JPH01228838A - Laminated metal plate with excellent damping property in improved corrosion resisting property - Google Patents

Abstract

PURPOSE:To obtain a laminated metal plate with an excellent damping property having vibratory damping capacity and also post processability by curing and unifying a thermoplastic resin film 1 with heat resistance and weatherability in one side or both sides of a metal plate through thermohardening type viscoelasticity component. CONSTITUTION:The thermohardening type viscoelasticity component 3 as an intermediate layering component for laminating and unifying the thermoplastic resin film 1 with an excellent weatherability and heat resistance in one side or both sides is inserted therebetween, and then the intermediate material layer is cured and integrated. The resin film such as polyamide resin, polyimide resin, polyester resin, halogenated vinyl resin and the resin film selected from the group of the combination thereof is suitable for the thermoplastic resin film 1. And the thermohardening type viscoelasticity component 3 contains natural rubber or synthetic rubber having unsaturated bond in the molecular structure, acrylic metallic salt or methacrylic acid metallic salt (B component), polymeride monomer compound except the B component tackifier, and curing catalyst.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a laminated metal plate with improved corrosion resistance, excellent post-processability, and good vibration damping properties. The intermediate layer composition used to laminate a plastic resin film to a metal plate is composed of a rubbery polymer having an unsaturated bond in the molecule, a metal acrylate or a metal methacrylate, and a polymerizable monomer. The present invention relates to a laminated metal plate with improved corrosion resistance and excellent post-processability by using a thermosetting viscoelastic composition as a main component.

In particular, 0-100 for vehicles such as ships, automobiles, trains, and aircraft, building materials such as flooring materials, wall materials, roofing materials, and stairs, and various types of equipment such as office equipment, communication equipment, and home appliances.
A damping metal plate with excellent damping properties that reduces the noise of vibrating members in the temperature range of °C, especially around room temperature, and has greatly improved the corrosion resistance of equipment used outdoors. The present invention provides a laminated metal plate with good properties.

(Prior art) In recent years, with the spread of vehicles such as automobiles, trains, aircraft, ships, high-rise buildings, general houses, office equipment, electrical products, etc., noise countermeasures for these equipment have been highlighted as an urgent issue. To date, many distributed metal plates have been proposed or commercially available as countermeasures.

In developing these distributed metal plates, attention has been paid mainly to vibration damping properties, adhesion between the damper material and metal, post-processability, etc., and improvements have been made at present.

However, since distributed metal plates generally use cold-rolled steel plates or hot-rolled steel plates as a base material, there have always been problems with countermeasures against corrosion, rust, etc. For this reason, countermeasures have been taken such as applying chromate treatment or galvanizing to the surface of the metal plate in advance, or painting the plate after making it into a damping metal plate, but most of the intermediate compositions used for vibration-damping metal plates are Since it is made of thermoplastic resin or self-adhesive material, there are problems such as baking failure, such as not being able to coat it sufficiently, and especially problems such as insufficient anti-corrosion measures for divided metal plates used in equipment used outdoors. is holding.

(Object of the Invention) An object of the present invention is to provide a laminated metal plate with good vibration damping properties that has both vibration damping ability and post-processability, which improves the above-mentioned problems of conventional distributed metal plates. It is in.

That is, as a result of intensive research, the inventors of the present invention have developed a structure as shown in Figures 1 to 6 of the attached drawings using a single metal plate or a laminated metal plate made of two or more laminated metal plates, and a weather-resistant and heat-resistant thermoplastic resin. By laminating and integrating the films, metal corrosion resistance can be greatly improved by 1) without post-processing such as painting, and
We have discovered a laminated metal plate that has good post-processing properties such as bending, drawing, and overhanging, and has good vibration damping properties, and has led to the present invention.

(Structure of the Invention) The gist of the present invention is to use a thermosetting viscoelastic resin film as an intermediate layer composition for laminating and integrating a thermoplastic resin film with good weather resistance and heat resistance on one or both sides of a metal plate. 100 parts by weight of the composition, particularly (A) natural rubber or synthetic rubber having unsaturated bonds in two molecules, alone or in a mixture of two or more, and (B) 1 niacrylic acid metal salt or methacrylic acid metal salt. ~90 parts by weight, and (C): 25 parts by weight of a polymerizable monomer other than the component (B).
~2''00 parts by weight, (D) 50 to 300 parts by weight of two adhesion agents, (E):
This invention consists in a laminated metal plate having improved corrosion resistance and good vibration damping properties, which is obtained by sandwiching a composition containing 0.1 to 10 parts by weight of a curing catalyst and by hardening and integrating an intermediate layer.

