JPS6089752A - Material for identifying tooth substance layer - Google Patents

Abstract

PURPOSE:To enable identification of the dentin and the dental enamel by constituting a material for identifying the tooth substance of a high polymer material having a carboxyl group, org. titanate comp. and pH indicator having a discoloration region in 2-7pH. CONSTITUTION:A material for idensifying the tooth substance layer is constituted of a high polymer material having a carboxyl group, org. titanate compd. and pH indicator having a discoloration region in 2-7pH. The reagent component reacts with the dentin and enables discrimination of the dentin and the dental enamel when the reagent consisting of such specific compsn. is used. A method for mixing the high polymer material having a carboxyl group, org. titanate compd. and pH indicator in the presence of an org. solvent is most adequately used as a method for mixing these materials. Ethanol, ethyl acetate or aceton is adequately used as the org. solvent as said solvent is genrally low in b.p. and is easily removable.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) The present invention relates to a dentin layer identification material made of a polymer having a xyl group.

Conventionally, in dental treatment, it has been difficult to distinguish between the tooth layers in the oral cavity, such as dentin and enamel, and it has been nearly impossible to treat them separately.

For example, when attempting to fill a cavity of a treated tooth in the oral cavity with a composite resin, it is necessary to create a mechanical retention form by, for example, demineralizing the enamel in advance with a phosphoric acid water bath. However, if the phosphoric acid aqueous solution enters the dentin, there is a risk of pulp stimulation through the dentinal tubules, so extreme care must be taken to prevent the phosphoric acid aqueous solution from entering the dentinal tubules. However, since it is generally difficult to distinguish between enamel and dentin, treatment that is likely to cause pulp stimulation has not been possible. For this reason, there was a lack of hope for an indicator that could make a clear distinction in some way.

The inventors of the present invention, Nagisa et al., have conducted intensive research to solve the above problems.
% 'jye 17) +114 e It has been discovered that by using a reagent called Ka2, the component reacts with dentin and it is possible to distinguish between dentin and enamel, leading to the present invention. That is, the present invention provides (1) a monomolecular compound having a carboxyl group, (11) a specific titanate compound, and a ρ11 compound having a discoloration range at pH 1 to 71.
It is an identification material for the tooth layer consisting of an indicator.

One of the main components of the discrimination phase of the present invention is a molecule having a carboxyl group.

The polymer needs to have a carboxyl group in order to have sufficient adhesion for image quality even under humid conditions such as in the oral cavity, and to be durable for use. Sweet,
The xyl group in particular quickly reacts with dentin, causing a change in the pH in the film, resulting in a change in the color of the indicator, which enables ink to sharply distinguish between dentin and enamel. An FC polymer in which two carboxyl groups are bonded to adjacent carbon atoms is effective for this purpose.

The carboxyl group-containing polymer is not particularly limited and any known polymer can be used, but generally the molecular weight is /,000~
A range of lOθ, 000 is most preferred. The method for obtaining the oval polymer is not particularly limited, and known methods can be used for stirring. - In the dispersion, a vinyl monomer having a carboxyl group or a carboxylic acid anhydride is homopolymerized, or a copolymerizable vinyl monomer having the functional group is copolymerized with other copolymerizable vinyl monomers having a hydrophobic group, among others. A vinyl monomer or a vinyl monomer having a carboxyl ester group is copolymerized with another copolymerizable vinyl monomer, and the resulting copolymer has a force that hydrolyzes the carboxyl ester group and converts it into a carboxyl group. Also, it is suitable for exploration.

In order to impart good adhesive properties to the identification material of the present invention, it is preferable that the amount of carboxyl groups in the polymer is 0.001 mol or more based on the polymer 11. be.

The carboxyl group is not limited to vinyl monomers having a carboxylic acid anhydride, but the following examples are generally suitable for use. That is, acrylic acid-based vinyl monomers such as acrylic acid and methacrylic acid, manic acid, fumaric acid, itaconic acid, maleic anhydride eAL itaconic anhydride vesicles λ (uniform, base carboxylic acid monomer; Preferably used are aromatic unsaturated carboxylic acid chloride or a vinyl monomer thereof to which a ceramic substituent group has been added.

Further, the vinyl monomer copolymerizable with the vinyl monomer containing the carboxyl group or anhydrous carboxylic acid group is not particularly limited, and known ones can be used.

