JPH09314751A - Manufacture of composite laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a composite laminate having good adhesion between rubber and metal or between rubber and synthetic resin and good breaking properties to be applicable to vibrationproofing rubber without requiring a special mold, in a short time, and with good productivity. SOLUTION: In a method for manufacturing a composite laminate in which rubber and metal or synthetic resin are laminated, the surface of the rubber is irradiated with ultraviolet rays of not exceeding 21,000Å wavelength, and the treated surface of the rubber is bonded to an adjacent material such as metal with at least one kind of adhesive selected from a group consisting of urethane type and epoxy type adhesives. The luminous energy of the ultraviolet rays is preferably in a range of 50-50,000mJ/cm<2> for wavelength of 2537Å.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a composite laminate of a rubber material and a metal or synthetic resin material.

[0002]

2. Description of the Related Art Conventionally, a composite laminate in which a soft material such as rubber and a dissimilar material such as a metal or a resin holding member are laminated has been used for various purposes. Widely used for seismic isolation structures.

These are generally manufactured by a method in which an unvulcanized rubber material and a metal or synthetic resin material are laminated, and then the rubber material is vulcanized and adhered to each other. It included various problems such as uniform equipment and vulcanization process.

Therefore, instead of laminating each material of the composite laminate as described above and then vulcanizing and adhering the rubber material,
A method of bonding a preformed rubber plate such as vulcanized rubber and a hard plate made of metal or the like with an adhesive has been attempted,
At present, due to problems such as compatibility between rubber materials and hard plates and adhesives, and durability of adhesive strength, they have not been widely used.

In order to improve the adhesiveness between this rubber material and a dissimilar material such as a metal or a synthetic resin material (hereinafter appropriately referred to as a hard material), it is attempted to perform an adhesion improving treatment on the surface of the rubber material. For example, degreasing treatment to remove the adhesion inhibitor on the surface of the rubber material, buffing treatment to remove the adhesion inhibitor and roughen the surface, apply chlorine-based substance dissolved in solvent to the surface As a typical example, a chlorination treatment for changing the surface properties is mentioned. Among them, the chlorination treatment is widely used from the viewpoint of adhesive strength and durability.

This chlorination treatment is generally carried out by applying an organic compound capable of giving chlorine to the rubber material to the surface of the rubber material molded body. The organic solvent used is diffused into the atmosphere,
There is a problem that a large amount of equipment is required to prevent the contamination of workers and the occurrence of fire due to the organic solvent, and the equipment cost increases.

Further, this chlorination treatment affects the rubber material itself and becomes a starting point of crack generation when a shearing force is applied to the rubber material, or when the rubber material is bonded to a metal material, the treatment is performed. The liquid comes into contact with the metal material, and rust is generated in that portion, which may significantly reduce the commercial value.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and a composite laminate having excellent adhesiveness between a rubber material and a hard material such as metal, particularly,
A composite laminate with excellent breaking properties used for seismic isolation rubber,
A method for manufacturing with high safety and high productivity without requiring excessive equipment, and for manufacturing various shapes and sizes of the composite laminate in a short time without manufacturing a special mold. It is intended to provide a method.

[0009]

The method for producing a composite laminate of the present invention is a method for producing a composite laminate in which a rubber material and a metal or a synthetic resin material are laminated, and the surface of the rubber material is 2100 Å or less. UV irradiation treatment of the wavelength of, and bonding the treated surface of the rubber material and the adjacent metal or synthetic resin material with at least one adhesive selected from the group consisting of urethane-based and epoxy-based adhesives. Is characterized by.

The method for producing a composite laminate according to a second aspect of the present invention is a method for producing a composite laminate in which a rubber plate made of a rubber material and a hard plate made of a metal having rigidity or a synthetic resin material are laminated. 2100 on the surface of the rubber plate
Å Applying a UV irradiation treatment of the following wavelength and bonding the treated surface of the rubber plate and the adjacent hard plate with at least one adhesive selected from the group consisting of urethane-based and epoxy-based adhesives. Characterize.

