JP3276091B2 - Acid group-containing (meth) acrylate monomer and composition thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the field of adhesion of metal materials, organic polymer materials, ceramic materials, and human hard tissues.
Particularly in the field of dentistry, an adhesive composition suitable as an adhesive for expressing high adhesive strength between a tooth substance and a composite restoration material, an acidic group-containing (meth) acrylate monomer used therefor, The present invention relates to a filling and restoring adhesive composition containing a group-containing (meth) acrylate monomer.

[0002]

2. Description of the Related Art Joining is an elemental technology in all industries, and welding, rivets, screwing, bonding and the like are widely put into practical use in accordance with the parts to be used. In recent years, in industry,
Adhesive bonding technology has been attracting attention because of the progress of industrial development, the lightening and shortening of the material, the development of new materials due to the progress of the material revolution, and the shortening of processes for the purpose of streamlining production.

[0003] In particular, adhesives have recently been widely used in various fields such as automobiles, the electronics industry, or construction and medical care. Among them, polymer-based adhesives that adhere by polymerization curing of monomers, urethane-based, acrylic-based monomers and the development of polymerization catalysts, in addition to high adhesive strength, durability,
Many features were found, such as heat resistance, water resistance, rapid curing, photo-curing, thermo-curing, and adhesion to various materials. As a result, polymer adhesives have provided adhesives having characteristics in accordance with their requirements in various fields.

Above all, a dental adhesive used for restoring teeth for medical use is required to have strong adhesiveness and durability that can withstand a special and severe environment in the oral cavity. For restoration of teeth damaged by dental caries or the like, a composite restoration material called a composite resin is mainly used. In general, this composite resin is used after filling into the cavity of a tooth and polymerizing and curing. However, since this material itself does not have adhesiveness to tooth material, a dental adhesive is also used.

Conventionally, in order to improve the adhesiveness of a dental adhesive, a pretreatment material for treating a tooth surface before applying the adhesive has been used. However, different pretreatments are applied to enamel and dentin. Had been applied. In other words, while enamel is subjected to strong decalcification with phosphoric acid and mechanically adhered to a rough surface,
Dentin is subjected to relatively weak decalcification using, for example, citric acid-ferric chloride, and is further applied with an adhesive containing a carboxylic acid monomer as an adhesion promoter, whereby adhesion using chemical affinity is performed. Have been.

[0006] However, the above-mentioned operation is clinically very complicated. In recent years, for simplification, a method for simultaneously treating enamel and dentin with an aqueous acid solution such as citric acid or maleic acid has emerged. However, in such a case, it was necessary to increase the acid strength of the pretreatment material in order to achieve high adhesive strength to enamel, but if the acid strength was increased, dentin would suffer excessive demineralization. Had become.
In other words, shavings called smears form a smear layer in close contact with the tooth surface on the dentin surface that is usually cut for cavity formation, and the smear penetrates from the dentin surface into the dentinal tubules leading to the pulp. A plug called a smear plug seals the tubule, but the excessive demineralization removes the smear plug and increases the permeability of the dentinal tubule (Shinkai, Kato, Nichibo, 35 (3), 634,199
2) Therefore, there has been a problem that harmful substances and the like easily enter the dental pulp through the tubule. Furthermore, in view of the recent widespread recognition that excessive demineralization may damage the living tissue, dentin, it is desirable to suppress dentine demineralization as much as possible.

On the other hand, if the pretreatment is performed with a dilute acid that leaves a dentin smear plug, there is a problem that the adhesive strength to enamel is reduced. In view of the above, there is a demand for an adhesive material that exhibits high adhesive strength to both dentin and enamel even when pretreated with a dilute acid that leaves a dentin smear plug.

[0008] When performing repair treatment of a cervical part which is constantly exposed to gingival exudate and it is difficult to maintain a dry state of a tooth, or a child who does not want to open the mouth for a long time, there is ample time for composite resin repair. A material called glass ionomer cement, which has a small amount of adhesive and does not require an adhesive, is often used. However, the glass ionomer cement has a low adhesive strength to the tooth substance and a low mechanical strength of the material itself as compared with the adhesive, so that it has a drawback that friction and fracture easily occur after filling and poor durability. In view of the above, there is a demand for a filling and restoring material which itself is strongly bonded to teeth and metals and has high mechanical strength by a simple operation which does not require an adhesive.

[0009]

An object of the present invention is to provide an adhesive which firmly adheres to a living material such as a composite material or a tooth by a simple operation, and an adhesive material which firmly adheres to a living tissue such as a composite material or a tooth by a simple operation. The purpose of the present invention is to provide a filling and restoring adhesive material that adheres to a material and exhibits high mechanical strength.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, an adhesive composition using a novel acidic group-containing (meth) acrylate monomer has been developed. It has been found that both dentin and enamel have high adhesive strength even when pre-treated with a dilute acid, in order to adhere firmly to living hard tissues such as composite materials and teeth, and especially to adhere to teeth. Further, it has been found that the adhesive composition for filling and restoring using the (meth) acrylate-based monomer having an acidic group strongly adheres to a living material such as a composite material or a tooth, and exhibits higher mechanical strength. Thus, the present invention has been completed.

