JPH06107514A - Primer composition - Google Patents

Abstract

PURPOSE:To obtain a primer composition, having a high initial bonding strength to a tooth hard tissue with a present general dental adhesive and capable of providing the durability so as to enable the maintenance of the strength for a long period with hardly any damage to the tooth hard tissue. CONSTITUTION:The objective primer composition is composed of an aqueous solution (solution A) of a chelating agent capable of forming a stable chelate both with Ca in the dentin and metallic ions and/or its partially substituted salt at 1-20wt.% concentration and an aqueous solution (solution B) of a metallic halide, reactive with the chelating agent or its partially substituted salt and capable of forming a stable chelate at 0.05-5wt.% concentration.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a primer composition. More specifically, the present invention is a biological hard tissue or an artificial substitute thereof, for example, when bonding and fixing ceramic materials such as artificial bone, artificial tooth root (implant) and artificial dental crown with an adhesive having a chelating ability, The fact that the adhesiveness and durability can be improved by treating them with the present primer is utilized. In particular, it is effective when bonding various dental adhesives, such as glass ionomer cement, resin cement, and bonding agent for composite resin, to the enamel or dentin of natural teeth.

[0002]

2. Description of the Related Art As a dental restorative material, composite resin, glass ionomer cement, polycarboxylate cement and the like are used. Further, the cement, the adhesive resin cement, the bonding agent for the composite resin, or the like is used as a bonding agent for a crown or inlay made of metal, ceramics, or resin.
However, since these dental adhesives generally have insufficient adhesiveness with the tooth substance, especially with respect to the dentin, the restoration or prosthesis may fall off or the edge of the restoration may be damaged. In some cases, bacteria invade from secondary leakage and cause secondary caries and pulp irritation.

[0003] In order to solve such problems, many methods for improving the adhesiveness between the restoration and the prosthesis and the tooth substance have been reported. For adhesion to enamel, by etching the enamel with an acid such as phosphoric acid, oxalic acid, citric acid, etc., it becomes possible to obtain a clinically satisfactory adhesiveness regardless of the type of dental adhesive. (J
Dent Res, Vol. 3 No. 6 849-
853, 1955; Arches Oral Bio
1, Vol. 13, 61-, 1968). But,
Bonding by this method is not a chemical bond between the tooth substance and the adhesive, but a mechanical fit formed by curing the adhesive that has penetrated into the microstructure of the tooth surface formed by deashing with acid. It is based.

On the other hand, it is the current situation that the present dental adhesives cannot provide sufficient adhesiveness to enamel which is not subjected to acid etching. In addition, a case has been reported in which a minute leak occurs due to polymerization contraction of the filled composite resin even at the rim of the enamel cavity subjected to acid etching. It is considered that this is due to the difficulty of adhesion in a wet environment such as the oral cavity and the fatigue in an environment where repeated stress is continuously applied by mastication.

Regarding the adhesion to dentin,
D. Aiming for chelate bond with dentin Ca C. Smit
Polycarboxylate cement developed by h (Br D
ent J, Vol. 125,381-384,196
8) and A. D. Glass ionomer cement developed by Wilson (Br Dent J, Vol. 132,
133-135, 1972). These are the so-called
At the time when there was no adhesive monomer, there was a certain degree of adhesiveness to dentin (shear adhesive strength: 40 to 50 kgf /
cm ² ), it was used as a backing agent used as a protective agent for dental pulp under the restorative material and as a bonding agent for crowns and inlays.

[0006] However, these cements have a strong water sensitivity and have a drawback that the adhesive strength is gradually decreased in a long-term immersion test in water and the like (Japanese Journal of Dental Materials, Vol. 2, No. 6, 691).
-703, 1983 and many other reports. ) In addition, due to the rise of composite resins as restorative materials, the development of bonding agents for adhering composite resins to the tooth structure has led to the production of numerous adhesive monomers, and the applications of these cements have gradually been limited. Came.

