JPH0684488B2 - Adhesive film forming material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive film forming material having an adhesive property to a living hard tissue, particularly a tooth, and having a film forming ability.

[Problems to be Solved by Prior Art and Invention]

Conventionally, various compounds are known as film-forming materials, which are required to have unique properties depending on the field of use. Above all, the film-forming material used for the purpose of tooth treatment must withstand the extremely unpredictable harsh environment such as the complexity of the force applied in the oral cavity, the variety of adherends and the wet condition, and it should not be toxic. The harsh conditions called are required.

The current tooth treatment film forming material improves the marginal sealability after filling by filling it before filling with amalgam. It is often used for the purpose of protecting the pulp from the phosphoric acid used and the unpolymerized monomers remaining after filling.

Already, there are some commercial products used for such purposes, but none of them yet achieves these purposes sufficiently.

On the other hand, although the fields of use are different, in JP-B-52-40577, a half-ester derivative of an alkyl vinyl ether- or styrene-maleic anhydride copolymer and one or more kinds of the half-ester derivative for dissolving the half-ester derivative of the copolymer are disclosed. A photocurable composition containing a photopolymerizable monomer and a photopolymerization initiator is disclosed.

However, although the photocurable composition shown here has a film-forming ability when used under the moist condition of the oral cavity, it hardly shows adhesion to tooth hard tissue.

[Means for solving problems]

Therefore, the present inventors have conducted earnest studies for the purpose of developing an adhesive film-forming material that has both adhesiveness and film-forming ability and can be sufficiently used for the above purpose. As a result, by using a novel acrylate compound in which two carboxyl groups are bonded to the same carbon atom, a specific polymer, and a radical initiator, good adhesion is exhibited, and a material having excellent film-forming ability. The present invention has been completed, and the present invention has been completed.

That is, the present invention provides (A) general formula An adhesive film forming material mainly composed of (A) a polymer having a carboxyl group and a polymerizable unsaturated double bond, and (C) a radical initiator.

One of the main components of the adhesive film forming material of the present invention is represented by the following general formula (1). Is a novel acrylate compound represented by.

R ₁ in the above general formula (1) can be used without any limitation as long as it is a hydrogen atom or an alkyl group, but for the reason of easy availability of raw materials, isolation and purification, etc., a hydrogen atom or a carbon number of 1 to 1 is used.
4 More preferably, 1-2 alkyl groups are suitable. Further, R ₂ in the above general formula (1) can be used without any limitation as long as it is an alkylene group, but it is preferable that R ₂ is in the range of 2 to 20 carbon atoms, more preferably 4 to 12 in order to obtain high adhesive strength. is there.
Further, R ₃ in the general formula (1) can be used without any limitation as long as it is a hydrogen atom or an alkyl group, but in the case of an alkyl group, the number of carbon atoms is 1 to 20, more preferably 1 to 10 Most suitable.

Examples of generally preferable alkylene groups or alkyl groups are as follows. For example, as the alkyl group of R ₁ , —CH ₃ , —C ₂ H _{5 and the} like can be mentioned, and as the alkylene group of R ₂ , CH _{2 8} , CH _{2 9} , CH _{2 10} , CH _{2 11} , CH _{2 12 and the} like are mentioned, and as the alkyl group of R ₃ , _{-C 7 H 15, -C 8 H} 17, -C 9 H 19, -C 10 H 21 and the like.

Among the acrylate compounds of the general formula (1), n is 1
When R ₃ is, a compound in which R ₃ is a hydrogen atom, a methyl group, and a compound in which n is 2 are preferable because of high adhesive strength. Further, among the above compounds, a compound in which R ₂ is an alkylene group having 4 to 12 carbon atoms tends to have excellent adhesive force.

Specific examples of particularly preferable acrylate compounds in the present invention are as follows.

The acrylate compounds represented by the general formula (1) are all colorless or pale yellow transparent liquids.

The acrylate compound used in the present invention is a novel compound, and it can be confirmed that it is the compound by the following measurement.

(A) Measurement of infrared absorption spectrum (IR) The IR of the compound represented by the general formula (1) is measured to be 30
Carbon aliphatic around 00~2800cm ^-1 - absorption based on hydrogen bonding, 1800～1600Cm ^-1 around a strong absorption based on the carbonyl group, absorption based on C = C double bond is observed near 1650～1620Cm ^-1 To be

(B) ¹ H- Measurement of nuclear magnetic resonance spectra ⁽¹ H-NMR) (tetramethylsilane standard; Measurement of [delta] ppm) peak based on protons of the methylene group or a methyl group appears in the vicinity of 0.8～2.0Ppm.

When R ₁ is CH ₃ in the general formula (1), a peak based on the proton of the methyl group appears at around 1.9 ppm.

In the general formula (1), when n is 1 and R ₃ is a hydrogen atom, a peak based on the proton of the methine group appears around 3.0 to 3.6 ppm.

Around 3.7-4.5ppm A peak based on the proton of the alkylene group next to is appears.

A peak based on the double bond proton appears around 5.2 to 6.6 ppm.

A peak based on the carboxylic acid proton appears around 9 to 12 ppm. This peak disappears by replacing with heavy water.

(C) Mass spectrometry As a means of mass spectrometry, the field desorption / ionization method (MS-FD and
(Abbreviation) can be used to confirm the molecular weight. Starting
If the molecular weight of the acrylate compound used in Ming is M,
M +1 or M A molecular ion peak is observed at the position
It

(D) Elemental analysis The acrylate compound used in the present invention can be confirmed by comparing the analysis results of carbon and hydrogen with the theoretical value calculated from the general formula (1).