In the above-mentioned manufacturing method, the soft material having viscoelastic properties is a pre-vulcanized rubber material, preferably natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, or ethylene propylene rubber. It is at least one selected from the group consisting of

Further, the UV treatment with a wavelength of 2100 Å or less irradiates the surface of the rubber material with UV rays to cause a chemical change, and a functional group having an affinity with the adhesive is generated on the surface of the rubber material. It is characterized in that it is a process to be performed.

In the method for producing the composite laminate of the present invention, after the surface of the rubber material is irradiated with ultraviolet rays of a specific wavelength, it is bonded to the hard material with a specific adhesive. A functional group with good affinity with is generated,
A rubber material and a hard material can be uniformly and firmly adhered by using the specific publicly known adhesive. This effect is not clear, but by irradiating the surface of the rubber material with ultraviolet rays, the molecular bonds on the surface of the rubber material are broken, oxygen in the atmosphere is bonded to this, and via the peroxide structure, It is presumed that a functional group such as a carbonyl group, a carboxyl group, and a hydroxyl group is generated on the surface, the surface polarity increases, and good adhesiveness is obtained. Therefore, unlike the conventional manufacturing method, a special mold or a large-scale manufacturing facility is not required, and a composite laminate excellent in adhesiveness between different materials and excellent in breakage property can be manufactured in a short time and safely. be able to.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing the composite laminate of the present invention will be described in detail.

The rubber material constituting the composite laminate is an organic material such as thermoplastic rubber, urethane rubber, various vulcanized rubbers, slightly crosslinked rubbers, elastomers and plastics, foams thereof, and mixtures thereof. Although various materials such as materials can be used, particularly, conventionally, unless using vulcanization adhesion after lamination, it was difficult to obtain good adhesive properties with a hard material, a pre-vulcanized rubber material, for example, The effect of the present invention is remarkable when at least one selected from the group consisting of pre-vulcanized natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, chloroprene rubber, and ethylene-propylene rubber is used.

As a method for manufacturing the rubber plate constituting the laminated body, a known manufacturing method can be applied. That is, in the case of a rubber material, a manufacturing method by mold vulcanization by step pressing, a manufacturing method in which a rubber sheet is manufactured by press vulcanization, rotocure, etc., and punched into a predetermined shape, etc., and other viscoelastic properties Also in the case of a material having, a general-purpose molding, punching after processing into a sheet, and the like can be applied.

As the hard material composing the composite laminate, various materials having required rigidity such as metal, plastics, FRP, and polyurethane can be cited. Here, the required rigidity largely depends on design conditions, but means rigidity that does not easily cause a buckling phenomenon when subjected to shear deformation. Generally, from the viewpoint of strength and durability, steel plate,
Flat plates made of metal materials such as iron plates and aluminum plates are widely used. (Hereinafter, a flat plate made of a hard material is simply referred to as a hard plate.) The thickness and shape of the hard plate are not particularly limited and can be selected according to the purpose for which the composite laminate is used, but the thickness is generally , Having a thickness of about 0.5 to 5 mm is used.

In the bonding step, first, in order to improve the adhesiveness of the surface of the rubber material, the soft plate surface is subjected to ultraviolet irradiation treatment.

The ultraviolet irradiation treatment is carried out in order to modify the surface of the rubber material, and the irradiated light is absorbed by the constituent molecules of the rubber material, and the absorbed energy has a size capable of breaking a chemical bond. is necessary. Therefore, it is preferable to use a region having a short wavelength (that is, a large amount of energy). In that sense, ultraviolet rays, X-rays, γ-rays and the like can be used, but from the viewpoint of safety and facility cost, ultraviolet rays are used. To be adopted.

