JPH09263960A - Pretreatment of solid surface and method for adhering solid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain secure adhesive power in the case where a metallic material and rubber as well as the rubber and a synthetic resin by blowing the superheated steam of a specific temp. to the surface of a solid. SOLUTION: The superheated steam of 200 to 500 deg.C is blown to the surface of the solid to be treated. The solid is formed to planar, columnar, tubular, sheet and other shapes. The material of the solid includes metallic materials, synthetic resins, rubber. After the surface of the iron of the solid is treated by the superheated steam of 200 to 400 deg.C, an adhesive is applied thereon to adhere the solid to the rubber. The superheated steam of 200 to 400 deg.C is blown to the solid surface of the vulcanized rubber and thereafter, the adhesive is applied thereon to adhere the rubber to the synthetic resin. As a result, the treatment method by a material which does not pollute the environment and is free from problems in hygiene and safety management is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for pretreatment of a solid surface and a method for adhering a solid.

[0002]

2. Description of the Related Art A cleaning process for a plate made of a metal material is a necessary pre-process before processing such as painting, bonding and plating. This is intended to remove deposits such as fats and oils that are attached to the surface and interfere with the processing. For this treatment, cleaning with an aqueous solution containing an acid or an alkali, a chlorine-based organic solvent and other organic solvents is performed. These cleaning liquids themselves are harmful environmental pollutants, and the cleaning liquid recovered after the cleaning operation further contains substances attached to the solid by the cleaning operation. It is not allowed from the viewpoint of environmental protection that the solution and the solvent, and the solution and the solvent containing the attached substance are leaked to the outside as they are, and a large amount of equipment is required for the waste liquid treatment. The cleaning treatment of the solid surface made of synthetic resin is also a pretreatment performed before the adhesion of the synthetic resin. This is intended to remove dust, oil and fat, mold release agent, etc. adhering to the surface of the plastic. Also in this treatment, treatment with a solvent is performed. The fact that a large amount of equipment is required for the treatment of these solvents is the same as in the case of the pretreatment of a solid made of a metal material. When the solid rubber and the synthetic resin are subjected to the adhesion treatment, the solid vulcanized rubber and the synthetic resin are bonded with an adhesive. In this case,
The strength of a laminated body composed of rubber and a synthetic resin obtained by simply applying an adhesive and adhering a synthetic resin without pretreatment of the solid surface of the vulcanized rubber to be adhered is not sufficient. The reason why sufficient strength cannot be obtained is that a bloom is generated on the surface of the vulcanized rubber, which acts as a substance that interferes with the adhesion between the rubber and the synthetic resin. To remove the bloom, a treatment with a volatile organic solvent such as acetone is usually performed. However, when such an organic solvent is used, it is necessary to prevent the organic solvent from leaking for hygiene and safety management.

[0003]

The object of the present invention is to prevent the pollution of the environment in the pretreatment for the removal of the substances adhering to the solid metal materials, synthetic resins and rubbers prior to the processing. Another object of the present invention is to provide a treatment method using a substance that does not cause a problem in hygiene and safety management, and an adhesion method in which a strong adhesive force can be obtained by performing a pretreatment.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies on this problem, and as a result, completed the present invention.
That is, according to the present invention, there is provided a pretreatment method for a solid surface, which comprises spraying superheated steam at 200 to 500 ° C onto the surface of the solid to be treated.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The solid subject to the pretreatment method of the present invention has various shapes such as plate, column, rod, tube, sheet and film.

Examples of the material forming the solid include metal materials, synthetic resins and rubber. Examples of the metal material include iron, aluminum and copper. Examples of iron include low carbon steel which is an iron alloy, cast iron and other alloys, and stainless steel. Examples of copper include copper and copper alloys such as brass and bronze. Examples of aluminum include aluminum and aluminum alloys. As the synthetic resin, a thermoplastic resin,
Specifically, polyamide resin, ABS resin, acetal resin, methacrylic resin, ethylene / vinyl acetate copolymer,
Examples thereof include fluororesin, polycarbonate, polyester resin, polyolefin resin, polyimide resin, polystyrene, polysulfone, polyphenylene sulfide, and polyhalogenated vinyl resin. Among these, the polyamide resin is most preferable because of its physical properties and wide range of utilization. Examples of the rubber include natural rubber and diene rubber such as styrene / butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, butyl rubber, ethylene / propylene rubber, ethylene / vinyl acetate rubber, chlorosulfonated polyethylene, etc. Synthetic rubbers such as olefin rubber, urethane rubber, fluororubber and silicone rubber can be used. In the case of anti-vibration rubber, JIS / A hardness 4 from the standpoint of anti-vibration property and durability
Natural rubber having a hardness of 0 to 80 Hs, synthetic rubber, or a mixture thereof is used.

