JPH11300889A - Composite panel excellent in adhesiveness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite panel excellent in adhesion durability without further applying an epoxy coating agent to a surface coated with a coating type chemical forming treatment agent at a time when the composite panel is produced by laminating thin metal panels to both surfaces of a polyolefin resin sheet by using the polyolefin resin sheet wherein films of an adhesive polyolefin resin are laminated to both surfaces of a polyolefin resin sheet. SOLUTION: Thin metal panels are coated with a coating type chemical forming treatment agent containing no synthetic resin and the coated surfaces of them are laminated to both surfaces to which an adhesive polyolefin film is laminated of a polyolefin resin sheet to obtain a composite panel.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated composite plate (hereinafter referred to as a "laminated composite plate") comprising a polyolefin resin sheet and a metal sheet.
(May be abbreviated as the composite plate of the present invention). More specifically, the present invention relates to a composite plate having excellent adhesion durability to a polyolefin resin sheet by improving a coating type chemical conversion treatment agent used for corrosion prevention without applying an epoxy coating or the like to an adhesive surface side of a metal thin plate. .

The composite board of the present invention has excellent adhesive performance and does not peel off between the metal sheet and the polyolefin resin sheet not only indoors but also outdoors. By this bonding, a composite board having a laminating effect such as rigidity, heat insulation, and weather resistance is used for indoor and outdoor wall materials, partition boards, display boards, and the like.

[0003]

2. Description of the Related Art Conventionally, a metal sheet is subjected to a chemical conversion treatment after a degreasing treatment in order to prevent corrosion. This chemical conversion treatment uses either a reaction type or a coating type chemical conversion treatment agent depending on the coating method. The use of the coating type chemical conversion treating agent is increasing because the facility is simple and it does not take up space, and there is no need for waste liquid treatment.

Conventionally, a coating type chemical conversion treatment agent used in a chemical conversion treatment is composed of a synthetic resin such as an acrylic resin and an organic metal salt, and the synthetic resin in the treatment agent is a coating type chemical conversion treatment. It acts to maintain the durability of the film by the agent.

Heretofore, in order to manufacture a composite board by laminating a sheet of polyolefin resin and a sheet of polyolefin resin which has been subjected to a chemical conversion treatment with such a coating type chemical conversion treatment agent, it is necessary to form an adhesive polyolefin resin on both sides of the sheet of polyolefin resin. A method of laminating a resin sheet on which a film is laminated and a metal sheet coated with an epoxy-based paint after a chemical conversion treatment on both sides of the laminated sheet, or using an adhesive. And laminating a polyolefin resin sheet and a chemically treated metal sheet.

However, when using an adhesive,
Although a metal sheet using such a coating type chemical conversion treatment as it is may be laminated on both surfaces of a polyolefin resin sheet, when laminating a metal sheet without using an adhesive,
Simply using a metal sheet coated with the coating type chemical treatment agent does not adhere to the polyolefin resin sheet, nor does it adhere to the resin sheet having the adhesive polyolefin film laminated on both sides. At present, a composite board having a sufficient adhesive strength cannot be obtained unless an epoxy-based paint or the like is further applied on the treated film.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have proposed a polyolefin resin in which a film of an adhesive polyolefin resin is laminated on both sides of a sheet in a composite plate in which a thin metal plate and a polyolefin resin sheet are laminated. When laminating a metal thin plate and the polyolefin resin sheet using a sheet to form a composite plate, it is excellent without requiring further application of an epoxy-based paint or the like on the surface coated with the coating type chemical conversion treatment agent. In order to obtain a composite board having good adhesion durability, we have studied diligently. As a result, the use of a coating type chemical treating agent excluding the synthetic resin, which is one component of the coating type chemical converting agent, provides a composite having excellent adhesive durability without further application of an epoxy paint or the like. They found that a plate could be obtained and completed the present invention based on this finding. As is apparent from the above description, an object of the present invention is to use a metal sheet treated with a coating-type chemical conversion treatment agent, and to manufacture a composite plate without further applying an epoxy-based paint. An object of the present invention is to provide a composite board having excellent adhesiveness to a resin sheet.

