JPS61127773A - Adhesive composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a curing agent consisting of a half perester of a bifunctional acid having a specific structure and a sulfinic acid salt and a polymerizable monomer, curable in a short time at ordinary temperature, and capable of bonding powerfully hard tissues of the human body and metal. CONSTITUTION:An adhesive composition obtained by polymerizing (A) a polymerizable monomer, e.g. methacrylic acid, in the presence of (B) a curing agent consisting of (i) a half perester of a bifunctional acid having the formula (R is 1-3C alkyl), e.g. mono-tert-butyl permaleate, and (ii) a sulfinic acid salt, e.g., sodium benzenesulfinate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition containing a polymerizable monomer and a curing agent, and a polymerization method, and particularly to a composition that strongly adheres to hard human tissue or metal.

BACKGROUND OF THE INVENTION Cements have traditionally been used as restoration materials for hard tissue in the human body, particularly for dentistry, but in recent years synthetic resins have come to be widely used in the field of dental treatment. For example, a mixture of polymethyl methacrylate and methyl methacrylate, a mixture of bispheno-ρ-A-diglycidyl methacrylate and triethylene glycol dimethacrylate, and an inorganic filler can be cured at room temperature by redox polymerization of peroxide and amine or photopolymerization. is used.

However, since this type of adhesion is not too high, the restorations fall off and leakage occurs at the periphery of the bonded area, which causes secondary caries. For this reason, many attempts have recently been made regarding bonding with tooth structure. For example, efforts are being made to develop 7-terminals that improve adhesion to tooth structure.

The present inventor believed that in order to obtain adhesion with the tooth structure, not only the hardening agent is important, but also the hardening agent, and as a result of repeated research, the present invention was completed.

The present invention is directed to an adhesive composition and a polymerization method developed in view of the above circumstances. The purpose is to provide.

The adhesive composition of the present invention is composed of a polymerizable monomer and a curing agent, and is particularly characterized by the curing agent. That is, as a curing agent, the formula (however, in the above formula, R is 1
When used in combination with a sulfinic acid salt and a half-ester of a difunctional acid represented by an alkyl group having three carbon atoms, it is possible to bond strongly to the tooth structure, and furthermore, it is possible to create a strong bond within one molecule. 〃Discovered that it polymerizes with phoxyl group,
This is what led to the present invention.

The feature of the present invention lies in the composition of the above-mentioned hardening agent. Whereas conventional dental hardening agents have been composed of peroxide and amine, in the present invention, the formula (however, in formula 1, the hill is The object of the present invention is to use a completely new curing agent consisting of a half-ester of a difunctional acid (alkyl group having 3 carbon atoms) and a salt of fulfinic acid.

Conventionally known tooth adhesive compositions are not strong against tooth bud dentin, except those that use organoborane catalysts or special polymerizable monomers. Nothing is known that exhibits adhesive strength.

The adhesive composition in the present invention has a
Provides adhesive strength of 70 #/Cj. Further, when a polymerizable monomer having a force μ phoxyl group in the molecule is added as a polymerizable monomer to be used in the composition of the present invention, it is very effective for adhesion to metals.

The adhesive composition of the present invention will be described in more detail. first,
Regarding the curing agent, the curing agent is a difunctional acid half ester represented by (in the above formula, B is an alkyl group having from I to 3 carbon atoms) and 2 rufin. Examples of half-peresters of bifunctional acids include mono-butyl permaleate and mono-t-buty-p perfumarate, and salts of sulfinic acids used include aryl groups or Any salt of sulfinic acid bonded to an alkyl group may be used, but salts of arylsulfinic acid are preferred, and examples thereof include sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium nutylenesulfinate.

The amount of these curing agents is 0.01~
The types of polymerizable monomers used within the range of 20% are
It is selected as appropriate while taking into consideration the curing speed, adhesive strength, etc.

Next, as polymerizable monomers, methyl methacrylate hydroxyethyl methacrylate, hydroxypropyl methacrylate, 212'-bis(4-methacryloxyethoxyphene=/L')7''lopane, 2,2'-bis(4
- methacryloxy fa bokinfueni/L') propane,
212'-BisCα-methacrylicylcoupyl β-hydroxypropoxyphenylene/l/I propane, ethylene glycol
Dimethacrylate, triethylene 7 glycol p dimethacrylate, urethane acrylate, glycidyl methacrylate, a compound derived from glycidyl methacrylate, etc. are used, but there are no special restrictions on the type.