Pretreatment of solids made of these materials includes
Superheated steam is used. Superheated steam is generally 200 ° C to
A temperature range of 500 ° C., preferably 230 to 400 ° C., more preferably 250 ° C. to 370 ° C. is used. If the temperature is below this range, the adhering substance cannot be sufficiently removed even if pretreatment is performed, and a satisfactory result cannot be obtained. Further, when the temperature exceeds this temperature range, even if pretreatment is performed, there is no particular change as compared with those within this temperature range, and it is not efficient. Superheated steam is generally used open to the atmosphere, and the treatment time differs depending on the type and amount of the substance attached to the solid, the volume and surface area of the solid to be treated, but it is generally a solid made of a metallic material. In the case of, it is 3 minutes to 20 minutes, preferably 7 minutes to 15 minutes. In the case of rubber surface treatment, 2 seconds to 30 seconds, preferably 7 seconds to 15 seconds
Seconds. When a solid surface is treated with superheated steam, not only substances adhering to the surface are removed but also physical or chemical changes may occur on the surface. Such a change may act effectively in the processing step after the pretreatment step.

This superheated steam was produced in a boiler.
It can be produced by heating water vapor at 0 ° C. or higher by a heating means. As the processing apparatus using superheated steam, a processing apparatus in the form of a container that can be sealed, a processing apparatus having means for moving in a suspended state in a tunnel-shaped processing space, or moving by a belt conveyor and the like are used. The solid to be treated is installed and fixed in these treatment devices, superheated steam is supplied, and the entire surface of the solid is uniformly encased by the superheated steam so that the superheated steam keeps sufficient contact with the solid surface. It is necessary. The superheated steam used for the treatment is discharged from these treatment devices. The discharged superheated steam contains substances attached to the surface of the solid. The discharged superheated steam can be circulated for use after being cooled by a cooling device or the like and then having impurities and the like removed by an appropriate separation means such as static separation. The solid thus treated is subsequently sent to a processing step for further processing.

When the rubber is bonded to the solid iron, the rubber is bonded immediately after the pretreatment with the superheated steam.
To perform the adhesion, an adhesive is applied to the solid surfaces to be adhered, rubber is laminated, and pressure is applied to adhere. The bonding step can be performed as follows. Immediately after treating the solid iron surface with superheated steam, a vulcanizing agent is uniformly applied to the iron surface, placed in a mold, unvulcanized rubber is injected, and injection molding is performed. In the production of anti-vibration rubber, after treating the surface of solid iron with superheated steam, blasting treatment was performed, chemical conversion film forming treatment was applied, vulcanizing adhesive was applied to the surface, and it was placed in the mold After that, it is extremely effective to inject unvulcanized rubber, perform injection molding, and perform vulcanization adhesion.

