JPH0813798B2 - ω-mercaptoalkyl (meth) acrylate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a novel compound, ω-mercaptoalkyl (meth) acrylate [in the present specification, the expression (meth) acrylate means both methacrylate and acrylate). Regarding]. The above compound is used as a component of an undercoating agent (sometimes called a primer) or a polymerization-curing type adhesive agent for adhesion of metal materials, and has a strong adhesion force to various metals, especially precious metals and precious metal alloys. .

(Prior Art) A polymerization-curable adhesive composed of a polymerizable monomer such as an acrylic monomer or an epoxy compound can be cured at room temperature and atmospheric pressure in a short time and has excellent workability. It is widely used for bonding metal materials and occupies an important position in the adhesive field. However, this type of polymerization-curable adhesive has major drawbacks depending on the application.
That is, if the adhesive interface is placed in an environment where it is constantly in contact with water, the adhesive force is rapidly reduced, and therefore it cannot be used in applications requiring water resistance.

In recent years, in the field of dental materials, attempts have been made to obtain a polymerization-curable adhesive having excellent adhesive strength against metals and excellent water resistance, and the results are being achieved. For example, JP-A-58-21
Disclosed in No. 607, dental adhesives containing a phosphoric acid ester compound are base metals such as iron, nickel, chromium, cobalt, tin, aluminum, copper, and titanium, and base metals containing these elements as main components. It exhibits extremely water-resistant adhesive strength to alloys and is in the practical stage as a dental adhesive. However, the adhesive strength of the adhesive to the precious metal alloys (gold, platinum, palladium, and silver-based alloys) that are mainly used as materials for dental castings, such as inlays, crowns, and bridges, are water resistant. Since it is inferior to the base metal alloy, it is necessary to pretreat the surface of the precious metal alloy such as a sprinkle or an oxidation treatment in order to secure the water resistance of the adhesive strength when bonding the precious metal alloy.

Recently, when N- (4-mercaptophenyl) methacrylamide was applied and adsorbed (primer treatment) on the surface of the noble metal in advance and then bonded with MMA-tributylborane adhesive, the water resistance of the adhesive strength to the noble metal was remarkably improved. It was found that dental materials and instruments Vol. 5 92-10
Published on page 5 (1986).

(Problems to be Solved by the Invention) As described above, when a noble metal or noble metal alloy material is bonded to a tooth or the like with the adhesive disclosed in Japanese Patent Laid-Open No. 58-21607, the metal surface is sprinkled. It is necessary to perform pre-processing such as, and there is a problem that the operation is complicated. In this respect, with the adhesive containing N- (4-mercaptophenyl) methacrylamide described above, such complication can be avoided, but the problem is that the water resistance of the adhesive strength is still insufficient for practical use.

Therefore, the problem to be solved by the present invention is to provide a primer for treating a metal object surface prior to application of an adhesive in order to strongly adhere a metal (particularly noble metal) object to another object, and Metals (especially precious metals)
It is to find a novel adhesive component which is the basis of an adhesive for bonding an object to another object.

(Means for Solving the Problem) Such a problem is caused by a novel compound represented by the following general formula. (In the formula, R represents hydrogen or a methyl group, and n is from 5
(Representing a natural number up to 20) and using such a compound as an adhesive component. In the group of compounds represented by the formula (I), the water resistance of the adhesive strength tends to improve as the value of n increases. Therefore, for applications that require water resistance, n is 6 or more. It is preferably used.

The following are examples of compounds represented by the above general formula.

The compound (I) of the present invention is synthesized from ω-hydroxyalkyl (meth) acrylate or ω-halogenated alkyl (meth) acrylate as a starting material through the following three-step or two-step synthetic route.

Step 1 [Synthesis of ω- (meth) acryloyloxyalkyl sulfonate] When ω-hydroxyalkyl (meth) acrylate is used as a raw material, the compound is aromatic sulfonyl chloride or aliphatic sulfonyl chloride, preferably p-toluenesulfonyl. The following sulfonates are made with chloride or methanesulfonyl chloride.

(In the formula, B ₁ represents hydrogen or a methyl group, B ₂ represents a hydrocarbon group, and n represents a natural number of 5 to 20.) In the reaction, an organic solvent such as ethyl ether, acetone or tetrahydrofuran is used as a reaction solvent. A tertiary amine such as triethylamine or pyridine is added as a reaction catalyst and as a neutralizing agent for hydrogen chloride generated. It does not matter if a tertiary amine is used as a reaction solvent. 1 mol to 2 mol of sulfonyl chloride is added to 1 mol of ω-hydroxy (meth) acrylate to synthesize the compound of the formula (II). The formula (II) compound and the ω-halogenated alkyl (meth) acrylate are guided to the formula (I) compound by the same route shown below.