Furthermore, as a polymerizable monomer, there is a force ρ-poly S/A in the molecule.
By adding a polymerizable monomer having a / group to the composition of the present invention, it is possible to further improve the adhesion to hard tissues, and to obtain a composition that has strong adhesion to metals. be able to.

Examples include methacrylic acid, 4-methacryloxyethyl phthalate, 4-methacryloxyethoxybenzoic acid, 4-acryloxyethyl trimellitic acid, 4-methacryloxyethyl trimellitic acid, and the like.

Fillers can also be used, and examples of such fillers include inorganic fillers such as aluminum oxide, silica powder, and quartz powder, and polymers or copolymers of polymerizable monomers such as polymethyl methacrylate. Other stabilizers as necessary include hydroquinone monomethyl ether,
-butyl-p-cresol, hydroxymethoxybenzophenone, etc. are added.

The two components of the curing agent used in the composition of the present invention are each stored separately, and upon use, are mixed and kneaded together to exhibit their polymerization curing ability. For example, (11 polymerizable monomers and 2 curing agents stored separately)
The components are added and mixed and kneaded to obtain an adhesive composition. Or (2) A in which the polymerizable monomer contains half ester
A composition is obtained by mixing and kneading the B agent and the filler containing a salt of S/L/finic acid at the time of application. Or (31
At the time of application, a filler containing a polymerizable monomer as the A agent, a semipermeable ester as the B agent, and a sulfinic acid salt as the C agent was mixed and kneaded with the KA%81C3 agent at the same time to form an adhesive. It is used to obtain compositions, etc.

As described above, when a composition containing a curing agent consisting of a semi-permeable ester of a difunctional acid and a salt of sulfinic acid and a polymerizable monomer is mixed and kneaded, it hardens in a short time at room temperature and hardens the human body. Adhesive compositions are provided that strongly adhere to tissue and metals.

The present invention will be explained below with reference to Examples.

Example 1゜ First, the following composition was prepared.

Part A: To 100 parts by weight of polymethyl methacrylate powder, 8 parts by weight of mono-t-butyl permaleate was added and thoroughly mixed to obtain a uniform dispersion.

Agent B: 8 parts by weight of sodium p-)luenesulfinate was added to 1001 parts of polymethyl methacrylate powder and thoroughly mixed to obtain a uniform dispersion.

Next, when 1 part by weight of agent A and 1 part by weight of agent B were left in methyl, the mixture was cured in 5 minutes, and no coloration was observed in the cured product.

Example 2 A fresh anterior tooth was ground with an emery vapor to No. 600 to create a horizontal enamel surface, and then treated with a 4 Q q61J acid aqueous solution for 30 seconds, washed with water, and dried. Example 1
The paste-like composition described in 1. was also applied to the adhering surface, and the civil engineering acrylic/l/resin rod was crimped, left in the air for 1 hour, and then immersed in VC water at 37C for 24 hours, and then autographed. Tensile strength (tensile extension 4 m/m1ni was measured and was found to be 170 #/d.

Example 3 1 part by weight of agent A and 1 part by weight of agent B described in Example 1 were thoroughly mixed and kneaded at the same time to 4 weights of a solution containing 5 wt % of 4-acryloxyethyl trimellitic acid added to methyl methacrylate. The paste-like composition obtained by mixing was applied to the horizontal surface of untreated tooth enamel ground with emery paper No. 600, an acrylic resin rod was crimped onto it, and the tensile strength was measured in the same manner as in Example 2. It was 65 phantom/C-.

After grinding the fallen tooth dentin with emery paper to a level of 6001) to create a horizontal surface, the corrugated surface was treated with an aqueous solution containing 10% citric acid and 3% ferric chloride for 30 seconds, and then carried out in Example 3. Apply the composition described above to the surface to be adhered, and apply 7 ml/L/
After the rod was crimped and immersed in 37C water for 24 hours, the tensile strength was measured and found to be 150 #/cd.

Example 5 C agent: permaleic acid monot-gucci/L/2 parts by weight 2-hydroxy-8(p-phenoxy) phenoxypropyl methacrylate 20 parts 4-methacryloxyethoxy heptamine, Cb 5 parts by weight Methyl methacrylate 73 parts by weight C above
A base-like crude acid compound prepared by mixing and kneading 1 part by weight of the fcE agent described in Example 1 with 2 parts by weight of the agent was applied to the horizontal surface of the dentin of a natural tooth, which had been surface-treated by the method described in Example 4. Acryloxy was pressed and immersed in 37C water for 24 hours, and the tensile strength was measured to be 270 kg/d.