The ultraviolet rays used for modifying the rubber material are required to have a short wavelength light in the deep ultraviolet region, that is, a wavelength of 2100 Å or less, that is, 1700 to 2100 Å, and further 1
It is preferable to use ultraviolet rays having a wavelength of about 700 to 1900Å as a main working wavelength. Irradiation with such ultraviolet rays causes a chemical change to generate functional groups having an affinity for the adhesive such as carbonyl group, carboxyl group and hydroxyl group on the surface of the soft plate material. the amount, for example, when the wavelength of 2537A, preferably in the amount range of 50~50000mJ / cm ^2, and even more preferably to a quantity range of 500~30000mJ / cm ^2. If the light amount of UV irradiation is less than 50 mJ / cm ² , the desired adhesive strength cannot be obtained due to insufficient modification, and if it exceeds 50,000 mJ / cm ² , the soft plate material itself may be deteriorated. Absent.

As for the irradiation amount of ultraviolet rays, since light having a wavelength of 1849Å cannot be measured by a conventional method, light having a wavelength of 2537Å is measured and used as a substitute. The amount of ultraviolet light can be measured by an ordinary method using an ultraviolet illuminometer (model UVR-2436, manufactured by Sen Engineering Co., Ltd.).

When the composite laminate according to the present invention has metal flanges and the like on the top and bottom, it is preferable that the surface of the rubber material to be bonded to the flange is also subjected to the above-mentioned surface treatment for improving the adhesion.

In these surface treatments, the surface of the rubber plate may be subjected to pretreatments such as cleaning and degreasing in advance. However, in the ultraviolet irradiation treatment according to the present invention, these pretreatments may be omitted. The desired treatment effect can be obtained, the use of the organic solvent for degreasing in the pretreatment can be omitted, and it is environmentally preferable.

Next, this surface-treated rubber plate is bonded to a hard plate with an adhesive. The adhesive may be applied to the surface-treated surface of the rubber plate, may be applied to the surface of the hard plate to be adhered to the rubber plate, or may be applied to both of them.

The adhesive used here is preferably one or more selected from the group consisting of urethane-based and epoxy-based adhesives from the viewpoint of adhesiveness. As the urethane-based adhesive, a two-component mixed adhesive of polyester polyol or polyether polyol and an isocyanate compound, a moisture-curable adhesive composed of a prepolymer obtained by reacting a polyester polyol or polyether polyol with an isocyanate, the prepolymer and the polyol And a two-liquid mixed type adhesive and the like. As the epoxy-based adhesive, a two-component mixed type adhesive containing an epoxy resin as a main component and mixed with a curing agent is generally used, and usable epoxy resins include bisphenol A type,
Bifunctional glycidyl ether type epoxy resins such as bisphenol type epoxy resin such as F type and AD type or alcohol type glycidyl ether type epoxy resin such as polyethylene glycol type and polypropylene glycol type can be mentioned, and curing agents include diethylenetriamine and tetra Aliphatic amines such as ethylenetetramine, polyamides obtained by modification with dimer acid, ketamine or isophoronediamine, alicyclic amines such as paramenthanediamine, diaminodiphenylmethane, amine-based curing agents such as aromatic amines such as diaminodiphenylsulfonic acid, Aliphatic compounds such as dodecenyl succinic anhydride and polyazelaic anhydride, alicyclic compounds such as hexahydrophthalic anhydride, aromatic compounds such as trimellitic anhydride and pyromellitic anhydride, and hard acid compounds such as halogen-based acid anhydrides. Agents and the like, these curing agents,
At least one kind is used in combination according to the epoxy equivalent of the epoxy resin. These adhesives preferably have a breaking elongation of 0.5% or more after curing.

To laminate a surface-treated rubber plate and a hard plate with an adhesive and form a composite laminate by adhesion, a positioning jig such as a pin or a matching jig is used by a conventional method. It can be performed by stacking while determining the position. In this case, it is preferable that the upper and lower positioning jigs or the upper and lower flanges provided on the composite laminated body are fixed by pressure with a bolt so that the adherend is bonded by applying a certain amount of pressure. Adhesion is performed by leaving it in a temperature atmosphere suitable for the type of adhesive for a predetermined time, and removing the pins, the alignment jig and the like to obtain a composite laminate. The ambient temperature at the time of bonding may be selected from room temperature to about 200 ° C. according to the type of adhesive. The time required for adhesion is usually several minutes to several hours. It is preferable that the adherends are preheated at the time of bonding and then stacked and bonded, from the viewpoint of shortening the heat treatment time and completing the bonding in a short time.