Adhesive monomers developed and put into practical use include NPG-GMA (J Dent R) which is an adduct of N-phenylglycine and glycidyl methacrylate.
es, Vol. 44, No. 5,903-905,19
65), 4-methacryloxyethyltrimellitic dianhydride 4-META (dentistry magazine, vol. 19, 179-18)
5, 1978), 2-methacryloxyethylphenylphosphoric acid Phenyl-P (Japanese Patent Laid-Open No. 53-110637).
No.), an adduct of N- (p-toluyl) glycine and glycidyl methacrylate NTG-GMA (Int Den
t J, Vol. 37, 158-161, 1987),
11-methacryloxyundecane-1,1-dicarboxylic acid MAC-10, 10-methacryloxydecane dihydrogenphosphoric acid MDP (Japanese Patent Publication No. 3-52508), adduct of pyromellitic dianhydride and 2-hydroxyethyl methacrylate PMDM (Dent Mater, Vol.
4, 225-231, 1988). Each of these monomers has a hydrophilic group (carboxyl group or phosphoric acid group) and a hydrophobic group (phenyl group or polymethylene group) in a well-balanced manner, and easily penetrates into acid-etched dentin. Since it has a polymerizable methacryloxy group, it penetrates into the demineralized dentin and polymerizes and hardens to form a hybrid layer of dentin and polymer, resulting in a relatively high adhesive force (50 to 180 kgf / cm ² ) Is believed to be obtained. The only part of the monomer was aimed at the chelate bond with Ca of the tooth substance. But in any case,
For untreated dentin, the effect of these monomers is low, and high adhesion is shown only when some treatment is performed. For example, aluminum oxalate treatment in NPG-GMA,
10% citric acid-3% ferric chloride treatment in 4-META, 10% citric acid-20% calcium chloride treatment in MDP, 40% phosphoric acid treatment, tin electrodeposition treatment, PMD
2.5% nitric acid-4% NPG treatment in M and the like. Even in the case of 4-META, which has been reported to have the highest adhesive strength, when combined with a tributylborane (TBB-0) catalyst having the ability to graft-polymerize methyl methacrylate (MMA) onto dentin collagen, The effect is recognized. That is, at present, clinically satisfactory adhesiveness has not been obtained unless some treatment is applied to dentin (J Dent Res, Vol. 59, No.
5,809-818,1980; Tooth material device, Volume 9, No. 6, 8
88-893, 1990). In addition, even if a bonding agent containing these monomers is bonded using a dedicated treatment agent, the durability of the bonding cannot be said to be sufficient, and a long-term immersion test in water or cold water at 4 ° C and hot water at 60 ° C is performed. There remains a problem that the adhesive strength is reduced in the thermal cycle test in which the restoration is subjected to thermal stress by alternately soaking it for 1 minute each alternately (tooth material device, Vol. 9, No. 6, 831-840,
1990; Vol. 6, No. 6, 841-849, 1990; 10
Vol. 1, 42-54, 1991 etc.).

[0008]

As described above, the dental adhesives currently used have a clinically substantially satisfactory initial adhesive force to biological hard tissues, particularly to enamel and dentin of natural teeth. Became. However, when its durability is tested, it cannot be said that it is still sufficient, especially for dentin. Therefore, the present invention was made for the purpose of developing a primer composition which can exhibit higher initial adhesive strength and durability capable of maintaining its adhesiveness for a long period of time by using the current dental adhesive.

[0009]

Means for Solving the Problems The present inventors have found that currently used dental adhesives have better adhesiveness to enamel than to dentin of natural tooth hard tissue. It was first noticed that also showed good adhesion to metal. The above-mentioned polycarboxylate cement, glass ionomer cement, and adhesive monomer each have a ligand capable of forming a complex such as a carboxyl group or a phosphoric acid group, and the chelate bond-forming ability is different to some extent. It is thought that the difference is due to the difference in adhesiveness depending on the adherend. That is, enamel has a larger content of hydroxyapatite than dentin, and in the state of being decalcified by acid treatment, the amount of Ca capable of forming a chelate is larger in enamel. It is also known that chelating agents generally form more stable complexes with metal ions than Ca ++ ions.

The second point of interest is that the initial adhesive strength and durability of the adhesive differ depending on the type of metal. We thought that this might be due to the difference in chelate stability (stability constant). Based on this hypothesis, if we proceed further with the idea, it is possible to form a stable chelate with Ca of the dentin and at the same time obtain a stable chelate with a metal that has excellent durability and adhesion. It has become clear that the tooth surface can be modified with a metal that can provide stable adhesion by treating the adherend surface and chelating the metal ion therewith. Based on this hypothesis, as a result of intensive research on the selection of chelating agents and metals, many plummer compositions were found from the combination of commercially available chelating agents and metals also used in dental alloys. The present invention has been accomplished. Solution A: 1-20% by weight aqueous solution of a chelating agent and / or its partially substituted salt capable of forming a stable chelate with Ca of tooth substance and metal ions contained in solution B, and solution B: solution A A primer composition comprising a 0.05 to 5% by weight aqueous solution of a metal halide capable of forming a stable chelate by reacting with the chelating agent or the partially substituted salt thereof. These are included in the present invention because the composition when mixed and used immediately before use and the composition made into one liquid by mixing are basically the same idea.

The chelating agent capable of forming a stable chelate with Ca of the tooth substance and metal ions in the present invention includes
Phytic acid (PYA), triethylenetetramine hexaacetic acid (TTHA), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), 1,3-diaminopropanoltetraacetic acid (DPTA-OH), diethylenetriaminepentaacetic acid (DTPA), Ethylenediaminetetraacetic acid (ED
TA), N-hydroxyethylethylenediaminetetraacetic acid (EDTA-OH), ethylenediaminetetrakis (methylenephosphonic acid) (EDTPO), glycol ether diaminetetraacetic acid (GEDTA), 1,2-diaminopropanetetraacetic acid (Methyl-EDTA), Examples thereof include nitrilotriacetic acid (NTA), nitrilotris (methylenephosphonic acid) (NTPO), and tannic acid (TA). However, since it is necessary to form a chelate with Ca and metal ions of the tooth substance, a ligand With many PYAs and TTs
HA, DPTA-OH or EDTA-OH having a hydrophilic hydroxyl group that wets the tooth substance well, and Cy-DTA or EDTA having a large chelate stability constant are preferable.