Thermoplastic resin films with good heat resistance and weather resistance used in the present invention to improve corrosion resistance include aliphatic polyamide resins, aromatic polyamide resins, polyimide resins, polyamideimide resins, polyethylene terephthalate resins, Films such as vinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, and polyvinyl fluoride resin are preferably used. There is no problem in coloring these thermoplastic resin films by adding pigments, paints, fillers, etc., and they are used depending on the purpose such as weather resistance or design.

These thermoplastic resin films can be used alone or in a laminated structure of two or more types of thermoplastic resin films, or laminated with other materials such as metal foils such as aluminum, copper, nickel, and stainless steel. It can be used.

The thickness of these thermoplastic resin films is preferably in the range of 0.01 to 1.0 mm in terms of corrosion resistance and post-processing performance, and more preferably in the range of 0.05 to 0.5 mm.

On the other hand, the metal plates used in the present invention include cold-rolled steel plates, hot-rolled steel plates, stainless steel, aluminum, etc., and various alloys, and these may be used alone or in a laminate of two or more sheets.

Metal plates having a thickness in the range of 0.1 to 3.0 mm can be suitably laminated, and a laminate with good post-processability can be obtained.

Next, each material of the viscoelastic composition of the present invention will be described in detail.

Rubbery polymers in the present invention include natural rubber, polyisobutylene, polybutadiene, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene-vinylpyridine copolymer, and isobutylene-isoprene copolymer. , acrylic acid-butadiene copolymer, methacrylic acid-butadiene copolymer, methyl acrylate-butadiene copolymer,
Methyl methacrylate-butadiene copolymer, ethylene-propylene-cyclopentadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-1°4-hexadiene copolymer, conjugated diene butyl rubber , Gingioctatic 1
．． 2-Polybutadiene, norbornene rubber, styrene-
It is a wide range of polymeric elastomers that have unsaturated bonds in their molecules, such as butadiene-styrene block copolymers and styrene-isoprene-styrene block copolymers. The molecular weight of these polymer substances is not limited in any way,
The polymer elastomer may be selected as appropriate depending on the purpose of use or conditions of use, but it is preferable to use one with a molecular weight of about 500 or more, mainly for the purpose of maintaining the physical properties of the raw polymeric elastomer. Furthermore, two or more types of polymers may be used in combination.

The metal acrylate or metal methacrylate used in the present invention is a reaction product of metal oxides such as zinc, aluminum, tin, calcium, nickel, cobalt, iron, magnesium, and lead with acrylic acid or methacrylic acid. There are zinc acrylate, aluminum acrylate,
Metals such as cobalt acrylate, lead acrylate, magnesium acrylate, tin acrylate, calcium acrylate, zinc methacrylate, aluminum methacrylate, cobalt methacrylate, lead methacrylate, magnesium methacrylate, tin methacrylate, iron methacrylate, etc. These compounds are salt compounds, and these compounds provide excellent adhesion to metal surfaces and thermoplastic resin surfaces.

Polymerizable monomers include styrene, α-methylstyrene,
Styrene derivatives such as β-methylstyrene and divinylbenzene; acrylic acid, methacrylic acid, methyl acrylate,
Methyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, lauryl methacrylate, glycidyl methacrylate, dimethylamine ethyl methacrylate, stearyl methacrylate, diethylaminoethyl methacrylate, ethyl dimethacrylate, dimethacrylic acid 1 , 3-butylene glycol, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and other acrylic and methacrylic acid derivatives; triallylisocyanurate, acetic acid Vinyl acrylonitrile, vinyl pyridine, etc. are used, and at least one of these is used, which enables design in a wide range of vibration damping ability, mechanical properties, etc.

The tackifier used in the present invention includes rosin, hydrogenated rosin glycerin ester, polyterpene resin, terpene/phenol resin, C5 petroleum resin, C9 petroleum resin, aliphatic cyclic hydrocarbon resin, hydrogenated carbonized Solid heavy molecular resins such as hydrogen resins; xylene resins, epoxy resins,
Fluid semi-open molecular resins such as unsaturated polyester resins and polyacrylic acid esters; plasticizers such as phthalic acid esters, aromatic polybasic acid esters, aliphatic dibasic acid esters, and low polymers such as polybutene and polyisobutylene. By using at least one of these, it becomes possible to freely design the temperature range in which the vibration damping ability is exhibited.

Furthermore, the curing catalyst used in the present invention includes ketone peroxides such as methyl ethyl ketone peroxide, cyclohexane peroxide, and acetylacetone peroxide; l,1-bis(tertiary-butyl peroxide) -3,3,5- ) Limethylcyclohexane, 1
．． Peroxyketals such as 1-bis(tertiary-butyl peroxide)-cyclohexane; tertiary-butyl hydroperoxide, cumene hydroperoxide,
Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; acetyl peroxide, isobutyl peroxide, and benzoyl peroxide. Diasilver oxinide such as oxide: peroxydicarbonate such as diisopropyl baroxydicarbonate, similystyl peroxydicarbonate; tertiary-butyl peroxyacetate, tertiary-butyl peroxybenzoate, tertiary-butyl Examples include peroxyesters such as peroxymaleic acid and tertiary-butylperoxyisopropyl carbonate, and at least one type of peroxide of these curing catalysts is used.

