an alkoxyaryl group, an acyl group, a haloacyl group, an allyl group, or a benzyl group.

More specifically, representative compounds represented by the above general formula of the present invention are exemplified as follows. That is, representative compounds represented by the general formula (I) include 2-methyl-6-methoxybenzoic acid; 2,4-dimethyl-6-ethoxybenzoic acid fl: 2,3.5-trimethyl- These include 6-methoxybenzoic acid; 2,4.5-trimethyl-3,6-dimethoxybenzoic acid: 3.4-dimethyl-2.6-dimethoxybenzoic acid; orcinoldicarboxylic acid dimethyl ether: olivetonate dimethyl ether. In addition, typical compounds represented by the above general (1[) 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-phenoxybutane*-0-carboxylic acid, α-phenoxyisobutanoic acid-〇-carboxylic acid, α-phenoxyvaleric acid,
2°-(β-(2-nitrophenoxy)-ethoxy)benzoic acid, 2[β-(4-nitrophenoxy)-ethoxy]benzoic acid, ethylene disalicylic acid.

2-phenoxybenzoic acid, 2-0-flexoxybenzoic acid, 2-m-cresoxybenzoic acid, 2-p-flexoxybenzoic acid, 2-(2,4-dimetrophenoxy)benzoic acid, 2-β-naphthyloxybenzoic acid acid, 2-
(2-methoxyphenoxy)benzoic acid 81.2-acetoxybenzoic acid, 2-benzoyloxybenzoic acid 11Q, 2-trichloroacetoxybenzoic acid, 2-bromoacetoxybenzoic acid, 2-tribromoacetoxybenzoic acid, succinyldisalicylic acid, carbomethoxysalicylic acid , carboethoxysalicylic 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 not particularly limited and any known organic solvent can be used, but it is generally preferable to use one that has a low boiling point and is easy to remove afterwards, for example, organic solvents such as methanol, ethanol, and ethyl acetate are preferably used. Furthermore, the amount of the benzoic acid derivative represented by the above general formula used in the present invention is not particularly limited, and may be determined as appropriate depending on the field of application in which the adhesive film forming material obtained in the present invention is used. One component of the present invention, 0.1
It is suitable to use it in a range of mol to 4 mol, preferably 0.5 mol to 2 mol. If a large amount of the benzene-resistant dichloromethane is used in relation to the titanate, the operation time for mixing the adhesive film-forming material with other mixtures will generally become longer. Around 1, the production speed of the cured product becomes slow.

The carboxyl group-containing polymer, organic ditanate, and benzoic acid derivative according to J3 of the present invention 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 method of storing in the presence of an organic solvent is most preferably used. As explained above, the organic solvent is not particularly limited, but is generally methanol, which has a low boiling point and can be easily removed.

Ethanol, isopropyl alcohol, ethyl acetate and the like 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. It is preferable because it can be used as a coating.

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 as a single solution, it is also possible to store the three components of the adhesive film-forming material of the present invention separately and mix the three components at the time of curing, or to store the organic ditanate and benzoic acid derivative in advance. It is also possible to adopt a method in which the materials are mixed and stored, and then a polymer having a carboxyl group is mixed therein during curing.

In the contactable liquid 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, the titanate, and the benzoic acid derivative.
Furthermore, it is also possible to improve the strength or adhesive force of the cured product by curing it in the coexistence of a polymerizable vinyl monomer and an initiator, if necessary.

As the above-mentioned polymerizable vinyl monomer, the copolymerizable vinyl monomers already described can be used as they are.

Among the copolymerizable monomers, acrylic acid and methacrylic acid derivatives are particularly preferably used because they can be polymerized at room temperature.

The initiator is not particularly limited, but it is generally preferable to use a mixed system of peroxide and amine.

The peroxide may be any peroxide commonly used as a curing agent, and dibenzoyl peroxide, dilauroyl peroxide, etc. are particularly preferably used.