Further, in the manufacturing method of the present invention, not only the rubber plate but also the surface of the hard plate made of the metal or the synthetic resin material to be adhered can be subjected to the adhesion improving treatment. Examples of the adhesion improving treatment applied to the surface of the hard plate include physical surface treatment such as sand blasting and shot blasting, and chemical conversion treatment applying an inorganic coating such as zinc phosphate and zinc calcium phosphate to the surface. Further, when the hard plate is a metal plate, it is also preferable to apply a thermosetting resin-based paint on the surface by baking. It is also preferable to perform these surface treatments on the surface of the metal flange that is to be bonded to the soft plate. Further, when the surface of the thermosetting resin-based paint that has been baked and coated is irradiated with ultraviolet rays and then adhered to a vulcanized rubber, the adhesion quality is further improved.

Physical surface treatment such as sand blasting and shot blasting can be carried out by a conventional method.

As the chemical conversion treatment, an inorganic coating film of zinc phosphate, zinc calcium phosphate, etc., having a crystal grain size of 0.5 to 50 μm is used.
m, preferably 10 μm or less, 1 to 20 g / cm ² ,
It is preferably applied at ² to 5 g / cm ² .

As a method for baking the thermosetting resin-based paint, an epoxy resin-based cationic paint or the like is added in an amount of 20 to 100.
A method of applying a coating of about μm and then performing a baking treatment at a temperature of about 160 to 180 ° C. may be mentioned.

Even when the hard plate is surface-treated, the surface of the hard plate can be subjected to pretreatment such as cleaning and degreasing in advance.

[0032]

The present invention will be described in detail below with reference to the accompanying drawings, but the present invention is not limited to these embodiments.

Example 1 A rubber composition having a composition shown in Table 1 below was used as a rubber material, and a steel material was used as a different material having rigidity. FIG. 1 shows a schematic sectional view of a composite laminate 10 obtained by the manufacturing method of the present invention. The composite laminate 10 is JI
A circular composite laminate defined by SK 6256 (1993 edition), which is a disc 12 made of two steel materials, 1
A rubber plate 16 made of a rubber material is arranged between the four.

The composite laminate 10 was manufactured as follows.

[0035]

[Table 1]

Production of plate-like rubber The rubber composition having the composition shown in Table 1 was vulcanized, and the surface of the vulcanized rubber thus obtained was vapor-degreased with a chlorine-based organic solvent.

Surface Treatment of Rubber Plate The surface of the obtained rubber plate 16 was irradiated with short wavelength ultraviolet rays under the following conditions.

(Ultraviolet irradiation conditions) Light source used: low-pressure mercury lamp (200 W, grid type) Irradiation distance: 20 mm from lamp tube wall Irradiation time: 100 seconds Mercury lamp measured by ultraviolet illuminance meter (model UVR-2436, Sen Engineering Co., Ltd.) Irradiation intensity is 10m
W / cm ² , and the amount of ultraviolet light at 2537Å of Example 1 was 1000 mJ / cm ² .

Hard plates 12, 14 made of steel are subjected to vapor degreasing with a chlorine-based organic solvent on the surface in contact with the rubber plate 16, and then subjected to surface treatment by shot blasting. .

Lamination and Adhesion Process A commercially available epoxy adhesive (HYSOL "FA9460", Dexter (THE DE
XTER CORP.)) Was applied so that the dry film thickness would be 300 μm.

After that, as shown in FIG. 1, they were laminated, placed in an oven under pressure and left standing in an atmosphere of 100 ° C. for 20 minutes for adhesion to obtain a composite laminate 10 to be a product 1 of the present invention.