Furthermore, a polymerization inhibitor, a curing accelerator, and an anti-aging agent may be added to the viscoelastic composition used in the present invention, if necessary, and other fillers and the like may be added without any problem.

The object of the present invention is achieved by mixing and integrating the above-mentioned materials, sandwiching them between a thermoplastic resin film and a metal plate, heating and curing them, and integrating them.

The laminated vibration damping metal plate using the viscoelastic composition of the present invention has extremely good adhesion between the intermediate layer, the thermoplastic resin film, and the metal plate, has excellent vibration damping properties, and is also thermally stable. Because it has excellent properties such as hardness, heat aging resistance, and impact resistance, there is no need for continuous welding for reinforcement, which greatly contributes to productivity.

In addition, methods for laminating and integrating a thermoplastic resin film with good weather resistance and heat resistance and a metal plate include a calendar device, roll coating device, comma bar coating device, doctor knife coating device, T-Gui extrusion coating. The coating is mainly applied to metal plates using industrial equipment, and then a thermoplastic resin film is laminated and pressure-bonded to form an integrated layer.

Further, the thickness of the intermediate layer for laminating the metal plate and the thermoplastic resin film is 0.01 to 1.0, preferably 0.05
It is used after adjusting to ~0.5 fl.

Next, the test method used to evaluate the performance of the laminated damping metal plate will be briefly explained.

(A) Adhesion test method 1806 is used to measure the adhesion between a metal plate and a thermoplastic resin.
Measured at a tensile rate of 5 (ln/min) according to the peeling method,
Adhesive strength.

(b) Vibration damping The loss coefficient, which is a measure of vibration damping ability, was measured using the mechanical impedance method. The loss coefficient was measured at a temperature of 25° C. and a frequency of 500 Hz.

(1) A cross-cut is made from the thermoplastic resin film side of the corrosion-resistant laminate to the metal substrate, and the test specimen is immersed in saline solution with a concentration of 5% and a temperature of 30°C for 500 hours. The amount of rust generated was evaluated by Hifufure, etc.

(1) Metal molding with bending workability is performed by bending a laminated metal plate with a resin film on the top side using a mold that can be bent at 90 degrees using a press. The state of occurrence was observed and evaluated.

(Example) The present invention will be specifically explained in detail by giving Examples and Comparative Examples below.

Comparative Example 1 A thermosetting viscoelastic composition as an intermediate material for laminating a metal plate and a thermoplastic resin was prepared as shown below.

Polybutadiene rubber (manufactured by Japan Synthetic Rubber, BR-10)
100 parts by weight, 100 parts by weight of cyclohexyl methacrylate (manufactured by Mitsubishi Rayon, acrylic ester CHO),
Zinc acrylate (manufactured by Asada Chemical Industry, Z-AA) 2
5 parts by weight, alicyclic hydrocarbon resin (manufactured by Arayo Kagaku Kogyo Gyu,
150 parts by weight of Alcon M], 00@) and 2.5 parts by weight of dicumyl peroxide as a curing catalyst were added, and mixed and stirred in a kneader to obtain a viscoelastic composition.

The formulation contents are shown in Table-1.

Table-1 Polybutadiene rubber 6100 parts by weight Cyclohexyl methacrylate "21oo Zinc acrylate" 25 //Alicyclic hydrocarbon resin 150 ・Dicumyl peroxide 2.5 Note: *l BR-Of Japan Made of synthetic rubber *2 Acrylic ester C1-1 Made of Mitsubishi Rayon (4) 'l'3 Z-AA Asada Chemical Industry 0
Chrysanthemum Binding 4 Alcon M100 Manufactured by Arayo Kagaku Kogyo U On the other hand, a cold-rolled steel plate with a thickness of 0.8 Tsuru was used as the metal plate as the laminate.

There are four types of thermoplastic resin films: nylon-6 (Example 1), polyethylene terephthalate (Example 2), polyimide (Example 3), and polyvinyl fluoride (Example 4), each having a thickness of 0. Ilm film was used.

In the lamination method, the above-mentioned viscoelastic composition is coated on a metal plate using a coating machine to a thickness of 0. I Im, and then the respective thermoplastic resin films were laminated and integrated.

Thereafter, it was heat-cured for 30 minutes in a heating furnace at a temperature of 150°C to obtain a laminate of metal and thermoplastic resin having the structure shown in FIG.

These laminates were evaluated for adhesive strength, vibration damping performance, and corrosion resistance using the evaluation test methods described above, and the results are shown in Table 2.

As a comparative example, a painted metal plate was used, which was a metal plate coated with an alkyd resin paint (Comparative Example 1).