When the solid vulcanized rubber and the synthetic resin are adhered, the surface of the solid rubber to be adhered is treated with superheated steam, the adhesive is applied, and then the synthetic resin is laminated.
Adhesion is performed while maintaining the pressure. A thermoplastic resin can be used as the synthetic resin. Specifically, polyamide resin, ABS resin, polyacetal resin, methacrylic resin, ethylene / vinyl acetate copolymer, fluororesin, polycarbonate resin, polyester resin, polyolefin resin, polystyrene resin, polyvinyl halide resin, polyimide resin, etc. Can be used. Adhesion is usually required to be performed under the condition of 90 to 150 ° C. The time required for adhesion is about 10 to 90 minutes. Usually, 20 to 40 under the temperature condition of 110 to 130 ° C.
Process for minutes. This is to activate the vulcanized rubber adhesive layer. The bonding can be performed by integral molding by injection molding. In this method, after the surface of the solid vulcanized rubber to be bonded is treated with superheated steam, an adhesive is applied, fixed in the mold, and brought into contact with the molten synthetic resin supplied into the mold. The vulcanized rubber and the synthetic resin are bonded by injection molding. This method is extremely effective especially for manufacturing plastic rods with rubber bushes for automobiles, resin brackets with rubber bushes for automobiles, and the like.
As the adhesive, a vulcanized adhesive containing a mixture of a resol type phenol resin and an aldehyde modified product of polyvinyl alcohol as a main component can be used. The resol type phenol resin is obtained by reacting formaldehyde and phenols in the presence of an alkali catalyst. Examples of phenols include phenol and its derivatives such as xylenol and resorcinol. As the resole-type phenol resin, a resole-type phenol-resorcinol resin which is a co-condensation product of a mixture of phenol and resorcinol and formaldehyde is particularly preferable. The mixing ratio of phenol and resorcinol in this resole-type phenol / resorcinol resin is 75:25 to 95: 5, particularly 85:15 to 95: 5 in terms of molar ratio.
It is preferred that The aldehyde modified product of polyvinyl alcohol is obtained by reacting polyvinyl alcohol with an aldehyde compound. In particular,
Examples thereof include polyvinyl formal resin, polyvinyl acetal resin, and polyvinyl butyral resin, and among these, polyvinyl butyral resin is particularly preferable. The weight ratio of the resol-type phenol resin to the aldehyde-modified product of polyvinyl alcohol is preferably 75:25 to 99: 1, and more preferably 85:15 to 97: 3. When the chlorination treatment and the adhesion are performed at the same time, a vulcanization adhesive containing chlorosulfonated polyethylene as a main component can be used. The laminated body made of vulcanized rubber and synthetic resin obtained by adhering can further increase the adhesive strength at the bonding interface when the obtained laminated body is immediately subjected to heat treatment. In this case, 90-140 ℃ in the oven
It is preferable that the treatment is performed for about 30 to 120 minutes. In addition to the rubber component, fillers such as carbon black, silica, calcium carbonate and mica, softening agents, antioxidants, vulcanization accelerators, cross-linking agents and other various additives are added to the solid made of vulcanized rubber. Used in the state.

[0011]

Examples of the present invention will be described below. The test for confirming the effect of the present invention is as follows. 1. Test for confirmation of removal of substances adhering to the surface of solid metal material After immersing the solid metal material in the rust preventive agent and taking it out, the rust preventive agent is adhered to the surface in an averaged state, In the process of removing the rust preventive agent, the surface is treated with superheated steam and the weight is measured. Next, washing with chloroform is performed, and the weight after washing is measured. The state of removal of the rust preventive agent is judged from the weight difference before and after the washing with chloroform. As a comparative example, without treating superheated steam,
The weight before and after the treatment with the conventionally used chloroform solution is measured. By comparing these results, the removal state of the substance adhering to the surface of the solid metal material is judged. 2. Test for determining the adhesion state of solid iron and rubber The adhesion state of solid iron and rubber is determined by treating the surface of solid iron with superheated steam and then vulcanizing and adhering the rubber And the result of adhesion peel test of solid iron. As a comparative example, instead of the treatment with superheated steam, a conventional cleaning agent such as trichlene is used for cleaning, and the other is treated under the same conditions to obtain an adhesion peeling test of a laminate of iron and rubber. To do. The adhesion state is determined by comparing these results. Adhesive peel test
According to the method of JIS K6301. The peeled state is the ratio of the broken area of the rubber portion to the adhesive area, and is judged by comparing each based on the number displayed in%. 3. Test for determining the adhesion state of solid rubber and synthetic resin To determine the adhesion state of solid rubber and synthetic resin, treat the surface of the solid rubber to be adhered with superheated steam, then apply an adhesive, It is determined based on the result of an adhesion peeling test of a laminated body of rubber and synthetic resin obtained by fixing in a mold, injecting molten synthetic resin and injection molding. As a comparative example, instead of the treatment with superheated steam, the one to which the surface of the solid rubber to be adhered was treated by acetone wiping and the untreated one were used, except that the treatment with acetone wiping or untreated was used. Then, the adhesion and peeling test is performed on the laminated body of the rubber and the synthetic resin obtained by treating under the same conditions. The adhesion state is determined by comparing these results. The adhesive peeling test is based on the method of JIS K6301. The peeled state is the ratio of the broken area of the rubber portion to the adhesive area, and is judged by comparing each based on the number displayed in%.