Typical examples that are generally preferably used include, for example, olefin compounds such as ethylene, propylene, butene, and halogen derivatives of olefin compounds such as vinyl chloride and hexafluoropropylene: butadiene,
Diolefin compounds such as pentadiene and their halodane derivatives; aromatic hynylated derivatives such as styrene, divinylbenzene, vinylnaphthalene; vinyl ester compounds such as vinyl acetate; methyl acrylate, ethyl methacrylate, euhydroxyethyl methacrylate, ethylene glycol Acrylic acid and methacrylic acid derivatives such as diacrylate, diethylene glycol dimecrylate, acrylic acid amide, and methacrylic acid amide; unsaturated nitrile compounds such as acrylonitrile; and vinyl etherified compounds such as methyl vinyl ether.

Also, the known copolymerizable vinyl monomer 1 is '
It can be used without being limited to %. Specific examples of generally preferred vinyl monomers include 1-styrene, methylstyrene, vinylnaphthalene, propylene, butene, ethyl vinyl ether, butyl vinyl ether, vinyl acetate, ethyl methacrylate, and butyl acrylate. Dissolved goomethacryloxyethyl trimellitic acid or its acid anhydride is also suitably used.

The vinyl monomers mentioned above have a xyl group or a xyl group. The method for carrying out the above polymerization is not limited to injury, and any known method may be used, but radicals are preferably used. As for the 1st case initiator used in the radical 11st case, generally known ones are employed. For example, benzoyl peroxide, oxidized MΦ oxides such as lauroyl chloride; potassium peroxymimetic acids, oxidized acid bases such as ammonium peroxide; azotized acids such as azobisbutyronitrile; An IR reaction carried out using a solid compound such as tributyl boron or a redox initiator can be suitably used.

Kowara's polymerization initiator is an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, or an acid anhydride. It is sufficient to use it within a range of %.

The '/14 titanate compound used in the present invention is not particularly limited, and any known compound can be used. -1ege, tetra-1so-globyl titanate, tetra-nH butyl titanate, tetrakis(2-ethylhexyl) titanate, tetrastearyl titanate, di-1so-f
Ropoxy bis(acetylacetone) titanate, di-n-butoxy bis(triethanolamine) titanate, dihydroxy bis(raftic acid P) titanate, tetraoctylene glycol titanate, tri-butoxy monostearyl nata, Inglobilt I+ -1-sunaallo-f-lutetanate, -t-noglobil tridodecylbenzenesulfonyl titanate, isoglobiltris(dioctyl-teriloposphate) titanate, tetra-1so-globilbis(dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra(1,,2-
Diallyloxymethyl-/-butyl) bis(di-tridecyl) phosphite titanate, bis(dioctyl pyrobosulfate) oxyacetate titanate, his(dioctyl pyrophosphate) ethylene titanate, etc. alone 4-#-, 1 Combination i + combination is preferably used for wounds. Also, is the above titanated @mono issue? Rimmers may also be used. The use of these titanate compounds is limited to drunkenness and is rejected, but in general, copolymer male titanate compounds are used.
It is preferable to add 0.02 mol to 2.0 mol per 1 mol of phosphoric acid.

Another component of the distinguishing material of the present invention is a natural hair indicator that has a discoloration range from p112 to p112. The indicator is not particularly limited as long as it changes color in the upper Rr' range -f
A known material is used for iI'. Representative indicators that are generally suitable for use include crystal violet, thymol blue (A), troveolin OO, methyl yellow, bromophenol blue, Congo red, methyl orange, and tetrabromophenol blue. , bromocresol green, methyl red, p-nitrophenol, bromophenol red,
Bromofrezi-lumi-4-glu, bromothymol blue,
Al with neutral red, phenol red, etc.

The indicator used is not particularly limited and may be used by determining in advance the t at which 1% of discoloration can be recognized.

In general, it is preferable to select from the range of o, i-##-% by weight based on the carboxyl group-containing polymer O 2 .

The polymer having the carboxyl group according to the present invention,
Although the method of mixing the organic titanate compound and the pH indicator is not particularly limited, a method of mixing them in the presence of an organic solvent is most preferably used. The organic solvent is not particularly limited, but ethanol, ethyl acetate, acetone, etc., which generally have a low boiling point and can be easily removed, are preferably used.