(Example 2) A composite laminate was obtained in the same manner as in Example 1 except that vapor degreasing was not performed on the surfaces of the hard plates 12 and 14 and the rubber plate 16 using a chlorine-based organic solvent. The present invention product 2 was obtained.

(Example 3) A composite laminate was obtained in the same manner as in Example 2 except that the irradiation time of ultraviolet rays was 10 seconds, and the product 3 of the present invention was obtained. The amount of ultraviolet light in Example 3 was 100 mJ /
cm ² .

(Example 4) The irradiation time of ultraviolet rays was set to 3000.
A composite laminate was obtained in the same manner as in Example 2 except that the time was set to be Second, and the product of the present invention was obtained. The ultraviolet light amount of Example 4 is 3000.
It was 0 mJ / cm ² .

(Comparative Example 1) A composite laminate was obtained in the same manner as in Example 1 except that the ultraviolet irradiation treatment was not carried out to obtain Comparative Product 1.

(Comparative Example 2) A composite laminate was obtained in the same manner as in Example 2 except that the irradiation time of ultraviolet rays was 3 seconds, and was designated as Comparative product 2. The ultraviolet light amount of Comparative Example 2 was 30 mJ / cm ^2.
Met.

(Comparative Example 3) The irradiation time of ultraviolet rays was set to 5000
A composite laminate was obtained in the same manner as in Example 2 except that the time was set to be Second and used as Comparative Product 3. The ultraviolet light amount of Comparative Example 3 was 50,000.
mJ / cm ² .

(Comparative Example 4) A composite laminate was obtained as Comparative Example 4 in the same manner as in Example 2 except that the surface treatment shown below was performed without performing the ultraviolet irradiation treatment.

Surface Treatment of Rubber Plate The surface of the rubber plate 16 made of the obtained rubber material was dipped in a 3% by weight acetone solution of trichloroisocyanuric acid, which is a chlorine-based compound, and naturally dried to be chlorinated. .

(Comparative Example 5) A composite laminate was obtained in the same manner as in Example 1 except that the same chlorination treatment as in Comparative Example 4 was performed without performing the ultraviolet irradiation treatment, and Comparative Example 5 And

(Comparative Example 6) The irradiation conditions of ultraviolet rays were changed as follows, except that the ultraviolet rays in the medium to long wavelength region were irradiated.
A composite laminate was obtained in the same manner as in Example 2 and was designated as Comparative Product 6. The amount of ultraviolet light at 2537Å of comparative product 6 is 10
It was 00 mJ / cm ² .

Surface Treatment of Rubber Plate The obtained rubber plate surface was irradiated with medium to long wavelength ultraviolet rays (main working wavelength 3650Å) under the following conditions.

(Ultraviolet irradiation conditions) Light source used: high-pressure mercury lamp (200 W, grid type) Irradiation distance: 20 mm from lamp tube wall Irradiation time: 200 seconds (Example 5) Commercially available urethane-based urethane rubber surface after ultraviolet irradiation treatment Adhesive (KU661 / 662, Konishi Co., Ltd.)
A composite laminate was obtained in the same manner as in Example 2 except that the product 5 was applied, and the product of the present invention was obtained. The amount of ultraviolet light in Example 4 is 1
It was 000 mJ / cm ² .

Comparative Example 7 A commercially available acrylic adhesive (Versilok 201) was applied to the surface of the rubber plate after the ultraviolet irradiation treatment.
/ Acc # 17, manufactured by Lord Co., Ltd.), and a composite laminate was obtained in the same manner as in Example 2 to obtain Comparative product 7. The amount of ultraviolet light was 1000 mJ / cm ² .

Performance Evaluation of Composite Laminate (Normal Adhesion) The obtained composite laminate was left at room temperature for one week, and then an adhesion test according to JIS K 6256 was conducted. The rate of rubber breakage remaining and adhering to the hard plate (steel plate) was determined, and the results are shown in Table 2. R100 indicates that the rate of rubber breakage is 100%, indicating good adhesion,
For example, R50 means that the rate of rubber breakage is 50%, and the remaining 50% means that interfacial peeling has occurred. The larger the value, the better the adhesiveness.