Step 2 [Synthesis of isothiuronium salt] [II] A thiourea is added to the formula compound or ω-halogenated alkyl (meth) acrylate to synthesize the following isothiuronium salt.

(In the formula, R represents hydrogen or a methyl group, and n is 5 to 20.
Represents a natural number up to. Y ^- represents a sulfonium ion or a halogen ion. The reaction is carried out in a solvent such as ethanol or methanol, and 1 to 2 mol of thiourea is added to 1 mol of the compound (II) or the ω-halogenated alkyl (meth) acrylate. In addition, hydroquinone monomethyl ether, hydroquinone, 2,2'-methylenebis (4-ethyl-6)
-Tert-butylphenol), 2,2'-methylenebis-
A polymerization inhibitor such as 6-tert-butyl-p-cresol is used as a compound of the formula (II) or ω-alkyl halide (meth).
Add 0.1-5.0% by weight to acrylate. The reaction proceeds from room temperature to the boiling point of the reaction solvent.

After completion of the reaction, the reaction solvent is distilled off under reduced pressure to obtain a crude product of the formula (III) compound. When the highly polymerized product is produced by the side reaction, the compound (III) is extracted with a solvent such as acetonitrile or methanol. The crude compound of formula (III) thus obtained can be purified by recrystallization from a solvent such as ethanol, methanol, acetonitrile or water.

Step 3 [Synthesis of (1) Formula Compound] Generally, isothiuronium smoke is added to a base to generate a mercaptide ion and then is converted to a thiol by adding an acid. )
In the case of a compound having an acryloyl group, the target thiol cannot be obtained in good yield because the side reaction in which the mercaptide ion existing in the free state is added to the (meth) acryloyl group competes. Therefore, in the case of the compound of the formula (III), a metal ion is made to exist in the reaction system in advance, and when a mercaptide ion is generated, it is immediately combined with the metal ion and precipitated as a salt. This salt is recovered and an acid is added to obtain the compound of formula (I).

Specifically, zinc chloride in polar solvents such as methanol and water,
A metal salt such as zinc acetate, lead acetate, silver nitrate, or mercury cyanide is dissolved in a large excess with respect to the compound of formula (III) to dissolve or suspend the compound of formula (III). An aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydrogen carbonate, ammonia, a base such as tetraethylenepentamine, and 2-aminoethanol is added to this solution to obtain mercaptide as a precipitate. After recovering the precipitate, it is washed with water or methanol and suspended in water or methanol. When strong acids such as hydrochloric acid and sulfuric acid are added to this suspension (I)
Since the formula compound is liberated, n-hexane,
Extract with an organic solvent such as cyclohexane, diethyl ether, benzene or toluene. After extraction, the solvent is distilled off under reduced pressure to obtain the compound of formula (I).

By the way, the compound of formula (I) is easily converted into the following mercaptide by substituting the hydrogen ion of the mercapto group with a metal ion. Therefore, the problem in the present invention can be solved by obtaining the following novel compound and using it.

(In the formula, R represents hydrogen or a methyl group, and n is 5 to 20.
Represents a natural number up to m, m represents a natural number from 1 to 4, and M ^{m +} represents an m-valent metal ion.) As metal ions, alkali metal ions such as Li ⁺ , Na ⁺ and K ⁺ , Mg ²⁺ , Alkaline earth metal ions such as Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , F ²⁺ , Fe ³⁺ , Cu ⁺ , Cu ²⁺ , Zr ⁴⁺ , Co ²⁺ , Co ³⁺ ,
Mention may be made of transition metal ions such as Ni ²⁺ , Zn ²⁺ , Pb ²⁺ and Ag ²⁺ . Of these, Zn ²⁺ ions are preferably used.

As a specific method for obtaining the compound of the formula (IV), in the case of an alkali metal ion, a method of adding an alkali metal to an ether solution of the compound of the formula (1) and collecting the precipitated white crystals is used. For polyvalent metal ions, a method is used in which a metal salt, for example, a metal chloride, an acetate, a metal hydroxide or a metal oxide is reacted with a solution of the compound of formula (I), and the precipitated crystals are recovered.