The acrylate compound represented by the general formula (1) can be confirmed by the various measuring methods described above.

The method for producing the acrylate compound represented by the general formula (1) is not particularly limited, and any method may be adopted. A concrete example of the industrially suitable method is as follows.

That is, the following formula (A) (However, R ₁ represents a hydrogen atom or an alkyl group, and Z represents a hydroxyl group or a halogen atom.) And a vinyl compound represented by the following formula (B): [However, R ₂ represents an alkylene group, R ₃ represents a hydrogen atom or an alkyl group, and n represents 1 or 2. ] The acrylate compound represented by the general formula (1) is obtained by reacting with an alcohol compound represented by

As the vinyl compound represented by the general formula (A), known compounds can be used without limitation. For example, when Z is a hydroxyl group, acrylic acid, methacrylic acid, ethyl acrylic acid and the like are listed. When Z is a halogen atom, acrylic acid chloride, methacrylic acid chloride, ethyl acrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, Ethyl acrylic acid bromide and the like are preferably used.

The method for reacting the vinyl compound represented by the general formula (A) with the alcohol compound represented by the general formula (B) is
Although not particularly limited, specifically, the following method is preferably adopted.

When Z of the vinyl compound represented by the general formula (A) is a halogen atom, the acrylate compound of the general formula (1) is obtained by the following reaction. That is, an equimolar or slightly excess amount of the vinyl compound represented by the general formula (A) is reacted with the OH group of the alcohol compound represented by the general formula (B). The solvent is not particularly limited, but solvents such as tetrahydrofuran, acetone, diethyl ether, dichloromethane, chloroform and benzene can be used. As the amount of the solvent, the concentration of the alcohol compound of the general formula (B) is 0.1 to 50% by weight, preferably 1 to 10% by weight. The reaction temperature is when dropping a vinyl compound
30 ℃ or less, preferably under ice-cooling, 70 after the completion of dropping
C. or lower, preferably in the range of 10 to 40.degree. This reaction is preferably carried out in the presence of an aliphatic amine such as trimethylamine or triethylamine or a base such as pyridine. The base is appropriately added in an equimolar amount or slightly in excess of the vinyl compound. Further, it is preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, butyl hydroxytoluene or the like. After completion of the reaction, the by-product salt is removed by filtration, and the solvent is distilled off under reduced pressure to isolate and obtain the acrylate compound used in the present invention. More preferably, the product is converted into dichloromethane, chloroform, benzene, toluene, n
It is preferable to dissolve in a solvent such as hexane or cyclohexane, wash with a dilute hydrochloric acid aqueous solution, further wash with water 2 to 5 times, and then distill off the solvent under reduced pressure for purification.

In the reaction of the vinyl compound represented by the general formula (A) and the alcohol compound represented by the general formula (B), when Z of the vinyl compound is a hydroxyl group, the acrylate compound used in the present invention is obtained by the following reaction. You can That is, the acrylate compound used in the present invention can be obtained by performing a dehydration reaction between the alcohol compound of the general formula (B) and the vinyl compound of the general formula (A). In the above reaction, it is preferable to use an acidic catalyst, and as the acidic catalyst, p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid and the like can be preferably used.
The amount of catalyst is preferably 0.1 to 20% by weight, and more preferably 1 to 10% by weight, based on the vinyl compound.

As the dehydration method, a method using reduced pressure, reflux dehydration with benzene or toluene and the like are used. The reaction conditions are not particularly limited, but the reaction temperature is suitably in the range of 50 to 120 ° C. It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether.
After the reaction was completed, the solution was transferred to a separating funnel, and benzene, toluene,
Solvents such as chloroform and dichloromethane are neutralized and washed with an aqueous solution of sodium carbonate, sodium hydrogencarbonate and the like, and after further washing with dilute hydrochloric acid and water, the solvent is distilled off under reduced pressure to obtain the compound represented by the general formula (1). The acrylate compound can be isolated and obtained.

Another one of the main components of the adhesive film forming material of the present invention is a polymer having a carboxyl group and a polymerizable unsaturated double bond. Here, the carboxyl group is necessary for imparting adhesiveness to the obtained film forming material, and the polymerizable unsaturated double bond is tough to the film obtained by curing the adhesive film forming material. And necessary for imparting durability.

The polymer used in the present invention is 30 to 700, particularly 40 to 6
Those having an acid value of 00 are preferable in terms of toughness and water resistance of the obtained coating film. The acid value is defined herein as the number of mg of KOH required to neutralize 1 g of resin.

Further, considering the toughness and durability of the obtained adhesive film forming material, the polymerizable unsaturated double bond is preferably present in an amount of 0.1 to 10 mmol per 1 g of the polymer.

Furthermore, the molecular weight of the polymer is 1,000 to 1 in order to improve the film forming ability of the adhesive film forming material.
It is preferably 00,000. More preferably 10,000
~ 100,000.

What is preferably used as a polymer having a carboxyl group and a polymerizable unsaturated double bond in the present invention is represented by the following general formula (2) The following general formula (3) And a monomer unit represented by

Here, the monomer unit represented by the general formula (2) is preferably contained in the polymer in the range of 10 to 60 mol%.

The alkylene group represented by R ₄ in the monomer unit represented by the general formula (2) is not particularly limited in carbon number,
Considering the adhesiveness of the obtained adhesive film forming material, the number of carbon atoms is preferably 2 to 12. The alkyl group represented by R ₅ , R ₆ and R ₇ is also not particularly limited in carbon number, but preferably has 1 to 6 carbon atoms. Further R _4
1 of the group represented by CH ₂ CH ₂ O ₁ of 1 is preferably 1 to 10.