Of these, PYA is the most preferable chelating agent because it has a strong metal chelating ability in a wide pH range from an acidic region of pH 1 to an alkaline region of pH 12. As the partially substituted salts of these chelating agents, alkali metal salts such as sodium salts, potassium salts and lithium salts, and I-valent salts such as ammonium salts and water-soluble salts are preferable. On the surface of the mechanically ground tooth, there is a sticky layer of tooth flakes, which is a smear layer that inhibits adhesion, and unless it is cleaned, high adhesion cannot be obtained as described above. The ligand (carboxyl group or phosphate group) of the chelating agent also acts as an acid, and also has the effect of dissolving and removing the smear layer. Therefore, it is not preferable to replace all the ligands,
It is preferable to leave about 50%.

The concentration of these chelating agents and partially substituted salts of chelating agents is 1 to 20% by weight, and particularly 3 to
10% by weight is preferred. That is, the amount of chelate that forms with the tooth structure is very small, and since these chelating agents also act as acids, the smear layer is removed because it does not damage the tooth structure as much as possible. As much as you can is enough. This amount depends on the chelating agent and also depends on the degree of substitution of the partially substituted salt. Also,
Some chelating agents are poorly soluble in water, and an organic solvent can be used depending on the case. The concentration at that time is based on the case of the above-mentioned aqueous solution. Furthermore, when actually used in the clinical setting, some cavities may face downward, and it is assumed that the primer solution will flow and the treatment effect will be diminished. Inactive fillers may be added in some cases.

The metal halide capable of forming a stable chelate with the above-mentioned chelating agent of the present invention is preferably a polyvalent metal halide. For elution of divalent metal ions, calcium, cobalt, chromium, copper,
Chlorides or fluorides of iron, magnesium, manganese, nickel, lead, tin, strontium, zinc, etc., which are used to elute trivalent metal ions include aluminum, chromium, iron, gallium, indium, lanthanum, ruthenium, manganese, For elution of chloride or fluoride such as samarium or ytterbium, tetravalent metal ion, chloride or fluoride of titanium or zirconium, for elution of pentavalent metal ion, tantalum chloride or Fluoride etc. are mentioned. However, since it is used in the oral cavity, it is preferably nontoxic.
In particular, stannous fluoride, indium fluoride (tooth material device, 6 volumes, special issue 13,190-191), which is also effective for adhesion and is expected to have an effect of suppressing dental caries and an effect of promoting remineralization of tooth structure ,
1987), lanthanum fluoride (Nichihoho, Vol. 35, 6
No. 648-656, 1992) and the like.

The concentration of these metal halides as a treating agent is in the range of 0.05 to 5% by weight, and the lowest possible concentration is preferable. That is, the amount that can be chelated with the chelating agent is very small, and it is preferable that the amount is as small as possible because it enters the oral cavity as ions. However, there are some metal halides that do not completely dissolve within this concentration range. However, depending on the eluted metal ions, some may be oxidized by a dissolved enzyme and further converted into polyvalent ions, and some may be preferably used in a supersaturated solution. For example, an aqueous solution of stannous fluoride is an inactive tin compound (inactive tin hydroxide, tin oxide, tin oxide fluoride, 4
It may be changed to a valent tin compound, etc.), and the amount of dissolved active tin ions may decrease, resulting in a decrease in adhesiveness and caries preventive effect. Therefore, by using a supersaturated solution, new stannous ions can be sequentially supplied from undissolved stannous fluoride. Therefore, depending on the stability of the eluted metal ions, it may be a supersaturated solution,
In some cases, a stabilizer (buffer, sparingly soluble compound of the same metal, etc.) may be added in order to stably supply it.

It is also possible to use a mixture of two or more metal halides. For example, highly adhesive zinc, aluminum, and manganese halides and stannous fluoride, indium fluoride, which are expected to prevent caries,
By mixing and using lanthanum fluoride or the like, in addition to improving the adhesiveness, an effect of suppressing secondary caries can be expected. Furthermore, when actually used in the clinical setting, some cavities may face downward, and it is assumed that the primer solution will flow and the treatment effect will be diminished. Inactive fillers may be added in some cases.