That is, the present invention provides the following general formula (1)

[0012]

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(Where R is a hydrogen atom or a methyl group, l,
(m and n are integers of 1 or 2).

Another invention relates to (A) 100 parts by weight of a (meth) acrylate monomer containing at least 5% by weight of an acidic group-containing (meth) acrylate monomer of the general formula (1), and (B) An adhesive composition containing 0.1 to 5 parts by weight of a polymerization initiator.

In still another invention, (A) 30% by weight of an acidic group-containing (meth) acrylate monomer represented by the general formula (1)
100 parts by weight of the (meth) acrylate-based monomer containing
The adhesive composition for filling and repairing comprises (B) 0.1 to 5 parts by weight of a polymerization initiator and (C) 50 to 700 parts by weight of an inorganic filler.

The acidic group-containing (meth) acrylate monomer represented by the general formula (1) is a novel compound. In the general formula (1), l, m, and n are integers of 1 or 2, but usually, it is difficult to separate and purify the raw material trimethylolpropane polyethyl ether triol, and it is commercially available as a mixture. The acidic group-containing (meth) acrylate monomer of the present invention exists as a mixture of 1 and 2.

Specific examples of the acidic group-containing (meth) acrylate-based monomer represented by the general formula (1) include the following.

[0018]

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[0019]

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The method for synthesizing the acidic group-containing (meth) acrylate monomer represented by the general formula (1) is not particularly limited, but a typical method will be described below.

First, as a first-stage reaction, trimethylolpropane polyethyl ether triol is subjected to a dehalogenation reaction with a two-fold molar amount or a small excess of (meth) acrylic acid halide, whereby trimethylolpropane polyethyl ether monoalcohol di (meth) ) After the synthesis of the acrylate, the trimellitic anhydride of trimethylolpropane polyethylether di (meth) acrylate is subjected to a dehalogenation reaction of the compound with an equimolar amount or a small excess of trimellitic anhydride halide as a second step reaction. A three-step production method of synthesizing a compound and then hydrolyzing an acid anhydride group of the compound as a third step reaction is exemplified.

The reactions of the first and second stages in the above production method are as follows:
In an inert organic solvent, for example, benzene, toluene, tetrahydrofuran, dioxane, ethyl acetate, methyl acetate, acetone, methyl ethyl ketone, methylene chloride,
0 to 100 in the presence of an equimolar amount of a tertiary amine such as pyridine, triethylamine, dimethylaniline, dimethylaminopyridine or the like with an acid halide in chloroform or the like.
The reaction can be carried out at ℃. When the reaction is carried out by the above-mentioned method, a halide salt of an amine is formed, and this salt can be removed by filtering or washing the reaction solution.

The above-mentioned first and second-stage reactions are continuously performed in the same reaction layer, and finally, the produced salt can be removed. Furthermore, after the first-stage reaction, the above-mentioned generated salt is removed, and then the second-stage reaction can be performed.

In the third step of the above production method, the trimellitic anhydride of trimethylolpropane polyethyl ether di (meth) acrylate is dissolved in an inert organic solvent such as ethyl ether or tetrahydrofuran, and further dissolved in water. And stirring vigorously for about 1 day at room temperature.

After the above operation, alkali washing and water washing can be performed to remove unreacted substances and catalyst. In order to further improve the purity, isolation and purification using a column chromatogram are also possible.

The acidic group-containing (meth) acrylate monomer obtained by the above production method is a yellow or brown viscous liquid.

In the adhesive composition of the present invention and the adhesive composition for filling and restoring, in addition to the above-mentioned acidic group-containing (meth) acrylate monomer, another (meth) acrylate monomer is further added. It is also a preferred embodiment to use. Representative examples suitably used as other (meth) acrylate-based monomers are specifically described below.

A) Monofunctional (meth) acrylate monomers Methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glyceryl monomethacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and their acrylates or acrylic acid ,
Methacrylic acid, 2-methacryloyloxyethyl dihydrogen phosphate.

B) Bifunctional (meth) acrylate monomer (i) Aromatic compound 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxy) Phenyl) propane, 2,2-bis (4
-Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
(4-methacryloyloxyethoxyphenyl) -2
(4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyl Oxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and their acrylates (ii) aliphatic compound ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate,
Neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates thereof c) Trifunctional (meth) acrylate Monomers Trimethylolmethane trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate and their acrylates and monomers represented by the following structural formula

[0030]

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(R ¹ , R ² , R ³ are hydrogen atoms or methyl groups) d) Tetrafunctional (meth) acrylate monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and urethane represented by the following structural formula System monomer

[0032]

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The above (meth) acrylate monomers can be used as a mixture of two or more kinds as necessary.

When the acidic group-containing (meth) acrylate monomer of the present invention is used as an adhesive composition for an adhesive, its compounding ratio in all (meth) acrylate monomers is 5% by weight. It is necessary to be above. If it is less than 5% by weight, the adhesive strength with the adherend will be reduced. However, the range varies depending on the intended use, and may be 5% by weight when used as an adhesive for metals and composite materials, and 30% by weight or more, preferably 50% by weight or more when used as an adhesive for dental use. It is desirable to let. If it is less than 30% by weight, the adhesive strength to dentin tends to decrease.

In the case where the acidic group-containing (meth) acrylate monomer of the present invention is used as an adhesive composition for filling and repairing, the mixing ratio in the total (meth) acrylate monomer is as follows: It needs to be 30% or more, preferably 5%.
0% by weight or more. If the compounding ratio is less than 30% by weight, the adhesive strength to the adherend and the mechanical strength of the material are reduced.

The polymerization initiator used in the present invention is not particularly limited, and a known radical generator can be used without any limitation.

For example, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane 2 Organic peroxides such as 5,5-dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate, azo compounds such as azobisisobutyronitrile, and organic acid compounds such as tributyl boric acid. It is suitable.

It is also possible to carry out polymerization at room temperature by using a combination of the above organic peroxide and an amine compound. Such amine compounds include secondary or amino compounds in which an amino group is bonded to an aryl group. Tertiary amine compounds are preferably used in terms of curing acceleration.

For example, N, N'-dimethyl-p-toluidine, N, N'-dimethylaniline, N'-β-hydroxyethyl-aniline, N, N'-di (β-hydroxyethyl) -aniline, N , N'-di (β-hydroxyethyl) -p-toluidine, N-methyl-aniline, N-
Methyl-p-toluidine and the like are preferred.

In a preferred embodiment, a photosensitizer which generates a radical upon irradiation with light is used as the polymerization initiator.

Examples of photosensitizers for ultraviolet light include benzoin, benzoin methyl ether, benzoin ethyl ether, acetoin benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone. In addition, a photosensitizer that initiates polymerization by visible light does not require ultraviolet rays harmful to the human body, and is therefore more preferably used. Examples of these are benzyl, camphorquinone,
α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-
Α-diketones such as phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone and naphthoquinone, 2-benzyl-dimethylamino-1
-(4-morpholinophenyl) -butanone-1,2-
Benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -propanone-1, 2-benzyl-2-diethylamino-1 − (4
-Morpholinophenyl) -propanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -pentanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl) Α-aminoacetophenones such as -pentanone-1 and the like. Among them, camphorquinone is most preferably used.

It is also preferable to use the photosensitizer in combination with a photopolymerization accelerator. Examples of such a photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine. ,
N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p- Dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydrido Xyethylaniline, N, N-dihydroxyethyl-p-toluidine, p
-Dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylysine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, Tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-
Ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-( tertiary amines such as n-butylimino) diethanol; 5-butylbarbituric acid;
Barbituric acids such as 1-benzyl-5-phenylbarbituric acid can be suitably used. At least one of these photopolymerization accelerators can be selected and used, and two or more can be used as a mixture.

Among these polymerization initiators, a combination of a photosensitizer and a photopolymerization accelerator is preferable from the viewpoint of adhesive strength.

The amount of the polymerization initiator to be added is in the range of 0.1 to 5% by weight with respect to all (meth) acrylate monomers in both the adhesive composition and the adhesive composition for filling restoration. You can choose from. When the addition amount is less than 0.1% by weight, curing is difficult, and when the addition amount is more than 5% by weight, the operation time becomes too short, such as high photosensitivity.

The adhesive composition of the present invention may further contain, if necessary, a polymerization inhibitor and a small amount of a filler as long as its performance is not reduced.

The adhesive composition for repair of filling of the present invention needs to contain an inorganic filler as one of the components.
By blending the inorganic filler, the mechanical strength of the cured product is improved, and the cured product can be used as a restoration material for filling and repairing dents and defects in metal or the like, and as a dental backing layer material and a filling restoration material. Further, if necessary, a pigment or a polymerization inhibitor may be contained.

Specific examples of the inorganic fillers that are generally preferably used include aluminosilicate glass, quartz, amorphous silica, silica-titania, silica-zirconia, silica-alumina, silicate glass, and the like. There are titania, zirconia, alumina and the like. As the inorganic filler, it is usually preferable to use one treated with a silane coupling agent, a titanate coupling agent, a zircoaluminate coupling agent, or the like. The amount of the inorganic filler to be added is 50 to 7 based on all (meth) acrylate monomers.
00% by weight, preferably 150 to 400% by weight. If the addition amount is more than 700% by weight, the (meth) acrylate-based monomer and the inorganic filler will not be uniformly mixed, and if it is less than 50% by weight, the mechanical strength such as the compressive strength will be reduced.

The method for preparing the adhesive composition of the present invention and the adhesive composition for filling and repairing are not particularly limited, and ordinary methods are employed. For example, it can be prepared by mixing a (meth) acrylate-based monomer and a polymerization initiator with a known mixer such as a magnetic stirrer or a propeller stirrer until a uniform solution is obtained. When an inorganic filler is further added to form an adhesive composition for filling restoration, a known mixer such as a planetary mixer or a Raikai machine may be used to add (meta) to the inorganic filler.
A mixed solution of the acrylate monomer and the polymerization initiator is gradually added and mixed.

The form of packaging is not particularly limited. In the case of the adhesive composition, when the polymerization initiator is a photosensitizer, the (meth) acrylate monomer and the polymerization initiator are packaged in one pack. When the polymerization initiator is a room temperature initiation system containing an organic peroxide, the (meth) acrylate monomer is divided into two, and one of the two is added with the organic peroxide. Can be made into a two-pack type in which an amine is added and both are mixed at the time of use. In the adhesive composition for filling restoration containing an inorganic filler material, for example, a (paste) type can be obtained by mixing a (meth) acrylate-based monomer and an inorganic filler and adding a photosensitizer thereto. Alternatively, the mixture of the (meth) acrylate-based monomer and the inorganic filler may be divided into two parts, and one may be added with an organic peroxide and the other may be added with an amine to form a two-paste type. Further, a powder-liquid type can be obtained by adding an organic peroxide to one of the inorganic filler and the (meth) acrylate-based monomer and adding an amine to the other.

[0050]

The adhesive composition containing the novel (meth) acrylate monomer having an acidic group of the present invention exhibits high adhesiveness to metals, composite materials, teeth and the like. Especially when used as an adhesive when filling and restoring with composite resin,
Even if pre-treated with a dilute acid that does not remove smear plugs, it shows high adhesive strength to both dentin and enamel, so it is unlikely that extraneous stimuli will reach the pulp in clinical practice, Achieve safe bonding.

The novel acidic group-containing (meta) of the present invention
An adhesive composition for filling and restoration in which an inorganic filler is added to a (meth) acrylate monomer containing an acrylate monomer,
Excellent in adhesiveness and mechanical strength, metal, composite materials,
It is preferably used for filling and repairing dents and missing parts of teeth and the like. Especially in dental treatment, when performing filling restoration and abutment formation for children and cervical region, only pretreatment with a dilute acid that does not excessively remove smear plugs, ivory without using adhesive It shows high adhesive strength to both materials and enamels and high mechanical strength. For this reason, in clinical practice, the possibility that an external stimulus reaches the pulp with a short operation is low, and more secure adhesion to the living body is realized, and durability against occlusal pressure and an external load is realized.

[0052]

EXAMPLES The following examples illustrate the acidic group-containing (meth) acrylate monomer and the composition thereof according to the present invention, but the present invention is not limited to these examples. The methods for measuring the physical properties of the materials shown in the text and in the examples are as follows.

(1) Adhesive strength of enamel and dentin The bovine anterior tooth was removed within 24 hours after sacrifice, and water was injected under # 80.
The enamel plane and the dentin plane were cut out with emery paper No. 0 so as to be parallel to the lips. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then a maleic acid aqueous solution having a concentration shown in Table 1 was applied to the surfaces with a small brush, and after 30 seconds, the surfaces were washed with water and dried. This plane has a diameter of 4
Fix the double-sided tape with a hole of
A simulated cavity was formed by fixing paraffin wax having a hole having a diameter of 6 mm and a diameter of 6 mm so as to be at the same center on the above-mentioned hole.

In order to measure the strength of the adhesive composition, a 35% aqueous solution of 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Yushi Co., Ltd.) was applied to the simulated cavity using a small brush, dried after 30 seconds, and dried. Apply the composition with a small brush and use a visible light irradiator White Light (Takara Labelmont)
For 10 seconds, and further filled with Parfique esterite (manufactured by Tokuyama Soda Co., Ltd.), pressed and pressed, and then irradiated with light for 30 seconds to cure. When measuring the strength of the adhesive composition for filling and restoring, the above cavity was directly filled with the adhesive composition for restoring and pressed, and then irradiated with light for 30 seconds to cure.

After one hour, the adhesive test piece was immersed in water at 37 ° C. for 24 hours, and then subjected to a crosshead speed of 10 using a tensile tester (Autograph, manufactured by Shimadzu Corporation).
The adhesive strength with the tooth was measured at mm / min.

(2) Dentin Demineralization Degree of bovine anterior teeth was removed within 24 hours after sacrifice, and water was injected.
The dentin plane was cut out with emery paper No. 0 so as to be parallel to the lips. Next, about 10 compressed air is applied to these surfaces.
After spraying and drying for 2 seconds, an aqueous solution of maleic acid having a concentration shown in Table 1 was applied and left for 30 seconds. After washing the application surface with water,
Twenty dentinal tubules in the image were observed with a scanning electron microscope (manufactured by JEOL Ltd.), and the degree of demineralization was evaluated using the ratio of the opening area to the area of the tubule closed with a smear plug as the degree of opening. That is, 0 indicates that decalcification has progressed to the peritubular dentin, 1 indicates the degree of opening of the tubule of 100 to 80%, and 80 to 60 hereinafter.
% To 2, 60 to 40% to 3, 40 to 20% to 4, 20 to
The evaluation was performed in six steps, where 0% was set to 5. Usually, if the degree of opening is 40 to 0% and 4 to 5 in a 6-step evaluation, it is determined that dentin demineralization is suitable.