Example 6゜The composition described in Example 3 was applied to a stainless steel plate mirror-polished with Emery Vapor No. 1000, a stainless steel rod with a diameter of 5 ff was crimped from the soil, and after being left in the air for 1 hour, VC24 in 37C water was applied. After being immersed for a period of time, the tensile strength in the cell was measured and found to be 300 #/cd.

Example? .

To too parts of polymethyl methacrylate powder, 15 parts by weight of permaleic acid mono-shiguchi/L was added and mixed until homogeneous, and 1 part was added, and p-) Luens was added to 100 parts of polymethyl methacrylate powder. Add 2 parts by weight of sodium μ finate and mix to make it homogeneous, then weigh 1 part.
A paste composition prepared by mixing and suspending 4 parts of methyl methacrylate containing 4-acryloethyl trimellitic acid and 5% methyl methacrylate was polished with φ600 emery paper, and the horizontal surface of the enamel of a natural tooth was polished with a 40% aqueous phosphoric acid solution for 30 minutes. It was treated for seconds, washed with water, dried, and applied to the surface to be adhered. An acrylic resin rod was crimped onto it, and the tensile strength was measured under the conditions described in Example 2 and found to be 200 phantom/i.

Example 8 After grinding the dentin of a natural tooth to No. 4600 with emery paper to create a horizontal surface, the paste composition described in Example 1 was applied to the surface of the dentin of the natural tooth, which had been surface-treated by the method described in Example 4. 5 at O diameter Aku IJ from above.
/I/ The rod was crimped, left in the air for 1 hour, and then immersed in 37C water for 24 hours. The tensile strength was measured and found to be 130 to/d.

Example 9゜ First, the following composition was prepared.

Agent D: To 100 parts by weight of polymethyl methacrylate powder, 5 parts by weight of monobutylene permaleate was added and thoroughly mixed to obtain a uniform dispersion.

Agent E: 2 parts by weight of sodium p-toluene μ phinate was added to 100 parts by weight of forimethi μ methacrylate powder and thoroughly mixed to obtain a uniform dispersion.

Next, 1 part by weight of Agent D, 1 part by weight of Agent E, and 4 parts by weight of methyl methacrylate were simultaneously mixed and thoroughly kneaded to obtain a paste composition, which was then mixed with beef surface-treated by the method described in Example 4. Glue the acrylic rod onto the dentin surface and apply 37C
The tensile strength was measured after immersion in water for 24 hours.
It was 0 ko/cd/Example 10°! i! Using the m paraboloid described in Example 2, adhesion to stainless steel was performed in the same manner as in Example 6. 21 Q k
It was o/cd.

Comparative Example 1 9 parts by weight of polymethyl methacrylate powder to which 1 wt % of benzoyl peroxide was added and 2 parts by weight of methyl methacrylate solution to which 1 wt % of diethanol puffed indium was added were mixed and thoroughly kneaded to form a paste composition. The tensile strength was 5 #/d when the adhesive was bonded to an untreated Lt material in the same manner as in Example 3.

Comparative Example 2 When the composition described in Comparative Example 1 was used to bond the stainless steel pieces described in Practical Example 6, the tensile strength was 2.
It was 20ka/c.

Comparative Example 3 The composition described in Himisaki Example 1 was used to adhere to the dentin of a natural tooth in the same manner as in Example 4, and the result was H) #e/d.

Comparative Example 4゜The composition described in Comparative Example 1 was bonded to natural tooth enamel in the same manner as in Example 2, and the result was 110 #/cd.
Met.

Claims (1)

[Claims] 1. In an adhesive composition containing a polymerizable monomer and a curing agent, the curing agent has a general formula ▲a mathematical formula, a chemical formula, a table, etc.▼ (However, in the above formula, R is 1 to 3. An adhesive composition characterized in that it consists of a hemi-perester of a difunctional acid having an alkyl group having 5 carbon atoms and a salt of a sulfinic acid. 2. A low-temperature polymerization method characterized by using a half-percent ester of a bifunctional acid represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and a sulfofinate salt when polymerizing with a polymerizable monomer. .