JPS5853438A - Metallic laminate - 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 provides a metal laminate consisting of a single layer of metal plates with an intermediate adhesive layer interposed therebetween. The present invention relates to a metal laminate having high interlayer adhesion and excellent durable adhesiveness, characterized by using a composition of magnesium oxide and magnesium oxide having specific physical properties.

Recently, materials for vehicles such as automobiles, electrical parts such as refrigerators, washing machines, and air conditioners, building materials such as doors, shutters, and walls, and materials for office equipment such as office desks and cabinets are becoming more and more popular. Reflecting the times, there is a shift from conventional steel materials to materials with functions such as lightness, vibration damping, and sound insulation, and with this, there is a strong demand for the development of high-performance materials. ing.

As a material having such performance, for example, a sand char steel plate is known, which is made by bonding thin steel plates via an adhesive resin and reinforcing the same.

By the way, as is well known, polyolefins such as polyethylene and polypropylene have various excellent physical and chemical properties, mechanical properties, and moldability. Widely used in industrial fields. However, since polyolefin is non-polar, it has poor adhesion to different base materials such as metals, glass, and polar polymer materials, and has the disadvantage that it is difficult to combine with these various base materials. .

In order to improve this drawback, conventional methods have been used to improve adhesiveness by introducing polar groups into polyolefins by graft-modifying them with unsaturated carboxylic acids such as acrylic acid and maleic anhydride, or their anhydrides. Are known. Additionally, various polyolefin compositions have been proposed for the purpose of further improving adhesiveness with metals, polymeric materials, and the like. For example, a composition obtained by adding an unsaturated carboxylic acid anhydride such as maleic anhydride and a metal oxide such as magnesium oxide to polio or refin, and graft-modifying it with a melted hinge (Japanese Patent Publication No. 51-48195, 1977
-98484, JP-A-50-10837)
, compositions obtained by adding metal oxides such as magnesium oxide to polyolefins graft-modified with acrylic acid or maleic anhydride (JP-A-51-23544, JP-A-52-121059), polyolefin and rubber Compositions obtained by graft-modifying a mixture with an unsaturated carboxylic acid anhydride or the like (JP-A-49-9546, JP-A-50-29659, JP-A-52-8
035, JP 55-18251, JP 56-41205), polyolefin and rubber-like polymer tonneau composition graft-modified with unsaturated p-bony acid anhydride, etc. Publication No. 9546, JP-A-50-2
9659, JP-A-51-80334), polyj "1" graft-modified with unsaturated carboxylic acid anhydride, etc.
Composition of No. 11 non and R4 Ren thread combination (4)
No. 8, JP-A No. 56-21850), a composition comprising a propylene polymer graft-modified with an unsaturated μ-bonic acid anhydride, an amorphous propylene polymer, and an ethylene polymer ( (Japanese Patent Application Laid-Open No. 54-90346)
Many polyolefin-based adhesive resin compositions are known. Additionally, these compositions are generally used as coatings for various inorganic and organic substrates such as metals, glass, polymeric materials, etc.
It is also known as ξ, which is widely used as a binder or lamination adhesive.

However, when these compositions are used as adhesives for various substrates, the adhesive strength at the adhesive interface is often insufficient depending on the type of substrate used, and even if initial adhesion is good, durable adhesiveness may be insufficient. There are problems such as insufficient adhesion, and it is difficult to obtain a material with satisfactory adhesion for a large number of base materials, and further improvements are desired41.
(Ll, /!h,l・,V) out m special rl' know, JP-A-Sho Fil, -23544F+ publication and JP-A-I+/
(52-1211) Compositions made by adding metal oxides such as magnesium oxide to polyolefins graft-modified with acrylic acid or maleic anhydride, as shown in FSU No. 1, are particularly effective in adhesion to metals. However, it is still difficult to obtain a material with highly satisfactory adhesive strength and durable adhesive properties. In addition, polyolefins graft-modified with unsaturated carboxylic acids such as acrylic acid have poor thermal stability and decompose and foam rapidly when molded at temperatures above 25()'q, making them difficult to use in practical applications. . The main reason for this is thought to be thermal decomposition of the low molecular weight polymer of acrylic acid inevitably produced during graft polymerization. In addition, as described in the above-mentioned Japanese Patent Publication No. 51-48195, a mixture of a polyolefin, an unsaturated carboxylic acid anhydride, and a metal oxide such as magnesium oxide is melt-denatured in one step and has an adhesion-improving effect. is small.

