JPH0222364A - Surface-treatment agent for hard tissue of human body - Google Patents

Abstract

PURPOSE:To provide the subject surface-treatment agent containing a specific methacrylate derivative and a hydroxyalkyl methacrylate and having excellent adhesive strength between the dentin of tooth and a filled composite resin. CONSTITUTION:The objective surface-treatment agent giving sufficient adhesive strength and applicable to clinical use without necessitating complicate operations is produced by adding (A) 1-10 pts.wt of a hydroxyalkyl methacrylate (e.g., 2-hydroxyethyl methacrylate) to (B) 1 pt.wt. of a methacrylate derivative having methacryloyl group on at least one molecular terminal and having amino group and/or amide group on the other molecular terminal {e.g., the compound of formula [X is CH2, C2H4, O, N or S; m is 0 or >=1; Y is -CH2CH(NH2) CONH2, -(CH2)nCONH2 or -(CO2)nNH2]}. The agent may be used as the 1st liquid in combination with the 2nd liquid comprising a liquid containing an aldehyde.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a surface treatment agent for human body hard tissues, and more specifically, a surface treatment agent used for treating human body hard tissues such as bones and teeth. The present invention relates to a surface treatment agent for bonding a composite resin for the treatment of dental caries to the dentin of a tooth.

[Prior art] In recent years, composite resins with excellent mechanical properties and aesthetic properties have been used to replace conventional dental cements such as zinc phosphate cement and silicate cement for the treatment of teeth affected by dental caries. It is being used.

However, if composite resin has poor adhesion to the tooth structure and is left in place for a long period of time, a gap may form between the composite resin and the tooth structure, causing secondary dental caries. may peel off.

In order to improve the adhesion between such a composite resin and the tooth structure, the tooth structure is usually etched with an acid such as phosphoric acid or citric acid or a chelating agent such as EDTA.
Next, an adhesion method is used in which a bonding agent is applied and a composite resin is filled. The bonding agent used here is one in which adhesive monomers such as phosphoric acid methacrylate and carboxylic acid methacrylate are added to monomers with low viscosity such as triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate, and a diluent such as ethanol. It is.

Furthermore, various adhesive monomers have been developed and applied to bonding agents in order to improve the adhesiveness between the composite resin and the tooth structure.

[Problems to be Solved by the Invention] 7. However, conventional bonding using phosphoric acid etching treatment and bonding agent application cannot firmly bond tooth enamel and composite resin to a considerable extent. However, it has not yet been possible to obtain satisfactory adhesion to the dentin of the tooth.

In contrast to this, it has been proposed and practiced to treat the dentin surface with an aqueous solution consisting of glutaraldehyde and 2-hydroxyethyl methacrylate. However, even with this treatment, the composite resin and dentin are sufficiently cannot be bonded with sufficient adhesive strength.

This invention was made based on the above-mentioned background, and its purpose is to provide a surface treatment agent that greatly improves the adhesive strength between composite resin and hard tissues of the human body such as bones and teeth, especially dentin. It is to provide.

[Means for solving the problem] As a result of various tests and research conducted by the wood inventors to solve the above-mentioned problem, they found that in order to firmly bond the composite resin to the tooth structure, especially the dentin, etching is necessary. We have found that treatment and application of a bonding agent alone are not sufficient, and that treating the tooth surface with a specific methacrylate derivative before applying the bonding agent is effective in achieving the objective of the present invention,
This invention was completed.

That is, the surface treatment agent for human hard tissue of the present invention comprises a methacrylate derivative having a methacryloyl group at at least one molecular end and an amino group and/or an amide group at the other molecular end, and 2-hydroxyethyl methacrylate, etc. hydroxyalkyl methacrylate, and may further contain an aldehyde.

In one aspect of the present invention, the surface treatment agent for hard tissue of the human body can be made of a first liquid containing the methacrylate derivative and hydroxyalkyl methacrylate, and a second liquid containing an aldehyde.

This invention will be explained in more detail below.

The methacrylate derivative, which is a component of the surface treatment agent for human hard tissue according to the present invention, has a methacryloyl group at at least one molecular end, and an amino group and/or an amino group at the other molecular end. Or it has an amide group. Specifically, for example, it is a compound represented by the following structural formula 1 or II.

(In the formula, X represents CH2, C2H4, O, N, or S, m and m' are integers of 0 or 1 or more, and Y represents the following structure A, H, or H, -CH2CH(NH2) CONH2...I (CH2>
n CON H2・uta (CH2>n NH2”・hancio or an integer of 1 or more) In this invention, a typical compound of a methacrylate derivative having an amino group and/or an amide group is 0-
Such as methacryloyltyrosinamide.

Specifically, the hydroxyalkyl methacrylate, which is the second component of the surface treatment agent for human hard tissue according to the present invention, is, for example, 2-hydroxymethyl methacrylate, 2-
Examples include hydroxyethyl methacrylate and hydroxypropyl methacrylate. Among these, preferred hydroxyalkyl methacrylates include 2-hydroxyethyl methacrylate.

