JPS61275205A - Agent for treating tooth surface - Google Patents

Abstract

PURPOSE:To provide the titled treating agent consisting of a combination of a solution containing a specific amount of TiF4 with a specific amount of a monomer having acidic group, capable of protecting the dentine by blocking the permeation of a dental pulp-stimulating factor through the dentine and enabling the firm bonding of dentine with a dental restoration material. CONSTITUTION:The surface of tooth is coated with a solution containing >=0.05wt% TiF4 (based on the solution), left for >=5sec, washed with water and dried. The treated tooth is then coated with an adhesive composed of (A) 0.1-100wt% polymerizable monomer having acidic group of formula I, formula II, formula III, etc., and (B) 99.9-0wt% copolymerizable monomer of e.g. formula IV such as (meth)acrylate monomer and bonded with a cast metal or a composite resin, etc. EFFECT:A synthetic resin adhesive can be used without using a cement backing layer even to a hypersensitive patient, a cavity close to dental pulp, or an abutment tooth having large exposed area of dentine, etc., to which the use of synthetic resin adhesive has been restricted.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention is directed to treating teeth, especially dentin, to form a dense outer coat layer on the dentin surface, and to remove factors that stimulate the dental pulp ( A tooth surface that protects the dental pulp by blocking the penetration of bacteria, chemicals, hydrostatic pressure changes, etc.) into the dentin, and also allows dental restorative materials such as metal castings and dental composite resins to be firmly bonded to the dentin. Regarding processing agents.

(Prior art) In recent years, due to advances in adhesive technology, crown restorative materials (hereinafter referred to as restorative materials) such as metal castings and dental composite resins have been made with polymerizable monomers having acidic groups. A treatment method that uses an adhesive consisting of an initiator and fixing the tooth to the tooth has become popular. Such adhesives are disclosed in Japanese Unexamined Patent Publications No. 53-69494 and No. 5
4-11149, JP-A-58-21607, JP-A-60
-69010 etc.

On the other hand, research has been conducted with the aim of increasing caries resistance by applying titanium tetra7ide as a fluorinating agent to the tooth surface in the form of an aqueous solution [for example, published in the Journal of the Oral Hygiene Society]. Volume 63-78, 1982; Power +) x,
;x, -17,t-chi (Caries Rea,) 1
7, pp. 412-418, 1983].

(Problems to be Solved by the Invention) As dental treatment methods using adhesives as described above have become widespread, clinical problems arising from incomplete adhesion between teeth and restorative materials, such as filling materials, Although the incidence of crown prosthesis falling off, marginal discoloration, and secondary caries was significantly reduced,
Not all clinical problems have been solved. For example, when synthetic resin adhesives and composite resins currently used in the dental field polymerize and harden within a cavity, unpolymerized monomers, catalysts, and various additives elute from the cured product and penetrate the dentin. It is thought that this may have an adverse effect on the dental pulp. Furthermore, under the harsh oral environment, the adhesive interface between the restorative material and the tooth is destroyed, allowing bacteria to invade the dentin through minute gaps and cause pulpitis. It is also said that changes in the oral environment, such as changes in hydrostatic pressure, are transmitted to the dentin through the gaps and stimulate the dental pulp through the dentinal tubules. In the current technology, the cut and ground dentin surface is washed with an aqueous solution of phosphoric acid or organic acid to dissolve and remove the cutting debris before bonding, in order to strengthen the adhesive force between the dentin and the restorative material. However, since acid cleaning causes the dentinal tubules to open widely, once a gap is created at the bonding interface, the above-mentioned problems may be exacerbated. Therefore, the problem to be solved by the present invention is to firmly adhere a restorative material to tooth tissues such as dentin, and to prevent polymerizable monomers and bacteria from penetrating into the dental pulp through the dentinal tubules. .

(Means for Solving the Problem) This problem has been solved by providing a tooth surface treatment agent consisting of a combination of a titanium tetrafluoride solution and an adhesive containing a polymerizable monomer having an acidic group. Ru. That is, after treating the dentin surface with a titanium tetrafluoride solution included in the surface treatment agent, a restorative material is adhesively fixed to the tooth with an adhesive containing a polymerizable monomer having an acidic group. It will be resolved.

The present inventors focused on the phenomenon in which a water-resistant and acid-resistant film called a "glaze" is formed on the enamel surface coated with an aqueous solution of titanium tetrafluoride. When we started basic research on the formation state of ``glazes'' and the adhesive strength between such ``glazes'' and adhesives containing the aforementioned polymerizable monomers having acidic groups, we discovered unexpected facts and developed the present invention. Reached. That is, the titanium tetrafluoride treatment forms a dense coating ("glaze") of a titanium compound on the dentin surface, and this coating also has an adhesive containing a polymerizable monomer having an acidic group. We have discovered the fact that they adhere strongly.

The concentration of the titanium tetrafluoride solution used in the present invention needs to be 0.05% by weight (based on the solution) (the following numbers indicate weight%), preferably 0.21 or more. If the concentration is too low, the formation of the "glaze" will be incomplete and the above-mentioned desired effect will not be fully expressed.

Further, the upper limit of the concentration is allowed up to the saturation solubility of titanium tetrafluoride, but since there is no particular advantage of a high concentration, it is usually used within a concentration range of 20%.