(Durability of Adhesion) Regarding the inventions 1 to 4 and the comparative example 4 which showed good adhesiveness in the above-mentioned evaluation of normal adhesiveness, the metal fittings 18, 1 as shown in FIG.
9 is fixed, only the metal fitting 19 is distorted in the shearing direction ± 20%,
Repeated deformation was applied at a frequency of 3 Hz, and the life until a crack was generated on the adhesive surface was measured. The results are shown in Table 2 below.

[0057]

[Table 2]

As is clear from Table 2, it was found that the composite laminates of the present inventions 1 to 4 obtained by the production method of the present invention are excellent in both normal state adhesiveness and adhesion durability. On the other hand, in the composite laminate of Comparative Example 1 which was not pretreated by the ultraviolet irradiation treatment, it was found that the rubber plate and the hard plate were not bonded even if the adhesive was used. Further, even though the ultraviolet irradiation treatment was performed, the comparative products 2 and 3 in which the amount of ultraviolet irradiation light was out of the range of the present invention showed an improvement in adhesiveness as compared with the comparative product 1 not subjected to the treatment, The adhesive strength between the rubber plate and the hard plate was insufficient. Among Comparative Examples 4 and 5 which were subjected to chlorination treatment as a pretreatment for improving adhesion, the composite laminate of Comparative Product 5 in which the solvent degreasing treatment and the chlorination treatment were used in combination had sufficient adhesiveness, In a durability test in which a cyclic strain is applied, it was found that cracks were considered to be caused by a chlorine-based compound after repeated about 300,000 times, and the durability of adhesion was insufficient.

[0059]

As is apparent from the above description, according to the method for producing a composite laminate of the present invention, a composite laminate excellent in adhesiveness between a rubber material such as rubber and a dissimilar material having rigidity such as metal. Can be manufactured with high safety and with high productivity without requiring excessive equipment. Furthermore, various shapes and sizes of the composite laminated body can be manufactured without a special mold. It could be manufactured in time.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a composite laminate obtained according to Example 1 of the present invention.

FIG. 2 is a schematic cross-sectional view showing a composite laminate fixed to a metal fitting for an adhesion durability test.

[Explanation of symbols]

 10: Composite laminate 12, 14: Hard plate 16: Rubber plate 18, 19: Metal fitting for durability test fixed to the composite laminate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/16 101 B32B 27/16 101 C08J 7/00 304 C08J 7/00 304

Claims (5)

[Claims] 1. A method for producing a composite laminate in which a rubber material and a metal or synthetic resin material are laminated, wherein the surface of the rubber material is subjected to ultraviolet irradiation treatment of a wavelength of 2100 Å or less, and the treated surface of the rubber material is treated. And a metal or synthetic resin material adjacent thereto with at least one adhesive selected from the group consisting of urethane-based and epoxy-based adhesives. 2. A method for producing a composite laminate in which a rubber plate made of a rubber material and a hard plate made of a rigid metal or a synthetic resin material are laminated, the ultraviolet light having a wavelength of 2100Å or less on the surface of the rubber plate. Irradiation treatment is performed, and the hard plate adjacent to the treated surface of the rubber plate is bonded with at least one adhesive selected from the group consisting of urethane-based and epoxy-based adhesives. Manufacturing method. 3. The method for producing a composite laminate according to claim 1, wherein the rubber material is a rubber material which has been vulcanized in advance. 4. The rubber material is at least one selected from the group consisting of natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, and ethylene propylene rubber. A method for producing the described composite laminate. 5. The ultraviolet treatment with a wavelength of 2100 Å or less irradiates the surface of the rubber material with ultraviolet rays to cause a chemical change, and a functional group having an affinity with the adhesive is generated on the surface of the rubber material. The method for producing a composite laminate according to claim 1 or 2, wherein the method is a treatment for performing the treatment.