Aldehyde Aldehyde, which is the third component of the surface treatment agent for human hard tissue according to the present invention, is an optional component in the present invention,
It can be used as needed.

Here, as the aldehyde, for example, formaldehyde,
Examples include glutaraldehyde, phthalaldehyde, glyceraldehyde, metafluroxybenzaldehyde having a methacryl group, and metafluroxyphthalaldehyde.

Among these, preferred aldehydes include glutaraldehyde and phthalaldehyde.

In addition to the three components mentioned above, the surface treatment agent for hard tissue of the human body of the present invention can contain various additives and solvents depending on the purpose.

■■I table 几.

The surface treatment agent for human body hard tissues of the present invention includes a methacrylate derivative having a methacryloyl group at at least one molecular end and an amino group and/or an amide group at the other molecular end, and a hydroxyalkyl methacrylate, and further comprises: In addition to these components, aldehydes can be included.

The components of the surface treatment agent for human hard tissues of the present invention can be used as a mixed liquid as is, as a solution by dissolving in a solvent such as water or alcohol, or as a paste.

In the embodiment containing an aldehyde, considering the reactivity of the constituent components, the first solution containing the methacrylate derivative and hydroxyalkyl methacrylate and the second solution containing the aldehyde are stored separately as two separate solutions. The two liquids can be mixed immediately before use.

The mixing ratio of each component is selected and changed as appropriate depending on the type of component, the type of combo resin, the use, etc., but for example, hydroxyalkyl methacrylate is 0.5 to 30 parts by weight per 1 part by weight of methacrylate derivative. It can be used by adding 1 to 10 parts by weight, preferably 1 to 10 parts by weight.

In an embodiment in which the solution is divided into two liquids, the first liquid is a solution consisting of 0.1 to 20% of the methacrylate derivative and 1 to 99% of hydroxyalkyl methacrylate, and the second liquid is a solution containing 0.1 to 20% of aldehyde. It can be made into a solution.

Method of Use Next, a method of using the surface treatment agent for hard tissue of the human body of the present invention will be explained.

Usually, after etching the dentin with phosphoric acid, citric acid or ED 'T' A, the surface treatment agent of this invention is applied, the excess agent is removed with compressed air, and then a conventional bonding agent is applied. Finally, fill with composite resin and glue.

The surface treatment agent for human hard tissue of the present invention can be used to firmly bond filling materials such as composite resin, posts and bottles used in crown restoration to dentin, and can also be used to firmly bond dentin to enamel. The surface treatment agent for human hard tissues of the present invention can be used for enamel since the adhesive strength does not decrease even when it comes to enamel.

[Function] In the surface treatment agent for human hard tissues of the present invention having the above configuration, although it is not necessarily theoretically clear, the methacrylate derivative of the surface treatment agent component has an amino group and/or an amide group at the molecular end. This functional group reacts and bonds with phosphoric acid, citric acid, or EDTA on the etched surface, and the methacryloyl group at the other end of the molecule is oriented on the surface.

Since this methacryloyl group is polymerizable with vinyl monomers, etc., it facilitates bonding of the tooth surface with a polymerizable bonding agent, and the surface treatment agent for human hard tissues of the present invention functions as a primer.

The above description is provided to facilitate understanding of the invention and is not intended to limit the scope of the invention.

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Two liquids A and B having the following compositions were prepared as surface treatment agents.

Jinjo 2-hydroxyethyl methacrylate...70% 0-methacrylic convex yltyronamide...6% water
... Remaining liquid glutaraldehyde ... 2% water
... As a substitute for residual dentures, we used fresh teeth that were frozen immediately after tooth extraction and thawed immediately before use.

The dentin of the raw tooth enamel was etched with 40% phosphoric acid, and after washing and drying, a mixture of equal amounts of liquids A and B was applied to the tooth surface. Next, the inner diameter is 3.2 mm, and the height is 2.0 mm +
Temporarily attach the mold to the tooth surface, apply a bonding agent (Clear Fill New Bond, manufactured by Kuraray Co., Ltd.) inside this mold, and then apply composite resin (Clear Fill F [,
(manufactured by Kuraray).

After curing, remove the mold and store it in water at 37°C for one day. As a result of measuring the adhesive strength with an Instron type universal testing machine, it showed a value of 25 to 30 MPa for enamel and 16 to 20 MPa for dentin.

Adhesive strength without surface treatment agent is only 2
MPa or less, and has a methacryloyl group at the molecular end,
Since the adhesive strength is 5 MPa or less when a surface treatment agent that does not contain a methacrylate derivative having an amino group and/or an amide group is applied, the adhesive strength is greatly improved by applying the surface treatment agent of the present invention. I know what you did.

Implementation failure Liquid C having the following composition was prepared as a surface treatment agent.