Further, in the monomer unit represented by the general formula (3), the alkyl group represented by R ₈ is preferably a lower alkyl group such as a methyl group or an ethyl group. The aryl group represented by R ₉ is preferably a phenyl group or a naphthyl group,
These substituents include halogen atoms, alkyl groups,
A halogenoalkyl group and the like are preferable. Further, the alkyl group in the alkyl group, alkoxy group and alkoxycarbonyl group represented by R ₉ is not particularly limited in the number of carbon atoms, but generally, one having 1 to 8 carbon atoms is preferable.

As the monomer unit represented by the general formula (2) contained in the polymer having a carboxyl group and a polymerizable unsaturated double bond used in the present invention, those suitably used in the present invention are specifically shown. , For example:

And the like.

The polymer having a carboxyl group and a polymerizable unsaturated double bond used in the present invention can be obtained by reacting a polymer having a carboxylic acid anhydride group with a compound having a hydroxyl group and an unsaturated double bond. .

The polymer having a carboxylic acid anhydride group is preferably a copolymer of a vinyl monomer having a hydrophobic group and maleic anhydride or itaconic anhydride.

As the vinyl monomer having a hydrophobic group, styrene,
Aryl compounds such as halogenated styrene, methylstyrene, halogenated methylstyrene and vinylnaphthalene;
Alkenes such as propylene and isobutene; vinyl ethers such as ethyl vinyl ether and n-butyl ether; methacrylic acid esters such as ethyl methacrylate and butyl acrylate are preferably used.

The ratio of the polymer having a carboxyl group and a polymerizable unsaturated double bond to the acrylate compound is 0.2 to 10 parts by weight with respect to 1 part by weight of the acrylate compound.
It is preferable that the content is in the range of 0.3 to 5 parts by weight, from the viewpoint of the adhesiveness of the adhesive film forming material of the present invention and the durability of the film.

The other part of the adhesive film forming material of the present invention is a radical initiator. As the radical initiator, various ones can be used depending on the curing method, and therefore the amount thereof cannot be unconditionally limited, but in general, it is 0 to the total amount of monomers.
It is preferably used in the range of 05 to 5% by weight.

The radical initiator that can be preferably used in the present invention and the suitable amount thereof will be described below.

A peroxide, an azo compound, or the like is preferably used as the radical initiator that generates a radical by heating. Known peroxides can be used without any limitation. Specifically, dibenzoyl peroxide, diacyl peroxide such as 2,4-dichlorobenzoyl peroxide, dilauroyl peroxide, dioctanoyl peroxide, decanoyl peroxide; cumene hydroperoxide, t-butyl hydroperoxide And the like; and ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide. As the azo compound, 2,2'-azobisisobutyronitrile, 4,4'-azohis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimerpareronitrile) and the like are preferable. Used for.

The above radical initiator is preferably added in an amount of 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the total amount of monomers.
Although the polymerization temperature varies depending on the curing catalyst used, it is generally in the range of 40 to 150 ° C, preferably 50 to 130 ° C.

Various photosensitizers can be used as the radical initiator by light. Although any known photosensitizer can be used, diacetyl, acetylbenzoyl, benzyl,
2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl, α-naphthyl, β-naphthyl, 4,4'-oxybenzyl, camphorquinone, 9,10-phenanthrenequinone, acetone Α-diketones such as naphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether; thioxanthone compounds such as 2,4-diethoxythioxanthone, methylthioxanthone; benzophenone,
Benzophenone compounds such as P, P'-dimethylaminobenzophenone and P, P'-methoxybenzophenone are preferably used.

The addition amount of these photosensitizers is 0.05 with respect to the total amount of monomers.
-5% by weight, preferably 0.1-2% by weight.

Further, when performing photocuring, a curing accelerator can be added at the same time as the photosensitizer. As a curing accelerator, amine compounds such as dimethyl paratoluidine, N, N'-dimethylbenzylamine, N-methyldibutylamine, dimethylaminoethyl methacrylate, ethyl p-dimethylaminobenzoate; dimethylphosphite, dioctylphosphite, etc. Phosphite compounds; and cobalt compounds such as cobalt naphthenate; barbituric acids such as barbituric acid, 5-ethylbarbituric acid, and 2-thiobarbituric acid are preferably used. The amount of the curing accelerator added is 0.05 to 5% by weight, preferably 0.1
It is preferably ˜1% by weight.

UV light from high, medium and low pressure mercury lamps for light curing;
It can be cured by irradiating it with visible light from a halogen lamp, xenon lamp or the like.

The adhesive film forming material of the present invention can obtain the most excellent adhesive force when photopolymerized.

A peroxide is used as a radical initiator for room temperature polymerization, but since this alone does not provide strong adhesiveness due to room temperature polymerization, a peroxide is used in combination with an amine or a salt thereof and an organic sulfinate. It

With respect to the above-mentioned peroxides, amines or salts thereof, and sulfinates, there are no particular restrictions on the specific substances used. However, as the organic peroxide, diacyl peroxide, that is, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, dilauroyl peroxide and the like are preferably used.

Further, as the amine, a secondary or tertiary amine having an amine bonded to an aryl group is preferably used in terms of accelerating curing.

For example, N.N'-dimethylaniline, N.N'-dimethyl-p-toluidine, N-methyl, N'-β-hydroxyethyl-aniline, N.N'-di (β-hydroxyethyl)-
Aniline, N · N′-di (β-hydroxyethyl) -p-
Preferred examples include toluidine, N-methyl-aniline, N-methyl-p-toluidine and the like. These amines may form salts with hydrochloric acid, acetic acid, phosphoric acid, organic acids and the like.