The compound of formula (IV) is stably stored in the solid state at room temperature, and can be easily converted to the compound of formula (I) by treating with a strong acid such as hydrochloric acid or sulfuric acid, if necessary. Therefore, in order to use it as an adhesive component,
Treating the compound of formula (IV) with an acid as described above,
It is preferable to convert to the compound represented by the formula (I).

The compound of formula (I) of the present invention is used for adhesion of metal (particularly noble metal or noble metal alloy) in the following two embodiments. (1) A compound of the formula (I) is applied to a metal surface as a low concentration solution (concentration 0.0001 to 10% by weight) of a volatile organic solvent (ethanol, acetone, ethyl acetate, etc.) or
Another known polymerization-curing type adhesive is applied thereon to adhere the metal surface to another object. The compound of formula (I) is used as an intermediate in the adhesion between a metal and an adhesive, that is, as a constituent of a primer. (2) The compound of the formula (I) is used as a part of the polymerizable monomer in a polymerization-curable adhesive composition composed of a conventional polymerizable monomer and a polymerization catalyst. In this case, since the mercapto group has a polymerization inhibitory action, it is desirable that the addition amount be 5% by weight or less based on the total polymerizable monomer, but the adhesive strength improving effect based on the compound of formula (I) In order to exert the above effect, the content should be 0.005% by weight or more.

In the case of the above (1), the adhesion enhancing effect is exhibited even when the concentration of the compound of the formula (I) is extremely small because the effect is exhibited when the compound adsorbs a single molecule of the compound on the metal surface. Even if the surface coated with the primer is washed with a solvent, the effect is not diminished, but when the primer with a high concentration of 1% or more is applied, it is better to wash the coated surface with the solvent. can get. It is considered that this is because the compound has a polymerization inhibiting effect.

The metals to be bonded are gold, platinum, palladium,
In addition to precious metals such as silver, ruthenium, rhodium, osmium, and iridium, a wide range of iron, nickel, cobalt, copper, zinc, tin, aluminum, titanium, vanadium, chromium, manganese, zirconium, molybdenum, cadmium, indium, antimony, etc. It also includes base metals. Further, the adhesion enhancing effect also appears in metal oxides such as aluminum oxide, titanium oxide and zirconium oxide and ceramics materials containing these metal oxides.

The surface coated with the primer is bonded with a known polymerization-curable adhesive, particularly preferably an adhesive containing an acrylic monomer. The adhesive strength depends on the mechanical strength of the adhesive itself, but usually the tensile adhesive strength is 200 kg / cm ³ or more, and almost all examples are cohesive failure of the adhesive. The adhesive interface has extremely excellent water resistance, and as long as the adhesive is stored in normal temperature water, no noticeable decrease in strength occurs during a period of several months.

When the compound of the formula (I) is used in the embodiment of (2), the copolymerizable monomer used is methyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neo. Pentyl glycol
Dimethacrylate, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (referred to as Bis-GMA), 2,2-bis (methacryloyloxyethoxyphenyl) propane, trimethylol Ethane triacrylate, pentaerythritol tetraacrylate, 4- (2-methacryloyloxyethyl) trimellitate, bis (2-methacryloyloxyethyl) hydrogenene phosphate, 2-methacryloyloxyethylphenyl hydrogen phosphate, 6-methacryloyloxyhexyldiene Hydrogenene phosphate, tris (2-methacryloyloxyethyl) phosphate, etc. are mentioned. On the other hand, as the polymerization catalyst, benzoyl peroxide-aromatic tertiary amine system, peroxide such as cumene hydroperoxide, tributylborane, aromatic sulfinic acid (or salt thereof) -aromatic secondary or tertiary Amine
Examples thereof include acyl peroxide type. Further, photopolymerization initiators such as camphorquinone, camphorquinone-tertiary amine type, camphorquinone-aldehyde type and camphorquinone-mercaptan type can be mentioned.
In addition, inorganic fillers such as quartz, glass, hydroxyapatite, calcium carbonate, barium sulfate, titanium oxide and zirconium oxide, and polymer powders such as polymethylmethacrylate, polystyrene and polyvinyl chloride are added as necessary.

The primer and the adhesive containing the compound of the present invention exhibit excellent water-resistant adhesive force, particularly to precious metals, and therefore are preferably used in the dental field. For example,
When adhering and fixing precious metal castings such as inlays, crowns, and bridges to teeth, bonding work for making a dental prosthesis made of precious metal, for example, bonding between bridging and denture, and bonding of split cast prostheses In the assembly and the like, improvement in performance and workability which cannot be obtained by the conventional technique is achieved. The compound of the present invention is used as a constituent component of a primer or an adhesive not only in the field of dentistry but also in any industrial field where adhesion of metal or metal oxide is required.