The method of using this primer is basically
Solution A is applied to adherends (enamel, dentin of natural teeth, bones and artificial bones which are artificial substitutes thereof, such as artificial tooth roots, crowns, inlays, etc.), washed with water, dried and then B
A two-step treatment of applying the liquid, washing with water and drying is preferable. However, depending on the case, it is also possible to mix and use the liquid A and the liquid B immediately before use. Further, it is also possible to make one liquid by adjusting the blending amounts of the components of the liquid A and the liquid B. In that case, the treatment method may be completed in one step. In this regard, I cannot give an example,
Stoichiometry is possible and is included in the basic idea of the invention. In this manner, the treated adherend is adhered using various commercially available dental adhesives (glass ionomer cement, polycarboxylate cement, resin cement, bonding agent for composite resin, etc.), The initial adhesiveness and durability obtained by the system can be greatly improved. Moreover, although this cannot be exemplified, among the primers of the present invention, the above-mentioned caries-preventing effect and plaque formation-inhibiting effect (Ac
ta Odont Scand, Vol. 36,21
1,1978), the secondary effects such as prevention of secondary caries and periodontal disease are expected.

[0018]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In addition, hereinafter, the concentration of each component is expressed in%, but unless otherwise specified, this means% by weight.

Examples 1 to 16 and Comparative Examples 1 to 3 In order to find the optimum concentration of the primer of the present invention, phytic acid (PYA) as a chelating agent and stannous fluoride (SnF ₂ ) as a metal halide. Was used to evaluate the adhesiveness of Photo Bond (a product of Kuraray Co., Ltd., a bonding agent for composite resin) to tooth dentin. The roots of the anterior teeth of bovine extraction were cut, and after pulp extraction, the pulp cavity was closed with polycarboxylate cement and embedded with polymethylmethacrylate resin. The dentin was prepared by polishing the labial side of the bovine tooth with # 1000 emery paper while pouring water into the adherend. The surface to be adhered is 3, 5, 7, 10,
Treatment with 20, 30, 40, and 50% aqueous solutions for 30 seconds,
It was washed with water and dried. Further, treatment with a 3% SnF ₂ aqueous solution (a supersaturated solution that is not completely dissolved) for 30 seconds, washing with water,
Dried. A polyethylene tube having an inner diameter of 6 mm and a height of 3 mm was temporarily attached to a surface to be adhered, which was subjected to only PYA treatment and then SnF ₂ treatment in combination, with a double-sided tape having a hole of 6 mmφ to define an adhesion area. Next, a bonding agent is applied, and after irradiating with a product name GC Light VL-I (light irradiator manufactured by GC Corporation) for 10 seconds, a composite resin product name Photo Clearfill Bright
(Product of Kuraray Co., Ltd.) was filled and irradiated with light for 30 seconds. After 30 minutes of light irradiation, the sample from which the tube and the tape that had been temporarily adhered were removed was immersed in distilled water at 37 ° C. for 24 hours, and then the adhesive strength was measured by a compression shear test. Test speed is 1mm / m
It was done in. In addition, as a comparative example, untreated, 40%
Phosphoric acid (Kuraray etching agent: trade name K-etch
The same test was performed on dentin treated with an SnF ₂ aqueous solution after ant) treatment and phosphoric acid treatment. The above tests and the tests described below were all performed at room temperature of 23 ± 2 ° C.

Seven samples were prepared and measured under each condition, and the adhesive strength was expressed as the average of the upper five measured values. ()
Figures in are standard deviations. Hereinafter, the tests described below are also displayed in the same manner. Clearfill Photo Bond
Table 1 shows the treatment effect (adhesion strength after immersion for 24 hours in 37 ° C. distilled water) on the adhesion strength to the dentin by the concentration of the primer. As can be seen from the examples, PYA alone gives higher adhesive strength than the untreated sample of Comparative Example 1, but the effect is not so noticeable. However, SnF ₂
When used together, the adhesive strength was improved. In particular, in the concentration range of 3 to 20%, where the effect of PYA alone is low, a high initial bond strength comparable to the 40% phosphoric acid treatment recommended by the manufacturer was obtained by using the SnF ₂ treatment together. Further, as shown in Example 3, in the combination of phosphoric acid and SnF ₂ ,
This effect does not appear. Again, it can be seen that the effect is exhibited in combination with the chelating agent PYA. It is also clear from the fact that even when the concentration is as low as 3%, the high initial adhesive strength can be obtained by using SnF ₂ together.

[0021]

[Table 1]

Examples 17 to 20 and Comparative Examples 4,5 Using phytic acid (PYA) as chelating agent and stannous fluoride (SnF ₂ ) as metal halide,
The adhesiveness of the product name Photo Bond (bonding agent for composite resin, a product of Kuraray Co., Ltd.) to tooth enamel was evaluated. The test method was exactly the same as in Examples 1 to 16 except that bovine tooth enamel was used as the adherend surface and the concentration of PYA in the A solution of the primer was limited to 5,7%, which was particularly effective in dentin. Is. Since it is generally recommended that the enamel be acid-etched, as a comparative example, 40% phosphoric acid treatment and enamel treated with a SnF ₂ aqueous solution after phosphoric acid treatment were similarly tested. Clea
Table 2 shows the effect of the primer treatment on the adhesive strength of rfil Photo Bond to enamel (adhesive strength after immersion in 37 ° C. distilled water for 24 hours). Example 1
As shown in Nos. 7 to 20, the effect was low even with enamel only by PYA treatment, and the adhesive strength was similar to that of the phosphoric acid treatment shown in Comparative Example 4. This is probably the result of only the removal effect of the smear layer mentioned above. However, SnF ₂
When the treatments were used in combination, a higher adhesive strength was obtained than the phosphoric acid treatment recommended by the manufacturer of Comparative Example 4. Clearly S
The effect of nF ₂ treatment was observed, and it was revealed that this primer also improves the initial adhesive strength.

