JP2653667B2 - Pretreatment agent for adhesion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to bonding a metal object, particularly a metal object containing a noble metal element, to another object (including a metal object) prior to bonding. The present invention relates to a pretreatment agent applied to a surface of a metal object.

(Prior art) The technology of firmly bonding organic materials to precious metals such as gold, platinum, palladium, and rhodium or precious metal alloys containing these as main components is used in the dental care, electronics,
Despite demands in a wide range of fields such as arts and crafts, practically satisfactory technologies have not been established.

In an attempt to strengthen the adhesion between precious metals and organic materials, N-
(4-mercaptophenyl) methacrylamide (hereinafter MP
The technique of applying MA to the surface of precious metals as a pretreatment agent is described in Dental Materials and Instruments, Vol. 5, pp. 92-105 (1986).
), There is no durable adhesive that can withstand the harsh environment of the oral cavity.

Recently, 6-702-707 (1987), 6- (N-
4-vinylbenzyl-Nn-propyl) amino-1,3,
It has been reported that 5-triazine-2,4-dithione (hereinafter sometimes abbreviated as VBATDT) is very effective in strengthening the adhesion of precious metal alloys.

(Problems to be Solved by the Invention) In dental care, a cast made of a noble metal alloy is frequently used as one of the materials for prosthesis for missing teeth. However, since there is no organic adhesive exhibiting excellent durability and adhesion to precious metals, it is still difficult to form a composite with a remarkable technologically advanced organic organic material and to bond and fix the cast to teeth. In the situation.

The above-mentioned method of dissolving MPMA or VBATDT in an organic solvent and applying it to a metal surface as a pretreatment agent is a promising technique for bonding between precious metals / organic materials, but it is subject to bonding durability and bonding. There are problems such as limitations on the types of metals that can be used.

Accordingly, an object of the present invention is to create a bonding pretreatment agent superior to MPMA and VBATDT, and to solve the above-mentioned problems.

JP-A-59-142268 discloses an adhesive characterized in that a monomer having a thiophosphate group is used as an adhesive component. 0.33% or more)
Adhesive strength to precious metals is insufficient and cannot be used in dentistry requiring precious metal adhesion.

(Means for Solving the Problems) The present inventors have synthesized sulfur-containing monomers in place of MPMA and VBATDT and studied the adhesive effect thereof. It has been found that the desired effect can be obtained by using the monomer in the concentration range, and the pretreatment agent for adhesion of the present invention has been completed.

That is, the present invention provides a pretreatment agent for adhesion, comprising 0.001 to 0.3 parts by weight of a monomer having a thiophosphate group and 100 parts by weight of a solvent.

The pretreatment agent for bonding referred to in the present invention refers to a metal object, particularly a metal object containing a noble metal element, which is used for bonding an object (including a metal object) to another object (including a metal object) in order to enhance the adhesive force. It is a pretreatment agent applied to the surface of an object.

In the present invention, the thiophosphate group is an atomic group represented by the following formula; [However, Y ₁ represents O, S or NH, and is bonded to a carbon atom, Y ₂ , Y ₃ , Y ₄ represents O or S, and at least one of Y ₂ and Y ₄ Represents S and l is 0
Or 1]. [These definitions are in the Chemical Glossary Dictionary (Gihodo, 19
The thiocarboxylic acid-containing monomer (hereinafter sometimes referred to as S-monomer) is described in JP-A-54-21438, JP-A-59-140276, and Any of the monomers described in JP-A-59-142268 can be used in the present invention. Specific examples thereof include the following compound groups. The compound shown in [] is a tautomer of the compound shown above.

Among the above compounds, a compound represented by the following formula is practically preferable from the viewpoint of storage stability.

(R: H or CH ₃ , m: 1 or 2, n: an integer of 2 to 20, m = 1
X: H or X when m = 2: The most important feature of the present invention is that these S-monomers have a concentration of 0.
The point is that a low concentration solution of 001 to 0.3% by weight is obtained. S-
The solvent for diluting the monomer is not particularly limited, and various organic solvents, water, or a mixture thereof can be used. A particularly preferred solvent is a volatile organic solvent having a boiling point of 150 ° C. or less. For example, methanol, ethanol, acetone, n-butyl acetate, octane,
Examples include benzene, toluene, methyl methacrylate, and styrene. The ratio of the S-monomer in these solvents is, as described above, 0.001 to 0.3% by weight (hereinafter referred to as% by omitting weight), preferably 0.01 to 0.3%. When the concentration is less than 0.001%, it is easily understood that the absolute amount of S-monomer when applied to a metal surface is insufficient and the adhesive effect is poor.
On the other hand, surprisingly, we have found that the amount of S-monomer is
It has been found that a remarkable decrease in the adhesive effect occurs even in a concentration range exceeding 0.3%.