Further, the identification material of the present invention is generally prepared by packaging (A) a polymer having a caroxyl group and an indicator (B) an organic titanate compound separately or together, and then packaging it on a podium immediately before use. Good to use. For example, when β-hydroxycarganic acid, benzoic acid having an alkoxy group at the ortho position, etc. are used as stabilizers for organic titanate compounds, (A)
It is possible to store it in sl k-liquid.

In addition, as mentioned above, (A) is preferably used in the Y form in which it is immersed in a specific solvent, and the organic #? As the medium, those with low boiling points such as ethanol, ethyl acetate, acetone, and tetrahydrofuran are preferred. These embodiments have the advantage that the film can be formed quickly after the above-mentioned composition is completely applied to the tooth. (As for 81, it is generally used after being dissolved in an organic solvent, and alcohols such as ethanol and isoglocknol, ethyl acetate, etc. are used.

The identification material of the present invention is a negative example V! When applied to a cross section of the dentin oil layer and the enamel layer, for example, into a cavity created during treatment, the enamel layer and the dentin layer exhibit different colors. Therefore, the dentin η layer and the enamel layer can be clearly distinguished. This distinction is extremely effective in dental treatment because, for example, when processing only the enamel layer or etching, it is possible to treat only areas of different colors.

Furthermore, the separation material of the present invention can also be used as ink to identify cavities by applying it to teeth that have been eaten away. By being able to make such an identification, it becomes possible to use ink to remove carious parts without damaging healthy teeth when treating cavities. EXAMPLES In order to specifically explain the present invention, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Production Example 1 Put 20 Oml of cyclohexane into a 300ml glass separable flask, add 200ml of cyclohexane,
Co ψ, maleic anhydride, q1, and penzoyl peroxide (hereinafter abbreviated as BPO) o and 'ost were added and stirred thoroughly.

Next, the inside of the container was depressurized and the mixture was exchanged with a high-purity powder, followed by 4 polymerizations by heating with stirring for 4 hours in a go''c chamber. After cooling in a room lagoon, the resulting precipitate was separated from door to door. 30
After washing thoroughly with 0 ml, dry smoke and get white & 1.1?
-g, 7! As a result of determining the composition of the copolymer produced from elemental analysis of this product, it was found that styrene'lg
, II mo, , e%, anhydrous? L/In&? 57.4
The mo was 1%.

Next, dissolve this product fgOme in dioxane and
Pour into a 00ml flask and stir thoroughly.
5w/1,000-cent potassium hydroxide aqueous solution/Q Q
ml was added and allowed to react at room temperature for 70 hours. Next, add concentrated local acid to neutralize it and make it even more concentrated! ! [Addition of 12 resulted in a white solid precipitate. After separating this solid in a furnace,
Rinse thoroughly with neutral moss, dry further,
The coM@body of oy- was wh. The infrared absorption spectrum of this product was analyzed to determine the dynamic absorption (' g 50 oIrr ',
/ 775 (!1-') Ka complete? F + lost t, new maleic acid calzu? A characteristic absorption derived from the nyl group appeared at /72θOur', and it was confirmed that the hydrolysis reaction was quantitatively progressing at h than at t'.

That is, the white solid obtained above is sgoolene lIg,t
imo-ex, -r ray heptacid! ; / , A moA
It was confirmed that the copolymer contained %. In addition,
The acid value of Nophorimer was 30.

□Ka, '・Contents Maleic anhydride, ? , tFf and qorRg azobisisobutyronitoheryl (hereinafter abbreviated as AIBN) was added to the benzene P pass Sθml, and the contents were exchanged under reduced pressure with nitrogen atmosphere while cooling in a dry ice-methanol bath. The purified globylene/21/ was then added by distillation through a liquefaction meter. Next, the entire copolymerization was carried out by stirring for 3 hours at %/)o''c. After the polymerization was completed, the contents were poured into a large amount of anhydrous ether to precipitate the resulting copolymer, and the resulting copolymer was precipitated using a decanting method. It was thoroughly washed and immediately dried in a vacuum dryer.The yield was BO
%Met. Maleic anhydride S S by elemental phase separation,
A moJ3%, globilene 1II1.4'mo2%
Met.