Examples 1 to 4 and Comparative Example 1 Metal fitting (JIS K6301) (material SPHC, weight 2)
6.4g, thickness 2.54mm, surface area 30.6cm ² )
A rust preventive (Preton R manufactured by Sugimura Chemical Co., Ltd.)
308), the metal fitting was pulled up, and the rust preventive agent was evenly adhered thereto, followed by drying at room temperature for 48 hours and then spraying superheated steam. After the treatment, the weight was measured, immediately washed with a chloroform solution, dried, and the weight of the metal fitting was measured again. In addition, as a comparative example, the same type of metal fitting is dipped in a rust preventive agent, the metal fitting is pulled up and the rust preventive agent is evenly attached, the weight is measured, and then the product is washed with a chloroform solution and dried. Then, the weight was measured again. The results are summarized in Table 1.

[0013]

[Table 1]

From the above results, the following facts can be seen. Treatment with superheated steam at 300 ℃ for 10 minutes and 350 ℃
In the case of 10 minutes treatment with superheated steam, the weight difference before and after washing with chloroform is in a negligible range,
By treatment with superheated steam before washing the chloroform,
It can be judged that the degreasing was completely performed. Therefore,
It can be seen that the treatment with superheated steam of the present invention can achieve removal equal to or higher than the conventional cleaning treatment method using a detergent such as chloroform.

Examples 5 to 8 and Comparative Example 2 Model type test pieces (material SPHC, weight 90.8)
g, thickness 2.80 mm, surface area 80.8 cm ² ), rust preventive agent (Sugimura Industry Co., Ltd., Plenton R308)
It was dipped in the inside, the metal fitting was pulled up, and the rust preventive agent was made to adhere uniformly, and after drying at room temperature for 48 hours, superheated steam was sprayed on. After the completion of the treatment, the weight was measured, and immediately after washing with a chloroform solution and drying, the weight of the metal fitting was measured. Comparative Example 2 was treated in the same manner as Comparative Example 1. The results are shown in Table 2 as Examples 5 to 8 and Comparative Example 2.

[0016]

[Table 2]

From the above results, the following can be seen. According to the method of the present invention, it can be seen that the deposits can be sufficiently removed as compared with the conventional cleaning method using the cleaning agent. In particular, the result shows that the deposit was completely removed when the treatment was performed at 300 ° C. for 10 minutes.

Examples 9 to 12 and Comparative Example 3 Metal plate (JIS6301) (Material SPHCP, weight 2)
6.4g, thickness 2.54mm, surface area 30.6cm ² )
Is immersed in rust preventive agent, pulled up, treated with superheated steam, coated with vulcanizing adhesive (LORD CORP Chemlock 205/220), placed in a mold, and unvulcanized rubber is injected. Then, vulcanization adhesion was performed at a temperature of 165 ° C. for 15 minutes. The rubber composition is shown in Table 3.

[0019]

[Table 3]

The conditions for the peeling test of the obtained metal plate-rubber bonded body are as follows: peeling angle 45 °, peeling speed 50 mm / min.
I went in. In the comparative example, trichlene washing was performed instead of the treatment with superheated steam to degrease, and the subsequent adhesion was performed under the same conditions as in the examples. A peeling test was performed on the obtained metal plate-rubber bonded body under the same conditions. The results obtained are summarized in Table 4.

[0021]

[Table 4]

From the above results, the following can be understood. Compared to trichlene cleaning, treatment with superheated steam is 3
Greater adhesive strength was obtained at 50 ° C. or higher.

