JPS62164535A - Metal-polypropylene laminated composite body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on a polypropylene sheet (hereinafter referred to as a core layer) in which crystalline polypropylene is filled with wood flour at a high concentration, and an unsaturated carboxylic acid or its derivative in crystalline polypropylene. ≠Modified polypropylene layer (
The present invention relates to a laminated composite consisting of a metal plate (hereinafter referred to as an adhesive layer) and a metal plate.

In recent years, metal plates have been made lighter, sound absorbing, and benign in the vibration range.
Laminated composites combining metal plates and plastic sheets have been developed from the perspective of providing heat insulation properties, and are widely used in civil engineering, construction, automobiles, home appliances, light electrical appliances, and other fields.

Some laminated composites using polypropylene resin have been put into practical use, but when molded parts are coated, burning occurs during processing (usually heat treated at about 180 to 200°C for 30 minutes). Molten resin flows out from the punching area and blocks the punching area, causing problems in post-processing.
The drawback is that the molten resin shrinks rapidly during the cooling and solidification process, causing deformation especially near the sheared parts, and the fact is that seizing cannot be used for parts that go through a process.

The present inventors have conducted extensive research to solve the above-mentioned problems regarding metal-polypropylene laminated composites. the result,
By using a composition containing a specific amount of wood flour in crystalline IJ propylene as a core layer, it has adhesive strength that can withstand secondary processing such as bending, punching, cutting, and deep drawing. Moreover, baking during painting is caused by resin flowing out from cut or punched parts or dripping of molten resin (
Hereinafter, it will be referred to as ``female fall''. ), and the thermal deformation near the cutting surface such as the cut portion or the punched portion is extremely small.The present invention was completed based on this knowledge.

As is clear from the above description, the object of the present invention is to provide metals with high adhesive strength, no burning during painting, no flow of molten resin during processing, and minimal thermal deformation. An object of the present invention is to provide a polypropylene laminated composite.

The present invention has the following configuration.

A metal plate is superimposed on both sides of a polypropylene sheet made of crystalline polypropylene mixed with 15 to 50% by weight of wood flour through a layer of modified polypropylene in which crystalline polypropylene is modified with an unsaturated carboxylic acid or its derivative, and bonded under heat. A metal-polypropylene laminated composite.

In the present invention, the crystalline polypropylene used in the core layer includes a propylene homopolymer, a propylene-ethylene block copolymer containing at least 70 wt. Examples include ethylene-butene-1 block copolymers and random copolymers, noa-pyrene-butene-1 random copolymers, and mixtures of two or more thereof. The crystalline polypropylene used in the present invention may also contain other polyolefins such as ethylene-propylene within a range that does not impair the effects of the present invention.
A, ethylene-propylene resin A%-poly4-methylpentene, ethylene-vinyl acetate copolymer, etc. can also be used in combination.

The modified polypropylene used for the adhesive layer in the present invention is the above-mentioned crystalline polypropylene modified with an unsaturated carboxylic acid or a derivative thereof.

Examples of the modification method include a known method in which crystalline polypropylene and an unsaturated carboxylic acid or a derivative thereof are heated to a temperature higher than the melting point of the crystalline polypropylene in the presence of an organic peroxide in a solvent or in the absence of a solvent. be able to.

Examples of unsaturated carboxylic acids or derivatives thereof used in the production of modified polypropylene include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, citraconic acid, and their acid anhydrides, esters, amides, imides, and metal salts. , such as maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate. ester, maleic acid diethyl ester, fumaric acid monoethyl ester, fumaric acid diethyl ester,
-1 Fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, fumaric acid monoamide, fumaric acid diamide , maleimide, N-butylmaleimide,
Examples include N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like. In particular, it is preferable to use maleic anhydride.

The amount of the above-mentioned unsaturated carboxylic acid or its derivative used in the production of modified polypropylene is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the crystalline polypropylene used.

Further, the above-mentioned modified polypropylene used for the adhesive layer in the present invention also includes a mixture of the above-mentioned modified boria'o-pylene and 50 to 95% by weight of the above-mentioned crystalline polypropylene.

Further, a hydrocarbon elastomer such as ethylene-propylene rubber, ethylene-butene-1 rubber, butanoene rubber, styrene-butadiene rubber, ethylene-butadiene rubber, etc. can be blended with the modified polypropylene as required.

The wood powder to be blended into the core layer of the present invention is made by crushing sawdust, planer dust, various wood chips, tree skin, etc. generated during sawmilling into a powder of 40 to 100 mesh,
It can be used regardless of the type or form of the tree. The blending amount of the wood flour is 15 to 50% by weight, preferably 20 to 4% by weight.
0Mfk%.

If the blending amount is less than 15%, when the resulting laminated composite is painted and treated for baking, resin may flow out from the cut or punched parts, and the cut surface of the laminated composite may This is not preferable because the thermal deformation in the vicinity becomes large, and if it exceeds 501 if 1:, the fluidity of the resin during melting and kneading will be significantly reduced, making molding difficult. The adhesive strength of the laminate is also reduced, which is not a good case.

