JPS6020426B2 - Adhesive for human hard tissue - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesives for human hard tissue such as dental bones.

More specifically, the present invention relates to adhesives that require strong adhesion to human tissues under humid conditions, such as adhesives for treating multiple residual fractures, filling materials for fixing artificial joints, tooth adhesives, and tooth filling materials. In the case of room temperature-curing fillings for teeth and fillings for fixing artificial joints, mixtures of polymethyl methacrylate and methyl methacrylate, mixtures of bisphenol-A-diglycidyl methacrylate and triethylene glycol dimethacrylate, etc. are used in the presence of inorganic fillers. Alternatively, curing has been carried out using a catalyst system that generates radicals mainly by mixing a peroxide and an amine in the absence of the compound.

In this method, the cured product shows almost no adhesion to the human shark, and the adhesive strength in a wet state is about 0 to 5k9/average. For this reason, for example, in the case of conventional fillings for dental caries treatment, a mechanical holding form called an undercut has been applied to the cavity to prevent the filling material from falling off after hardening. However, this method has the drawback of removing healthy tooth structure, and since there is no adhesiveness between the filling material and the tooth structure, the margin sealing property is poor and cavities are likely to recur. In recent years, adhesives containing Q-cyanoacrylate as a main component have been developed as fillers for caries prevention and orthodontic adhesives for the purpose of adhering to tooth structure. It is said that there are problems with its durability and operability during use.

Additionally, dental adhesive fillers using trialkylboron as a polymerization initiator have been developed. (Nittoku Koko Showa 42-1
(No. 4318, Nittokuko No. 45-29195) Although it exhibits strong adhesion to tooth dentin, it does not have sufficient adhesion to tooth enamel, which has little organic matter, and the main component of the microwave is methacrylic. Because it uses acid methyl, it has not reached the point where it is fully satisfactory as a dental filling material. Furthermore, a method has been discovered that uses a vinyl compound containing divalent phosphoric acid, which is expected to bind to the calcium content of tooth substance.

(Nittoku Seki No. 51-44152, Journal Dental Research No. 39, page 846) However, this adhesive has a low level of adhesive strength and cannot be said to be sufficient for practical use. Additionally, US Pat. No. 260-260 describes that by adding a small amount of an addition-polymerizable organic phosphoryl monofluoride compound to a tooth adhesive composition, the adhesive strength between the tooth and the composition is increased. has been done. However, this compound has reactivity with tooth substance, which is thought to be due to the fact that it is a compound having a P-F bond, and there is a problem in terms of safety for the dental pulp. Therefore, the object of the present invention is to have a material that is suitable for the purpose of use, such as high hardness, high compressive strength, and low water absorption, and is also strong against the bones that form the hard tissues of the human body, and the dentin and enamel of teeth. Another object of the present invention is to provide an adhesive for hard tissue of the human body that has stable adhesive strength over a long period of time and does not cause writing on the human body.

Yet another object of the present invention is to provide an adhesive for human hard tissue as a tooth filling composition.

Yet another object of the present invention is to provide a bush adhesive for human hard tissue that is useful as an adhesive for bonding between teeth and tooth fillings or filling materials.

These purposes are based on a phosphoric acid ester or phosphonic ester compound having at least one polymerizable functionality and/or a bond, or a polymer obtained by polymerizing this compound as one component, and a polymerizable monomer. and a hardening agent consisting of a peroxide, an amine, and a sulfinic acid (or a salt of a sulfinic acid); The product is packaged in at least two parts so that the ingredients are not contained in one package, and then distributed to doctors, etc.

Among the phosphoric acid ester or phosphonic acid ester compounds having at least one inorganic functional group and/or a bond used in the present invention, compounds represented by the following formula are preferably used.

or a bond (R represents a radical neck group having at least one polymerizable functional group), and compounds represented by formulas [11 to '7} are more preferably used.