Next, this product was hydrolyzed in the same manner as in Production Examples 1 and 151 to obtain 211.2 g of globile/-maleic acid copolymer. As a result of measuring the infrared absorption spectrum of this monomer, it was confirmed that the maleic anhydride groups in the w phase were almost quantitatively converted to maleic acid. The acid value of this polymer was SOg.

Preparation Example 3 Itacon m3ot, styrene, 20ffl-dioxane 200ffKfd, BPO'5r: 1% of Q was added to the monomer, and the mixture was heated at 10°C for S hours.

Urara fc, JP II Mama-Hexane 1. ．． The unreacted Itacone eIl was removed by placing the mixture in E and separating it by precipitation, and then drying it by fp over-drying (1#) and washing with distilled water. The yield was 'l-, 2%. From the results of the original analysis, itaconic acid lIq, o mol%, styrene! I found out that this is r/, 0 mole nine. This polymer awakening song Fi31I.

Met.

Δ Shield Example Dastyrene and fumaric acid diethyl ester f AIBN were used as initiators and polymerization was carried out at θ°C for 1.20 hours to obtain a polymer. The composition of the copolymer was found to be styrene 5 based on elemental analysis.
A, 5 mol%, fumaric acid diethyl ester, 3.5 mol%. Next, 0.5P of the polymer @IQθm/ was added to the Erlenmeyer flask, #sulfuric acid,
30rni was added and left at room temperature. In 2 days, the polymer was completely dissolved and a yellow solution was obtained. The mixture was poured into a large jar of ice water, and the trichlorofluoric acid copolymer precipitated out. This was filtered, thoroughly rinsed with water, and finally dried to obtain a solid of 0.1 lsrt. The acid value of this polymer was 93.

Example 1 The labial surface of an extracted human tooth was polished with No. 320 Emily Hae Riichi to remove the interface between enamel and dentin. Next, the styrene-anhydrous polymer obtained in Production I11
Twin acid copolymer hydrolysis eF'! IJlO Heavy Department,
Solution A consisting of 9 parts of ethanol and 1 part of methyl orange, and 1 part of tetra-n-butylsacnate, 1 part.
FiY force to part and ethanol 10θ1) +: J, 1 part to 8 liquid and '! Mix enamel η and dentin:E? It was also applied to the 7th world. 4911s - By leaving it for 2 minutes, ethanol is emitted, and the germination is enamel V! The color was red, and the color was 7j.

The polymers obtained in Example 1 and 7 to 4 tons were mixed with liquid A consisting of 5 parts by weight of each of Σ11, 1 part of 95% ethanol, and 1 part of MC of methyl oxidation. , Tetrabutylchik; ``・-to 2 heavy metropolitan area and 100% ethanol
The color of enamel and dentin was examined in the same manner as in Example 11 using B shark whose composition was 7 parts. As a result, the enamel of all abK products was red, and the dentin was yellow.

The above '4AI:! , example ko ~ q and parable C) Sai1π'
4 (Instead of coalescence, polyacrylic acid was added or outside kl-1
: Note [Implemented by b1] [Also. As a result, the enamel was red and the ivory was yellow.

Implementation fA+3 Hydrolyzate of the styrene-maleic anhydride copolymer obtained in Production Example 1/0*1 part, 90 parts by weight of ethanol, 2 parts of methyl orange, and a first liquid
The color of enamel and dentin was determined using the same tH method as in Example 1 using liquid B containing the titanates shown in the table. Examined. The results are shown in 1st fi.

Example Hiro: Styrene-maleic anhydride copolymer hydrolyzate IQif obtained in Production Example 1, parts by weight of ethanol, 90 parts by weight of ethanol,
Example using Solution A consisting of M composition with 11 parts of the acid-base indicator shown in the table, and Solution B consisting of 2 parts of tetra-n-butyl titanate and 100 parts of ethanol.
I was able to learn all about the color of enamel and dentin using the same method. The results are shown in Table 2.

Table 2 Example S In an extracted human tooth with caries in the enamel part, a window cavity with a diameter of 18 mm and a depth of 1 was formed so as to expose the negative part inside. Next, mix together the A and B solutions prepared as in Example 11 and 1i1 and apply them to the entire cavity wall. After 2 minutes of natural drying,
It was confirmed that the healthy enamel part was red, while the enamel part was yellow.

Patent applicant: Tokuyama Sotatsu Co., Ltd.

Claims (1)

[Claims] (1) A tooth layer identification material made of a polymer having a xyl group.