Ω丞2-Hydroxyethyl methacrylate...35% 0-methacryloyltyronamide...3% water
... A cavity with a depth of 2.0 mm and an inner diameter of 3.0 mm is formed in the dentin that has been removed.
．． After etching with 5M EDTA, washing with water, and drying, C.
The solution was applied to the inner surface of the cavity. Next, a bonding agent (Clear Fill New Bond, manufactured by Kuraray Co., Ltd.) was applied, and then Compo Fluor 1 to Resin (Clear Fill F [, manufactured by Kuraray Co., Ltd.) was filled.

As a result of observing the contractile gap using an optical microscope, no contractile gap was observed in 8 of the 10 samples. Moreover, the percentage of the contracsidine gap to the diameter of the cavity was only 0.02% on average.

EXAMPLE 2 Two liquids and E having the following compositions were prepared as surface treatment agents.

2-Hydroxyethyl methacrylate...70% 0-methacryloyltyronamide...4% water
... Remainder two-part phthalaldehyde ... 2% water
... A cavity with a depth of 2 Om and a diameter of 3 □ 5 m is formed on the labial surface of the remaining extracted tooth,
The inner surface of the cavity was etched with 65% phosphoric acid, and after washing with water and drying, an isostatic mixture of solutions D and E was applied to the inner surface of the cavity.

Next, bonding agent (Clear Fill New Bond,
Kuraray Co., Ltd.) and then filled with composite resin (Adatic, Johnson & Johnson Co.).

After being stored in water at 37°C for one day, a percolation test was performed in which the samples were immersed 100 times alternately in 4°C and 60°C aqueous solutions of 1 minute each. Next, the extracted tooth was cut at the center, and it was observed whether there was any dye (tsuksin) infiltrating between the cavity and the filling. As a result, it was observed that there was no infiltration of pigment (tsukushin).

[Effects of the Invention] The present invention having the above configuration and operation has the following effects.

(b) The surface treatment agent for human hard tissue according to claim 1,
As demonstrated in the examples, human hard tissues such as teeth and bones,
In particular, the adhesive strength between the dentin and the composite resin filling, which is a heavy burden, can be greatly improved.

In an embodiment that does not use aldehyde, sufficient adhesive strength is ensured, and there is no need to mix two separate liquids immediately before use, which is a complicated clinical operation.

(b) In the surface treatment agent for human hard tissue according to claim 2,
Since it is mixed with aldehyde, it more reliably adheres to the hard tissue of the human body and the composite range filling, ensuring long-term durability even in humid environments such as in the oral cavity or inside the body.

(c) The surface treatment agent for human hard tissue according to claim 3,
Since it is a two-liquid format, the aldehyde and other components do not react with each other, preventing the surface treatment agent from deteriorating, and is convenient for transportation, storage, etc.

(d) In the surface treatment agent for human hard tissue according to claims 4.5.6.7 and 8, a more limited composition and type are selected, so that it can be applied not only to Shigenobu's dentin but also to enamel. It also shows sufficient adhesive strength. It can be used regardless of the dentin or enamel, even in complex cavities.

Claims (1)

[Claims] 1. having a methacryloyl group at at least one molecular end;
A surface treatment agent for hard tissues of the human body, comprising a methacrylate derivative having an amino group and/or an amide group at the other molecular end, and a hydroxyalkyl methacrylate. 2. The surface treatment agent for human hard tissue according to claim 1, further comprising an aldehyde. 3. The surface treatment agent for human hard tissue according to claim 2, comprising a first liquid containing the methacrylate derivative and hydroxyalkyl methacrylate, and a second liquid containing an aldehyde. 4. Claim 1, 2 or 3, wherein the hydroxyalkyl methacrylate is 2-hydroxyethyl methacrylate.
The surface treatment agent for human hard tissue described above. 5. Any one of claims 1 to 4, wherein the methacrylate derivative is a compound represented by the following structural formula I or II.
A surface treatment agent for human hard tissue as described in . ▲There are mathematical formulas, chemical formulas, tables, etc.▼…I ▲There are mathematical formulas, chemical formulas, tables, etc.▼…II (In the formula, X represents CH2, C2H4, O, N, or S, and m and m' are 0 or 1 or above, Y indicates the following structure a, b, or c, -CH_2CH(NH_2)CONH_2...i-(CH
_2)_nCONH_2...Rho-(CH_2)_nNH_2...Hn is an integer of 0 or 1 or more) 6. The surface treatment agent for human body hard tissue according to claim 1, wherein the methacrylate derivative is o-methacryloyltyrosinamide. 7. The surface treatment agent for human hard tissue according to claim 1, wherein 1 to 10 parts by weight of hydroxyalkyl methacrylate is added to 1 part by weight of the methacrylate derivative. 8. The first liquid contains 0.1 to 20% of the methacrylate derivative and hydroxyalkyl methacrylate 1
~99%, and the second liquid contains 0 aldehyde.
．． The surface treatment agent for human hard tissue according to claim 3, which is a solution containing 1 to 20%.