Further, as the amine, N,N'-dimethylaniline,
N,N'-dimethyl-Pt-luidine.

N-medyl NP -β-hydroxyethyl-aniline, N,N'-dimethyl-P-(β-hydroxyethyl)-aniline, N,N'-di(β-hydroxyethyl)-P-toluidine, etc. are preferred. used for. Furthermore, in addition to the above-mentioned initiators, it is often a preferred embodiment to use co-catalysts such as metal salts of sulfinic acids or carboxylic acids.

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. The resulting 1=film exhibits excellent weather resistance, chemical resistance, solvent resistance, and adhesion, and is a tough film that also has gloss.

The adhesive film forming material of the present invention is, for example, a base for mnl,
It is useful for resin and glass coating materials, dental treatment and restorative materials, etc.

The above-mentioned @Used therapeutic restorative material refers to a material that is used in the treatment and restoration of a tooth and is applied to the surface of a tooth or a cavity provided in a tooth, and is the most preferred of the adhesive film-forming materials of the present invention. This is a serious use. With a material like this,
Examples include adhesives for teeth, lining materials for protecting dental pulp, and marginal chain materials for 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 1rA.

However, since conventional adhesive materials exhibit almost no adhesion to the tooth structure, it was necessary to demineralize the tooth structure by previously treating the tooth structure with a highly concentrated phosphoric acid aqueous solution and create a mechanical retention form. However, this method has the disadvantage of using a highly concentrated phosphoric acid aqueous solution, which can damage even healthy tooth structure, and especially when etching dentin, it is difficult to expect a bonding point. There is a risk that the phosphoric acid aqueous solution may reach the dental pulp through the tubules. In addition, since the above-mentioned method inevitably leaves unreacted monomers, there is a risk that this monomer may cause damage to the dental pulp.

However, when the adhesive film-forming material of the present invention is used as an adhesive, it can be directly adhered to dentin without being pretreated with the phosphoric acid aqueous solution, and since the cured product itself is originally a polymer, there is no need to react or cause problems. - J: Excellent in that there is no harmful effect on the pulp. 1 = Effective.

Next, conventional lining materials used to protect the pulp include calcium hydroxide-based materials and cement. It is used to protect the. 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 above-mentioned filling material, it is possible to protect the tooth structure from the phosphoric acid etching solution even though it is thin, and moreover, it can be bonded to the filling material. J-ru exhibits excellent functions.

In addition, zinc phosphate cement 1~, which is commonly used for adhesion between metal and tooth structure, contains a large amount of phosphoric acid in its composition, so there is a risk of causing pulp damage. This included using a lining material to protect the dentin.

However, conventional lining materials with thick coatings could not be used because their own compressive strength was a problem.

Therefore, the adhesive film forming material of the present invention is used as the backing material.
When used, since it is a thin film, its own strength is not necessary, and moreover, it exhibits the ideal effect of not allowing phosphoric acid to pass through.

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 to tooth structure or amalgam, and has no wedge effect when 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, it is believed that this function is due to properties other than adhesiveness, such as adhesion and hydrophobicity. Seem.

In addition to amalgam fillings, composite restorative resins,
It is also possible to improve the edge sealing properties of cement filling and rubber capping by using the above-mentioned adhesive film forming material.

It is possible to use the adhesive film forming material of the present invention for purposes other than those described above. For example, it can be used as a barrier material against external stimuli by removing the material that filled the tooth cavity or by applying the adhesive film-forming material of the invention to the wedge-shaped defect in the tooth cavity. It is.

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, conventionally, in one case, it was necessary to use multiple materials in combination, which made the operation very complicated, and because multiple materials were used in combination, it was necessary to use multiple materials in combination. Considering that it had the disadvantage of decreasing
The adhesive film-forming phase of the present invention is an extremely useful composition as a therapeutic and restorative material for teeth.