(3) Compressive strength of cured product The adhesive composition for filling and repairing was filled into a mold having a hole of 3 mm × 4 mmφ, pressed and pressed, and irradiated with a visible light irradiator White Light (manufactured by Takara Labelmont). After curing by irradiating with light for 2 seconds, the cured product was immersed in water at 37 ° C. for 24 hours, and the compression strength was measured at a crosshead speed of 1 mm / min using a compression tester (Autograph, manufactured by Shimadzu Corporation). .

Example 1 A 300 ml three-necked flask was charged with trimethylolpropane polyethyl ether triol (trade name: Wyginol ™).
P35, manufactured by Yokkaichi Gosei Co., Ltd.), 11.5 g, triethylamine 8.08 g, and toluene 150 ml were added, and methacryloyl chloride 8.36 was stirred in a nitrogen atmosphere under ice cooling.
g was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was heated and stirred in a 60 ° C. water bath for 2 hours. The obtained reaction solution is filtered,
After removing the hydrochloride of triethylamine, it was washed once with a 0.1N aqueous sodium hydrogen carbonate solution and twice with ion-exchanged water. Add anhydrous sodium sulfate to the organic layer and dry,
After filtration, the solvent is removed under reduced pressure to obtain a pale yellow viscous liquid 1
4.2 g were obtained.

In a 300 ml eggplant-shaped flask, 12.8 g of the above pale yellow viscous liquid, 2.56 g of pyridine and 1 part of toluene
50 ml was added, and a toluene solution of 6.81 g of trimellitic anhydride chloride was dropped at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated and stirred in a water bath at 80 ° C. for 2 hours. After the obtained reaction solution was filtered to remove the pyridine hydrochloride, the solvent was removed under reduced pressure, and tetrahydrofuran 15
0 ml and ion-exchanged water 150 ml were added, and the mixture was stirred at room temperature overnight. 200 ml of toluene was added to this solution to extract the product, which was then washed once with a 0.1N aqueous sodium hydrogen carbonate solution and twice with ion-exchanged water. The organic layer was dried over anhydrous sodium sulfate, filtered, the solvent was removed under reduced pressure, and the residue was purified by gel permeation chromatography (manufactured by Shimadzu Corporation) to give 6.2 g of a yellow viscous liquid.
I got From the results of infrared spectroscopic analysis and nuclear magnetic resonance analysis of this product, it was confirmed that the product was a compound represented by the following structural formula (2).

[0060]

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Infrared spectroscopy 1500, 1580, 1610 cm ^-1 (absorption based on aromatic ring) 1640 cm ^-1 (absorption based on C = C double bond) 1730 cm ^-1 (absorption based on carbonyl group of carboxylic acid) Nuclear magnetism Resonance analysis 0.7-0.9 ppm, multiplet, 4H (absorption of CH ₂ ) 1.2-1.4 ppm, multiplet, 1H (absorption of CH) 1.9 ppm, singlet, 6H (of CH ₃ absorption) 3.4~3.7ppm, multiplet, 13H (-OCH ₂ -
Absorption) 4.1~4.3ppm, multiplet, 7H (-COOCH ₂
- absorption) 5.5,6.1ppm, 2 doublets, 4H (= absorption of CH ₂₎ 7.1~8.5ppm, multiplet, 3H (absorption of the benzene ring) 10.6 ppm, 1 single line, 2H (absorption of COOH) Example 2 In a 300 ml three-necked flask, trimethylolpropane polyethyl ether triol (trade name: Widinol ™)
P35, manufactured by Yokkaichi Gosei Co., Ltd.) 11.5 g, triethylamine 8.08 g, and toluene 150 ml were added, and the mixture was stirred under ice-cooling under a nitrogen atmosphere under ice-cooling and 5.76 g of acryloyl chloride
Was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was heated and stirred in a 60 ° C. water bath for 2 hours. The resulting reaction solution was filtered to remove triethylamine hydrochloride, and then washed once with a 0.1N aqueous sodium hydrogen carbonate solution and twice with ion-exchanged water. 10. Anhydrous sodium sulfate was added to the organic layer, followed by drying. After filtration, the solvent was removed under reduced pressure.
8 g were obtained.

In a 300 ml eggplant-shaped flask, 10.6 g of the above brown viscous liquid, 2.60 g of pyridine and 15 parts of toluene
0 ml was added, and a toluene solution of 6.94 g of trimellitic anhydride chloride was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated and stirred in a water bath at 80 ° C. for 2 hours. After the obtained reaction solution was filtered to remove the pyridine hydrochloride, the solvent was removed under reduced pressure, and tetrahydrofuran 15
0 ml and ion-exchanged water 150 ml were added, and the mixture was stirred at room temperature overnight. 200 ml of toluene was added to this solution to extract the product, which was then washed once with a 0.1N aqueous sodium hydrogen carbonate solution and twice with ion-exchanged water. The organic layer was dried by adding anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting solution was separated and purified by gel permeation chromatography (manufactured by Shimadzu Corporation) to obtain 4.5 g of a brown viscous liquid.
I got From the results of infrared spectroscopic analysis and nuclear magnetic resonance analysis of this product, it was confirmed that the product was a compound represented by the following structural formula (3).