The inventors of the tree have conducted intensive studies to improve the defects such as nickel, and to create a polypropylene resin composition that has much stronger adhesive strength and durable adhesive properties than conventional products, especially when adhering to metals. As a result, it is necessary to select not only the type of propylene polymer used for modification, but also the type of modifier and the modification method, and it is also necessary to specify a specific amount of oxidation that has specific physical properties for the modified resin. It has become clear that the addition of magnesium has a significant effect, leading to the present invention.

Here, the metal laminate obtained using the adhesive resin composition of the present invention has extremely excellent adhesive strength as described above, and also has excellent physical properties of the crystalline propylene-ethylene copolymer. Due to the reinforcing effect based on , it has sufficient practical strength as a composite metal plate. As a result, not only the weight of the metal material can be reduced, but also a sandwich metal plate with excellent vibration damping and sound insulation properties can be obtained. As described above, the metal laminate obtained by the present invention can be used for vehicle parts, ship parts, aircraft parts, building materials, electrical parts,
It can be widely used in various industrial fields such as office equipment, furniture, packaging materials, and as a composite metal material in place of metals.

That is, the present invention provides a metal laminate in which metal plates of the same type or different types are laminated via an intermediate adhesive layer, in which a crystalline propylene-ethylene random copolymer with an ethylene content of 0.5 to 7% by weight is used as the intermediate adhesive layer. An unsaturated carboxylic acid obtained by graft-modifying a polymer and/or an ethylene-containing crystalline propylene-ethylene block copolymer of ti to 30 tS with an unsaturated carboxylic anhydride in the presence of a radical initiator while melting. It consists of a modified polymer having an anhydride content of 0.001 to 2% by weight and a melt index of 1 to 300, or a mixture of the modified polymer and an unmodified olefinic polymer, and an unsaturated carboxylic acid anhydride in the mixture. A polymer mixture in which the content of O, OO is 1% or more by weight (
It consists of using an adhesive resin composition consisting of 1100 parts by weight of B, a median diameter of 10 J1 or less, an iodine adsorption amount of 20"P-1/p, and magnesium oxide (CIo, 1 to 10 weight parts) of MgO or more. This invention relates to a metal laminate.

In the present invention, the ethylene content of the modified polymer (crystalline propylene-ethylene random copolymer used as one of the base resins for Al) is 0.5 to 7% by weight, particularly 1 to 5% by weight. The ethylene content of the crystalline propylene-ethylene propylene copolymer is preferably from 1 to 39% by weight, and preferably from 2 to 20% by weight. These crystalline propylene-ethylene copolymers are produced using general number ζ Ziegler-Natsuta catalysts in the presence or absence of a solvent, and have a crystalline polymer as the main component. ,
The melt index of these copolymers is generally preferably 15 or less. Here, when these crystalline propylene-ethylene copolymers are used, modified polymers with a higher grafting rate than propylene homopolymers can be obtained, and as mentioned above, it is possible to limit the ethylene content to a specific range. Depending on the number, a product with an excellent balance of adhesiveness and resin strength can be obtained.

The modified polymer was produced by graft-modifying the above-mentioned propylene polymer with an unsaturated carboxylic acid dihydride in the presence of a radical initiator using a melt mixing method.

Here, examples of unsaturated μ-bonic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, imicic anhydride, bicyclo(2,2,2)octa-5
-Conic-2,3-cyclic acid anhydride, 4-methylcyclohex-4-cyclonic acid anhydride, 1
゜2.3,4,5,8,9.10-octahydronaphthalene-2,3-cica μboxic anhydride, bicyclo(2,2
,1) Octa-7-nin-2゜3.5.6-Chitraka〃
Bonic acid-2,3*5 *6-dianhydride, 7-oxabicyclo(2,2.