The crystalline polypropylene used in the core layer and the modified polypropylene used in the adhesive layer of the present invention may contain various additives such as heat stabilizers, weather stabilizers, lubricants, slip agents, etc., as long as their functions are not affected. Flame retardants, antistatic agents, nucleating agents, and inorganic fillers can be blended.

Furthermore, the sheet for the core layer and the film for the adhesive layer of the present invention may be formed in advance, respectively.
Alternatively, a core layer and an adhesive layer formed by a known method such as a coextrusion method or an extrusion lamination method may be laminated and used in the form of a nine-layer sheet. At this time, the thickness of the core layer is 0.1~
5 cm, preferably 0.2 to 2 m11, the thickness of the adhesive layer is 1
It is desirable that the thickness be within the range of 0 to 100μ, preferably 20 to 60μ.

The metal plates used in the present invention include metal plates made of iron, steel, aluminum, copper, zinc, tin, nickel, titanium, etc., and metal plates made of alloys containing one or more of these as main components. be able to. The thickness of the metal plate is 0.05 to 2 mm, preferably 0.15 to IM. Further, it is preferable that the metal plate is usually subjected to a surface treatment such as degreasing treatment or sandblasting treatment on its adhesive surface. Furthermore, it is also preferable to use a metal plate whose adhesive surface has been subjected to a brimer treatment such as coating with an epoxy resin.

The laminated composite of the present invention can be obtained by stacking the above-mentioned metal plates whose adhesive surfaces have been surface-treated via adhesive layers made of modified polypropylene on both sides of the core layer and heat-pressing them using a compression molding machine, hot rolls, etc. can be obtained by The heating temperature at this time is 160 to 220℃, and the pressure is 1 to 5.
0 kl/an” G and 0.1 seconds ~ under such conditions
It is preferable to press for 10 minutes.

The laminated composite obtained by the present invention can be obtained by cutting the laminated composite,
Even if secondary processing such as punching, bending, and deep drawing is performed, the core layer and metal plate will not separate, and even if the secondary processed laminated composite is painted, baking will not occur. Is the resin of the core layer flowing out from the cut or punched parts? There is no dusk, and the deformation due to heat near the cut and punched parts is extremely small, making it suitable for automobile interior and exterior panels, home appliances,
It can be suitably used for a wide variety of applications such as various panels for light electrical products and architectural panels.

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

1, + ψ ÷ 1 (-Kyobushi Todaku i4 Te [Examples 1 to 3. Comparative Examples 1 to 5] 70e of ethylene t12.5 weight f% + pyrene-ethylene random copolymer as a radical initiator% 113-
Bis(1-butylperoxyisopropyl)benzene o
Modified polypropylene 25 weight US obtained by heat treatment with 13 weight % maleic anhydride, unmodified crystalline propylene alone < 6 weight % combined, and ethylene-fe + pyrene rubber 15 weight % using the o s z weight ratio. Add the and into Hensel mixer (trade name) K, stir and mix for 3 minutes,
The mixture (melt flow rate) 8.5, ij/10
The resin was melt-kneaded and extruded at 200°C using an extruder with a T-die having a diameter of 4 (hs+) to obtain a film with a thickness of 40 μm.

Next, as a filler in the crystalline propylene homopolymer, 8
A composition prepared by blending the wood powder of the 0.0-metssy burr tree in the proportions shown in Table 1 below was extruded at a resin temperature of 200°C using an extruder with a diameter of 65M T-die to form a sheet with a thickness of 0.45 mm. did. In addition, as Comparative Examples 1 to 5, crystalline propylene homopolymers mixed with various fillers in the proportions shown in Table 1 below were extruded using a T-die with a diameter of 65 mm according to Examples 1 to 3. A sheet of 0.45 mm thick was formed using a machine. As the metal plate, a cold-rolled steel plate with a thickness of 0.27 m whose surface was cleaned with triclean was prepared.

Each material is steel plate/modified, l? A layer of polypropylene film/boria pyrene sheet/modified polypropylene film/steel plate was preheated at 180°C for 4 minutes and then crimped at the same temperature for 1 minute at a pressure of 20 k+9/cm''G. 6854 for T-shaped peeling of laminated composites
This was done in accordance with the.

However, the tensile speed was 200 m/min. In addition, for heat treatment, a test piece was prepared by drilling a hole with a low diameter in the center of a laminated composite that was cut into 1 ocrn square, and the test piece was
The experiment was carried out by suspending the test piece in a heated open air chamber maintained at 0°C for 30 minutes. The results are shown in Table 1.

The laminated composite of Yen's invention, which is blended with a specific ratio of Shoshi wood powder shown in Table 1, has high peel strength, and there is no flow of resin after heat treatment, and near the cut surface such as the cut part or punched part. There was also very little deformation.

Claims (1)

[Claims] (1) 15-50% by weight of wood flour in crystalline polypropylene
A metal-polypropylene laminated composite obtained by laminating metal plates on both sides of a blended polypropylene sheet via a modified polypropylene layer in which crystalline polypropylene is modified with an unsaturated carboxylic acid or its derivative, and bonding them under heat.