[0023]

[Table 2]

Examples 21, 22 and Comparative Example 6 Phytic acid (PYA) was used as the chelating agent and stannous fluoride (SnF ₂ ) was used as the metal halide.
Adhesion durability of the product name Photo Bond (bonding agent of composite resin by Kuraray Co., Ltd.) to tooth dentin was evaluated by a thermal cycle test. The method for producing the adhesive sample is exactly the same as in Examples 1 to 16 except that the concentration of PYA in the A solution of the primer was limited to 5 and 7%. Here, as an example, only the case where the SnF ₂ treatment was used together was performed. As a comparative example, the same test was performed on dentin treated with 40% phosphoric acid recommended by the manufacturer. For the thermal cycle test, the sample is cold water at 4 ℃ and 60 ℃.
Was alternately immersed in warm water for 1 minute to apply heat stress to the adhesive interface, and the tester used was generally used in the dental field. After the adhesion, after being immersed in 37 ° C. water for 24 hours, it was set to 0 times, and after applying a thermal cycle of 500 and 1000 times, the compression shear adhesive strength was measured.
Table 3 shows the effect of the treatment of the primer on the adhesion durability of the Clearfil Photo Bond to dentin. As shown in Examples 21 and 22, when treated with this primer, the initial bond strength was maintained after 1000 thermal cycles. On the other hand, as shown in Comparative Example 6, when treated with phosphoric acid, the thermal cycle 50
It decreased to about 60% of the initial adhesive strength at 0 times, and was halved at 1000 times. This primer treatment showed an excellent effect on adhesion durability.

[0025]

[Table 3]

Examples 23 and 24 and Comparative Example 7 Using phytic acid (PYA) as a chelating agent and stannous fluoride (SnF ₂ ) as a metal halide,
Adhesion durability of the product name Photo Bond (bonding agent of composite resin by Kuraray Co., Ltd.) to tooth enamel was evaluated by a thermal cycle test.
The test method is exactly the same as in Examples 21 and 22 except that bovine tooth enamel was used as the adherend. However, the number of thermal cycle tests was extended to 3000 times. Clear
Table 4 shows the effect of the treatment of the primer on the adhesion durability of the fil Photo Bond to the enamel.
As shown in Examples 23 and 24, when treated with this primer, a high initial bond strength was maintained even after 3000 thermal cycles. On the other hand, as shown in Comparative Example 7, in the phosphoric acid treatment, the thermal cycle showed a decreasing tendency after 500 cycles, and after 3000 cycles, it reached about 70% of the initial adhesive strength. This primer treatment improved the initial bond strength with respect to enamel and showed excellent effects on the bond durability.

[0027]

[Table 4]

Examples 25 to 39 and Comparative Example 8 Phytic acid (PYA) was used as a chelating agent, and various metal chlorides shown in Table 5 were used as metal halides. The adhesiveness of the composite resin bonding agent) to the tooth dentin was evaluated. The preparation method and test method of the adhesive sample are exactly the same as in Examples 1 to 16 except that the concentration of the PYA aqueous solution is 7% and the concentration of the metal chloride aqueous solution is 3%. Treatment effect of various metal ions when combined with phytic acid (bonding strength after immersion in 37 ° C distilled water for 24 hours)
Is shown in Table 5. For reference, the data of only the 7% PYA treatment shown in Example 3 was cited as a comparative example and added to the table as Comparative Example 8. Compared to the 7% PYA treatment only,
In each of the groups to which the metal chloride treatment of the example was applied in combination, a high initial adhesive strength was obtained. In particular, cobalt chloride (CoCl
₂ ), magnesium chloride (MgCl ₂ ), manganese chloride (MnCl ₂ ), nickel chloride (NiCl ₂ ), zinc chloride (ZnCl ₂ ), aluminum chloride (AlCl ₃ ), indium chloride (InCl ₃ ), vanadium chloride (VC)
l ₃ ), ytterbium chloride (YbCl ₃ ) and tantalum chloride (TaCl ₅ ) showed almost the same initial adhesive strength as stannous fluoride shown in Example 11, and therefore, to enamel. Also, the same improvement in initial adhesiveness as that of stannous fluoride shown in Example 20 is expected.

