JP2521994B2 - Pretreatment agent for metal adhesion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a pretreatment agent for metal adhesion, and more specifically, it adheres a metal to an organic polymer material, ceramics, metal or a composite thereof. The present invention relates to a pretreatment agent for metal adhesion, in which the adhesion strength is enhanced, and particularly the adhesion strength does not decrease when the adhesive comes into contact with water.

<Prior Art> Conventionally, various ester compounds have been provided as a pretreatment agent for adhesion used on a metal surface in order to improve adhesion between metal and other materials for industrial, household or medical use. Has been done. For example, Japanese Examined Patent Publication No. 58-17513 discloses 4
Disclosed is an adhesive pretreatment agent for teeth, metal and undercoat of paint, which contains methacryloyloxyethoxycarbonylphthalic acid and / or its acid anhydride, a vinyl compound, a free radical generator and / or a photosensitizer. In addition,
JP-A 60-76580 discloses a pretreatment for adhesion in which a unsaturated carboxylic acid and / or its acid anhydride, an organic silane compound and a (meth) acrylic acid modified product of an epoxy resin are dissolved in a vinyl compound in a specific ratio. Agent is shown.

<Problems to be Solved by the Invention> However, when the metal and the organic polymer material, ceramics, metal or a composite thereof are used, when the above-mentioned conventional adhesive pretreatment agent is used, a dry state or a short term is used. Although the adhesive strength is maintained during immersion in water for a while, there is a drawback that the adhesive strength is drastically reduced when the material is immersed in water for a long period of time or subjected to heat history in water.

<Purpose of the Invention> An object of the present invention is to provide a pretreatment agent for metal adhesion, which does not deteriorate in adhesive force even by immersion in water for a long time or heat history in water.

<Means for Solving Problems> According to the present invention, the general formula (I) There is provided a pretreatment agent for metal adhesion, which comprises an organic thiophosphoric acid compound represented by the formula (n is an integer of 2 to 14 and m is 1 or 2).

 The present invention will be described in more detail below.

In the following general formula (I) used in the present invention, In the formula, n represents an integer of 2 to 14, particularly preferably 4 to 12. At this time, when n is 0 or 1,
It cannot be used because the water resistance decreases, and when n is 15 or more, the solubility in an organic solvent decreases, so that it cannot be used.

Examples of the method for producing the organic thiophosphoric acid compound represented by the general formula (I) used in the present invention include 4-vinylbenzoic acid in the case where n = 10 and m = 1 in the general formula (I). And 1,10-decanediol are refluxed in benzene in the coexistence of a condensing agent such as paratolusulfonic acid and a polymerization inhibitor such as hydroquinone to produce 10- (4-vinylbenzoyloxy) decanol. Then the above
By reacting 10- (4-vinylbenzoyloxy) decanol and phosphorus thiochloride in the presence of a dehydrochlorinating agent such as triethylamine while cooling, and then adding water, 10- (4-vinylbenzoyloxy) decyl is obtained. Examples thereof include a method for obtaining dihydrogen thiophosphate.

In the present invention, the pretreatment agent for metal adhesion containing the organic thiophosphoric acid compound represented by the general formula (I) can be dissolved in an organic solvent and used. Although the organic solvent is not particularly limited, for example, acetone, methyl ethyl ethone, ketones such as methyl isobutyl ketone, ethyl acetate, butyl acetate, methyl benzoate, esters such as methyl propionate, tetrahydrofuran, dioxisan, Ethers such as dimethoxyethane, cellusolves such as methyl cellosolve, ethyl cellosolve and diethylene glycol monomethyl ether, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene,
A halogenated hydrocarbon such as carbon tetrachloride, chloroform and dichloromethane and a compound such as dimethylformaldehyde and dimethylsulfoxide or a mixture of two or more kinds thereof can be preferably used. It can be arbitrarily selected according to the bonding conditions such as the temperature, the shape of the bonded product and the surface condition. The pretreatment agent for metal adhesion containing the organic thiophosphoric acid compound represented by the general formula (I) can be used as a mixture with a polymerizable monomer. The polymerizable monomer is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxydiethyl (meth) acrylate, ethylene glycol di (meth) acrylate, di- or tri- or tetraethylene. Glycol di (meth) acrylate, bisphenol A
Di (meth) acrylate, 2.2′-bis ((meth) acryloyloxyethoxyphenyl) propane, 2 ·
Compounds such as 2′-bis (γ- (meth) acryloyloxy-β-hydroxypropoxyphenyl) propane, N · N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl acetate or the like. A mixture of one or more kinds can be suitably used, and the amount of the polymerizable monomer at that time is arbitrarily selected depending on the bonding conditions such as the temperature during bonding, the shape of the bonded product, and the surface condition. be able to.