(Function) When a primer and an adhesive containing the compound of the present invention are applied to a metal surface, the mercapto group promptly reacts with the metal atom or metal oxide on the surface to form a chemical bond excellent in water resistance. It is presumed that the (meth) acryloyl group at the molecular end opposite to the mercapto group is later copolymerized with other monomers in the adhesive layer and cured. Therefore, the adhesive layer and the adherend metal are connected by a chemical bond,
It is believed that a durable bond is obtained.

(Effect) The primer and the adhesive containing the compound of the present invention exhibit excellent water-resistant adhesive force to a noble metal, and thus are preferably used in the dental field. For example, in the case of adhesively fixing a noble metal casting such as an inlay, a crown, and a bristle to a tooth, a bonding operation for producing a dental prosthesis made of a noble metal, for example, bonding a bristle and a denture, a split cast prosthesis In the assembly by adhesion or the like, improvement in performance and workability which cannot be obtained by the conventional technique is achieved. The compound of the present invention is used not only in the field of dentistry but also in any industrial field where adhesion of metal or metal oxide is required.

(Examples) Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A 500 cc three-necked flask was charged with a mixture of 10-hydroxydecyl methacrylate and 1,10-dimethacryloyloxydecane (containing 59% of 10-hydroxydecyl methacrylate).
50 g was added and cooled in an ice bath. 30 g of p-toluenesulfonyl chloride was dissolved in 60 cc of pyridine, placed in a dropping funnel and connected to a three-necked flask. While stirring the inside of the flask, a pyridine solution of p-toluenesulfonyl chloride was slowly added dropwise. After the dropwise addition was completed, the temperature was kept at 0 ° C. for 2 hours, then the temperature was raised to room temperature, the stirring was continued for 2 hours, the flask contents were neutralized with 6N HCl, and the liberated organic matter was extracted with methylene chloride. After washing with water several times, it was dried over anhydrous magnesium sulfate, 0.1 g of hydroquinone monomethyl ether was added, and methylene chloride was distilled off under reduced pressure at 40 ° C or lower,
79 g of a mixture of 1-hydroxydecylmethacrylate p-toluenesulfonate and 1,10-dimethacryloyloxydecane were obtained.

This mixture and thiourea 11 g, 2,2'-methylenebis (4
-Ethyl-6-tert-butylphenol) 0.4 g was dissolved in 150 cc of ethanol, heated and refluxed for 30 minutes.
The ethanol was distilled off under reduced pressure. The isothiuronium salt was extracted from the residue with acetonitrile, and the acetonitrile was distilled off under reduced pressure to obtain a crude product of the isothiuronium salt. The crude product was washed with a large amount of n-hexane,
High-purity isothiuronium salt was obtained by removing 10-dimethacryloyloxydecane. When 48 g of this isothiuronium salt and 40 g of zinc chloride were dissolved in methanol and a methanol solution of sodium hydroxide was added dropwise with vigorous stirring, a zinc salt of 10-mercaptodecyl methacrylate was produced as a white precipitate. Sodium hydroxide solution was added until no further precipitation occurred. Aside from salt,
After washing with methanol and water, it was dried to obtain 31 g of salt. When 200 ml of methanol is added to 20 g of this salt, it becomes a suspension state, but when diluted hydrochloric acid is added, the salt is dissolved and 10-mercaptodecyl methacrylate is liberated. N the compound
-Extract with hexane, dry over anhydrous magnesium sulfate,
When n-hexane was distilled off under reduced pressure, 10-
12 g of mercaptodecyl methacrylate was obtained.

When 90 MHzNMR measurement was carried out at room temperature using the compound as a 10% CDCl ₃ solution, the signals of the ethylenic protons of the methacryl group at δ = 5.35-5.00 and 5.90-6.05 were δ = 1.
The signal of the methyl proton of the methacrylic group at 75 to 1.85 is δ = 3.90 to 4.10, the proton signal of the methylene adjacent to the oxygen atom is δ = 2.15 to 2.60, and the proton signal of the methylene adjacent to the sulfur atom is δ = 0.8 to 1.7. The remaining methylene protons and mercapto group proton signals were observed. Further, when the measurement was carried out by mass spectroscopy, a molecular ion peak was observed at m / e258, and it was confirmed that the compound was 10-mercaptodecyl methacrylate.