[0008]

The present invention is shown as follows. (1) The surface of a thin metal plate coated with a coating type chemical conversion treatment agent containing no synthetic resin was coated on both surfaces of a polyolefin resin sheet having an adhesive film laminated on both surfaces. Composite board. (2) The coating amount of the coating type chemical conversion treating agent containing no synthetic resin is represented by the content of metal ions in a metal compound containing at least one metal selected from chromium, zirconium and titanium in the coating. And this is 5-100 mg /
^2. The composite plate according to the above item 1, wherein m2 is m2. (3) A sheet thickness of 5 in which the metal sheet is formed from one or more of the following:
2. The composite plate according to claim 1, which is a thin plate having a thickness of 0 to 1000 μm. Aluminum plate, aluminum alloy plate, iron plate, steel plate, galvanized steel plate, tinned steel plate, corrosion-resistant steel plate, copper plate, copper alloy plate and titanium plate.

[0009] The coating type chemical conversion treatment agent containing no synthetic resin used in the present invention includes three types of treatment agents: a chromium-based treatment agent, a zirconium-based treatment agent and a titanium-based treatment agent.
Commercially available products include Alsurf manufactured by Nippon Paint Co., Ltd., and Paltop manufactured by Nippon Parkerizing Co., Ltd. These processing agents are generally of two-pack type, and are therefore commercially available. Use the one that does not contain resin.
Since the synthetic resin can be easily removed from the one-liquid type, the synthetic resin may be removed before use. The coating amount of the coating type chemical conversion treatment agent that does not contain such a synthetic resin is represented by the content of metal ions in a metal compound containing at least one metal selected from chromium, zirconium and titanium in the coating, This is 5-100
It is preferably mg / m ² .

Examples of the raw resin for the polyolefin resin sheet used in the present invention include the following. Ethylene homopolymer, ethylene 60
A copolymer of ethylene and one or more of α-olefins having 3 or more carbon atoms or a polar monomer, a crystalline propylene homopolymer, 60% by weight or more of propylene, and the propylene and ethylene or Crystalline copolymers with one or more α-olefins or polar monomers having 4 or more carbon atoms, and mixtures of two or more of the above polymers can be mentioned.

A modified resin obtained by copolymerizing or graft-polymerizing such a resin with an unsaturated carboxylic acid such as maleic anhydride, acrylic acid, or fumaric acid, or a derivative such as an acid anhydride or ester; Modified resins that have been subjected to neutron radiation treatment or cross-linked with a cross-linking agent can also be used depending on the application.

In the present invention, various fillers (or reinforcing agents) can be added to the polyolefin resin. Examples of the filler used include fibrous fillers such as glass fiber, carbon fiber and vinylon fiber, flake-like fillers such as mica and talc, spherical fillers such as glass beads, and amorphous fillers such as calcium carbonate and wood chips. Further, in addition to these fillers, flame retardants, extenders, coloring agents, deterioration inhibitors, antistatic agents, lubricants, and the like can be added.

The method for producing the polyolefin resin sheet is not particularly limited, and any production method for producing a polyolefin sheet can be employed. For example, an extruder equipped with a T-die can be used. Thus, it can be obtained by extrusion molding under ordinary molding conditions into a sheet having an arbitrary film thickness. Further, the polyolefin resin sheet of the present invention does not affect the adhesiveness even if foamed.