(2) That is, the compound has the general formula {R is an organic residue having at least one polymerizable functional group, Rc represents X or OX, and × is substituted with a hydroxyl group, halogen, amino group, or carboxyl group. linear, cyclic, or branched, with 1 to 1 carbon atoms
30 aliphatic, cycloaliphatic or aromatic hydrocarbon residues or polyether, polyester or polyurethane compound residues.

} is a compound represented by More specifically, the phosphate ester compound represented by the formula [1-] is as follows:
Examples include compounds represented by formula 21.

The compound has the general formula {wherein Ra represents H or CH3, and Rb represents COO
Y, OCOY, OY, Y, C○ (OC is CH2) m (m
is an integer of 1 to 5), (m is an integer of 1 to 5), or C.

(〇CH2CH2)I (1 is an integer of . to 3), and Y has 1 to 3 carbon atoms, which may be substituted with a hydroxyl group, an alkoxyl group, or a halogen.
0 linear, cyclic or branched aliphatic, aromatic or alicyclic hydrocarbon residue.

Rc is a compound represented by the same } as above. This compound also includes cases where Rc is or (Ra' and Rb' are synonymous with Ra and Rb, respectively).

'B- The compound has the general formula (However, Ra and Rc are the same as above.

R is synonymous with Ra. Rb is or represents vinegar.

) is a compound represented by [q The compound has the general formula or (Ra and Rb are the same as above.

Ra', Ra'' and Ra... are synonymous with Ra. Rb', R
b'' and Rb... are synonymous with Rb.Re is -○-Z-○-
, one○-Z- or one Z-, and Rf or Rg represents or.

Here, Z is a compound represented by (synonymous with X).

Imitation The compound has the general formula (In the formula, Ra is the same as above.

Rh represents COOY, OCOY, OY or Y;
is the same as above. Rc' is synonymous with Rc. Rc is the same as above. ) is a compound represented by As is clear from the above description, in the present invention, the carbon atoms of the bond or bond P-C, P-○-C may form a ring.

Next, specific examples of the phosphoric acid ester compounds used in the present invention will be shown.

As a compound represented by the formula '21, a compound represented by the formula 81 is used, for example, a phosphate ester compound having the following structural formula.

It is represented by the formula '4', '5 or {61, and includes, for example, the following compounds.

It is represented by the formula '7}, and the following compounds are used, for example.

In addition, a reaction product of finchic acid and glycidyl methacrylate can also be used.

Among these compounds, bonded phosphonate ester compounds are more resistant to hydrolysis than striped phosphate ester compounds and retain higher adhesion strength over a longer period of time under humid conditions. It is preferable because

Furthermore, in the compound represented by the second formula, those in which x is an alicyclic or aromatic group have better adhesive strength than those in which x is an aliphatic hydrocarbon residue.

Furthermore, in general, compounds represented by formulas '21, ■, '61 and '61, which have two or more polymerizable functional groups, are better than phosphate ester compounds which have one polymerizable functional group, in which one P-0-C bond is Even if it is hydrolyzed, it can be said to be more stable because the other P-○1C bond is present.

These phosphate ester compounds are preferably acid compounds from the viewpoint of adhesion to hard tissue of the human body.

However, some of the phosphoric acid protons (10 to 9
0 mol %) may be substituted with a salt. Examples of the elements or compounds that form salts include alkali metals such as sodium and potassium, alkali metals such as magnesium and calcium, transition elements, ammonium, and amines. In the present invention, the phosphate ester compound (
Hereinafter, the term may be used to include phosphonate ester compounds.

) may be polymerized and cured when adhering to a hard tissue, and
It may be polymerized in advance, mixed with other monomers, and cured upon adhesion to hard tissues. Among these, it is preferable from the viewpoint of adhesive strength to use the phosphate ester compound in the form of a monomer and to cure it upon adhesion to a hard tissue. In such cases, the phosphate ester compound may be homopolymerized, but it is usually copolymerized in the presence of other monomers that can be used as adhesives for human hard tissue. Therefore, in the present invention, the term "polymer" of the compound also includes copolymers with other monomers. The polymerizable monomers that are mixed with the compound, copolymerized with the compound, and further mixed with the polymer of the compound include those that have no tactile properties on the human body and are polymerizable monomers. Any of them may be used, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, di-, tri-, or tetra-ethylene glycol di(meth)acrylate. acrylate, bisphenol A di(meth)acrylate, 2,2-bis((meth)acryloxyethoxyphenyl)propane, 2,2-pis(y-(meth)acryloxy-8-hydroxypropoxyphenyl)propane, Examples include N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, styrene, and vinyl acetate.