Example 2 24 g of 5-hydroxypentyl methacrylate was added to a 500 cc three-necked flask and cooled in an ice bath. 30 g of p-toluenesulfonyl chloride was dissolved in 60 cc of pyridine, placed in a dropping funnel, connected to a three-necked flask, and a pyridine solution of p-toluenesulfonyl chloride was slowly added dropwise while stirring in the flask. After the dropwise addition was completed, the temperature was kept at 0 ° C. for 2 hours, then the temperature was raised to room temperature, the stirring was continued for 2 hours, the flask contents were neutralized with 6N HCl, and the liberated organic matter was extracted with methylene chloride. After washing it several times,
The extract was dried over anhydrous magnesium sulfate, 0.1 g of hydroquinone monomethyl ether was added, and methylene chloride was distilled off at 40 ° C. or lower to obtain 45 g of 5-hydroxypentyl methacrylate p-toluenesulfonate.

This p-toluenesulfonate and thiourea 11g, 2,2 '
0.4 g of methylenebis (4-ethyl-6-tert-butylphenol) was dissolved in 150 cc of ethanol and refluxed for 15 minutes, and then ethanol was distilled off under reduced pressure to obtain a composition of isothiuronium salt. The crude product was first recrystallized from acetonitrile and then from water to obtain 41 g of highly pure isothiuronium salt.

Hereinafter, the same operation as in Example 1 was performed to obtain 10 g of a colorless transparent liquid.
I got From the measurement results of NMR and mass spectroscopy, it was confirmed that the compound was 5-mercaptopentyl methacrylate.

Example 3 26 g of 6-hydroxyhexyl methacrylate was added to a 500 cc three-necked flask and cooled in an ice bath. 30 g of p-toluenesulfonyl chloride was dissolved in 60 cc of pyridine, put in a dropping funnel and connected to a three-necked flask, and a pyridine solution of p-toluenesulfonyl chloride was slowly added dropwise while stirring in the flask. After the dropwise addition was completed, the temperature was kept at 0 ° C. for 2 hours, then the temperature was raised to room temperature and the stirring was continued for 2 hours. After washing with water several times, it was dried over anhydrous magnesium sulfate, 0.1 g of hydroquinone monomethyl ether was added, and methylene chloride was distilled off at 40 ° C. or below.
47 g of p-toluenesulfonate of hydroxyhexylmethacrylate were obtained.

This p-toluenesulfonate and thiourea 11g, 2,2 '
0.4 g of -methylenebis (4-ethyl-6-tert-butylphenol) was dissolved in 150 cc of ethanol and refluxed for 15 minutes, then ethanol was distilled off under reduced pressure to obtain a crude product of isothiuronium salt. The crude product was first recrystallized from ethanol and then from water to give 42 g of highly pure isothiuronium salt.

Hereinafter, the same operation as in Example 1 was performed to obtain 10 g of a colorless transparent liquid.
I got From the measurement results of NMR and mass spectroscopy, it was confirmed that the compound was 6-mercaptohexyl methacrylate.

Example 4 A mixture of 10-hydroxydecylmethacrylate and 1,10-dimethacryloyloxydecane in Example 1 was used.
The same procedure as in Example 1 was repeated except that 78 g of a mixture of -hydroxyeicosyl acrylate and 1,20-diacryloyloxyeicosan (containing 62% of 20-hydroxyeicosyl acrylate) was used, and 16 g of a colorless transparent liquid was obtained. Obtained. From the measurement results of NMR and mass spectroscopy, it was confirmed that the compound was 20-mercaptoeicosyl acrylate.

Example 5 3.0 g of zinc chloride was dissolved in 150 cc of diethyl ether, and 10.4 g of 10-mercaptodecyl methacrylate synthesized in Example 1 was added thereto. When a 1N NaOH methanol solution was added to this solution with stirring, a zinc salt of 10-methacryloyloxydecyl mercaptide was deposited as a white precipitate.
A 1N NaOH methanol solution was added until no new precipitate was formed, the precipitate was separated, and washed with diethyl ether, methanol, and water in this order to obtain 9.8 g of a white solid. The elemental analysis results of the compound are C: 57.62%, H: 8.22%, O: 11.56.
%, S: 11.33% (calculated value C: 57.96%, H: 8.69%, O: 11.03
%, S: 11.05%), and it was confirmed that the compound was zinc 10-methacryloyloxydecyl mercaptide.