1) Hebuta-5-ene-2,3-cica μboxic acid anhydride and the like. Among these, maleic anhydride is particularly preferably used.

In addition, if necessary, these unsaturations, monomers copolymerizable with enoic acid, such as esters derived from these carboxylic acid anhydrides, amides, derivatives such as acids, (meth)acrylic acid, ( meth) methyl acrylate, (meth)
(meth)acrylic acid derivatives such as ethyl acrylate, vinyl esters such as vinyl acetate, styrenic monomers,
Acrylonitrile, A/type monomers, vinylsilane type monomers, etc. can also be used. Modified polymer (content of unsaturated carboxylic acid anhydride in Al is 0.0012012
The amount is preferably 0.01 to 1 part by weight.

Here, the content of unsaturated carboxylic anhydride is 0.001
If it is less than 2% by weight, the effect of improving adhesion and reinforcing it is small;
Increasing the amount more than 10% is difficult from a manufacturing standpoint, and increasing the amount even more has no significant effect.

Any known radical initiator can be used as the radical initiator added during the production of the modified polymer. For example, 2,2'-azobisisobutyronitri/L',2,2'-azobis(2
, 4,4-)limethylvaleronitrile), methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,5.5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)butane, t- Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-cybidrobaroxide, di1-butyl peroxide, 2,5-dimethyA/-2,5- Di((-butylperoxy)hexane, 2,5-dimethy/L'-2,5-di(
1-butylperoxy)hexyne-3, lauroyl peroxide, 3.5.5-trimethylhexanoyl peroxide, benzoyl peroxide, 1-butyl peracetate, -butyl peroxyisobutyrate,
t-Butylperoxybivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-)limethylhexanoate, t-butylperoxylaurate, (- Butyl peroxybenzoate, di-t-butylshiba-oxyisophthalate, 2.
5-dimethyA/-2,5-di(benzoylperoxy)
Examples include various organic peroxides such as hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and polystyrene peroxide. Among these, preferably for 1 minute or more at 100'C
Organic peroxides with a half-life of decomposition of minutes or more are particularly effectively used. In addition, these radical initiators are 2
Kernels can be made by mixing more than seeds.

The amount of these radical initiators added is generally 0.001 to 2 parts by weight per 100 parts by weight of the copolymer, considering the graft reaction rate and the slight decrease in molecules due to the decomposition of the crystalline propylene-ethylene copolymer by the radical initiator. A range of 50% is preferred. Particularly preferred addition amounts are O', O'5-1
Parts by weight.

(within the graft-modified polymer) is the crystalline propylene L/7-
It can be easily produced by melt mixing a mixture of an ethylene copolymer, an unsaturated carboxylic acid anhydride, and a radical initiator.

In this case, in order to improve the dispersion of the unsaturated carboxylic acid anhydride and the radical initiator into the raw material crystalline propylene-ethylene copolymer, they may be added as a solution in a small amount of a good solvent. can. The melt mixing is generally carried out using a scree inserter, a Banbury mixer, a kneader, or the like. The crosstalk temperature at this time is usually 170~3
00°C, preferably 190-250°C, time 0.5-250°C
A range of 10 minutes is suitable. Further, the reaction atmosphere may be air, but preferably an inert gas such as nitrogen.

In addition, in order to remove unreacted unsaturated carboxylic acid anhydride and low molecular weight by-products contained in the obtained modified polymer,
It is also possible to perform vacuum evacuation or solvent extraction while melting. The melt index of the modified polymer thus obtained is limited to 1-300. Here, if the melt index is lower than 1, the processability will be poor, while if it is higher than 300, the resin strength will be 3 points below and 6 IL). Mixtures (B) with unmodified olefinic polymers can also be used as components of the reinforced polyolefin compositions of the present invention. Here, examples of the unmodified olefin polymer include crystalline propylene-ethylene copolymer, crystalline or amorphous polypropylene, amorphous ethylene-propylene copolymer, low-density or high density polyethylene, polybutene-1, poly-4-methylpentene-
1. Propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid partial metal salt copolymer, ethylene-(meth) Acrylic acid-(meth)acrylic acid ester copolymer, ethylene-methyl(meth)acrylate copolymer, ethylene-ethyl(meth)acrylate copolymer, ethylene-glycidyl/I/(meth)acrylate copolymer , mainly tyrene-aminoalkyl (meth)acrylate copolymer, ethylene-vinyl alcohol copolymer,
Examples include homopolymers and copolymers of various olefins, such as ethylene-styrene copolymers.