When using the pretreatment agent for metal adhesion of the present invention to bond a metal with an organic polymer material, ceramics, metal or a composite thereof through a room temperature curable resin, a thermopolymerizable resin or a photopolymerizable resin In, for example, the pretreatment agent for metal adhesion of the present invention dissolved in the organic solvent is applied to the metal surface,
Leave for a certain time. Then form a coating on the metal surface,
When the resin is washed with the organic solvent and then the room temperature curable resin is used for adhesion, it can be polymerized and cured by a polymerization initiator such as an organic peroxide-amine type, and a thermopolymerizable resin or a photopolymerizable resin. Also in the case of using, it is possible to firmly bond by polymerizing and curing by each treatment method or the like.

<Effects of the Invention> By adhering a metal to an organic polymer compound, ceramics, a metal or a composite thereof by using the pretreatment agent for metal adhesion of the present invention, the adhesive is immersed in water for a long time or in water. The strong adhesive force can be maintained without being affected by the heat history in.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 5 parts by weight of 10- (4-vinylbenzoyloxy) decyldihydrogenthiophosphate having the composition of was dissolved in 95 parts by weight of tetrahydrofuran to prepare a pretreatment agent solution for metal adhesion. Then, on a titanium adherend with a diameter of 5 mm,
The pretreatment agent solution for metal adhesion was applied, and after 1 hour, washed with tetrahydrofuran and dried. On top of this, 99 parts by weight of polymethylmethacrylate and 1 part of benzoyl peroxide
The powder added by weight was moistened with a solution in which 0.5 parts by weight of N, N-diethanol paratoluidine was added to 99.5 parts by weight of methyl methacrylate, and the powder was added. 5m diameter from above
An acrylic rod of m was pressure-welded to remove the protruding resin.

After curing, soak it in water at 37 ℃ for 1 day, and
20 heat cycles of alternating immersion in 60 ° C water for 1 minute each
I gave it 00 times.

The Shimadzu Autograph DSS-500 type was used to measure the bond strength of this test piece at a tensile speed of 2 m / min.

The titanium adherends used in the test were those whose surface was polished with # 800 emery paper and those whose surface had been sandblasted to 50 μm. The test results are shown in Table 1.

Comparative Example 1 A titanium coating was prepared in the same manner as in Example 1 except that 5 parts by weight of 4-methacryloyloxyethoxycarbonylphthalic anhydride was dissolved in 95 parts by weight of tetrahydrofuran as the pretreatment composition for metal adhesion. The adhesive strength between the adhered body and the acrylic rod was measured.

The titanium adherend used had its surface polished with # 800 emery paper.

 The test results are shown in Table 1 together with Example 1.

Example 2 5 parts by weight of 10- (4-vinylbenzoyloxy) decyldihydrogen thiophosphate was dissolved in 95 parts by weight each of tetrahydrofuran and benzene to prepare a pretreatment agent for metal adhesion. Next, the adhesion surface of the 5 mm diameter titanium, cobalt, cobalt-chromium alloy, nickel-chromium alloy and stainless steel (SUS-304) adherend
After polishing with 4000 alumina polishing sheets, the respective pretreatment solutions for metal adhesion were applied, left for 1 hour, and washed with tetrahydrofuran and benzene. This adherend is made into a set of two for each material, and an adhesive tape having a hole with a diameter of 5 mm is attached to one of the adherends, and in the hole portion, the same method as in Example 1 is applied. Powdered with 99 parts by weight of polymethylmethacrylate and 1 part by weight of benzoyl peroxide, and wetted with a solution of 99.5 parts by weight of metal methacrylate and 0.5 parts by weight of N, N-diethanolparatoluidine. One adherend was pressed.

After curing, soak this in water at 37 ℃ for 1 day, then at 4 ℃
Heat cycle by alternately immersing in water of 60 ℃ for 1 minute and 2000
Gave twice.

The adhesive strength of this sample was measured in the same manner as in Example 1. The results are shown in Table 2.

Claims (1)

(57) [Claims] 1. A general formula (I) (In the formula, n is an integer of 2 to 14 and m is 1 or 2.) A pretreatment agent for metal adhesion comprising an organic thiophosphoric acid compound represented by the formula: