JPS6169704A - Dental resin material - Google Patents

Abstract

PURPOSE:A dental resin material showing improved bond strength to ebur dentis and low irritation to dental pulp, having low change in volume caused by polymerization, comprising 5,6-benzo-2-methylene-1,3-dioxepane and a polymerization initiator. CONSTITUTION:A dental resin material usable as a filler, an adhesive, resin for plate, etc., comprising 5,6-benzo-2-methylene-1,3-dioxepane shown by the formula IV obtained through a compound shown by the formula III which is prepared by reacting a compound shown by the formula I with a compound shown by the formula II, as a polymerizable component, and a polymerization initiator (preferably radical polymerization initiator or hydrous organic acid polymerization initiator, and an amount of it used is preferably 0.1-50wt% in the dental resin material), which are packed into or applied to the affected part such as tooth cavity, etc., thermally polymerized or subjected to photopolymerization, and stuck fast to the affected part.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a dental resin material that exhibits small volume changes due to polymerization, exhibits excellent adhesion to tooth structure, and is less irritating to the dental pulp. It is something.

[Prior art] Various types of cements have traditionally been used as restorative materials in the field of dental treatment, such as the repair of partial defects, but recently, cements have been used as restorative materials, such as those with superior strength, aesthetics, and operability. Photopolymerizable resin materials have been proposed, and their usage is expanding.

However, with conventional thermally or photopolymerizable resin materials, various problems have arisen due to the large volume change (amount of shrinkage) during polymerization. When filling the photopolymerizable resin material 3,
Polymerization progresses quickly in the surface layer where the amount of light irradiation is large, so this area is first solidified and positioned, and then as the polymerization progresses in the deep side, the resin material 3 contracts and the lower layer resin material 3 moves upward. A gap 4 is created at the bottom of the cavity 2 due to the tension. If such a gap 4 exists, there will be a drawback that the compressive strength will be reduced due to insufficient supporting force. In addition, when a room temperature polymerizable resin material is used for the above purpose, the polymerization reaction itself proceeds simultaneously, but as shown in Figure 3, shrinkage due to polymerization itself is not avoided, so the inner surface of the cavity 2 In areas where the degree of adhesion is weak depending on roughness, shape, etc., the resin material 3a separates from the inner wall of the cavity, creating a gap 4a.
occurs. And due to the gap 4a, the resin material 3d
The compressive strength of the product decreases. Furthermore, when the above resin material is used as an adhesive to adhere to teeth (enamel trabeculae and dentinal tubule walls) (see Figure 4) or to the etched surfaces of teeth (see Figure 5), polymerization can occur. Due to the shrinkage caused by this, the resin material 3b and the tooth cavity wall surface 1a may separate, and a minute gap 4b may be generated between the resin material 3c and the tooth etched surface 1b, resulting in a decrease in adhesive strength. In addition, when the above-mentioned resin materials are used as resins for denture bases or hard resins for dental crowns, problems such as poor dimensional accuracy, warping, and deformation occur due to shrinkage due to polymerization.

[Problem 1 to be solved by Proposal 1: 1-As stated above, in conventional heat- or photopolymerizable resin materials, the sealing condition between the resin material and the tooth deteriorates due to large shrinkage during polymerization. However, serious problems such as the occurrence of secondary irritation and stimulation of the dental pulp have occurred.The present invention was developed as a result of repeated studies focusing on these circumstances. It is an object of the present invention to provide a dental resin material which has a small amount of adhesive force to the tooth substance, and which has less irritation to the dental pulp.

[Means for solving problems] The dental resin material of the present invention achieves the above objects.

The gist is that it contains 5,6-benzo-2-methyleneno-1,3-dioxepane represented by the chemical formula and a polymerization initiator.

[Function J] The dental resin material according to the present invention firmly adheres to the affected area by thermal polymerization or photopolymerization after being filled or applied to the affected area such as a meatus cavity, and the polymerizable component in the resin material and means 5,6-benzo-2-methylene-1,3-dioxepane represented by the chemical formula (1). The 7-membered ring compound contains 21 bonds (vinyl group) in its molecule, and is polymerized and cured by the action of a polymerization initiator (described later).

Incidentally, 5,6-benzo-2-methylene-1,3-dioxepane is produced, for example, according to the following reaction formula.

Next, as the polymerization initiator to be blended with the 7-membered ring compound, a radical polymerization initiator, a hydrous Jja, and an acid polymerization initiator are used. First, examples of the former radical polymerization initiator include peroxide-heating system, peroxide-amine system, peroxide-sulfinic acid system, peroxide-amine-sulfinic acid system, peroxide-tributylporane system, etc. heating or room temperature polymerization initiators, camphorquinone, biacetyl, benzoyl, 1, l'-dinaphthoyl, 2,2-dinaphthoyl.

Examples include a photopolymerization initiator that can be activated by light energy to initiate polymerization, such as acetonaphthacene, and a mixture of the above heating or room temperature polymerization initiator and a photopolymerization initiator. It is desirable that these radical polymerization initiators be contained in the dental resin material in an amount of 0.01 to 10% (meaning % by weight, the same applies hereinafter).

In the above, examples of peroxides include acyl peroxides such as benzoyl peroxide, acetyl peroxide, and lauroyl peroxide, hydroperoxides such as cumene hydroperoxide, and alkyl peroxides such as di-tert-butyl peroxide. The above-mentioned amine added as a polymerization accelerator is N,N-jetanol-P-
) Ruijin.

Examples include N,N-dimethyl-P-toluidine, and examples of sulfinic acids include aromatic acids such as p-)toluenesulfinic acid and benzenesulfinic acid; On the other hand, as the latter hydrous organic acid polymerization initiator, there may be mentioned one in which an organic acid having an acid dissociation constant (pKa) of 1.5 or more is dispersed in wood. The organic acids mentioned above include benzenesulfinic acid, p-1 luenesulfin #, and P
-Toluenesulfonic acid, etc.; acetic acid, propionic acid, methacrylic acid, benzoic acid, cyclohexanecarboxylic acid, glycolic acid, malic acid, ascorbic acid.

Organic carboxylic acids such as tartaric acid, citric acid, adipic acid, and succinic acid; l- to divalent organic phosphoric acids; carboxylic acids, sulfonic acids, and organic phosphorus vI having a polymerizable functional group as shown in the chemical formula below: etc. Illustrated.

HC=CH-5o3H H h2*=c-P-OH (However, R1-R4 are monovalent organic residues, and X represents a halogen.) Also, in the above water-containing organic #polymerization initiator, there is a It is desirable to mix 0.01 to 20% of water, and furthermore, it is desirable to contain 0.1 to 50% of the polymerization initiator having the above composition in the dental resin material.

The basic structure of the present invention is as described above, but an inorganic filler and/or an organic filler can be added as necessary. Examples of the inorganic filler include silica, alumina, titania, etc. As the material, polymers known for dental use are exemplified, and the above-mentioned polymers may be added in the form of polyesters, or may be added in the form of polymerizable polymers and polymerized to form a polymer. as methyl M
A (MA means methacrylate. The same applies below);
Hydroxyethyl MA; mono-, di- or triethylene glycol-di-MA, bisphenol A-diglycidyl MA, 2,2'-bis(methacryloxyethoxyphenyl)propane, trimethylolpropane-tri-M
A, MA such as glycidyl MA, d conductors, and mixtures thereof can be mentioned. It is desirable that the above-mentioned filler is blended in an amount of 50 to 80% with respect to the resin material according to the present invention.

[Example] Example t: Pernival test The photopolymerized filling material shown in Table 1 was placed in the first class cavity 114 (diameter 4+sm, depth 3.5mm) of an extracted tooth etched with 40% phosphoric acid. Filled 0 then visible light irradiator 0P
The filling material was polymerized by irradiating it with visible light (wavelength: 360L, 500 nm) for 40 seconds using TILUX (manufactured by Demetran, USA). The obtained sample was immersed alternately in O"C and Tsukushin solution at 60°C (1 minute x 60 times each) to examine the degree of penetration of the dye, and the margin sealing Table 1 (parts by weight) *I GMA Nigericidyl MA *22G = Diethylene glycol MA *3TMPT Nitrimethylolpropane TriMA TMPT containing silane-treated quartz powder (80$) and benzoyl peroxide (
IX) was added, polymerized by heating, and then re-pulverized.