Further, monomers having groups capable of ring-opening polymerization such as epoxy, spiro-orthoester, and bicyclolactone, and urethane diacrylates can also be used. Polymers such as polymethyl methacrylate, polyethyl methacrylate, polystyrene, unsaturated polyester resin, and high molecular weight epoxy acrylate resin may also be used in combination to adjust viscosity, curing speed, polymerization shrinkage, etc. In these compositions, the above-mentioned phosphate ester compound and/or polymer of the compound is contained in the adhesive in an amount of 0.1% by weight or more as monovalent phosphorus, thereby exhibiting excellent adhesive strength to hard tissues of the human body. show. The curing agent used in the present invention is a three-component curing agent consisting of a peroxide, an amine, and a sulfinic acid (or a salt of sulfinic acid).

By using such a curing agent, the adhesive can be cured in a short time at room temperature, the cured product will not be colored, and moreover, the above-mentioned phosphoric acid ester compound can maintain high adhesive strength to human hard tissues. I can do it. The sulfinic acid used in the present invention may be any organic sulfinic acid, that is, a sulfinic acid bonded to an aryl group or an alkyl group, but sulfinic acids bonded to an aryl group are more advantageous from the viewpoint of stability of the curing agent.

Since sulfinic acid compounds, except for some, have poor storage stability, it is more convenient to use sulfinic acid salts in carrying out the present invention. As the salt, salts of alkali metals, alkaline earth metals, amines, etc. are used. However, the effects of the present invention can be achieved in any case where sulfinic acid or its salt is used. Examples of sulfinic acid salts include sodium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, ammonium benzenesulfinate, triethylene ammonium benzenesulfinate salt, and benzenesulfinic acid/NN'dimethyl-P-toluidine salt. Alternatively, salts of P-toluenesulfinic acid, 8-naphthalenesulfinic acid, and styrenesulfinic acid can be mentioned. The peroxide may be any peroxide commonly used as a curing agent, but diacyl peroxides such as dibenzoyl peroxide, di-P-chlorobenzoyl peroxide, and dilauroyl peroxide are particularly suitable. Preferably used.

Furthermore, as the amine used in the present invention, compounds in which an amino group is bonded to an aryl group are particularly effective.

Further, secondary or tertiary amines have a more remarkable effect of accelerating curing than primary amines, and are therefore preferred. For example, NN'
-dimethylaniline, NN'-dimethyl-P-toluidine, N-methyl, N'-8-hydroxyethylaniline, NN'-di(8-hydroxyethyl)-aniline,
Preferred examples include NN'-di(8-hydroxyethyl)-P-toluidine, N-methyl-aniline, and N-methyl-P-toluidine. The amount of these curing agents is used within the range of 1 to 20% based on the polymerizable monomer, and is appropriately selected so that the curing time is within 1 minute. In the present invention, in addition to the above-mentioned phosphate ester compound and curing agent, glass beads with a particle size of about 1 to 100 French, fillers such as alumina oxide, Q-quartz powder, colloidal silica, hydroquinone monomethyl ether, , a polymerization inhibitor such as 6-di-tert-butyl-P-cresol, or an antioxidant, an ultraviolet absorber,
Colorants etc. can be added as necessary.

As described above, the adhesive of the present invention contains a phosphate ester compound as a component, or a mixture of a polymer obtained by polymerizing the compound as one component and a polymerizable monoleather, and an amine and a peroxide. The adhesive contains a curing agent consisting of three components: and sulfinic acid (or sulfinic acid salt), but from the viewpoint of storage stability, the components are divided into at least two parts and stored separately. , and are mixed for the first time before use.