Further, as the sulfinate, an alkali metal salt, an alkaline earth metal salt or an amine salt of arylsulfinic acid is preferable from the viewpoint of the stability of the curing agent. For example, sodium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, ammonium benzenesulfinate, triethylammonium benzenesulfinate, benzenesulfinate ・ N ・
Examples thereof include N'-dimethyl-p-toluidine salt, p-toluenesulfinic acid, β-naphthalene sulphonic acid, and styrenesulfinic acid.

In the above radical initiator, the amounts of peroxide and amine used are preferably 0.05 to 5% by weight, and more preferably 0.1 to 2% by weight, based on the total amount of monomers. The amount of the organic sulfinate used is preferably 0.05 to 2% by weight, more preferably 0.1 to 0.9% by weight, based on the amount of the monomer.

It is preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or butylhydroxytoluene to the adhesive film forming material of the present invention, if necessary.

In the present invention, it is preferable to add a filler depending on the object of adhesion. The addition of filler improves mechanical strength and water resistance, and can control fluidity and coating property. Examples of fillers are quartz,
Amorphous silica, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride,
Inorganic substances such as titanium nitride, silicon carbide, boron carbide, calcium carbonate, hydroxyapatite, calcium phosphate and the like can be mentioned. These fillers are usually preferably treated with a silane coupling agent such as γ-methacryloyloxypropyltrimethoxysilane or vinyltriethoxysilane.

Further, an organic solvent can be added if necessary.
As the organic solvent, those which easily volatilize such as acetone, methylene chloride, chloroform and ethanol are preferable.
These organic solvents make the adhesive film forming material of the present invention in a liquid state and facilitate application. Therefore, it is preferable to use an organic solvent in an amount sufficient to dissolve the above-mentioned polymer, generally 2 to 20 parts by weight based on 1 part by weight of the polymer.

The acrylate compound of the general formula (1) may be used alone as the monomer component of the adhesive film forming material of the present invention, or may be used as a copolymerization component mixed with another acrylate. Other acrylates can be used without any limitation, but the following compounds are preferably used.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3 butanediol di (meth) acrylate, 1,4 butanediol (meth) acrylate, 1,6 hexadiol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,10 decanediol di (meth) acrylate
Acrylate, bisphenol-A di (meth) acrylate, 2,2-bis [(meth) acryloyloxypolyethoxyphenyl] propane, 2,2'-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) Examples thereof include phenyl] propane, trimethylolpropane (meth) acrylate, trimethylolethane tri (meth) acrylate, and tetramethylolmethane tetra (meth) acrylate.

When the acrylate compound of the general formula (1) is used in combination with one or several kinds of the above-mentioned other acrylates, the amount of the other acrylate is determined by the adhesiveness and the coating film of the adhesive film-forming material of the present invention. The amount may be within the range that does not impair the durability, and generally, it may be used within the range of less than 50% by weight in the total amount of the monomers.

INDUSTRIAL APPLICABILITY The adhesive film forming material of the present invention is useful, for example, as a covering material for skin and a therapeutic and restorative material for living body hard tissue, especially for dentistry.

The skin covering material is a material that blocks irritation by blocking air and water by applying it on an affected area such as a wound or stomatitis. In this case, in combination with the antibacterial action described later, it is possible to protect the affected area such as a cut or stomatitis.

Furthermore, a compound having a pharmacological action can be positively used as a local coating material in addition to the intended use.

Further, the above-mentioned dental therapeutic restorative material is a material that is used in the therapeutic restoration of teeth and is applied to the surface of the tooth or the surface of the cavity or the like provided on the tooth, and forms the adhesive film of the present invention. This is the most important use of wood. Examples of such a material include an adhesive material for teeth, a film forming material for protecting the tooth structure, and an edge sealing material for the tooth and the filling material.

(Effects) In the past, when filling and filling a cavity of a tooth with a filling material such as a composite restoration resin in the healing and restoration of a tooth, an adhesive material has been used to bond the tooth substance and the filling material. However, since the conventional adhesive material shows almost no adhesiveness to tooth substance, it is necessary to decalcify the tooth substance in advance by treating it with a high-concentration phosphoric acid aqueous solution to mechanically form a holding form. However, this method has a drawback that even a healthy tooth substance is damaged because a high concentration phosphoric acid aqueous solution is used. Especially for dentin, not only the improvement in adhesive strength due to etching cannot be expected, but also the pulp solution may be affected by the phosphoric acid solution through the dentinal tubule.

However, when the adhesive film forming material of the present invention is used as an adhesive, the excellent effect of directly adhering to dentin without pretreatment with the phosphoric acid aqueous solution is exhibited.

Next, calcium hydroxide, dental cement, etc. have been conventionally known as a film-forming material for protecting the dentin. From the phosphoric acid etching performed when filling the resin-based filler such as the composite restoration resin to the dentin. It is used to protect
However, these materials do not have adhesiveness with resin-based fillers, and since the properties before film formation are viscous, it is difficult to form a thin film, and it is almost impossible for filling and repairing treatment of shallow cavities and small cavities. It was unusable. However,
By dissolving the adhesive film forming material of the present invention in an organic solvent and using it as the barrier film forming material, a thin film having durability against a phosphoric acid etching solution can be easily formed on the tooth structure. Moreover, it exhibits an excellent function of adhering to the filler.