Suitable solvents include water, ethanol, methanol, and mixed solvents thereof, and among these, an aqueous solution is preferable. The time the titanium tetrafluoride solution is left in contact with the dentin, that is, the time it is left to stand after application, must be at least 5 seconds; the lower the concentration, the longer the time required.
At ss concentration, it takes more than 5 minutes. After application, after the required time has elapsed, the titanium tetrafluoride aqueous solution on the dentin surface is washed off with water, and the surface is dried using an air syringe, etc., and then a polymerizable solution containing 0.1 to 100% acidic groups is applied. monomer and 9
An adhesive solution consisting of 9.9-0% copolymerizable monomer is applied. The acidic group referred to in the present invention refers to a -C-X group (where X is a halogen) and the like. The polymerizable monomer having such an acidic group has an ethylenic double bond having a general formula (Kudashi, R1% R2, R3 is hydrogen or an organic group; R4
is an organic group; m and n are integers from 1 to 4; l is 3n≧e
A polymerizable monomer represented by an integer satisfying ≧1 (A is an acidic group) is used, and usually the following (meth)acrylate monomers are preferably used.

H 0-P-fOH)2'H2C=C-C00CH2CH20-P-OCH2C
Monomers having acidic groups such as H2Br are usually used as diluents with copolymerizable monomers, such as (meth)acrylate monomers,
More specific examples include methyl (meth)acrylate,
lauryl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate), 1. 10-decanediol di(meth)acrylate, neobentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, bisphenol-A di(meth)acrylate, 2,2-bis[(meth)acryloyloxyethoxyphenyl] Furopane, 2,2-bis(4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl)furopane, trimethylolpropane tri(meth)acrylate, etc. are added to form an adhesive solution.

The effective concentration of the monomer having an acidic group is the total polymerizable monomer [
monomer having an acidic group + copolymerizable monomer] 0.
1% or more, preferably 0.5% or more. Note that if the monomer having an acidic group is liquid at room temperature, it can be used at 100% concentration without adding a diluent. The adhesive solution further contains a polymerization initiator (a room temperature curing redox initiator, a photopolymerization initiator), a diluent such as ethanol, inpropatol, and ethyl acetate as necessary, silica powder,
It is also possible to add fillers such as glass powder and alumina powder, and various other additives. Such adhesives include the above-mentioned Japanese Patent Application Laid-Open No. 53-69494.54-1114.
Any of those disclosed in No. 9.58-21607.60-69010 can be used.

Such an adhesive is applied to the surface of dentin treated with titanium tetrafluoride, and then bonded to a metal casting or composite resin.

(Effect) When a titanium tetrafluoride solution is applied to dentin, the composition of instant resin (Methyl methacrylate) 49% PM
MA powder 50ti polymerization initiator
Organic molecule blocking effect of 1% (11) titanium tetrafluoride treatment The following experiment was conducted to clarify the organic molecule blocking effect of the coating layer formed on the dentin surface by titanium tetrafluoride treatment.

The chain side or lingual side of eight molars was ground parallel to the horizontal axis to expose the dentin, and a band of wax was applied along the horizontal axis in the center of the dentin surface.The surface was divided into two. . A 40% phosphoric acid aqueous solution was applied to both divided surfaces for 1 minute to perform acid etching, followed by washing with water and drying according to a conventional method. Next, apply a 1% titanium tetrafluoride aqueous solution to one side [3
After a few minutes, it was washed with water and dried. This tooth was immediately immersed in a 0.9-basic fuchsin aqueous solution, and after 2 hours, it was taken out and embedded in an epoxy resin. Under water injection, the sample was cut with a rotary cutter in a plane perpendicular to the horizontal axis, and the degree of penetration of the 7Cuxin dye was observed. From the dentin surface that was treated with titanium tetrafluoride (Example), a very small amount of pigment penetration was observed only near the surface layer, but on the dentin surface that was not treated with titanium tetrafluoride (
A large amount of pigment penetrated from the comparative example) and reached the pulp cavity. Furthermore, when the dentin surface treated with titanium tetrafluoride was observed using a scanning electron microscope, it was found that it was covered with a dense coating layer and the dentinal tubules were occluded.

(iiD Evaluation of adhesive strength) 30 eight molars were embedded in epoxy resin, the chain side or lingual side was ground parallel to the horizontal axis to expose the dentin, and the dentin surface was treated with a 40% +77 acid aqueous solution. The adherend sample was subjected to acid etching for 1 minute.

These were divided into 6 groups of 5 pieces each, and stainless steel disks (6 φ x 3 m) were placed on the dentin surface using the tooth surface treatment agents A to E in Table 1 and the treatment conditions listed in Table 2. Alternatively, an acrylic disk (6 φ x 31, used only when applying a surface treatment agent) was glued. Ten minutes after bonding, each sample was immersed in water at 37°C, and 24 hours later, the shear bond strength between the dentin and the stainless steel or acrylic disk was measured. All fractures occurred at the dentin-adhesive interface or within the dentin. The results are shown in Table 2.

Table 2 fIX/) Durability test of adhesive strength Samples bonded under the conditions of Example 3 and Comparative Example 20 were tested at 37°C.
After 24 hours of immersion in water, it was placed in a water bath at 4°C and 60°C alternately.
A heat shock test was conducted in which the samples were immersed 10,000 times for 10,000 minutes, and the durability of the adhesive strength was compared. 1000 times, 2500
Table 3 shows the shear adhesive strength after heat shock 10,000 times.

Table 3

Claims (1)

[Claims] (1) (a) A solution containing 0.05% by weight or more (based on the solution) of titanium tetrafluoride, (b) 0.1 to 100% by weight of a polymerizable monomer having an acidic group, and 99.9% by weight of a polymerizable monomer having an acidic group. ~0% by weight
A tooth surface treatment agent comprising a combination with an adhesive comprising a monomer having copolymerizability with the monomer.