[0063]

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Infrared spectroscopy 1500, 1580, 1610 cm ^-1 (absorption based on aromatic ring) 1640 cm ^-1 (absorption based on C = C double bond) 1730 cm ^-1 (absorption based on carbonyl group of carboxylic acid) Nuclear magnetism resonance analysis 0.7~0.9ppm, (absorption of CH ₂₎ multiplet, 4H 1.2~1.4ppm, (absorption of CH) multiplet, 1H 3.4~3.7ppm, multiplet, 13H ( -OCH ₂ -
Absorption) 4.1~4.3ppm, multiplet, 7H (-COOCH ₂
5.8 to 6.4 ppm, multiplet, 6H (—CH ＝ CH ₂₎
7.1-8.5 ppm, multiplet, 3H (absorption of benzene ring) 10.6 ppm, singlet, 2H (absorption of COOH) Example 3 The structural formula (2) synthesized in Example 1 10% by weight of an acidic group-containing methacrylate monomer, 50% by weight of bisphenol A diglycidyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
40% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was mixed, and the mixture was divided into two portions of 50% by weight, and 1% by weight of benzoyl peroxide was dissolved in one of them to obtain an adhesive composition A, 1% by weight of N, N-dimethyl paratoluidine was dissolved in the other, and this was used as adhesive composition B.

One side of a 10 × 10 × 3 mm silver-nickel-cobalt alloy was polished with # 800 emery paper and subjected to alumina sand blasting, and a double-sided tape having a hole having a diameter of 4 mm was fixed on this plane.

An equal amount of each of the adhesive compositions A and B was added to a mixing dish, mixed quickly with a small brush, applied to the above-mentioned holes, and pressed against a stainless steel bar having a diameter of 6 mm, which had been subjected to alumina sandblasting. After storing this test piece at 23 ° C. for 24 hours, the adhesive strength to metal was measured at a crosshead speed of 10 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). The adhesive strength was 18.5 MPa.

Example 4 80% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 40% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed and mixed. It was a liquid component.

33% by weight of silica, aluminum hydroxide 1
1% by weight, artificial cryolite 8% by weight, aluminum phosphate 2
2 wt% of r-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.) is obtained by melting and pulverizing a powder composed of 1 wt%, aluminum fluoride 7 wt%, and calcium fluoride 20 wt%. To make a powder component.

100% by weight of this liquid component and 150% of powder component
The mixture was divided into two parts each having 125% by weight, and 1% by weight of benzoyl peroxide was dissolved in one of them, followed by defoaming under vacuum to obtain an adhesive composition A for filling and repairing. After dissolving 1% by weight of N, N dimethyl paratoluidine in
Vacuum defoaming was performed to obtain an adhesive composition B for filling and repairing.

One side of a 10 × 10 × 3 mm silver-nickel-cobalt alloy was polished with # 800 emery paper and subjected to alumina sand blasting. Then, a double-sided tape having a hole having a diameter of 4 mm was fixed on this plane. Further, paraffin wax having a thickness of 1.5 mm and a hole having a diameter of 6 mm was fixed on the circular hole so as to be at the same center, thereby forming a simulated cavity.

Adhesive Compositions A and B for Filling and Restoring Washi Paper
Were added in equal amounts, and the mixture was quickly mixed with a mixing rod, and filled and pressed into the simulated cavity. After storing this test piece at 23 ° C. for 24 hours, the adhesive strength to metal was measured at a crosshead speed of 10 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). Adhesive strength is 19.3M
Pa.

Examples 5 to 6 In a mixture of 80% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.5% by weight of each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester were dissolved, and the resulting mixture was used as an adhesive composition. It was measured.
Table 1 shows the results.

Example 7 A mixture of 80% by weight of the acidic group-containing acrylate monomer of the structural formula (3) synthesized in Example 2 and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to camphorquinone. , 0.5% by weight of each of p-dimethylaminobenzoic acid ethyl ester was dissolved,
This was used as an adhesive composition, and the adhesive strength to a tooth pretreated with maleic acid at the concentration shown in Table 1 was measured. Table 1 shows the results
Shown in

Example 8 A mixture of 60% by weight of the acidic group-containing acrylate monomer of the structural formula (3) synthesized in Example 2 and 40% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to camphorquinone. , 0.5% by weight of each of p-dimethylaminobenzoic acid ethyl ester was dissolved,
This was used as an adhesive composition, and the adhesive strength to a tooth pretreated with maleic acid at the concentration shown in Table 1 was measured. Table 1 shows the results
Shown in

Example 9 A mixture of 80% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 20% by weight of 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Yushi Co., Ltd.) was added to camphorquinone. 0.5% by weight of each of p-dimethylaminobenzoic acid ethyl ester was dissolved, and this was used as an adhesive composition. The adhesive strength to a tooth pretreated with maleic acid at the concentration shown in Table 1 was measured. Table 1 shows the results.