As shown in Table 1, in No. 1, infiltration of the dye into the inner wall of the cavity was observed, and a satisfactory margin sealing property could not be obtained. On the other hand, for Nos. and 2, excellent peripheral sealing properties were obtained.

Example 2: Adhesive strength test Using the universal liquid shown in Table 2 and the catalyst liquid shown in Table 3, the adhesive strength was measured according to the method shown in the following procedure, and the results shown in Table 4 were obtained. .

(Sample Preparation and Tensile Strength Measuring Method) (I) After scraping the surface of a fresh tooth flat and finishing it with emery paper, the sample was immersed and stored in water at 37±1°C.

(II) In a measurement chamber adjusted to an air temperature of 23±1° C. and a humidity of 50 tlO%, the sample was taken out, and its surface was treated with kneeling (·402 phosphoric acid aqueous solution), washed with water, and dried with air.

(m) Apply a thin layer of adhesive 9 obtained by mixing universal liquid and catalyst liquid one drop at a time on a dropping plate with a piece of sponge or cotton ball to the surface of the sample 5 as shown in FIG. (2.2 kg/cra2) was sprayed for 10 seconds to evaporate volatile components.

(ff) Composite resin 8 kneaded on kneading paper (
Adaptic (manufactured by Johnson & Johnson, USA) was filled into a stainless steel tube 8 equipped with a handle 7. The obtained resin-filled stainless steel tube 8 was brought into close contact with the surface coated with the adhesive 9.

(V) After being immersed in water at 37±1° C. for 24 hours, the adhesive strength was measured using an autograph.

Autograph: Full scale 50kg or 00kg Tensile speed 1/min Adhesion Area: Diameter 6mm for enamel, diameter 5mm for ivory If there was a difference, the test was repeated. If 1 point out of 5 points differs by ±15% from the average value, average the remaining 4 points Table 2 (parts by weight) *1. *2...Same as Table 1 *4...Hydroxyethyl MA Table 3 (Heavy duty I) As shown in Tables 2 to 4, N004 to 7 were all very superior to N083. It was confirmed that the adhesive had good adhesive strength.

Example 3: Sensitivity test Resin material 1.2 shown in Table 1 of Example 1 was selected,
The results shown in Table 5 were obtained when the dental pulp irritation was investigated by applying it to the dental treatment of 30 patients.

Table 5 (persons) [Effect of the invention J The present invention is constructed as described above, and since the change in volume due to polymerization is extremely small, there is no gap between the body and the affected area, and it can be used according to the purpose. Various effects can be obtained.

When used as a filler, it improves edge sealing properties, increases the compressive strength of the filler, and provides excellent drop-off resistance. When used as an adhesive, it has good adhesion to the adhesive surface, and in combination with the excellent adhesive performance of the resin material of the present invention itself, high adhesive strength can be obtained. When used as a resin for denture bases, denture bases with excellent dimensional accuracy can be obtained.

Furthermore, when applied to the affected area, the irritation to the dental pulp is small and the pain caused to the patient can be alleviated.

Although the reason why the above effects are obtained in the present invention has not necessarily been clarified, the reason why the volume change during polymerization is small is that the molecular chain length increases due to the cleavage of the ring structure, resulting in polymerization condensation (volume This is thought to be because the amount of change) becomes smaller. The reason for the high adhesive force is thought to be that there is little volume change between the monomer and its polymer, and that there is little displacement at the adhesive interface during polymerization. Furthermore, the reason why the pulp irritation is low is thought to be because the adhesive force is sufficient, so there is less saliva, foreign matter, and bacteria entering the adhesive interface.

[Brief explanation of the drawing]

Figure 1 is a perspective explanatory diagram showing the adhesive strength test method, Figures 2 to 5
The figure is an explanatory cross-sectional view showing how a gap occurs when a conventional dental resin material is used. 1... Tooth 2... Cavity 3... Resin material 4... Gap 5... Sample 6.
...Resin 7...Handle 8...Stainless steel tube 9...Adhesive material

Claims (1)

[Claims] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 5,6-benzo-2-methylene- shown by the above chemical formula
A dental resin material containing 1,3-dioxepane and a polymerization initiator.