The adhesive polyolefin film used in the present invention is usually made of polyethylene adhesive resin, polypropylene adhesive resin or vinyl acetate adhesive resin.
A resin referred to as an adhesive polyolefin resin may be used, for example, Adma (trademark) of Mitsui Chemicals, Inc.
Examples include Modic (trademark) manufactured by Mitsubishi Chemical Corporation and Cranbeta (trademark) manufactured by Kurashiki Spinning Co., Ltd. The method for producing the film is also not particularly limited. For example, an extrusion molding method in which a film is formed by melt-kneading and extruding using an extruder equipped with a T-die under ordinary molding conditions can be exemplified. Further, the film of the adhesive polyolefin resin,
Those having a thickness of 20 μm to 100 μm are preferred.

The metal thin plate used in the present invention is a plate formed from at least one of an aluminum plate, an aluminum alloy plate, an iron plate, a steel plate, a galvanized steel plate, a tin-plated steel plate, a corrosion-resistant steel plate, a copper plate, a copper alloy plate, and a titanium plate. 50-1000 μm thick
It is preferable to use a thin plate of

[0016] The composite plate of the present invention uses a coating type chemical treatment agent which does not use a synthetic resin such as an acrylic resin as a chemical conversion treatment agent for a metal thin plate as a surface material. The adhesive force with the polyolefin resin can be sufficiently exhibited without applying any paint or the like. The adhesive strength of the composite board of the present invention is preferably at least 25 N / 25 mm or more, and if it is less than 25 N / 25 mm, the adhesive durability deteriorates, and peeling between the thin metal sheet and the polyolefin resin sheet with time occurs. There is a risk of occurring.

The composite plate of the present invention can be prepared, for example, by the following procedure. ◆ Core sheet To obtain the core sheet, the above-mentioned polyolefin resin is extruded by an appropriate means such as an extruder equipped with a T-die.
It is formed into a sheet having an arbitrary thickness to obtain a core sheet of a composite plate.

(4) Coating of a coating type chemical conversion treatment agent containing no synthetic resin After diluting the coating type chemical conversion treatment agent with deionized water, the surface of the metal sheet after degreasing is bonded to the polyolefin resin sheet. Apply with a roll coater and dry with hot air.

(2) Preparation of composite plate A metal sheet treated with a coating type chemical conversion agent containing no synthetic resin is placed on both sides of the core sheet with the above-mentioned adhesive polyolefin resin film interposed therebetween. And heat press-bonding each layer. Thus, the composite board of the present invention is obtained.

Alternative 1 (using adhesive polyolefin resin (continuous film)) The above-mentioned core material sheet is prepared by an extruder equipped with a T-die, and the above-mentioned adhesive polyolefin resin film is laminated from both sides. Further, from both sides thereof, a metal sheet subjected to the above-mentioned coating chemical conversion treatment is laminated, and these multilayers are sandwiched while being continuously supplied between a nip composed of a pair of opposed rotating rolls for lamination. The composite board of the present invention is continuously manufactured by a take-off machine equipped with multi-layer rolls. In this method, it is important that the laminating roll has a sufficient temperature and pressing force to bond the thin metal plate and the core material sheet via the adhesive polyolefin resin film layer.

As a modification of Alternative 1, a production method using a hot press can be adopted, but since it is not compatible with integrated production, it exerts its power in cases where it is difficult. That is, the present invention can be flexibly adapted to a production mode in which specifications such as the use of a core sheet and / or a thin metal plate and / or an adhesive polyolefin resin layer subjected to a coating type chemical conversion treatment are required for every several products.

[0022]

The present invention will now be described in detail with reference to examples and, where necessary, comparative examples. However, the scope of the present invention is not limited to the examples. Embodiments in which additions and / or changes, etc., which can be easily made by those skilled in the art, are also included in the scope of the present invention.