Moreover, two or more types of these olefin polymers can be used in combination. From the viewpoint of adhesive effect, the amount of these olefin polymers added is such that the content of unsaturated carboxylic acid anhydride in the mixture of modified polymer and unmodified olefin polymer is 0.401 weight or more. Magnesium oxide (C1) used as an effective component of the adhesive resin composition in the present invention has a median diameter of 10# or less and an iodine adsorption amount of 20#I/F, M
Limited to gO or more.

The diane diameter and iodine adsorption amount are values determined by the method described below. The effect of adding magnesium oxide having this specific value is extremely large, and the adhesion can be dramatically improved. It is preferable to use a particle with a diameter larger than 10#, as it is less effective in improving adhesion than a small particle size of 10μ or less at the same amount. do not have. Furthermore, when the iodine adsorption/adsorption amount is lower than 20Mg・1/f-MgO, there is no remarkable adhesion improvement effect. For example, high-purity magnesium manufactured by Kyowa Chemical Industry ■, industrial magnesium oxide, magnesium oxide for synthetic rubber, and Ki1-Wamag 20.
Wamag 30, Wamag 40, Wamag lσ0゜ heavy magnesium oxide, extra light magnesium oxide, etc.
Other examples include industrial magnesium oxide manufactured by Shima Kagaku Kogyo (■), magnesium oxide for neoprene, and mixtures thereof. From the viewpoint of the adhesion improving effect and the physical property balance of the resin composition, the amount of magnesium oxide added in (B) is based on 1100 parts by weight of the graft-modified polymer (excluding the graft-modified polymer) or the mixture CB of the graft-modified polymer and the unmodified olefin polymer. It is limited to the range 1 of 0.1 to 10 parts. Furthermore, the preferable addition amount of magnesium oxide is 0.5 to 5
This is ffi@department. Further, it is desirable to add magnesium oxide in an amount equal to or more than the equivalent mole of unsaturated carboxylic anhydride contained in the modified polymer. In this case, if the amount of magnesium oxide is less than 0.1 part by weight, there will be no significant effect of improving the adhesion, and if it exceeds 10 parts by weight, the inherent properties of the polyolefin resin will be lost, which is not preferable.

In the present invention, the adhesive resin composition used as the intermediate adhesive layer is generally a mixture of a graft-modified polymer and magnesium oxide, or a mixture of these and an unmodified olefin polymer added to the above-mentioned melt mixer. manufactured using The composition thus produced can take any shape depending on the purpose of use, such as powdered ice, pellets, sheets, films, fibrous materials, net-like materials, cloth-like materials, and tube-like materials. There is no particular limit to the thickness of this composition as an intermediate adhesive layer, but it is generally used within a range of 0.01 to 2 m. Additionally, antioxidants, heat stabilizers,
Various additives such as light stabilizers, nucleating agents, lubricants, plasticizers, antistatic agents, inorganic or organic fillers, crosslinking agents, foaming agents, and rust preventives are added to the composition during the manufacturing process or subsequent processing steps. It can be added in

The metal materials used in the present invention are I-B and I-B of the periodic table.
, (2), (2), (2), and (2) group metals, or an alloy containing these as one component. Among these, particularly suitable metals include aluminum, iron, nickel, cobalt, chromium, zinc, titanium, tin, gold, silver, copper, etc., or carbon steel, stainless steel, brass, bronze, and Jura IV.
These include alloys of these metals such as iron, and surface-treated products of iron such as galvanized iron and tinplate. The thickness of the metal plate may be any thickness depending on the purpose of use, but a thickness of 0.02 to I'm is usually used.

When carrying out the present invention effectively, organic solvents such as petroleum benzene, toluene, chloroethylene, and surfactants are generally used to remove oil and deposits that adhere to the surface of metal materials. It is recommended to use a cleaning agent. In addition, blasting treatments such as sandblasting and syrup blasting, alkali treatment, phosphate treatment,
Treatment can also be carried out by chromate treatment or a combination of these various treatment methods.