In addition, zinc phosphate cement, which is often used for bonding metal and tooth, contains a large amount of phosphoric acid in the composition,
The phosphate component remaining after hardening stimulates the pulp. Therefore, as one of the measures to prevent such defects, a thin film-forming material for protecting the tooth structure having phosphoric acid resistance has been desired. As described above, it is difficult to form a thin film with the conventional film forming material. When the adhesive film forming material of the present invention is used for such a purpose, since it is a thin film, it exhibits the ideal effect of not impeding the adhesiveness between the metal and the tooth structure, and of not permeating phosphoric acid.

Further, the third function of the adhesive film forming material according to the present invention is edge sealing property.

Known substances that are expected to have the above-mentioned functions include, for example, those obtained by dissolving a resin such as coparlite used for filling amalgam in an organic solvent. Certainly, when this material is used, a thin film is formed, but it has a poor affinity for tooth substance and amalgam, and the effect of marginal blockage cannot be expected so much. However, the adhesive film forming material of the present invention also exhibits a remarkable effect when it is used as such a material for edge sealing.

The reason why the above-mentioned effects are exhibited is not clear at present, but it is considered that the adhesive film forming material has excellent affinity to amalgam as well as adhesiveness to tooth structure.

Further, even in the case of filling and repairing treatment by compound restoration resin other than amalgam filling, cement filling, rubber capping, etc., it is expected that the edge sealing property is improved by using the above adhesive film forming material.

Also, teeth and restoration alloys such as gold, gold-palladium alloys,
It can also be used for restoration treatment using platinum-gold alloy, silver-gold alloy, platinum-palladium alloy, nickel-chromium alloy, and the like.

Further, in addition to the above-mentioned applications, for example, the adhesive coating forming material of the present invention is formed on the cavity wall after the material filled in the tooth is removed, or the part where the dentin is exposed on the tooth surface due to the wedge-shaped defect of the dentition or the like. It can also be used as a material for temporarily blocking external stimuli by applying.

As described above, the functions as the tooth adhesive, the tooth-protecting film forming material, and the edge blocking material have been individually described. However, since the adhesive film forming material of the present invention has these functions, In one case, all of the above-mentioned functions can be exhibited only by using the adhesive film forming material of the present invention. Therefore, in the past, considering that the operation was complicated due to the need to use multiple materials in one case, and that the functions of both materials were reduced due to the combined use of multiple materials, The adhesive film forming material of the invention is a composition which is extremely useful as a dental restorative material. In particular, when the adhesive film-forming material of the present invention is used as the adhesive between the tooth structure and the composite restoration resin, the carboxyl group has an affinity for the tooth structure while the hydrophobic group forms the composite restoration structure. Since it has an affinity for the resin, the adhesive strength is remarkably improved as compared with the conventional adhesive material.

Furthermore, the adhesive film forming material of the present invention has an antibacterial action, and the action is observed against anaerobic bacteria. The adhesive film forming material of the present invention has an antibacterial action against the following bacteria, for example.

Bacteroides gingivalis 381 Actinomyces naeslundii ATCC12104 Actinomyces viscosus ATCC15987 Propionibacterium acnes EXC-1 Actinomyces israeli ATCC12102 Furthermore, a compound having a pharmacological activity such as a fluorine compound or chlorhexidine can be added to the adhesive film forming material of the present invention.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Production Example-1 33.8 g of diethyl malonate and 150 ml of ethanol were placed in a 300 ml three-necked flask equipped with a dropping funnel and a cooling tube, and 4.85 g of metallic sodium was placed under ice cooling, and stirring was performed until a uniform solution was obtained. . Then 10-Brom-1 Decanol
After 50.0 g was added dropwise with a dropping funnel, the mixture was heated at 80 ° C. for 3 hours.

The above solution was transferred to a 500 ml eggplant flask, and ethanol was distilled under reduced pressure. Next, add 120 ml of 20 wt% NaOH solution and heat at 100 ° C for 2 hours.
H was set to about 2. The obtained solid was filtered and washed with a glass filter, dissolved in acetone, and dehydrated with anhydrous sodium sulfate and anhydrous magnesium sulfate. Subsequently, acetone was distilled off under reduced pressure at room temperature.

Next, 10 g of the above solid, 4.27 g of triethylamine, 20 mg of hydroquinone and 200 ml of tetrahydrofuran were placed in a 300 ml three-necked flask equipped with a dropping funnel, and 4.42 ml of methacrylic acid chloride was added dropwise with a dropping funnel while cooling with ice. Subsequently, the mixture was allowed to stand overnight at room temperature with stirring and then filtered through a 0.5 μm filter to remove triethylamine hydrochloride. This solution was distilled under reduced pressure at room temperature to remove terrahydrofuran, and then 200 ml of dichloromethane and 0.1 N hydrochloric acid 10
Extract and purify with 0 ml and concentrate the dichloromethane layer.
8.5 g of a viscous pale yellow liquid was obtained. The isolated product was confirmed to be an acrylate compound represented by the following formula by the following various measurement results.

(A) Absorption based on an aliphatic carbon-hydrogen bond at 3000 to 2800 cm ^-1 , absorption based on a carbonyl group at 1800 to 1640 cm ^-1 ,
Absorption based on the C = C double bond was observed between 1640 and 1620 cm ^-1 .

(B) ¹ H-NMR (tetramethylsilane standard, δppm, 60MH
z) Two protons of carboxylic acid appear in a single line at 9.5 ppm (disappeared by substitution with heavy water), two double bond protons appear at 5.6 ppm and 6.2 ppm in a doublet at 4.3 to 3.9 ppm. Two protons of the methylene group next to the ester bond appear in the triplet, one proton of the methine group appears in 3.55 to 3.15 ppm in the triplet, and one proton of the methyl group appears in the single line at 1.9 ppm. 18 protons of a methylene group centered at 1.3 ppm appeared in a wide single line.

(C) Mass spectrometry (MS-FD) Mass spectrum measurement result shows that M / e329 is M +1 peak
Appeared.

(D) Elemental analysis values The elemental analysis values are C62.05% and H8.61%, which is the theoretical value of C6.
It was in good agreement with 2.17% and H8.59%.

Production Example-2 33.8 g of diethyl malonate and 150 ml of ethanol were placed in a 300 ml three-necked flask equipped with a dropping funnel, and 4.85 g of metallic sodium was placed under ice cooling, followed by stirring until a uniform solution was obtained. Then 10 brom-1-decanol 50
g, and heated at 70 ° C. for 5 hours.

Transfer the above solution to a 500 ml eggplant flask and add 20 wt% NaOH.
120 ml of the solution was put and ethanol was distilled off while carrying out hydrolysis at 100 ° C. for 2 hours. To this, 130 ml of 6N hydrochloric acid was added dropwise to adjust the pH of the solution to about 2. The obtained solid was filtered and washed with a glass filter.

Then, 30 g of the above solid, 60 g of methacrylic acid, 1 g of paratoluene sulfonic acid, and 0.1 g of HQME were placed in a 300 ml three-necked flask, and dehydration reaction was performed under reduced pressure (100 to 200 mmHg) while blowing dry air at 80 ° C. for 3 hours. . This liquid was transferred to a 1-minute separating funnel, 200 ml of dichloromethane and 200 ml of water were added, and sodium carbonate was further added little by little to adjust the pH to about 8. After the dichloromethane layer was washed with water 2-3 times, 1N hydrochloric acid was added to adjust the pH to about 2, washed with water and concentrated to obtain the same acrylate compound as in Production Example 1.

Production Example-3 44.2 g of diethyl malonate and 100 ml of ethanol were placed in a 300 ml three-necked flask equipped with a dropping funnel and a cooling tube, and 6.4 g of metallic sodium was added while cooling with ice, and stirring was continued until a uniform solution was obtained. Then 6-bromo-1-decanol 50.0
After adding g by a dropping funnel, the mixture was heated at 70 ° C. for 5 hours.

The above solution was transferred to a 500 ml round-bottomed flask, 100 ml of 30 wt% NaOH aqueous solution was added, and the mixture was heated at 110 ° C. for 1 hour. After cooling, 12N hydrochloric acid was added dropwise to adjust the pH to 2 or less, and most of ethanol was distilled off by vacuum distillation. The above solution was transferred to a 500-ml secretory funnel, 200 ml of ethyl acetate was added, and the mixture was washed with water three times, and then the ethyl acetate layer was dehydrated with anhydrous sodium sulfate and anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 33.8 g of a malonic acid compound.

Then, methacrylic acid chloride was reacted in the same manner as in Production Example 1 to obtain the following acrylate compound.

(A) IR 3000 to 2800 cm ^-1 absorption based on aliphatic carbon-hydrogen bond, 1800 to 1640 cm ^-1 absorption based on carbonyl group, 1640
Absorption based on the C = C double bond was observed at -1620 cm- ¹ .

(B) ¹ H-NMR (tetramethylsilane standard; δppm, 60MH
z) The spectrum was the same as that of the acrylate compound obtained in Production Example 1 except that 10 protons of the methylene group centered at 1.30 ppm appeared in a wide single line.

(C) Mass spectrometry (MS-FD) Mass spectrum result m / e 273 M +1 peak appears
It was

(D) Elemental analysis values Elemental analysis values are C57.20%, H7.45%, theoretical value 57.34%,
It was in good agreement with H7.40%.

Production Example-4 The same operation as in Production Example-1 was performed except that the following compound was used as a raw material to obtain the following acrylate compound.

Acrylate compound (A) IR 3000 to 2800 cm ^-1 absorption based on aliphatic carbon-hydrogen bond, 1800 to 1640 cm ^-1 absorption based on carbonyl group, 1640
Absorption based on the C = C double bond was observed at -1620 cm- ¹ .

(B) ¹ H-NMR (tetramethylsilane standard; δppm, 60MH
z) Two protons of carboxylic acid appear on a single line at 9.8 ppm (disappeared by substitution with heavy water), and two protons of double bond with 5.6 ppm and 6.2 ppm appear on a doublet at 4.3 to 3.9 ppm. Two protons of the methylene group next to the ester bond appear on the triplet, and three protons of the methyl group on the double bond appear on the single line at 1.9 ppm. 21 protons of the methyl group on the quaternary carbon appeared in a wide single line.

(C) Mass spectrometry (MS-FD) Mass spectrum result m / e343 M +1 peak appears
It was

(D) Elemental analysis values Elemental analysis values are C63.19% and H8.91%, which is the theoretical value C6.
It was in good agreement with 3.13% and H8.83%.

Production Example-5 33.8 g of diethyl malonate and 150 ml of ethanol were placed in a 300 ml three-necked flask equipped with a dropping funnel and a condenser, and 4.85 g of metallic sodium was added while cooling with ice, and stirring was continued until a uniform solution was obtained. Then 10-bromo-1-decanol 50
After g was added dropwise with a dropping funnel, the mixture was heated at 80 ° C. for 3 hours. After cooling this solution, 4.85 g of metallic sodium was further added and dissolved therein, 50 g of 10-bromo-1-decanol was added dropwise, and then the mixture was heated at 80 ° C. for 5 hours. Then, the same operation as in Production Example-1 was performed to obtain the following acrylate compound.