Test Methods and Conditions in Examples (1) Preparation of Core Sheet T-Polymer was prepared using the polyolefin resin of each Example and Comparative Example.
A sheet (300 mm long x 200 mm wide x 3 mm thick) was prepared by a die method. (2) Application method of chemical conversion treatment agent The coating chemical conversion treatment agent is composed of an organic metal salt using a synthetic resin such as an acrylic resin as a binder. Since its form causes precipitation of the contained metal, it is often a two-liquid type of a synthetic resin component and a contained metal component. Among the coating type chemical conversion treatment agents, the liquid not containing synthetic resin in each example and the two-liquid type liquid in the comparative example were diluted with deionized water to obtain a metal after degreasing. It was applied to the adhesive side of the thin plate with a roll coater and dried in a hot air drier (220 ° C. × 1 min).

(3) Measurement of coating amount The amount of chromium, zirconium, titanium or the like as the main component in the film was measured by X-ray fluorescence analysis or atomic absorption analysis, and the amount of adhesion was defined as the coating amount. (4) Method of preparing a composite board The obtained polyolefin resin sheet was used as a core sheet, and the adhesive polyolefin resin films of Examples and Comparative Examples were laid on both surfaces thereof, and a coating chemical conversion treatment was performed thereon. The thin plate is placed and thermocompression-bonded (150
C. × 5 min) to produce a composite plate. (5) Adhesion evaluation of composite board The obtained composite board is cut into (length 150mm x width 25mm), the metal sheet of the surface material is peeled by hand to the position of 80mm in length, and the remaining is measured using a tensile tester. Was measured as the adhesive strength per 25 mm width (JI
SK 6854 180 degree peeling method).

Example 1 Polyethylene as core resin [abbreviation: PE; density 0.963 g / c]
c], a chemical blowing agent azodicarbonamide [Vinihole
(Trademark, manufactured by Eiwa Chemical Co., Ltd.)] 0.5 parts by weight and n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate as various additives.
03 parts by weight and 0.1 part by weight of calcium stearate were impregnated with liquid paraffin.

This was melted and kneaded to obtain a polyethylene resin sheet by the T-die method (die temperature: 200 ° C.). Next, the metal sheet is coated on a degreasing-treated metal aluminum sheet (length 300 mm x width 300 mm x thickness 0.2 mm; abbreviated as "AL") by a coating-type chemical conversion treatment agent [Paltop (trademark, manufactured by Nippon Parkerizing Co., Ltd.)] Was added to 1 liter of deionized water, mixed well, and applied with a roll coater. The coated aluminum sheet was dried with a hot air drier (220 ° C. × 1 min). This aluminum thin plate was cut into 50 mm squares, and the amount of chromium was measured with fluorescent X-rays, which was taken as the coating amount.

An adhesive polyolefin film [Admer (trade name, manufactured by Mitsui Chemicals, Inc.)] was spread on both sides of the resin sheet, and both sides were treated with a coating type chemical conversion treating agent from both outsides.
A sheet of aluminum is sandwiched so that the treated surface is on the adhesive side, and pressed and pressed (5 min) with a hot press (130 ° C.) to obtain a composite plate of the present invention [total thickness 3 mm; AL // HDPE // AL]. After cutting the obtained composite board (25 x 150 mm), peeling the aluminum sheet to a position of 80 mm in length and then peeling off the remaining part using a tensile tester, the adhesive strength per 25 mm width Was measured. The results are shown in Table 1 (JIS
Complies with K 6854 180-degree peeling method).

Comparative Example 1 250 g of each of the coating chemical conversion treatment agents A and B used in Example 1 were put into 1 liter of deionized water and mixed and diluted sufficiently. This solution was prepared according to Example 1,
A composite plate was prepared by measuring the amount of chromium and bonding the thin plate to an aluminum thin plate, and the adhesive strength was measured. Table 1 shows the results.
Shown in

Example 2 and Comparative Example 2 The procedure of Example 1 was repeated except that the case where the amount of the agent B of the coating type chemical conversion treatment agent was 100 g was referred to as Example 2 and the case where the amount was 50 g was referred to as Comparative Example 2. Then, the amounts of chromium were measured and bonded to form a composite board, and the adhesive strength was measured. Table 1 shows the results.