[0029]

[Table 5]

Examples 40 to 49 and Comparative Example 9 Phytic acid (PYA) was used as a chelating agent, and 10 kinds of metal chlorides which were particularly effective among the various metal chlorides exemplified in Examples 25 to 39 were used as metal halides. Was used to evaluate the adhesion durability of Photo Bond (a product of Kuraray Co., Ltd., a bonding agent for composite resin) to tooth dentin by a thermal cycle test. PYA
The concentration of the aqueous solution of 7 was set to 7%, and the concentration of the aqueous solution of metal chloride was set to 3%. Also, as a comparative example, 7% P
The same test was performed on dentin treated with the YA aqueous solution only. The test method is exactly the same as in Examples 21-23. However, the number of thermal cycle tests was limited to 500. Table 6 shows the treatment effects on the adhesion durability of various metal ions when combined with phytic acid. Thermal cycle 5
When compared after 00 times, the PYA treatment of Comparative Example 9 alone maintained the initial adhesive strength, but the adhesive strength was about 70 kgf / cm ² , which was lower than that of the example. Also, in the case of phosphoric acid treatment recommended by the manufacturer mentioned above, 5
After 00 times, it has decreased to about 60% of the initial adhesive strength,
The adhesive strength was as low as about 43 kgf / cm ² (Comparative Example 6). On the other hand, when the metal chloride treatments shown in Examples 40 to 49 were used in combination, the initial adhesive strength was almost maintained, although there was a degree of difference depending on the type of the metal chloride used. The lowest strength was 75 kgf / cm ² or more, which was higher than that of the comparative example and maintained a high adhesive strength. It was clarified that this primer group contributed to the durability in the adhesion to dentin.

[0031]

[Table 6]

Examples 50-57 and Comparative Examples 10-25 Using phytic acid (PYA) as the chelating agent and stannous fluoride (SnF ₂ ) as the metal halide,
The adhesion of six commercially available glass ionomer cements to tooth dentin was evaluated. The ionomer cement used in the test is used as a backing layer under the trade name of Vitrabond
(3M company photo-polymerization type) and product name Fuji Lin
2 of ing LC (photopolymerization type by GC Co., Ltd.)
As a joint wear used when attaching seeds, crowns, inlays, etc., the product name is Fuji Bond (conventional type by CZ Inc.) and the product name Ketac-Cem M.
Two types of axicap (conventional type of ESPE company), and for the same restoration (filling) as the composite resin, the product name is Fuji Ionomor Type II LC (photopolymerization type product of GC Co., Ltd.) and the product name Ketac-F.
il Application (conventional ESPE product) 2
It is a seed. The powder-liquid ratio of these cements, the mixing time, the irradiation time in the case of the photopolymerization type, etc. were in accordance with the manufacturer's instructions. As an example, for each material, SnF was applied after 7% PYA treatment.
_The test was carried out when the _two treatments were used in combination, and as a comparative example, only the 7% PYA treatment was performed. Furthermore, as a comparative example, three products (Ketac
-Cem Maxicap and Ketac-Fil Ap
Kicac Conditioner for licap
However, Fuji Ionomer Type II LC has Dentin Conditioner attached to it), but if the treatment is applied to the other three species, it is recommended to adhere to untreated dentin. The strength was measured.

The method of preparing the adherend, the method of adhesion, the method of measuring the adhesion strength, etc. were in accordance with Examples 1 to 16. However, in bonding, the first three cements among the above six cements were in conformity with the usage of these materials in dentistry. That is, after the cement is adhered to each treated dentin surface, the product name Sco
Tchbond 2 (composite resin bonding agent manufactured by 3M) is applied, and the product name is GC Light V
After irradiating light for 30 seconds with LI, trade name Pyrofil Li
ght Bond-A (composite resin manufactured by Sankin Industry Co., Ltd.) was filled and irradiated with light for 30 seconds to prepare an adhesive sample. Further, since the ionomer cement has a strong water sensitivity, after leaving for 1 hour after adhesion, the temporarily attached tube and the double-sided tape were removed and immersed in water, and the adhesion strength was measured after 24 hours. Furthermore, for some products, with the filling tube attached,
Fuji varnish (waterproofing material for ionomer cement, a product of GC Co., Ltd.) is applied to the filling surface and the periphery of the bonding surface for waterproofing, and after being immersed in water for 24 hours, the tube and tape are removed and subjected to a shear test. I did what I did.

Table 7 shows the treatment effect (adhesion strength after soaking in 37 ° C. distilled water for 24 hours) of the (7% phytic acid + SnF ₂ ) primer on the adhesion of various glass ionomer cements to dentin. When using any cement except Vitrabond, 7% PY of the example
The highest initial bond strength was obtained when the A treatment and the SnF ₂ treatment were used together. In particular, a photopolymerization type Fuji Linin
With g LC, a surprisingly high bond strength of 140 kgf / cm ² was obtained for an ionomer cement. Even with the conventional cement, although the adhesive strength of the 7% PYA treatment and SnF ₂ treatment combined group is low, when the fracture surface is observed, the cement remains on the tooth surface, causing cohesive failure in the cement. Many samples were found. It is speculated that the difference in the adhesive strength between the photopolymerizable type and the conventional type is considerably affected by the difference in the strength of the cement itself. Also, the Fuji Ionomor Type II LC and Ke for filling
When the waterproofing treatment performed with tac-Fil Apricap was added, the treatment effect of this primer became clearer and a high initial adhesive strength was obtained.