(A) IR 3000 to 2800 cm ^-1 absorption based on aliphatic carbon-hydrogen bond, 1800 to 1640 cm ^-1 absorption based on carbonyl group, 1640
Absorption based on the C = C double bond was observed at -1620 cm- ¹ .

(B) ¹ H-NMR (based on tetramethylsilane, δppm, 60MH
z) Two protons of carboxylic acid appear in a single line at 9.3 ppm (disappeared by deuterium substitution), and four double bond protons appear at 5.6 ppm and 6.2 ppm in a double line, 4.3 to 3.9 ppm. The proton of the methylene group next to the ester bond is a triplet
It appears that the number of protons of the methyl group is 6 in a single line at 1.9 ppm.
36 protons of the methylene group centered at 1.3 ppm appeared in a wide single line.

(C) Mass spectrometry (MS-FD) Mass spectrum measurement result m / e554 M +1 peak
Appeared.

(D) Elemental analysis values The elemental analysis values are C67.45% and H9.51%, which is the theoretical value C6.
It was in good agreement with 7.36% and H9.48%.

Abbreviations in the following examples represent the following compounds.

Bis-GMA 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane TEGDMA triethylene glycol dimethacrylate BPO dibenzoyl peroxide DEPT N, N-diethanol paratoluidine BHT butylhydroxytoluene HQME hydroquinone Monomethyl ether Example 1 The following tests were conducted using the adhesive film forming material shown in Table 1.

(1) Adhesiveness to dentin (2) Marginal sealing property to cavity (3) Barrier property to phosphoric acid aqueous solution The test relating to the above was evaluated by the following methods.

First, as a dental composite resin, a visible light curable type resin was prepared according to the following formulation.

Bis-GMA 42 parts by weight TEGDMA 28 〃 Tetramethylolmethane triacrylate 30 〃 Camphorquinone 0.4 〃 DEPT 0.4 〃 HQME 0.05 〃 Silane-treated quartz fine powder 200 〃 (1) Adhesion to dentin Emery Paper (# 320)
After polishing, the smooth dentin was exposed, the polished surface was washed with water for 30 seconds, and then air was blown to dry the surface. next,
The adhesive film forming material shown in Table 1 was applied to the dentin surface,
The solvent was blown off by blowing air.

A plate-like wax with a diameter of 4 mm and a thickness of 2 mm was attached to this surface using double-sided tape, and then a composite resin adjusted for photocuring was filled in, and a commercially available visible light irradiator "Optical The composite resin was cured by irradiating for 30 seconds using "Lux". The test piece was prepared by removing the paraffin wax and stored in water at 37 ° C. for 24 hours. A metal attachment was attached to the test piece, and the tensile bond strength was measured with a tensile tester (crosshead speed 10 mm / min). The obtained results are shown in Table 1.

(2) Marginal sealing to the cavity A cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of a human extracted tooth. Next, using the adhesive film forming material shown in Table 1 and a commercially available product (Corparite) conventionally used for comparison, each was lightly applied to the cavity wall and then filled with cement or amalgam. One hour after filling, store in water at 37 ° C, and after 1 day, alternately in aqueous solution of fuchsin at 4 ° C and 60 ° C for 1 minute each
The percolation test of dipping was performed 60 times to test the edge sealing property.

After that, the extracted tooth was cut at the center, and it was examined whether or not there was invasion of a dye (fuchsin) between the cavity and the filling material.

The reproducibility of the above test was confirmed using 5 samples for each type of experiment. As a result, in the case where the amalgam or cement was directly filled without using the above composition, or in the case where colalite was applied and then the amalgam or cement was filled, the infiltration of the dye was observed in all the samples.

On the other hand, with regard to the adhesive film forming materials of No. 1 to No. 19 in Table 1, invasion of the dye was not recognized in any of them, and good results were obtained.

(3) Barrier to 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 having a pore size of 3 μ was immersed in distilled water for 1 hour, taken out, and the surface was blown with nitrogen gas to be dried.

Next, commercially available corparite as a blocking material (backing material), diecal, and the adhesive film forming material used in Table 1 of (1) of Example 1 were applied to the back surface, and air was blown again to remove the solvent. did. A 37% orthophosphoric acid aqueous solution was used as the phosphoric acid aqueous solution, and one drop was dropped on the barrier material and left to stand naturally.

To detect phosphoric acid that permeates the adhesive film forming material, a pH test paper is placed under the membrane filter,
The time when the color changed was defined as the passage time.

As a result, those that did not use any blocking material had a permeation time of 15 seconds for the phosphoric acid aqueous solution, 1 minute and 10 seconds for those that used Couperite (trade name), and those that used Dical (trade name). It was more than 10 minutes.

On the other hand, as a result of using the adhesive film forming material of the present invention shown in Table 1 as the blocking material, the permeation time of the phosphoric acid aqueous solution was 10 minutes or more.

Example 2 As a dental composite resin, a paste (A) and a paste (B) were prepared according to the following formulations.

The bovine tooth dentin exposed in the same manner as in Example 1 was added with Table 2
A mixture of the adhesive film forming material (I) liquid and the liquid (II) shown in (4) was applied, and air was blown to remove the solvent.

Next, after the paraffin wax shown in Example 1 was attached, air was blown to remove ethanol and excess adhesive. On top of that paste (A) and (B)
It was mixed and filled at a ratio of 1: 1. The plate-like wax was removed after standing for 1 hour, and the plate was immersed in 37 ° C. water for a day and night, and then the tensile strength was measured. Tensilon manufactured by Toyo Baldwin was used for the measurement, and the tensile speed was 10 mm / min. The obtained results are shown in Table 2.

