JPH07187941A - Composition for dental purpose - Google Patents

Abstract

PURPOSE:To obtain a composition which is useful as a pretreating material for realizing high adhesion strength between the filler and the dentin by using an acid, an acidic group-bearing (meth)acrylate monomer and N-substituted aromatic glycine in a specific proportion. CONSTITUTION:This composition comprises (A) an inorganic or organic acid of less than 4, preferably 1 to 4 dissociation constant such as phosphoric acid or formic acid, (B) an acidic group-bearing (meth)acrylate monomer (for example, monomer of the formula), (C) an N-substituted aromatic glycine such as N-phenylglycine, (D) a polar organic solvent such as ethanol and (E) water where the amount of (A) is 1.0 to 200mmol per 100 grams of (B)+(C)+(D)+(E), the amounts of (B), (C), (D) and (E) are 1 to 30 pts.wt., 1 to 20 pts.wt., 10 to 90 pts.wt. and 5 to 80 pts.wt. per 100 pts.wt. of (B)+(C)+ (D)+(E) in total, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental composition suitable as a pretreatment material for realizing high adhesive strength between the filling material and the tooth substance when filling and repairing teeth in the field of dentistry.

[0002]

2. Description of the Related Art A filling material called a composite resin is mainly used for repairing a tooth damaged by caries or the like. This composite resin is generally used by filling the cavity of the tooth and then polymerizing and hardening. However, since this material itself does not have adhesiveness to tooth structure, a dental adhesive is used together. This adhesive material is required to have an adhesive strength sufficient to overcome internal stress generated during curing of the composite resin, that is, tensile stress generated at the interface between the composite resin and the tooth structure. Otherwise, it may fall off due to long-term use in a harsh oral environment, and it may create a gap at the interface between the composite resin and the dentin, from which bacteria may invade and adversely affect the pulp. This is because.

The hard tissue of teeth consists of enamel and dentin, and clinically requires adhesion to both. Conventionally, for the purpose of improving the adhesiveness, a method of pretreating the surface of the tooth before applying the adhesive has been used. As such a pretreatment material, an acid aqueous solution that decalcifies the tooth surface is generally used, and an acid aqueous solution of phosphoric acid, citric acid, maleic acid, etc. has been used. In the case of enamel, the mechanism of adhesion to the treated surface is macro mechanical fitting in which the adhesive penetrates and hardens on the rough surface by decalcification of the acid aqueous solution, whereas in the case of dentin It is said that it is a micro mechanical fitting in which the adhesive penetrates into the minute voids of the sponge-like collagen fiber exposed on the tooth surface after decalcification and hardens. However, permeation into collagen fibers is not so easy as that on the surface of enamel, and a permeation enhancer called a primer is generally used after the acid treatment, resulting in complicated operation. For example, USP4659751 discloses a bonding method in which a tooth surface is decalcified with a mixed aqueous solution of a strong acid and N-phenylglycine, and then an acetone solution of a methacrylate containing an acidic group is applied as an adhesive. However, the tooth bond strength obtained by this method was not satisfactory.

As another problem, when treating enamel and dentin at the same time with the generally used aqueous acid solution, it is necessary to decalcify the enamel more strongly in order to obtain sufficient adhesive strength. The dentin was subject to excessive demineralization. That is, shavings called smear adheres to the dentin surface to form a smear layer on the dentin surface that is usually cut to form a cavity, and smear further penetrates from the dentin surface into the dentinal tubule leading to the pulp. A plug called a smear plug blocks the tubule, but the excessive demineralization removes the smear plug and increases the permeability of the dentinal tubule (Shinkai, Kato, Nihonhoho, 35 (3)). , 6
34, 1992), there is a problem that harmful substances and the like easily enter the dental pulp through the thin tube. More recently,
Considering that the recognition that excessive demineralization damages dentin, which is a living tissue, is spreading, it is desirable to suppress demineralization of dentin as much as possible.

[0005]

From the above point of view, in the method of pretreatment, adhesive application, filling of composite resin for cavity restoration, complicated operation such as primer application as a pretreatment material is not required, and enamel, It has been desired to develop a material that gives both dentin a high adhesive strength and is appropriately decalcified to the extent that a smear plug is left on the dentin.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to overcome the above technical problems. As a result, a composition containing an acid, an acidic group-containing (meth) acrylate monomer, an N-substituted aromatic glycine, a water-soluble organic solvent and water has high adhesion to enamel and dentin without using a primer. They have found that the pretreatment material gives strength and leaves a proper smear plug on the dentin, and completed the present invention.