[0035]

[Table 7]

Examples 58, 59 and Comparative Examples 26-31 Using phytic acid (PYA) as the chelating agent and stannous fluoride (SnF ₂ ) as the metal halide,
The adhesion of two commercially available glass ionomer cements to tooth enamel was evaluated. The ionomer cements used in the test are 2 types for filling, and the brand name is Fuji Ion.
Omor TypeII LC and trade name Ketac-F
il Application. Except that the adherend became enamel, the method of preparing the adherend, the method of adhesion, the measurement of the adhesion strength, etc. are exactly the same as in Examples 50-57. However, as a comparative example, a product name CA-agent, which was recently reported to be effective for adhesion of glass ionomer cement,
It was also added when treated with (Kuraray's product, a treating agent for restoration of composite resin). (7% phytic acid + Sn
Table 8 shows the treatment effects (adhesion strength after immersion in 37 ° C. distilled water for 24 hours) of the F ₂ ) primer on the adhesion of various glass ionomer cements to enamel. In any of the cements, the example in which the PYA treatment and the SnF ₂ treatment were used together showed the highest adhesive strength, and it was revealed that the present primer is also effective in adhering the ionomer cement to the enamel. became.

[0037]

[Table 8]

Example 60 and Comparative Example 32 Using phytic acid (PYA) as a chelating agent and stannous fluoride (SnF ₂ ) as a metal halide,
The adhesion durability of the glass ionomer cement Fuji Lining LC, which had a high initial adhesive strength obtained in Example 51, to tooth dentin was evaluated by a thermal cycle test. The method of preparing the adherend, the method of bonding, the method of measuring the adhesive strength, etc. are exactly the same as in Examples 50-57. Further, the thermal cycle test method is the same as in Examples 21 to 22, and 5
It was performed 00 times. As an example, 7% PYA treatment and Sn
The case where the F ₂ treatment was used in combination was tested as an untreated case as a comparative example. Table 9 shows the treatment effect of the (7% phytic acid + SnF ₂ ) primer on the adhesion durability of the glass ionomer cement to dentin. After 500 thermal cycles, in the case of the comparative example, 6 out of the 7 tested samples had already broken before the shear test. On the other hand, in the case of the example, all the samples were adhered even after 500 times without waterproof treatment, and the high adhesion strength of 113 kgf / cm ² was maintained as an average value. Clearly, it can be seen that this primer contributes to the improvement of durability.

[0039]

[Table 9]

Examples 61 to 71 and Comparative Examples 33 and 34 Partially substituted salts of phytic acid (PYA) as chelating agents and partially substituted salts of various other chelating agents were used as stannous fluoride (metal halide). SnF ₂ ),
The adhesiveness of the product name Photo Bond (a bonding agent for composite resin, a product of Kuraray Co., Ltd.) to tooth dentin was evaluated. The partially substituted salt of PYA is 1 of PYA.
It was prepared by adding sodium hydroxide to a 0% aqueous solution in a molar amount 2, 4, 6 times that of PYA. 10% PYA-2N each
It is abbreviated as a, -4Na, -6Na. In addition, partially substituted salts of other chelating agents were similarly prepared. That is, 10% TTHA-4 prepared by adding 4 times mol of sodium hydroxide to a 10% aqueous solution of triethylenetetramine hexaacetic acid (TTHA).
Na, diaminopropanol tetraacetic acid (DPTA-OH)
10% aqueous solution of 10% DPTA-OH-2Na, trans-1,2-
Cyclohexanediaminetetraacetic acid (CyDTA) 9.4
9. Double molar amount of sodium hydroxide was added to 1% aqueous solution.
8.06% EDTA-2Na, hydroxyethylethylenediaminetriacetic acid (EDTA-OH) prepared by adding twice the molar amount of sodium hydroxide to an 8.06% aqueous solution of 41% CyDTA-2Na and ethylenediaminetetraacetic acid (EDTA).
Sodium hydroxide was added to the 7.70% aqueous solution of 2 times the molar amount of 7.70% EDTA-OH-2Na and diethylenetriaminepentaacetic acid (DTPA) was added to the 10.6% aqueous solution of the double molar amount of sodium hydroxide 10. 6% DTPA-
11.6% EDTPO-2 obtained by adding 2 mol of sodium hydroxide to a 11.6% aqueous solution of 2Na, ethylenediaminetetrakis (methylenephosphonic acid) (EDTPO).
5.42% NT in which sodium hydroxide is added in an amount of 2 times mol to a 5.42% aqueous solution of Na and nitrilotriacetic acid (NTA)
A-2Na. Since CyDTA to NTA were unified to have a 0.3 M aqueous solution and a molar concentration, the numerical value was not complete at wt%.