When using the adhesive film-forming material of the present invention as a dental treatment restorative material, the polymer having carboxyl 75, which is one of the components of the present invention, has a hydrophobicity of 01V. This is preferable in order to further improve its function as a therapeutic and restorative material. This is 100% in the oral cavity.
It is effective in imparting water resistance under severe humid conditions. Also, is the adhesiveness of the present invention to the adhesive between tooth structure and composite restoration resin? j1. When a film-forming material is used, the carboxyl group has an affinity for tooth substance and J3, -
1) Since the hydrophobic group has an affinity for the composite repair resin, the adhesion strength is significantly improved compared to conventional grafting.

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

Production example 1 200 m of cyclohexane was put into a 500 m/capacity glass sieve, and 5.2 m of styrene was added to it.
(7. 14.9 g of maleic anhydride and 0.05 g of penzoyl peroxide (hereinafter abbreviated as BPO) were added and stirred thoroughly.

Next, the inside of the container was depressurized and replaced with nitrogen, and then heating polymerization was carried out at 80° C. for 4 hours while stirring, and after cooling to room temperature, the formed precipitate was filtered. The obtained solid was further diluted with 300 ml of benzene.
8.7g of white polymer after thoroughly washing with water and drying
I got it. As a result of elemental analysis of this product, the composition of the produced copolymer was determined to be 48.4 moJ% styrene, 1% maleic anhydride,
f251.6mo, /.

Next, dissolve this product in 8Qm di-A cylinder,
500m, i? 5i1[% potassium hydroxide aqueous solution 100]
m1! was added and reacted for 10 hours at room temperature. 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 a copolymer.

As a result of measuring the infrared absorption spectrum of this product, the characteristic absorption (185
0 cm', 1775 cm-') completely disappeared, and a new characteristic absorption derived from the carbonyl group of maleic acid appeared at 17
It appeared at 20 cm"1, and it was confirmed that the hydrolysis reaction was progressing almost quantitatively.

However, the white solid obtained above is styrene 48゜4mo.
It was confirmed that the copolymer contained 51.6 mo% of maleic acid and 51.6 mo% of maleic acid.

Production Examples 2-3 Copolymer of styrene-maleic anhydride Tablc
Two commercially available products with different compositions (Arco Ch
Hydrolysis was carried out in the same manner as in Production Example 1 using a copolymer (manufactured by Emica 1), and from the elemental analysis results of the raw material copolymer and the measurement results of the infrared absorption spectrum after hydrolysis, the results are shown in Table 1. 1 q of styrene-maleic acid copolymer having the following composition was obtained.

Table 1 Production Example 4 Contents 50 ffl of benzene containing 1350 m of anhydrous maleic acid and 9 omo of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added, and the mixture was cooled in a dry ice-methanol bath. While the contents were purged with nitrogen under reduced pressure, purified propylene 1
2 g were added by distillation through a liquefaction ffl m vessel. Next, copolymerization was carried out by stirring at 60° C. for 36 hours. After the polymerization was completed, the contents were poured into a large volume of anhydrous ether to precipitate the resulting copolymer, thoroughly washed by a decanting method, and immediately dried in a vacuum drying mold. The yield was 60% and Ic.

Elemental analysis showed that maleic anhydride was 55.6 mO, propylene was 44.4 mO, and 7%.

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.

Manufacturing example 5 Contents 300IIIJ! 35.7g in a pressure-resistant glass container
of maleic anhydride and 50 m of BenU containing 1 g of AIBN are added. 12.51y of isobutyne was added to this by distillation through a liquefaction meter, and then 60y
Copolymerization is carried out for 15 minutes at °C. After the polymerization is complete, the contents are poured into a large amount of anhydrous ether to precipitate the resulting polymer.The resulting polymer is decanted, the supernatant is discarded, the mixture is thoroughly washed with anhydrous ether, and then dried under reduced pressure.

The yield was 43.3%. From elemental analysis, this product contains 47.1+oJ% of isobutyne and 52.9% of maleic anhydride.
It was a copolymer containing moJ%.