[0007] That is, the present invention is (A) acid dissociation index (hereinafter p
(Abbreviated as Ka) 4 or less acid, (B) acidic group-containing (meth)
Acrylate monomer, (C) N-substituted aromatic glycine,
Comprising (D) a water-soluble organic solvent and (E) water,
The compounding amount of (A) is 10 to 200 mmol with respect to 100 g of the total amount of (B), (C), (D) and (E),
The blending amounts of (B), (C), (D) and (E) are each 1 to 30 with respect to 100 parts by weight of the total amount of (B), (C), (D) and (E). Parts by weight, 1 to 20 parts by weight, 10
It is the dental composition characterized by being -90 weight part and 5-80 weight part.

The acid used in the present invention is not particularly limited as long as the pKa is in the range of 4 or less, and known inorganic acids and organic acids can be used, but those having a pKa in the range of 1 to 4 are preferably used. It The pKa for polybasic acid is a value calculated from the dissociation constant of the first step.

Examples of the inorganic acid used in the present invention include nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid and the like. Among them, phosphoric acid is preferable. As the organic acid, monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid can be used. Examples of monocarboxylic acids and the like include formic acid, lactic acid, pyruvic acid, glycolic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, cyanoacetic acid and the like. Examples of the dicarboxylic acid include tartaric acid, succinic acid, glutaric acid, maleic acid, fumaric acid, malonic acid, citraconic acid, (o, m, p) phthalic acid and the like. Examples of tricarboxylic acids include citric acid, tricarballylic acid, 1,
Examples include 3,5-pentanetricarboxylic acid and trimellitic acid. Further, if necessary, it is possible to mix and use a plurality of acids from the above-mentioned inorganic acids or organic acids.

When the pKa of the acid used in the present invention is 4 or more, it is impossible to sufficiently decalcify the tooth structure and practical adhesive strength cannot be obtained.

The preferred amount of the above acid is 10 to 200 mmol per 100 g of the total amount of acidic group-containing (meth) acrylate monomer, N-substituted aromatic glycine, water-soluble organic solvent and water described below. More preferably 15-
It is 150 mmol. If the blending amount is larger than the above range, the smear plug is completely removed, and if it is less than the above range, demineralization of enamel becomes insufficient.
Incidentally, among the above-mentioned acids which are usually used as an aqueous solution, the water in the aqueous solution is calculated as being equivalent to water which is one of the constituents of the present invention described later.

The acidic group-containing (meth) acrylate monomer of the present invention comprises a carboxyl group or its anhydride in the molecule,
Alternatively, a known compound can be used without particular limitation as long as it is a (meth) acrylate monomer having an acidic group such as a phosphoric acid group.

A typical acidic group-containing (meth) acrylate monomer is represented by the following general formula.

[0014]

[Chemical 1]

(In the above general formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a divalent to hexavalent organic residue having 1 to 20 carbon atoms, which may have an ether bond and / or an ester bond, X
Represents a group containing a carboxyl group, an anhydrous carboxyl group, a phosphoric acid group, or a phosphoric acid ester group) In the above general formula, X represents a group containing a carboxylic acid, a carboxylic acid anhydride, a phosphoric acid group, or a phosphoric acid ester group. And its structure is not particularly limited, but preferable specific examples are as follows.

[0016]

[Chemical 2]

In the above general formula, the structure of R ₂ is not particularly limited, and a known divalent to hexavalent organic residue having a carbon number of 1 to 20 having an ether bond and / or an ester bond can be adopted. However, a specific example is as follows.

[0018]

[Chemical 3]

Acid group-containing (meta) represented by the above general formula
The preferred specific examples of the acrylate monomer are as follows.

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

(However, R ₁ is a hydrogen atom or a methyl group.) From the viewpoint of tooth adhesion, among the acid group-containing (meth) acrylate monomers specifically exemplified above, particularly a carboxyl group or an anhydrous group is used. Those having a carboxyl group are preferably used.

The preferable amount of the acidic group-containing (meth) acrylate monomer in the present invention is an acidic group-containing (meth) acrylate.
When the acrylate monomer, N-substituted aromatic glycine, water-soluble organic solvent and water are 100 parts by weight, the amount is 1 to 30 parts by weight, and more preferably 2 to 20 parts by weight.

The N-substituted aromatic glycine used in the present invention is not particularly limited, and it is possible to use an ordinary product which is generally commercially available for reagents or for industry.
Specific examples of the N-substituted aromatic glycine include N-phenylglycine, N-tolylglycine, and N-xylylglycine. The N-substituted aromatic glycine in the present invention contributes to the improvement of the adhesive strength with the tooth structure, and N-phenylglycine or N-tolylglycine is preferable from the viewpoint of such effects. The mechanism of action is not clear at present, but it is presumed that it contributes to the improvement of the polymerization rate of the pretreatment material and the adhesive at the dentin interface. The preferable blending amount of the N-substituted aromatic glycine of the present invention is 1 to 2 when the acidic group-containing (meth) acrylate monomer, the N-substituted aromatic glycine, the water-soluble organic solvent and water are 100 parts by weight.
0 parts by weight.