For storage, the three components of the curing agent are packaged in at least two parts so that the three components do not fit into one package,
It is necessary to store the adhesive, and such two-part adhesive packages are supplied to doctors as a set. A doctor can mix appropriate amounts of components from a set of at least two divided adhesive packages depending on the usage mode. The following examples are examples of how the components of the adhesive are packaged separately and how they are used. A method in which a liquid or paste-like polymerizable monomer containing the above-mentioned phosphate ester compound (fillers and polymers may be mixed) and a ternary curing agent are each packaged separately and mixed immediately before use; The amine is pre-dissolved in a polymerizable monomer and packaged, and then mixed with a peroxide such as powdered penzoyl peroxide and a sulfinic acid salt (in some cases, together with filler and polymer powder). ) in a separate package and mixing them immediately before use, or divide the paste-like polymerizable monomer (in some cases slurry form containing fillers and polymers) into two or three parts and add peroxide to this. A method in which a paste-like product, an amine, and a sulfinic acid salt are mixed in advance to form two or three-part packaging, and these are thoroughly kneaded just before use. A liquid polymerizable monomer or a volatile solvent is mixed with a peroxide and an amine in advance. For use by doctors, a liquid containing sulfinic acid (or its salt) is first applied thinly to the tree wall, and then the two halves of the paste are mixed and filled. There is a method in which three hardening agents are mixed at the filling site to achieve adhesion to the recessed wall, and the paste of the main body is hardened with a hardening agent system consisting of peroxide and amine.

The adhesive of the present invention can improve the adhesion between the filler and human hard tissues by being mixed with the filler, and can also be applied as a liner to the surface of teeth or bones, and then used as a liner. By applying this filler, the adhesion between the filler and the hard tissue of the human body can be improved.

Furthermore, since the adhesive of the present invention exhibits good adhesion to metals, it can also be used as an adhesive for inlays, crowns, etc. As mentioned above, the adhesive of the present invention contains a phosphate ester compound,
or a mixture of a polymer obtained by polymerizing said compound as one component and a polymerizable monomer, and a curing agent consisting of a peroxide, an amine, and a sulfinic acid (or a salt of a sulfinic acid). By using this adhesive, it is possible to obtain strong adhesion to hard tissues of the human body such as teeth and bones, which could not be achieved using conventional techniques.

It has been confirmed that this adhesive strength has long-term durability under moist conditions such as in the oral cavity or in the body. Furthermore, in clinical use, the present invention provides strong adhesion to the target hard tissue by applying conventional techniques almost unchanged, so that doctors etc. can use the adhesive based on the present invention extremely easily. be able to. In addition, as far as the phosphate ester compound of the present invention has been investigated, its acute oral toxicity is small, and no special stimulant effect on the dental pulp has been observed. The present invention will be explained below with reference to Examples.

However, the present invention is not limited thereto. Example 1 As a powder-liquid mixing type instant curing range, the following A agent,
Eight drugs were created.

Agent A: A mixture of 95 parts by weight of polymethyl methacrylate having a molecular weight of 250,000, 3 parts by weight of sodium P-toluenesulfinate, and 2 parts by weight of dibenzoyl peroxide.

Powder composition. Agent 8: 8 parts by weight of methyl methacrylate, 1 part by weight of ethylene glycol dimethacrylate, 9 parts by weight of bis-(2-methacryloxyethyl) acid phosphate, and 1 part by weight of N,N'-jetanol-P-toluidine.
A mixture of parts by weight.

Liquid composition. Equal weights of Parts A and B were placed in a Dubben glass, mixed for one minute, and then applied to the wet cross sections of the ivory rod and acrylic rod, and bonded together. Then 37
The adhesive strength was measured by placing the rods in water at a temperature of 0.0 and separating the two rods after immersion for a certain period of time. Adhesion strength is the average value of 8 measurements. The results are shown in Table 1.