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

As a result of measuring the infrared absorption spectrum of this copolymer, it was confirmed that the maleic anhydride groups in the raw material were almost quantitatively converted to maleic acid.

Production example 6 0゜5g in a 100Lt' Erlenmai A7-flask
of polymethyl methacrylate and 30 m of If acid were added,
It was left at room temperature.

The polymer was completely dissolved in 2 days and a yellow solution was obtained. When this was poured into a large amount of ice water, polymethacrylic acid precipitated out. This was filtered, thoroughly washed with water, and finally dried to obtain a solid of 0.45a. Elemental analysis of the obtained polymer revealed that 32% of the ester groups were converted to carboxyl groups by hydrolysis.

Production example: Fitacon M30Q, styrene 20o dioxane 200o
g, add 0.1% BPO to the monomer,
Polymerization was carried out at 10°C for 5 hours.

(The polymer thus obtained was placed in hexane 1) to be precipitated, filtered and dried, and then unreacted itaconic acid was removed by washing with distilled water. The yield was 4.2%. The results of elemental analysis revealed that itaconic acid was 49.0 mol% and styrene was 51.0 mol%.

Production Example 8 Vinyl chloride and itacon dimethyl ester were polymerized at 50° C. for 6 hours using AIBN as an initiator.

The polymer was dissolved in benzene and poured into methanol to precipitate it, which was filtered and dried under reduced pressure.

The composition of the copolymer was determined by elemental analysis to be 41 mol% vinyl chloride and 59 mol% methyl itaconate. This polymer was hydrolyzed in the same manner as in Production Example 6, and elemental analysis revealed that 28% of the ester groups were converted to carboxyl groups.

Production Example 9 Styrene and fumaric acid diethyl ester were polymerized at 60° C. for 20 hours using AIBN as an initiator to obtain a polymer. The composition of the copolymer was found to be styrene "56.
It was 5 mol% diethyl fumarate and 43.5 mol%. This polymer was hydrolyzed in the same manner as in Production Example 6, and elemental analysis revealed that 35% of the esters were converted to carboxyl groups.

Example 1 A solution of a polymer having a carboxyl group shown in Table 2 (
The storage stability when A) was mixed with a solution (B) containing an organic titanate and a benzoic acid derivative was investigated.

The test method was as follows. That is, (A) and (
B) was prepared in a composition similar to that shown in Table 2, mixed in a glass container, immediately capped, and stored in a constant temperature room at 20°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 precipitation occurred for more than 12 months, no loss of transparency occurred, and no gelation occurred.

Example 2 '1 Solution A consisting of 10 parts by weight of the styrene-maleic anhydride copolymer hydrolyzate obtained in Example 1 and 90 parts by weight of ethanol was mixed with the composition solution ('B) shown in Table 3. death,
Storage stability was investigated. As a result, no precipitate was observed in any of them even after more than 12 months, and they remained transparent and did not form a gel. Diagram 3 Flmr-r [r
-r is an abbreviation for tetra-n-butyl ditanate.

? 53 Comparative Example 1 Instead of the benzoic acid derivative used in Example 1, Table 4
Storage stability was measured in the same manner as in Example 1, except that the benzoic acid derivative shown in the B solution composition column was used. The results are also listed in Table 4.

Application Examples The following tests were conducted using the adhesive film forming materials shown in Examples 1 and 2.

(1) Adhesion to dentin.

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

First, paste (I) &5 and P~ using the following recipe.
St. (II) was prepared.

(1) Apply emery vapor (#320) to the labial surface of a freshly extracted tooth that adheres to the dentin.
) to expose smooth dentin, the polished surface was washed with water for 30 seconds, and then nitrogen gas was blown to dry the surface.

Attach a 2 mm thick plate of wax with a 4 mm diameter hole to the dry surface using double-sided tape.