Example 10 40% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1, 30% by weight of 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Yushi Co., Ltd.), and trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd.) 3
0% by weight of a mixture of camphorquinone and p-dimethylaminobenzoic acid ethyl ester in an amount of 0.5% each.
% Of the resulting mixture was used as an adhesive composition, and the adhesive strength to a tooth pretreated with maleic acid at the concentration shown in Table 1 was measured. Table 1 shows the results.

Examples 11 to 12 A mixture of 80% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was prepared. 0.5% by weight of each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester was dissolved to obtain a liquid component.

33% by weight of silica, aluminum hydroxide 1
1% by weight, artificial cryolite 8% by weight, aluminum phosphate 2
2 wt% of r-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.) is obtained by melting and pulverizing a powder composed of 1 wt%, aluminum fluoride 7 wt%, and calcium fluoride 20 wt%. To make a powder component.

The liquid component 100% by weight and the powder component 150
% By weight, mixed under light shielding, and then degassed in vacuo. This was used as an adhesive composition for filling and restoring. The adhesive strength with each tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured product were measured. It was measured. Table 1 shows the results.

Example 13 100% by weight of the liquid component shown in Example 11 and 100% by weight of the powder component
% By weight, mixed in a light-shielded state, vacuum-degassed, and used as an adhesive composition for filling and restoring. The adhesive strength with the tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured body were measured. did. Table 1 shows the results.

Example 14 100% by weight of the liquid component shown in Example 11 and powder component 400
% By weight, mixed in a light-shielded state, vacuum-degassed, and used as an adhesive composition for filling and restoring. The adhesive strength with the tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured body were measured. did. Table 1 shows the results.

Example 15 The acid group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 was 40% by weight, triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 30% by weight, and trimethylolpropanetriene. 0.5% by weight of each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester was dissolved in a mixture of 30% by weight of acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), and this was used as a liquid component.

33% by weight of silica, aluminum hydroxide 1
1% by weight, artificial cryolite 8% by weight, aluminum phosphate 2
2 wt% of r-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.) is obtained by melting and pulverizing a powder composed of 1 wt%, aluminum fluoride 7 wt%, and calcium fluoride 20 wt%. To make a powder component.

100% by weight of the liquid component and 150% of the powder component
% By weight, mixed in a light-shielded state, vacuum-degassed, and used as an adhesive composition for filling and restoring. The adhesive strength with the tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured body were measured. did. Table 1 shows the results.

Example 16 Camphorquinone was added to a mixture of 80% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). And p-dimethylaminobenzoic acid ethyl ester in an amount of 0.5% by weight, respectively, to give a liquid component.

100% by weight of this liquid component and spherical silica
After mixing 150% by weight of a titania filler (average particle size: 0.6 μm, manufactured by Tokuyama Soda Co., Ltd.) under light shielding, the mixture was vacuum-degassed, and this was used as a filling and restoring adhesive composition. The adhesive strength to the pretreated tooth and the compressive strength of the cured product were measured. Table 1 shows the results.

Comparative Examples 1-2 Commercially available adhesives containing 11-methacryloyloxy-1,1-undecadicarboxylic acid, 2-hydroxyethyl methacrylate, bisphenol A-diglycidyl methacrylate and triethylene glycol dimethacrylate as monomer components. Toxorite Bond (manufactured by Tokuyama Soda Co., Ltd.)
Was used as an adhesive composition, and the strength with a tooth pretreated with maleic acid at the concentration shown in Table 1 was measured. Table 1 shows the results.

Comparative Example 3 2% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1, 15% by weight of bisphenol A-diglycidyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A mixture of 10% by weight of 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Yushi Co., Ltd.) and 73% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added with 0.5% each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester. % Of the resulting mixture was used as an adhesive composition, and the adhesive strength to a tooth pretreated with maleic acid at the concentration shown in Table 1 was measured. Table 1 shows the results.

Comparative Example 4 Camphorquinone was added to a mixture of 20% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 80% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). And p-dimethylaminobenzoic acid ethyl ester in an amount of 0.5% by weight, respectively, to give a liquid component. 33% by weight of silica, 11% by weight of aluminum hydroxide, 8% by weight of artificial cryolite, 21% by weight of aluminum phosphate, 7% by weight of aluminum fluoride,
And a powder obtained by melting and pulverizing a powder composed of 20% by weight of calcium fluoride and a surface treatment with 2% by weight of r-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.) to obtain a powder component. .

100% by weight of the liquid component and 150% of the powder component
% By weight, mixed in a light-shielded state, vacuum-degassed, and used as an adhesive composition for filling and restoring. The adhesive strength with the tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured body were measured. did. Table 1 shows the results.

Comparative Example 5 Camphorquinone was added to a mixture of 80% by weight of the acidic group-containing methacrylate monomer of the structural formula (2) synthesized in Example 1 and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). And p-dimethylaminobenzoic acid ethyl ester in an amount of 0.5% by weight, respectively, to give a liquid component.