Example 3 A cavity having a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of a human extracted tooth. Next, after thinly applying the adhesive film forming materials shown in Tables 1 and 2 and corparite as conventionally used to the fossa wall, respectively, the adhesive film forming materials shown in Table 1 were compared with those in Example 1. Similarly, it was irradiated with visible light, and then each alloy shown in Table 3 was filled. One hour after filling, store in water at 37 ° C, and after 1 day, put in 1% Fuchsin aqueous solution at 4 ° C and 60 ° C.
The percolation test of dipping was alternately performed 60 times every minute to test the edge sealing property.

After that, the extracted tooth was cut at the center, and it was examined whether or not there was invasion of a dye (fuchsin) between the cavity and the filling material.

The reproducibility of the above test was confirmed using 5 samples for each type of experiment. As a result, when the alloys shown in Table 3 were directly filled without using the above composition,
Alternatively, in the case of coating with Coparite and then filling with the alloy shown in Table 3, penetration of dye was observed in all the samples.

On the other hand, with respect to the adhesive film forming materials shown in Tables 1 and 2, no dye penetration was observed, and good blocking results were obtained.

Example 4 To confirm that the adhesive film forming material of the present invention has the ability to block unreacted phosphoric acid of zinc phosphate cement,
The test was conducted using the following method.

First, a membrane filter having a pore diameter of 3 μ was immersed in distilled water for 1 hour, taken out, and the surface was blown with air to be dried.

Next, the adhesive film forming materials shown in Tables 1 and 2 were applied to the surface as a blocking material, and air was blown again to remove the solvent.
Here, the adhesive film forming materials shown in Table 1 were irradiated with visible light as in Example 1.

Further, Elite 100 was used as a commercially available zinc phosphate cement, and after kneading according to the prescription, it was placed on a barrier material, a glass plate was placed thereon, and a load of 100 g was left to stand.

To detect phosphoric acid that permeates the adhesive film forming material, a pH test paper is placed under the membrane filter,
The time when the color changed was defined as the passage time.

As a result, while no adhesive film-forming material was used at all, the permeation time of the phosphoric acid aqueous solution was 15 seconds, while those using the adhesive film-forming material of the present invention were all 10 minutes or longer. there were.

Example 5 A cavity having a diameter of 3 mm and a depth of 2 mm is formed on the labial surface of a human extracted tooth,
After applying the adhesive film forming material shown in Table 1 to the cavity, it was dried with air and irradiated with visible light in the same manner as in Example 1. Next, fill the cavity with an aqueous solution of fuchsin, and at 37 ° C for 1
It was stored in a thermostatic chamber at a humidity of 00% for 1 day. Next, in order to examine the water resistance of the adhesive film forming material of the present invention, the extracted tooth was cut at the center, and it was examined whether or not the fuchsin aqueous solution had penetrated into the dentin. As a result, as a blank, the one without application of the adhesive film forming material of the present invention was found to be colored in fuchsin on the tooth structure, but the one to which the adhesive film forming material of the present invention was applied was a dye. No intrusion was observed and good results were obtained.

Example 6 For a patient who has a wedge-shaped defect in the tooth neck and feels pain when touched by air or cold water, the adhesive film-forming material shown in No. 1 of Table 1 is applied to the wedge-shaped defect, When irradiation with visible light was performed in the same manner as in Example 1, the pain caused by contact with air and cold water was resolved.

Further, the NO.2 adhesive film forming material of Example 1 was applied to the skin incision and irradiated with visible light. As a result, the wound was blocked and the pain was soft.

In addition, as a result of application to the affected area of stomatitis, it was no longer bleeding only by food and drink.

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

After the No. 1 adhesive film forming material of Example 1 was covered with a disc paper, ethanol was evaporated and visible light was irradiated, and the plate was placed on a flat plate and anaerobically cultured for 48 hours.

After 48 hours, the width of the fungus paper is a few mm on both sides.
An antibacterial zone was produced.

Bacteroides gingivalis 381 Actinomyces naeslundii ATCC 12104 Actinomyces viscosus ATCC 15987 Propionibacterium acnes EXC-1 Actinomyces israeli ATCC 12102 Comparative Example 1 Comparative Example 1 An adhesive film-forming material using a known acrylate compound was prepared.

Next, apply the emery paper (#
320) to expose smooth dentin, and the polished surface is
After washing with water for 0 seconds, air was blown to dry the surface.
Subsequently, the prepared adhesive film forming material was applied to the dentin surface and air was blown to remove the solvent. Then, after irradiating with visible light in the same manner as in Example 1, the sample was stored in distilled water at 37 ° C. for 24 hours, and further subjected to a thermal cycle test at 4 ° C. and 60 ° C., and the state of the coating film was repeated 60 times. Was observed. The results are shown in Table 4.

Comparative Example 2 A film forming material using the acrylate compound shown in Table 4 was prepared in the same manner as in Comparative Example 1, and the adhesion to dentin was examined. The test was conducted in the same manner as in Example 1, and the results are shown in Table 5.

Further, the edge sealing property with respect to the cavity was examined by using the same method as in Example 1 and is shown in Table 5.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C09J 4/06 JBT 7921-4J

Claims (1)

[Claims] 1. A general formula (A) With respect to 100 parts by weight of the acrylate compound represented by 10 to 60% mol of the monomer unit represented by A polymer containing 40 to 90 mol% of a monomer unit represented by
1000 to 5 parts by weight and (C) radical initiator 0.05 to 5 relative to the total amount of monomers
Adhesive film-forming material mainly consisting of weight%.