Examples 6-9 and Comparative Example 1-2 Four compounds shown in Table 1 and the above-mentioned known compounds.
Substance N- (4-mercaptophenyl) methacrylamide
Each was used to investigate the adhesion effect on precious metals. This
These compounds are 1% acetone solution (primer),
Polished with adherend # 1000 silicon carbide polishing paper
Pure gold plate (10 x 10 x 1 mm, 4 mm thick stainless steel back
Reinforced surface) and dental gold-silver-palladium alloy
"Castwell" (manufactured by Jijisha, 10 x 10 x 1 mm, similarly
Reinforced) surface was applied with a brush. One minute later
Wash the coated surface with pure acetone and only the molecules adsorbed on the surface
The surface was adjusted so that 5mmφ hole on this surface
The opened adhesive tape was attached to the surface to be adhered. on the other hand,
Prepare a 7 mmφ × 25 mm SUS304 round bar, and make the end surface of the round bar 50
Sandblasting was performed with alumina abrasive grains of μm. This side
In addition, 100 parts by weight of methacrylic acid ester, sodium sulfinate
-Benzoyl peroxide-tertiary amine-based polymerization
3 parts by weight of initiator, 320 parts of silane-treated inorganic filler
Dental adhesive consisting of parts "Banavia EX (Kuraray
Of the kneading paste) and press it against the surface
I put on my clothes. After 1 hour, soak the adhesive test piece in 37 ℃ water
After 24 hours, the universal testing machine (manufactured by Instron) (Cross
・ Tensile adhesive strength was measured at a head speed of 2 mm / min.
The measured values of 8 test pieces are averaged, and the measured results are shown in Table 1.
showed that.

Example 10 and Comparative Example 3 A 1% acetone solution of the compound used in Example 8 was applied to “Castwell” according to the method of Examples 6 to 9,
After 1 minute, wash the coated surface with pure acetone and then use "Banavia E
A stainless rod was adhered with "X" (manufactured by Kuraray Co., Ltd.) to obtain an adhesion test piece (Example 10). On the other hand, as a comparative object, a test piece (Comparative Example 3) in which the "castwell" and a stainless steel rod were directly bonded by Vanavia EX without applying the acetone solution was also prepared. For the purpose of evaluating water resistance, these test pieces were immersed in 37 ° C. water 1 hour after adhesion, transferred to 70 ° C. water 24 hours later, and allowed to stand for 10 days. Then, the tensile adhesive strength was measured by the method of Examples 6-9. The average adhesive strength of Example 10 was 280 kg / cm ² , whereas the average adhesive strength of Comparative Example 3 was 31 kg / cm 2.
^{It was 2} .

Example 11 and Comparative Example 4 A two-paste mixed type adhesive having the following compositions A and B was prepared.

Paste A Bis-GMA 12.5 parts by weight Triethylene glycol dimethacrylate 12.5 Adhesive component of Example 8 0.1 NN-diethanol-p-toluidine 0.5 Silane treated quartz powder 74.5 Paste B Bis-GMA 12.5 parts by weight Triethylene glycol dimethacrylate 12.5 Benzoyl Dental gold alloy "Haradol H", which was polished with # 1000 silicon carbide abrasive paper in the same manner as in Examples 6-9, using an adhesive prepared by mixing peroxide 0.5 silane-treated quartz powder 74.5 Pastes A and B. (Solder made by Herlaus Co., West Germany; containing Au: 79%, Pt: 10%, and Pd: 8%) was bonded to a stainless steel rod subjected to sandblasting. Adhesive sample 37 ℃
After immersing in water for 24 hours, the tensile adhesive strength was measured. As a result, cohesive failure of the adhesive occurred and the average strength (n = 8) was 23.
4 kg / cm ² (Example 11).

On the other hand, a paste A ′ having a composition obtained by removing the adhesive component of Example 8 from the composition of paste A was prepared, and the same adhesion as in Example 11 was performed by combining A ′ + B. Fracture occurred at the interface between the gold alloy and the adhesive, and the average adhesive strength was 106 kg / cm ² (Comparative Example 4).

Claims (5)

[Claims] 1. A general formula (In the formula, R represents hydrogen or a methyl group, and n is from 5
A compound represented by a natural number up to 20). 2. The compound according to claim 1, wherein n is a natural number of 6 to 20. 3. General formula (In the formula, R represents hydrogen or a methyl group, and n is from 5
Represents a natural number of up to 20, m represents a natural number of 1 to 4, and M ^{m +} represents an m-valent metal ion). 4. The compound according to claim 3, wherein n is a natural number of 6 to 20. 5. The compound according to claim 3, wherein M ^{m +} is a divalent zinc ion.