Examples 13 to 20 and Comparative Examples 4 and 5 In Examples 13 to 16, as in Examples 9 to 12, model type test pieces (material SPHCP, weight 90.8) were used.
g, thickness 2.80 mm, surface area 40.4 cm ² ) was treated with superheated steam, vulcanized adhesive was applied, placed in a mold, and unvulcanized rubber was injected, as in Examples 9-12. A laminate composed of rubber and a metal material was obtained by vulcanization adhesion. Example 1
In Nos. 7 to 20, after treatment with superheated steam, shot treatment was further performed to form a zinc phosphate film, and then a metal plate and rubber were adhered. Then, the breaking load of the obtained test body was examined by performing a breaking test. In the comparative example, instead of the treatment with superheated steam, trichlene degreasing and alkali degreasing were performed, and a destructive test was performed in the same manner as the test body subjected to the superheated steam treatment to examine the destructive load. A model type test piece was used as the test piece, and the breaking conditions were a breaking angle of 180 degrees and a breaking speed of 200 mm / min. Table 5 summarizes these results.

[0024]

[Table 5] (R in the broken state is the ratio of the broken area of the rubber part to the bonded area, and is expressed in%.)

From these results, the following facts can be seen. When the metal fitting is blasted and the chemical conversion film is formed by the superheated steam treatment, the breaking load is relatively increased due to the rise in the temperature of the superheated steam, and the superheated steam treatment condition is 300.
At a temperature of ° C, the adhesion performance is further improved as compared with the alkali treatment and the treatment with trichlene.

Examples 21 to 32, Comparative Examples 6 to 9 Rubber test pieces (weight: 23.5 g, thickness: 5.37 m)
m, width 25.40 mm, length 127 mm), a part of the surface is treated with superheated steam, coated with a vulcanizing adhesive, placed in a mold, and a resin (polyamide resin, Mitsubishi Engineering Plastics Co., Ltd.) MXD) was injection-molded to produce a composite of rubber and synthetic resin. A peel test was performed to determine the adhesion state. As a comparative example, instead of the superheated steam treatment, the rubber adhesion surface was cleaned with acetone and molded with a 60T injection molding machine to produce a composite of rubber and synthetic resin. As test conditions, peeling speed 50 mm / m
The test was carried out under a peeling angle of 45 degrees. Example 2
Nos. 1 to 26 are cases where Chemlock 252 was used as an adhesive. In Examples 27 to 32, Chemloch 7701 was used as the surface modifier and Chemloch LJ200 was used as the adhesive.
This is the case where is used. The composition of the rubber is shown in Table 6. The results are summarized in Tables 7 and 8.

[0027]

[Table 6]

[0028]

[Table 7]

[0029]

[Table 8] From this result, it can be seen that when the adhesive surface is treated with superheated steam, the adhesive strength is higher than that when the adhesive surface is cleaned with conventional acetone.

[0030]

According to the method of the present invention, with respect to the pretreatment of solids, it is possible to treat with superheated steam that does not pollute the environment, and by performing this pretreatment, solid metal materials and rubbers can be treated. In the case of adhering and the case of adhering solid rubber and synthetic resin, it is possible to obtain stronger adhesive force than before.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C23G 1/00 C23G 1/00 // B29K 21:00

Claims (7)

[Claims] 1. A method for pretreatment of a solid surface, which comprises spraying superheated steam at 200 to 500 ° C. on the surface of the solid. 2. The method of claim 1, wherein the solid is made of a metallic material. 3. The method of claim 1, wherein the solid is rubber. 4. The method for pretreatment of a solid surface according to claim 1, wherein the solid is made of synthetic resin. 5. A method for adhering solid iron and rubber, which comprises treating the surface of solid iron with superheated steam at 200 to 400 ° C. and then applying an adhesive to adhere it to rubber. 6. A solid iron, characterized in that the surface of solid iron is treated with superheated steam at 200 to 400 ° C., a chemical conversion film is formed on the surface, an adhesive is applied, and the iron is adhered to rubber. How to glue rubber. 7. A solid surface made of vulcanized rubber having a surface area of 200 to 4
After spraying superheated steam of 00 ℃, apply the adhesive,
A method for adhering solid rubber and synthetic resin, which comprises adhering to a synthetic resin.