The water-soluble organic solvent of the present invention is necessary in order to dissolve other components to form a uniform solution. As a specific example,
Methanol, ethanol, propanol, butanol,
Ethylene glycol, propanediol, butanediol, pentanediol, butenediol, glycerin,
Trimethylolpropane, hexanetriol, allyl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol , 2-ethoxyethanol, 2- (methoxyethoxy) ethanol, 2-isopropoxyethanol, 2-
Alcohols or ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin ether, acetone, methyl ethyl ketone, etc. Examples thereof include ketones.

Among them, those having less harmful effect on the living body are desirable, and from this viewpoint, ethanol, propanol, ethylene glycol, propanediol, butanediol, pentanediol, glycerin, trimethylolpropane, hexanetriol, allyl alcohol, diethylene glycol, diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin ether,
Acetone and the like are preferred, and alcohols such as ethanol, propanol, ethylene glycol and propanediol are most preferably used.

The water-soluble organic solvent of the present invention can be used as a mixture of two or more kinds, but when the above alcohols are used as a mixture with other water-soluble organic solvent, the blending amount thereof is water-soluble organic solvent. It is preferably 30 parts by weight or more, and preferably 50 parts by weight or more, of the entire solvent in order to form a uniform film of the acidic group-containing (meth) acrylate monomer described later, and to improve the adhesive strength of the tooth structure.

The preferred amount of the water-soluble organic solvent used in the present invention is 10 when the acidic group-containing (meth) acrylate monomer, N-substituted aromatic glycine, water-soluble organic solvent and water are 100 parts by weight. ~ 90 parts by weight.

The water used in the present invention is necessary for demineralization of tooth structure. This water preferably contains substantially no impurities harmful to storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water and distilled water. The preferable blending amount of water in the present invention is acidic group-containing (meth).
When the acrylate monomer, N-substituted aromatic glycine, water-soluble organic solvent and water are 100 parts by weight, the amount is 5 to 80 parts by weight.

The composition of the present invention may further contain other (meth) acrylate monomers. In particular, hydroxy or dihydroxy (meth) acrylate monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, and glyceryl di (meth) acrylate are preferable in terms of tooth adhesion. .

Furthermore, it is possible to add a slight amount of a non-water-soluble organic solvent or a thickening agent to the composition of the present invention within a range that does not deteriorate the performance. The water-insoluble organic solvent, hexane, heptane, octane, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, methyl ethyl ketone, pentanone, hexanone, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, There is butyl acetate and the like, and examples of the thickener include high molecular compounds such as polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, and highly dispersible silica. Further, an edible dye as a coloring material can be blended.

The method for preparing the composition of the present invention is not particularly limited, and the acid, the acidic group-containing (meth) acrylate monomer, the N-substituted aromatic glycine and water are weighed in a desired ratio in a container. Take and mix with stirring until uniform.

The dental composition of the present invention is generally a method of filling and repairing by applying a pretreatment material to the tooth surface, washing with water, drying, applying an adhesive, curing an adhesive, filling a filling material, and curing a filling material. Used as pretreatment material in formula. At this time, in order to obtain good adhesive strength, it was confirmed that a film of acidic group-containing (meth) acrylate monomer needs to be uniformly formed on the tooth surface after washing with the pretreatment material. There is. Adhesion that a layer suitable for adhesion to the tooth substance is formed by diffusing the adhesive component that is applied later in the film of the acidic group-containing (meth) acrylate monomer formed on the tooth surface Assuming the above mechanism, it is presumed that the formation of a uniform coating film is a prerequisite for forming a suitable adhesive layer.

The packaging form of the composition of the present invention can be appropriately determined on condition that the storage stability is not impaired. For example, a liquid consisting of acid, water and N-substituted aromatic glycine,
It is possible to separately package a liquid composed of an acidic group-containing (meth) acrylate monomer and a water-soluble organic solvent and mix them at the time of use. It can also be packaged in a liquid of acid and water, a liquid of an acidic group-containing (meth) acrylate monomer, a water-soluble organic solvent, and an N-substituted aromatic glycine.

However, when the composition of the present invention is used, it is necessary to mix all the components and process them simultaneously. For example, the tooth surface is previously decalcified with a liquid containing acid, water, and N-substituted aromatic glycine, washed with water, and dried, and then a liquid containing an acid group-containing (meth) acrylate monomer and a water-soluble organic solvent is applied. However, sufficient adhesive strength for tooth structure cannot be obtained. Although the reason for this is not clear, the coexistence of the acid group-containing (meth) acrylate monomer in the decalcification process promotes the penetration of the acid group-containing (meth) acrylate monomer into the tooth surface. I'm thinking of it.

[0038]

EFFECTS OF THE INVENTION In adhering the tooth and the filling material with an adhesive, by pretreating the tooth surface with the composition of the present invention, enamel and dentin can be treated at the same time. In contrast, high adhesive strength can be obtained. Furthermore, it does not remove excessively the smear plug of the dentin that blocks the dentinal tubules that occurs during the formation of the filling cavity, and the external stimulus is less likely to reach the pulp, making it safer for the living body. Achieve adhesion.

[0039]

EXAMPLES The composition of the present invention will be specifically shown by the following examples, 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) Enamel and dentin adhesive strength bis-GMA 6 g, triethylene glycol dimethacrylate 21 g, hydroxyethyl methacrylate 8
camphorquinone and p-dimethylaminobenzoic acid ethyl ester were added to 15 g of 11-methacryloyloxy-1,1-undecanedicarboxylic acid, respectively.
An adhesive was prepared by dissolving 2 g to prepare a uniform solution.

The bovine anterior teeth were removed within 24 hours after the slaughter, and the enamel or dentin plane was carved under water with an # 800 emery paper so as to be parallel to the labial surface. The surfaces were then blown with compressed air for about 10 seconds to dry and then treated with a pretreatment of the composition of the invention for 20 seconds. Then, the treated flat surface is washed with water and dried, and then a double-sided tape having a hole with a diameter of 4 mm is fixed to this flat surface, and then paraffin wax with a hole having a thickness of 1.5 mm and a diameter of 6 mm is applied to the circular hole. Imitation cavities were formed by fixing them on the same center. The composition of the present invention was thinly applied in this simulated cavity, left for 20 seconds, and then compressed air was blown for about 10 seconds to dry. Next, the adhesive was applied and irradiated with a visible light irradiator (white light, manufactured by Takara Belmont Co., Ltd.) for 10 seconds to cure the adhesive.
Further, a dental composite resin (Palfique Esterite, manufactured by Tokuyama Soda Co., Ltd.) was filled therewith, and irradiated with a visible light irradiator for 30 seconds to prepare an adhesive test piece.
After immersing the adhesion test piece in water at 37 ° C. for 24 hours,
The adhesive strength with the tooth was measured at a crosshead speed of 10 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation).

The adhesive strength of enamel is greatly affected by the degree of deashing, and the higher the degree of deashing, the higher the adhesive strength. The enamel bond strength needs to be about 15 MPa in order to prevent the formation of gaps between the filling material and the tooth surface. On the other hand, there is no general correlation between the degree of demineralization and the adhesive strength.

(2) Demineralization of dentin Within 24 hours after slaughter, bovine anterior teeth were removed, and under water injection, # 80.
The dentin plane was carved so as to be parallel to the labial surface with 0 emery paper. Then, apply compressed air to these surfaces about 10
After spraying for 2 seconds to dry, a pretreatment material of the composition of the present invention was applied and left standing for a predetermined time. After washing the coated surface with water, 20 dentin tubules in the image were observed with a scanning electron microscope (manufactured by JEOL Ltd.), and the degree of decalcification was evaluated as the ratio of the opening area to the tubule. That is, 0 when decalcification progressed to the peritubular dentin, 1 when the tubule opening degree was 100 to 80%, and 8 below.
The evaluation was carried out in 6 levels, with 0 to 60% being 2, 60 to 40% being 3, 40 to 20% being 4, 20 to 0% being 5. Usually, if the openness is 40 to 0% and the rating is 4 to 5 in the 6-point evaluation, demineralization of dentin is judged to be suitable.

Example 1 A uniform solution was obtained by mixing 1.2 g of maleic acid, 1.0 g of N-phenylglycine, 3.0 g of ethanol and 6.0 g of distilled water. 1.0 g of 11-methacryloyloxy-1,1-undecanedicarboxylic acid (hereinafter referred to as MAC-10),
A uniform solution was obtained by mixing 9.0 g of ethanol. Both solutions were mixed at a weight ratio of 1: 1 to prepare a pretreatment material, and enamel, dentin adhesive strength, and dentin decalcification degree were measured. The results are shown in Table 1. In addition, the amount of acid in Tables 1 and 2 is an acid group containing (meta)
Expressed in mmol per 100 g of the total amount of the acrylate monomer, N-substituted aromatic glycine, water-soluble organic solvent and water.

Examples 2 to 8 According to the method of Example 1, pretreatment materials having the compositions shown in Table 1 were prepared, and the enamel bond strength, dentin bond strength, and dentin decalcification degree were measured. The measurement results are shown in Table 2. The structure of each of the acidic group-containing methacrylate monomers used and their abbreviations are shown below.

[0046]

[Chemical 8]

[0047]

[Table 1]

[0048]

[Table 2]

Examples 1, 2 and 6 represent the results when the above-mentioned different acidic group-containing methacrylate monomers are used,
Examples 1, 5 and 6 are representative of the results with different acids. Examples 4 and 5 are contents of acid and acid group-containing methacrylate monomer, Examples 2 and 3 are contents of N-substituted aromatic glycine, and Examples 2 and 3 are contents of water-soluble organic solvent and water. Represents the range tested. The pretreatment material of Example 5 contains a small amount of chloroform, which is a non-water-soluble organic solvent, in addition to the water-soluble organic solvent, and in other examples, the organic solvent is a water-soluble organic solvent only. .
Examples 2, 3, 5 and 6 are examples using a plurality of water-soluble organic solvents, and Example 7 is an example adding a hydroxy (meth) acrylate monomer. In all the above examples, the dentin decalcification degree, the dentin adhesive strength, and the enamel adhesive strength all showed good results.

Comparative Examples 1 to 8 Pretreatment agents were prepared and evaluated in the same manner as in Example 1.
The composition of the pretreatment material used is shown in Table 3 and the results are shown in Table 4.

Comparative Example 9 N-phenylglycine 6 was added to a 2.5 wt% aqueous solution of nitric acid.
g was dissolved to obtain a uniform solution. This solution was applied to bovine tooth enamel and dentin as a pretreatment material, and after 60 seconds, washed with water,
Dried. On this treated surface 1 mol of pyromellitic dianhydride and 2 mol
A 5 wt% acetone solution of a reaction product (commonly called PMDM) containing 2 mol of hydroxyethyl methacrylate was applied and dried. Further, a dental composite resin (Palfique Esterite, manufactured by Tokuyama Soda Co., Ltd.) was filled therewith, and irradiated with a visible light irradiator for 30 seconds to prepare an adhesive test piece. As a result, the enamel adhesive strength is 9.3MP.
a, the dentin adhesive strength was 4.1 MPa. The degree of demineralization of dentin after the pretreatment was 1.

[0052]

[Table 3]

[0053]

[Table 4]

In Comparative Examples 1 and 2, the acid content was out of the range, which caused problems in deashing degree and enamel bond strength, respectively.
In Comparative Examples 3 and 4, the content of the acidic group-containing (meth) acrylate monomer was out of the range, and in both cases, the dentin adhesive strength, particularly the dentin adhesive strength, decreased. The pretreatment material of Comparative Example 5 contained no water, and the demineralization of the enamel was weak, so that the adhesive strength was lowered.
Comparative Example 6 contained no water-soluble organic solvent, the acidic group-containing (meth) acrylate monomer was not dissolved in water, and a uniform solution could not be obtained. Comparative Example 7 contained no N-substituted aromatic glycine, and the dentin adhesive strength was reduced. Comparative Example 8 uses acetic acid having a pKa of 4.76 as an acid, and has a dentin adhesive strength,
In particular, the enamel adhesive strength decreased. Comparative Example 9 is an example in which an acetone solution of an acidic group-containing (meth) acrylate monomer was used as an adhesive after decalcification with an aqueous solution of nitric acid and N-phenylglycine, but sufficient dentin adhesive strength was obtained. I couldn't do it.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikio Kimura 1-1, Mikagecho, Tokuyama City, Yamaguchi Prefecture Tokuyama Soda Co., Ltd.

Claims (1)

[Claims] 1. (A) an acid having an acid dissociation index of 4 or less, (B)
An acidic group-containing (meth) acrylate monomer, (C) N-substituted aromatic glycine, (D) water-soluble organic solvent and (E) water are contained, and the blending amount of (A) is (B), ( C),
10 to 20 per 100 g of the total amount of (D) and (E)
0 mmol, and the respective blending amounts of (B), (C), (D), and (E) are each 100 parts by weight of the total amount of (B), (C), (D), and (E). 1 to 30 parts by weight, 1 to 20
A dental composition, which is 10 parts by weight, 10 parts by weight to 90 parts by weight, or 5 parts by weight to 80 parts by weight.