Next, liquid (A) and liquid (13) of the adhesive film forming material were mixed in a ratio of 1:1, applied to the dentin surface surrounded by plate wax, and nitrogen scum was blown (no ethanol The excess adhesive was blown off.The above paste (I
) 73 and ('■) were mixed at a ratio of 1:1 and filled. After leaving for one hour, the wax plate was removed, and the sample was immersed in water at 37°C for one day, and then its tensile strength was measured. The tensile strength "J" manufactured by Toyo Baldwin Co., Ltd. was used for the measurement, and the tensile speed was 10 m...5.7 minutes. The results obtained are shown in Table 5.

(2) Marginal sealing of the cavity A cavity with a diameter of 3n1m and a depth of 2mm was formed on the labial surface of a human treated tooth. Next, after applying the adhesive film forming materials shown in Table 2 of Example 1, Nos. 1 to 09, and the conventionally used CC Cory 1 to the window wall,
Semen] ~ Or, he was charged with the Amal sword.

After 1 hour of filling, store in water at 37°C, and add 1EI IU to 4°C and 60°C Tsukusin aqueous solutions alternately for 1 minute each.
A percolation test was performed in which the sample was immersed 0 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 the above test, 5 samples were used for each type of actual product to confirm the resiliency. As a result, pigment intrusion was observed in all samples that were directly filled with 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, with respect to the adhesive film forming materials No. 1 to No. 9 in Table 2 of Example 1, no penetration of the dye was observed, and good aggregation was obtained.

(3) Breakability 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.
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, commercially available Copalite, Dical, and the adhesive film forming material used in Example 1 were applied to the back side as a blocking material (backing material), and the solvent was removed by spraying nitrogen gas.

A 37% orthophosphoric acid aqueous solution was used as the phosphoric acid aqueous solution, and one drop was dropped onto the barrier material and left to stand.

In order to detect phosphoric acid passing through the M section, a PH test paper was placed under the membrane filter, and the time when the color changed was defined as the passage 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 or more.

On the other hand, when the adhesive film forming material of the present invention shown in Examples 1 and 2 was used as the barrier material, the permeation time of the phosphoric acid aqueous solution was 10 minutes or more in both cases.

patent applicant Tokuyama Soda Co., Ltd.

Claims (1)

[Scope of Claims] (11) an organic titanate, and (iii) an alkyl group, an alkoxy fl-4, a carboxyl group, or an acylalkyl group, and R is an alkyl group or a haloalkyl group. Alkoxyalkyl group, carboxyalkyl group, phenoxyalkyl group. Aryl group, alkoxyaryl group. An acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a benzyl group. ) Benzoic acid derivatives. Adhesive film forming material whose main component is (2) The adhesive film forming material according to claim (1), wherein the polymer on which the carboxyl group is located has a hydrophobic group. (3) The adhesive coating according to claim (1), wherein the polymer having carboxyl groups is a polymer in which two carboxyl groups (-CO21-1) are bonded to adjacent carbon atoms. Forming material. (4) The molecular weight of the polymer is 1,000 to 100°00
The adhesive film forming material according to claim (1), which is 0. (5) The adhesive film forming material according to claim (1), wherein the polymer is a copolymer of a copolymerizable vinyl monomer having a hydrophobic group and a vinyl monomer having a carboxyl group. (6) The adhesive film forming material according to claim (1), wherein the organic titanate is a tetraalkyl titanate. (7) The benzoic acid derivative has the general formula (n is an integer of 1 to 4, X is an alkyl group, an alkoxy group,
A carboxyl group or an acylalkyl group, R' is an alkyl group)
1) Adhesive film forming material as described. (8) When the benzoic acid derivative has the general formula R″, it is an alkyl group, a haloalkyl group, an alkoxyalkyl group, a carboxyalkyl group, a phenoxyalkyl group,
Aryl group. The adhesive film-forming material according to claim (1), which is a compound represented by ') which is an alkoxyaryl group, an acyl group, a haloacyl group, an acyloxyacyl group, an alkoxycarbonyl group, an allyl group, or a benzyl group.