The pretreatment agent for adhesion of the present invention brushes the surface of a metal object,
It is applied using a device or material that can contain and hold the liquid, such as a cotton ball or sponge, or it is applied using a spray. A method of immersing a metal object in the pretreatment agent is also used.

After application, the diluting solvent in the pretreatment agent is dried to leave only a thin S-monomer coating on the metal surface before bonding. A preferred adhesive used in combination with the pretreatment agent of the present invention is an acrylic adhesive, which comprises methacrylate or / and acrylate monomers and a polymerization initiator as essential components. In addition, a polymer such as polymethyl methacrylate or various inorganic fillers may be added to the adhesive.

Specific examples of the (meth) acrylate monomer include:
Methyl methacrylate, 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-META), 10-methacryloyloxydecyl dihydrodiene phosphate, 2-hydroxyethyl methacrylate, triethylene glycol dimethacrylate, 2,2-bis [4- (3
-Methacryloyloxy-2-hydroxypropoxy)
[Phenyl] propane (commonly called Bis-GMA), pentaerythritol tetraacrylate and the like.

Specific examples of the polymerization initiator include benzoyl peroxide (BPO) -N, N-diethanol-p-toluidine (DE
Redox initiators such as PT), alkyl metal compounds such as tributylborane, and photopolymerization initiators such as camphorquinone-N, N-dimethylaminoethyl methacrylate.

The surface of the metal object coated with the pretreatment agent of the present invention is S
-It is bonded to another object via the monomer and the adhesive, but the other object to be bonded is a tooth, a metal, an organic polymer, a ceramic, or the like, and is not particularly limited.

(Effect of the Invention) Although the pretreatment agent of the present invention is effective for base metals,
Particularly effective for precious metals that are considered to be difficult to adhere,
It is suitably used in dental care. For example, when trying to pre-attach a rigid resin or composite resin to a metal frame, when trying to fix and fix an inlay, onlay, crown, bridge, or other prosthesis to a tooth with an acrylic dental adhesive, or split casting When the assembled prosthesis is to be assembled using the dental adhesive,
By applying the pretreatment agent of the present invention to these precious metal alloy prostheses, highly reliable adhesion can be obtained by a simple operation.

The pretreatment agent for bonding of the present invention is applicable not only to the dental field, but also to any industrial field that requires a technique for bonding a metal object to another object.

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

Examples 1 to 4 and Comparative Example 1 After applying the pretreatment agent for adhesion of the present invention to various pure metals and dental alloy blocks, they were adhered with an acrylic adhesive, and the pretreatment was performed by measuring the adhesion strength. The effect was confirmed. The experimental methods and results are described below.

(I) Various metals used as adherends Table 1 shows the types, compositions, and sizes of metals used in the experiments. Each metal piece is made of silicon carbide abrasive paper #
After polishing sequentially in the order of 800, # 1200, and # 1500, polishing was performed with # 2000, then # 4000 of the imperial wrapping film (3M, USA) to which alumina particles were attached, and then the following pretreatment was performed. .

(Ii) Pretreatment 10-methacryloyloxydecyldihydrodienethiophosphate having the following chemical structure (abbreviation: M10PS)
And synthesize it with 0.001, 0.01, 0.1, 0.3, and 1%
(Hereinafter referred to as M10PS-solution).

5 μm of M10PS-solution was applied to the end surface (adhered surface) of a metal piece (cylindrical type), and benzene was air-dried.

(Iii) Bonding method Two metal pieces of the same metal composition (pre-treated) were prepared, and a cellophane tape with a 5 mmφ hole drilled on the surface to which one of the metal pieces was adhered was applied for the purpose of limiting the bonding area. I attached. Then, in this hole, methyl methacrylate / poly (methyl methacrylate) / benzoyl peroxide / N, N-
Excessive paste-like adhesive consisting of diethanol-p-toluidine (50/50 / 0.5 / 0.25) is applied excessively, and another metal piece is pressed against this surface to form a metal / PMMA / metal cycling structure. An adhesion test specimen having the same was prepared. The test specimen was stored in air at 37 ° C. for 1 day, then immersed in water at 37 ° C., stored for 1 day, and then subjected to the following adhesive strength test.

(Iv) Adhesion strength test After repeating the thermal cycling test in which the adhesion test specimen was alternately immersed in water at 4 ° C. and 60 ° C. for 1 minute every 2000 times, the tensile speed was 2 m using Shimadzu Autograph DSS-500.
Tensile tests were performed at m / min. Five specimens for each metal were subjected to the measurement, and the average value was defined as the adhesive strength.

(V) Results Table 2 shows the test results of each metal.

Depending on the type of adherend, the concentration of S-monomer is 0.001.
% Showed sufficient adhesive strength, and 0.01% showed sufficient adhesive strength.

Claims (1)

(57) [Claims] 1. An adhesive pretreatment agent comprising 0.001 to 0.3 parts by weight of a monomer having a thiophosphate group and 100 parts by weight of a solvent.