The following is clear from the above results.

1. High adhesive strength.

2. The vibration damping performance is higher than that of the comparative example, and the vibration damping performance is large.

3. Corrosion resistance is good with less rust compared to painted steel sheets.

4. The laminate was successfully bent without any damage to the resin film.

On the other hand, the comparative example was not acceptable because the coating film was destroyed.

Examples 5 to 6 and Comparative Example 2 Between two cold-rolled steel plates with a thickness of 0.81 as metal plates,
The viscoelastic composition used in Examples 1 to 4 with the composition shown in Table 1 was sandwiched and heated to harden to produce a composite damping steel plate having a structure of two metal plates laminated together. there was.

The thermoplastic resin films to be laminated on one side of this damping steel plate include a nylon-6 film (Example 5) with a thickness of 0.1 mm and a polyvinyl fluoride film (Example 6).
type was used. The method of laminating these films and metal plates was to use the viscoelastic composition shown in Table 1 as an intermediate material, and the coating method was carried out under the same conditions as the method of Examples 1 to 4, followed by heating and curing. A laminate having the structure shown in FIG. 3 was obtained.

These laminates were evaluated for adhesive strength, vibration damping performance, and corrosion resistance using the evaluation test methods described above, and the results are shown in Table 3.

As a comparative example, a painted metal plate obtained by applying an alkyd resin paint (Comparative Example 2) to the metal plate having the above-mentioned two-metal plate lamination structure was used.

The following is clear from the above results.

1. High adhesive strength between metal plate and resin film.

2. The vibration damping performance was good in both Examples and Comparative Examples since composite vibration damping metal plates were used as the metal plates.

3. Corrosion resistance is good with less rust occurrence compared to comparative examples.

4. The bending processability of the laminate does not cause damage to the resin film.
I was able to process it well. On the other hand, the painted steel sheet of Comparative Example was not acceptable because the coating film was damaged.

Note that, although typical examples of embodiments of the laminate according to the present invention are shown in the accompanying drawings 1 to 6, the present invention is not limited thereto.

In Figure 1, a thermoplastic resin film 1 (hereinafter referred to as resin film) is cured and integrated with a metal plate 2 via a thermosetting viscoelastic composition 3 (hereinafter referred to as viscoelastic composition). 2 shows the metal plate 2 of the laminated metal plate shown in FIG. 1 in which another resin film 1 is further cured and integrated with the viscoelastic composition 3, and FIG. 3 shows the laminated metal plate of FIG. Another metal plate 2 is further hardened and integrated with the metal plate 2 of the plate using a viscoelastic composition 3. In FIG. 4, a viscoelastic composition 3 is added to the metal plate 2 of the laminated metal plate of FIG. Other resin films are cured and integrated with each other, and FIG. 5 shows resin film 1, viscoelastic composition 3, metal foil 4,
6 is a laminated metal plate in which a laminate of a viscoelastic composition 3 and a metal plate 2 is cured, and FIG. 6 shows the laminate of FIG. This is a laminated metal plate in which a viscoelastic composition 3 and a resin film 1 are laminated and cured into one piece.

[Brief explanation of the drawing]

1 to 6 are partially broken vertical cross-sectional schematic diagrams showing various embodiments of the laminated metal plate according to the present invention. 1... Thermoplastic resin film, 2... Metal plate, 3...
...Thermosetting viscoelastic composition, 4...Metal foil. Agent Patent Attorney 1) Osamu Umi Figure 1 Figure 2 Figure 3

Claims (5)

[Claims] (1) A laminated metal plate with improved weather resistance and good vibration damping properties, in which a thermoplastic resin film with good heat resistance and weather resistance is integrated with a thermosetting viscoelastic composition on one or both sides of the metal plate. . (2) A thermoplastic resin film with good heat resistance and weather resistance is coated on one side of the metal plate with a thermosetting viscoelastic composition, and at least one metal plate is further coated with the above thermosetting viscoelastic composition on the other side of the metal plate. A laminated metal plate with improved corrosion resistance and good vibration damping properties, which is hardened and integrated with a composition. (3) The thermosetting viscoelastic composition has the following components: A component: natural rubber or synthetic rubber having an unsaturated bond in its molecular structure, B component: acrylic acid metal salt or methacrylic acid metal salt, and C component: polymerizable. The laminated metal sheet according to claim 1 or 2, which contains a monomer compound other than component B, component D: an adhesion promoter, and component E: a curing catalyst. (4) The thermoplastic resin film is a resin selected from the group consisting of polyamide resin, polyimide resin, polyester resin, halogenated vinyl resin, and combinations thereof. laminated metal plate. (5) Claim (1), (2), (3) or (4), wherein the thermoplastic resin film is an integrally laminated layer of metal foil.
Laminated metal plate as described in section.