The method of preparing the adherend, the method of adhesion, the method of measuring the adhesion strength, etc. are exactly the same as in Examples 9 to 16. However, some of the chelating agents were treated for 60 seconds.

[0042]

[Table 10]

Treatment effect of various chelating agents in combination with SnF ₂ on adhesion to dentin (37 ° C.)
The adhesive strength after immersion in distilled water for 24 hours) is shown in Table 10.
For Comparative Examples 33 and 34, the data of Comparative Examples 1 and 2 were cited for reference. As shown in Examples 61-63, PY
Even when A was partially neutralized with sodium hydroxide, a high adhesion strength comparable to that of the 40% phosphoric acid treatment of Comparative Example 34 was obtained. This means that a treatment agent which does not damage the tooth substance, which is required in dentistry, has been realized together with the treatment effect on enamel described later. In addition, it is currently considered necessary to treat dentin with acid, and many commercially available materials treat enamel and dentin with separate treatment agents. However, partial replacement salts of PYA and PYA are used. And S
The primer in combination with nF ₂ is also promising as a treating agent capable of treating enamel and dentin at the same time. Also in the case of the partially substituted salts of other chelating agents shown in Examples 64 to 71, the treatment time must be taken into consideration, but the adhesive strength is almost equal to or higher than that of Comparative Example 34. Especially 10
60% treatment of% TTHA-4Na, 10% DPTA-O
Treatment of H-2Na for 60 seconds, 8.06% EDTA-2Na
60 seconds treatment, 7.70% EDTA-OH-2Na treatment for 30 seconds, etc., gave higher adhesion strength than the 40% phosphoric acid treatment of Comparative Example 34 recommended by the manufacturer. Further, when the surface treated with these treatment agents is observed, streaks generated during polishing remain, and like PYA, it is promising as a treatment agent with little damage to dentin.

Examples 72 to 82 and Comparative Example 35 Phytic acid (PYA) partially substituted salts as chelating agents and partially substituted salts of various other chelating agents as stannous fluoride (SnF ₂₎ as metal halides. ) Was used to evaluate the adhesiveness of the trade name Photo Bond (a bonding agent for composite resin, which is a product of Kuraray Co., Ltd.), to tooth enamel. The partially substituted salt of the chelating agent used is exactly the same as in Examples 61 to 71. The methods for preparing the adherend, the method for adhesion, the method for measuring the adhesion strength, etc. are described in Examples 9 to 1.
It is exactly the same as 6. However, some of the chelating agents were treated for 60 seconds.

[0045]

[Table 11]

Effect of various chelating agents in combination with SnF ₂ on adhesion to enamel (3
Table 11 shows the adhesion strength after immersion in 7 ° C. distilled water for 24 hours. For reference, the data of 40% phosphoric acid treatment recommended by the manufacturer (Comparative Example 4) was cited as Comparative Example 35.
As shown in Examples 72 to 74, when treated with the partially substituted salt of PYA, the adhesive strength equal to or higher than that of the comparative example was obtained. In addition, 10 shown in Examples 75, 77, 78, 79
% TTHA-4Na 60 seconds treatment, 9.41% CyDT
A-2Na 30 seconds treatment, 8.06% EDTA-2Na
30 seconds treatment and 7.70% EDTA-OH-2Na
The treatment for 30 seconds also showed an adhesive strength equal to or higher than that of Comparative Example 35. As described above, these treatment agents are more promising as a mild treatment agent capable of simultaneous treatment of enamel and dentin, because they are more effective than untreated dentin as described above. In addition, 10% DPTA-OH-2Na (Example 7) was found to have no clear effect on enamel.
6) 10.6% DTPA-2Na (Example 80), 1
1.6% EDTPO-2Na (Example 81) and 5.4
2% NTA-2Na (Example 82) and the like are effective as a treatment agent for dentin. Further theoretically, there is a possibility that an effective treating agent for enamel will be produced by changing these concentrations, the substitution degree of Na and the metal halide to be combined.

[0047]

EFFECTS OF THE INVENTION Tooth hard tissues capable of exhibiting higher initial adhesive strength and durability capable of maintaining the adhesive properties for a long period of time by using a dental adhesive that is currently generally used for tooth hard tissues. We have developed a primer composition with less damage.

Claims (4)

[Claims] 1. Liquid A: 1 to 20% by weight of an aqueous solution of a chelating agent and / or a partially substituted salt thereof capable of forming a stable chelate with Ca of tooth substance and a metal ion contained in liquid B, and liquid B 0.0 of a metal halide capable of reacting with a liquid chelating agent or a partially substituted salt thereof to form a stable chelate
A primer composition comprising an aqueous solution of 5 to 5% by weight. 2. A primer composition prepared by mixing the two components according to claim 1 into one solution. 3. The primer composition according to claim 1, further comprising an organic solvent and / or a shelf life stabilizer. 4. The primer composition according to any one of claims 1 to 3, further comprising an inert filler such as silica or alumina as a thickener.