The adhesive of the present invention exhibits high adhesive strength and remains stable even when immersed in water for a long time. - Example 2 40 parts (by weight) of diethylene glycol dimethacrylate, 6 parts of bisphenol-A-diglycidyl methacrylate
Ikaribe, silane-treated Q-quartz powder 3 with a particle size of 10 to 50 particles
The 3 Botos were mixed well and divided into two equal parts.

To one part of the mixture was added 1 part of sodium chloride and 2 parts of penzoyl baroxide.

To the other, 2 parts of N,N dimethyl-P-toludine and 2 parts of sodium p-toluenesulfinate were added. Before use, equal amounts of both pastes were thoroughly kneaded and placed between the teeth to harden. This paste begins to harden approximately 3 minutes after the start of mixing, and after 1
It hardened enough after the beard. The adhesion strength of ivory sticks bonded with this paste after being kept in water at 37°C for 3 days was investigated using an Instron tensile tester. Although there were variations between ivory samples, the adhesion strength was determined for 10 ivory samples tested. 1 female to 19
Gave 0k9/ground, average 178k9/ground. In addition, these two pastes were mixed and filled into the phosphoric acid-etched first-class cavity of the extracted tooth.

When we conducted a percolation test in which dye water was immersed 100 times at 1 minute intervals at 4°C and 60°C, most of the samples tested showed no penetration of the dye into the gap between the tooth and the filling. was found to have good adhesion to teeth.

Example 3 In a powder/liquid composition as an adhesive, agents C and D having different types of phosphoric acid monomers were prepared.

Agent C: 2 parts by weight of penzoyl peroxide and 3 parts by weight of sodium P-toluenesulfinate were added to 100 parts by weight of polymethyl methacrylate fine powder and mixed uniformly to obtain a powder composition.

8 parts by weight of methyl methacrylate, 10 parts by weight of ethylene glycol dimethacrylate, 1 part by weight of 2-methacryloxyethyl phenyl phosphonic acid and N,
N'-jetanol-P-toluidine 1. A liquid composition was obtained.

Agent D: 2 parts by weight of penzoyl peroxide and 3 parts by weight of P-tresosulfinate sodium salt were added to 100 parts by weight of polymethyl methacrylate fine powder and mixed uniformly to obtain a powder composition. 8 parts by weight of methyl methacrylate, 1 part by weight of ethylene glycol dimethacrylate, 1 part by weight of 2-methacryloxyethyl, inbutyl phosphonic acid, and 1 part by weight of N,N'-jeta/-P-toluidine.
．． A liquid composition was obtained by adding parts by weight of .

Mix equal amounts (weight) of powder and liquid of the above C or D agent (adhesive) and apply it relatively thickly to the end face of the wet ivory horn. It was glued and hardened using the method of butting sticks together. After that, it was placed in 370° water and soaked for 4 hours, and then the adhesive strength was measured using an autograph. The average adhesion strength for agent C was 160k9/base, and the average adhesive strength for agent D was 148k9/base, which was much better than the average adhesive force of 35k9/base for agents C and D in systems that did not contain phosphate ester compounds. There is.

Example 4 A three-necked flask with a capacity of 300 mm was equipped with a koji extractor, a condenser, and a thermometer, and 200 mm of toluene, 40 mm of methyl methacrylate, and 2 mm of (2-methacryloxyethyl)phenylphosphonic acid were added to it. , 0.2 hours of penzoyl peroxide was added, and the polymerization was continued at 90:00 for 3 hours with good lighting.

After cooling, the polymerization solution is added to a large amount of ethyl ether to reprecipitate the polymer. After thoroughly drying this polymer, it is pulverized to obtain a fine powder of 20 mesh or less. To 100 parts by weight of this polymer fine powder, 3 parts by weight of sodium p-toluenesulfinate and 2 parts by weight of penzoyl peroxide are added and mixed well to prepare a powder composition.