100% by weight of this liquid component and spherical silica
After mixing 30% by weight of a titania filler (average particle size: 0.6 μm, manufactured by Tokuyama Soda Co., Ltd.) under light shielding, vacuum defoaming was performed, and this was used as an adhesive composition for filling and restoring. The adhesive strength to the pretreated tooth and the compressive strength of the cured product were measured. Table 1 shows the results.

Comparative Example 6 Acid-Containing Methacrylate Monomer 8 of Structural Formula (4)
0.5% by weight of camphorquinone and p-dimethylaminobenzoic acid ethyl ester were dissolved in a mixture of 0% by weight and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). did.

[0094]

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33% by weight of silica, aluminum hydroxide 1
1% by weight, artificial cryolite 8% by weight, aluminum phosphate 2
2 wt% of r-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.) is obtained by melting and pulverizing a powder composed of 1 wt%, aluminum fluoride 7 wt%, and calcium fluoride 20 wt%. To make a powder component.

100% by weight of the liquid component and 150% of the powder component
% By weight, mixed in a light-shielded state, vacuum-degassed, and used as an adhesive composition for filling and restoring. The adhesive strength with the tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured body were measured. did. Table 1 shows the results.

Comparative Example 7 A mixture of 80% by weight of an acidic group-containing (meth) acrylate monomer represented by the following structural formula (5) and 20% by weight of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to camphorquinone and p -0.5% by weight of each of dimethylaminobenzoic acid ethyl ester was dissolved and used as a liquid component.

[0098]

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33% by weight of silica, aluminum hydroxide 1
1% by weight, artificial cryolite 8% by weight, aluminum phosphate 2
2 wt% of r-methacryloxypropyltrimethoxysilane (A-174, manufactured by Nippon Unicar Co., Ltd.) is obtained by melting and pulverizing a powder composed of 1 wt%, aluminum fluoride 7 wt%, and calcium fluoride 20 wt%. To make a powder component.

100% by weight of the liquid component and 150% of the powder component
% By weight, mixed in a light-shielded state, vacuum-degassed, and used as an adhesive composition for filling and restoring. The adhesive strength with the tooth pretreated with maleic acid at the concentration shown in Table 1 and the compressive strength of the cured body were measured. did. Table 1 shows the results.

[0101]

[Table 1]

The adhesive compositions shown in Examples 5 to 10 from Table 1 have dentin demineralization degrees of 4 to 5 and have dentin and enamel even when treated with a pretreatment material which leaves most of the smear plugs. Both materials have an adhesive strength of 10 MPa or more. In addition, the adhesive composition for restoration and restoration described in Examples 11 to 16 has an adhesive strength of 10 MPa or more for both dentin and enamel even if the tooth is treated with a pretreatment material having a dentin decalcification degree of 4 to 5. And a compressive strength of 200 MPa or more.

From Table 1, the adhesive compositions containing no novel (meth) acrylate monomer containing an acidic group according to the present invention, which are listed in Comparative Examples 1-2 and Comparative Examples 6-7, and for filling restoration When the tooth of the adhesive composition is treated with a pretreatment material having a dentin demineralization degree of 4 to 5, the adhesive strength of dentin or enamel becomes 10 MPa or less. In addition, the adhesive composition containing a small proportion of the acidic group-containing (meth) acrylate monomer of the present invention, which is listed in Comparative Example 3, has a dentin demineralization degree of 4 to 4.
When the tooth is treated with the pretreatment material of No. 5, both dentin and enamel show an adhesive strength of 10 MPa or less. Similarly, the adhesive composition for filling and restoration described in Comparative Example 4 in which the mixing ratio of the acidic group-containing (meth) acrylate-based monomer of the present invention is small is a pretreatment material having a dentin decalcification degree of 4 to 5, , The adhesive strength is 10MPa for both dentin and enamel
Or less, and the compression strength is 200 MPa or less.
Further, the adhesive composition for filling restoration described in Comparative Example 5 in which the blending ratio of the inorganic filler is small shows a compressive strength of 100 MPa or less.

Continuation of the front page (56) References JP-A-5-255035 (JP, A) JP-A-4-214708 (JP, A) JP-A-57-38750 (JP, A) (58) Fields studied (Int .Cl. ⁷ , DB name) C07C 69/76 A61K 6/00 A61K 6/083 500 C09J 4/02 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (Where R is a hydrogen atom or a methyl group, and l, m, and n each represent an integer of 1 or 2). 2. (A) 100 parts by weight of a (meth) acrylate-based monomer containing 5% by weight or more of the (meth) acrylate-based monomer according to claim 1, and (B) a polymerization initiator. An adhesive composition containing 1 to 5 parts by weight. (A) 100 parts by weight of a (meth) acrylate-based monomer containing at least 30% by weight of the (meth) acrylate-based monomer according to claim 1, and (B) a polymerization initiator.
An adhesive composition for filling and repairing, comprising 1 to 5 parts by weight and (C) 50 to 700 parts by weight of an inorganic filler.