Example 3 An example using a coating type chemical conversion treating agent [Alsurf (trademark, manufactured by Nippon Paint Co., Ltd.)] as Example 3
The composite plate was prepared by diluting and coating only the contained metal component and bonding the same with the measurement of the amount of chromium in accordance with the standard. Table 1 shows the results.

Comparative Example 3 An aluminum thin plate was applied in the same manner as in Example 1 except that a solution obtained by diluting the coating type chemical conversion treating agent used in Example 3 was used. Together, a composite plate was prepared, and its adhesive strength was measured. Table 1 shows the results.

Example 4 As a polyolefin resin, polypropylene [abbreviation: P
P; a density of 0.910 g / cc], except that an aluminum thin plate was treated and an adhesive polyolefin film [Kranbetter (trademark, manufactured by Kurashiki Boseki Co., Ltd.)] in accordance with Example 1 except that a density of 0.910 g / cc was used.
Was used to prepare a composite plate by thermocompression bonding (150 ° C. × 5 min). The adhesive strength of the obtained plywood was measured. Table 1 shows the results.

Example 5 A composite plate was prepared in accordance with Example 1 except that a corrosion-resistant steel plate having a total thickness of 200 μm was used as a thin metal plate placed on both surfaces of the composite plate, and the adhesive strength was measured. Table 1 shows the results.

As is clear from Table 1 showing the evaluation results of the adhesiveness of the composite plates obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the composite plate of Example 1 was a coating type chemical conversion treating agent. Is 20 mg / m ² and the adhesion is good. Also,
Even in the case of the coating type chemical conversion treating agent used for the composite board of Example 3, the adhesion was good as in Example 1.

The composite plate of Comparative Example 1 had the same amount of the chemical conversion treatment as in Example 1, but did not adhere to the polyolefin resin because both the A and B agents were added. Similarly, the coating type chemical conversion treating agent used in Comparative Example 3 did not adhere. That is, it is understood that the synthetic resin in the coating type chemical conversion treating agent does not adhere to the polyolefin resin unless it is removed.

The composite plate of Example 2 had a coating amount of the coating type chemical conversion treatment agent of 6 mg / m ² , and had good adhesiveness. But,
Comparative Example 2 hardly adheres because the applied amount is 3 mg / m ² . That is, the coating amount of the coating type chemical conversion treatment agent is 5 mg / m ^2.
It is understood that the adhesiveness cannot be maintained unless the above conditions are satisfied. Further, the composite plate of Example 4 had good adhesiveness as in Example 1. That is, it is effective whether the adhesive polyolefin resin film is an admer or a cran butter.

The composite plate of Example 5 had good adhesion as in Example 1. That is, the thin metal plates placed on both surfaces of the composite plate are effective even if they are made of corrosion-resistant steel.

[0038]

The composite plate of the present invention has the following various effects: (1) It is not necessary to apply an epoxy paint to the bonding surface side of the thin metal plate. (2) It has excellent adhesive durability and can be suitably used as an interior / exterior material.

[0039]

[Table 1]

Claims (3)

[Claims] 1. A metal sheet coated with a coating type chemical conversion treatment agent containing no synthetic resin, the surface of the metal sheet coated with the treatment agent is applied to both surfaces of a polyolefin resin sheet having an adhesive polyolefin film laminated on both surfaces. A laminated composite board. 2. The coating amount of the coating type chemical conversion treating agent containing no synthetic resin is determined by the content of metal ions in a metal compound containing at least one metal selected from chromium, zirconium and titanium in the coating. , Which is 5-1
Composite board according to claim 1, wherein the 00mg / m ^2. 3. The composite plate according to claim 1, wherein the metal sheet is a sheet having a thickness of 50 to 1000 μm formed from at least one of the following. Aluminum plate, aluminum alloy plate, iron plate,
Steel plate, galvanized steel plate, tin plated steel plate, corrosion-resistant steel plate, copper plate, copper alloy plate and titanium plate.