In addition, a monomer composition prepared by adding 1 part by weight of N,N'-jetanol-P-toludine to 8 parts by weight of methyl methacrylate and 20 parts by weight of ethylene glycol dimethacrylate and the above powder composition were applied to the end surface of an ivory horn rod by a brush stroke method. A relatively thick layer of paint was applied, and acrylic horns were attached and cured on top of this.

After putting this product in 370 water and soaking it for 2 hours, the adhesive strength was measured using an autograph, and the average adhesive strength was 154.
It showed excellent adhesion of k9/young (count of 10).

In addition, the above-mentioned (2-methacrylate).

instead of phenylated phosphonic acid (
A composition was prepared using 2-methacryloxyethyl) phenyl phosphoric acid under the same conditions, and the adhesion was measured under the same conditions. An adhesive force of 162k9/enemy was obtained. Example 5 A two-component liner adhesive and two-paste composite resin having the following composition was prepared.

Agent E: parts by weight of 2-methacryloxyethyl phenyl acid phosphate 2, parts by weight of pisphenol-A-diglycidyl methacrylate 1, parts by weight of neobentyl glycol dimethacrylate 6, parts by weight of methacrylic acid 1, peroxide A mixture of 3 parts by weight of Penzoyl and 0.05 parts by weight of hydroquinone monomethyl ether.

Liquid composition. Agent F: 40 parts of 2-hydroxyethyl methacrylate, 4 parts by weight of bisphenol-A-diglycidyl methacrylate, 2 parts of diethylene glycol dimethacrylate, 2 parts of sodium benzenesulfinate
A mixture of 3 parts by weight of N,N-jetanol-P-toluidine and 0.05 parts by weight of hydroquinone monomethyl ether.

Liquid composition. G agent: Bisphenol A diglycidyl methacrylate (hereinafter referred to as Bis-GMA) 16 boxes parts by weight triethylene glycol dimethacrylate 2. Base weight part Silanized quartz powder 80.1 parts by weight N,N
-diethanol-P-toluidine 0. Round weight part H agent; Bjs-GMA 16. Box weight part triethylene glycol dimethacrylate 2. Silanized quartz powder by weight 80. 0.4 parts by weight of penzoyl peroxide A window cavity with a diameter of about 2 skins and a depth of 4 feet was formed in the extracted tooth.

A paste made by adding 10% particulate silicic acid to a 50% aqueous solution of orthophosphoric acid is applied to the tunnel and surrounding enamel, and 1
After a few minutes, it was washed with water and dried with air. Equal amounts of Agent E and Agent F were taken and mixed, and then applied to the wall and surrounding area of the sinus cavity. Equal amounts of agent G and agent H were taken and mixed, and then filled into the window cavity. Five minutes after filling, it was polished with a diamond tool and finished with a paste abrasive. Using this method, the high cave was restored both aesthetically and technically. The margin of the tunnel was completely sealed. Example 6 Four packages having the following compositions each having high storage stability were prepared.

1 package; Pisphenol A diglycidyl methacrylate 180 parts by weight triethylene glycol dimethacrylate 3. Milk weight part Silane treatment Q-quartz powder 77. Kame weight part penzoyl peroxide
0. Part by weight of milk Hydroquinone monomethyl ether 0.1 part by weight J packaging; Bisphenol-A diglycidyl methacrylate 18. q parts by weight triethylene glycol dimethacrylate 3
．． $ parts by weight Silane treatment Q-quartz powder 77.2 parts by weight NN'-diethanol-P-toluidine 0. Parts by weight Hydroquinone monomethyl ether 0.1 parts by weight K packaging: Hydroxyethyl methacrylate 3 parts by weight Triethylene glycol dimethacrylate 6 parts by weight Di(methacryloxyethyl)phosphoric acid 1 part by weight L packaging: Hydroxyethyl methacrylate 3 parts by weight Triethylene glycol dimethacrylate 6 parts by weight Sodium dodecylbenzenesulfinate
% orthophosphoric acid aqueous solution.

Claims (1)

[Claims] 1 (A) b) having at least one polymerizable functional group,
and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Phosphate or phosphonate compounds having a bond, or b) The compound is
A mixture of a polymer obtained by polymerization and a polymerizable monomer as components, and (B) a curing agent consisting of a) peroxide, b) amine, and c) sulfinic acid or a salt of sulfinic acid. Adhesive for hard tissues of the human body. 2 The compound has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {In the formula, Ra represents H or CH_3, and R_b represents C
OOY, OCOY, OY, Y, CO(OCH_2CH_
2) m (m is an integer from 1 to 5), ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (m is an integer from 1 to 5) or ▲ there are mathematical formulas, chemical formulas, tables, etc. (an integer), and Y represents a straight chain, cyclic or branched aliphatic, aromatic or alicyclic hydrocarbon residue having 1 to 30 carbon atoms which may be substituted with a hydroxyl group, an alkoxyl group or a halogen. R_c represents X or OX, X is a hydroxyl group,
Straight chain, cyclic or branched, carbon number 1-30, which may be substituted with halogen, amino group or carboxyl group
represents an aliphatic, alicyclic or aromatic hydrocarbon residue, or represents a polyether, polyester or polyurethane compound residue. } The adhesive for human hard tissue according to claim 1, which is a compound represented by the following.
3. Claim No. 3 in which Rc is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼ (In the formula, R_a' and R_b' have the same meaning as the above-mentioned R_a and R_b, respectively) Adhesive for human hard tissue according to item 2. 4. The compound has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (However, R_a, R_c are the same as R_a, R_c in claim 2. R_a' has the same meaning as R_a. , table, etc. ▼ or ▲ mathematical formula, chemical formula, table, etc. ▼ . Y is the same as above. 5 The compound has a general formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼ (Ra and Rb are the same as above. R_a′, R_a″ and R_a′″ are synonymous with R_a.
R_b', R_b'' and R_b''' are synonymous with R_b.
R_e represents -O-Z-O-, -O-Z- or -Z-, and Rf stands for ▲Mathematical formula, chemical formula, table, etc.▼ or ▲Mathematical formula, chemical formula, table, etc.▼ Rg stands for ▲Mathematical formula, There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents. The adhesive for human hard tissue according to claim 1, which is a compound represented by the following formula (where Z has the same meaning as the above-mentioned X). 6 The compound has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Ra is the same as above. R_h represents COOY, OCOY, OY or Y,
Y is the same as above. R_c' is synonymous with R_c. R_c is the same as R_c in claim 2. ) The adhesive for human hard tissue according to claim 1, which is a compound represented by: 7 Claim 2, wherein the compound is 2-methacryloxyethylphenyl phosphoric acid
Adhesives for human hard tissue as described in Section 1. 8. The adhesive for human hard tissues according to claim 2, wherein the compound is 2-methacryloxyethylphenylphosphonic acid. 9. The adhesive for human hard tissue according to claim 3, wherein the compound is bis(2-methacryloxyethyl) acid phosphate. 10. The adhesive for human hard tissue according to claim 1, wherein the peroxide is diacyl peroxide. 11. The adhesive for human hard tissue according to claim 10, wherein the diacyl peroxide is dibenzoyl peroxide. 12. The adhesive for human hard tissue according to claim 1, wherein the amine is a secondary or tertiary amine in which an amino group is bonded to an aryl group. 13 The amine is N,N-di(β-hydroxyethyl)
-P-Toluidine The adhesive for human hard tissue according to claim 12. 14. The adhesive for human hard tissue according to claim 1, wherein the sulfinic acid salt is an alkali metal, alkaline earth metal, or amine salt of arylsulfinic acid. 15. The adhesive for human hard tissue according to claim 14, wherein the sulfinic acid salt is sodium benzenesulfinate. 16. The adhesive for human hard tissue according to claim 1, wherein a copolymerizable monomer is further added to the phosphoric acid ester or phosphonic acid ester compound. 17. The adhesive for human hard tissue according to claim 1, further comprising a filler. 18. The adhesive for human hard tissue according to claim 1, wherein the adhesive is divided into at least two parts so that the three components of the curing agent are not contained in one package.