Further, if necessary, the surface can be treated with various primers such as epoxy resin, urethane resin, polybutadiene resin, etc. These surface treatments result in a metal laminate that is very strong and has excellent durable adhesive properties.

41 of the present invention! The metal laminate can be manufactured using known processing techniques, such as a heat-pressing method, an extrusion coating method, a dry lamination method, and the like.

The processing temperature at that time is generally higher than the melting point of the adhesive resin,
The temperature is 00°C or lower, preferably 250°C or lower.

These methods can produce a metal laminate in which metal plates of the same or different types are bonded together. Furthermore, depending on the purpose of use, it is possible to improve the thermal properties and strength of the adhesive resin material, or the dimensional stability of the intermediate adhesive layer during lamination. Therefore, for such purposes, polymeric materials having a higher melting point, lower melt flow, properties, higher molecular weight, or higher strength than the adhesive resin composition are generally used. These high polymer materials include, for example, crystalline polypropylene, crosslinked polyethylene, crosslinked ethylene copolymers, ethylene-diene copolymer rubber, natural or synthetic rubbers, cellulose and its derivatives, polyamides, polyimides, polyesters, polyacrylonite. μ
Sulfone, polycarbonate, polyurethane, epoxy resin, alkyto resin, melamine resin, pheno-p resin,
Examples include natural or synthetic polymeric materials such as urea resin, wool, leather, wood, and bamboo. These materials can be used in a variety of shapes, such as films, sheets, fibrous materials, net-like materials, cloth-like materials, and sponge-like materials. Furthermore, as the material to be interposed between the adhesive resins, inorganic materials such as glass fiber, asbestos, carbon fiber, a/l/'i, and su fiber, or composites made of these and polymeric materials can be used.

The metal surface of the metal laminate produced by the above method may be coated with various paints or polymeric materials for corrosion prevention or decorative purposes.
. 41. 821.4 Auto parts such as car body, bonnet, fender, dash board, floor, air cleaner, oil pan, seat frame, trim; home appliance parts such as refrigerator, washing machine, audio, air conditioner, etc. Widely used as building materials such as doors, shutters, walls, soundproof fences, and elevator interiors; office supplies such as office desks and cabinets; containers such as trunks and containers; and color decoration materials.

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

The various measured values shown in the present invention were measured by the following methods.

(1) Median diameter of magnesium oxide was measured using a light transmission type particle size distribution analyzer using ethyl alcohol as a medium. The median diameter is a value expressed by the 50 inch particle diameter of the cumulative particle size distribution curve.

(2) Amount of iodine adsorbed by magnesium oxide A sample was placed in a carbon tetrachloride solution of iodine (0, IN), and the sample was sealed and
After shaking for 5 minutes and leaving it for 5 minutes, remove only the supernatant with 0.03
In addition to N-iodopotassium solution, it was determined by adjusting with 0.05N-sodium 1,000 sulfate solution.

(3) The ethylene content of the crystalline propylene-ethylene copolymer was determined by NMR measurement at 13.

(4) Unsaturation power μ-bonic acid-free content in modified polymer The modified polymer was purified by dissolving it in xylene and precipitating it with acetone, and was determined by Purcali suitable method.

(5) Melt index Measured in accordance with JIS K-7210 or NI-6730 under a load of 2.18 kg at 230°C for propylene polymers and 190°C for polyethylene. The unit of measurement value is F/10m1n.

(6) Adhesive strength with the steel plate is interposed with an adhesive composition, 210°C, 10 Q/cx
? They were pressed together for 5 minutes. This steel plate force) width 1
A 0-layer test piece was prepared and the temperature was 20°C.

Peel strength was measured at an angle of 90'' at a tensile speed of 200 m/min.

(7) Adhesive strength to aluminum After degreasing an aluminum plate with a thickness of 0.3 m with a mixed solvent of acetone and toluene, an adhesive composition was interposed between the aluminum plates, and the adhesive composition was placed between the aluminum plates at 200°C and lO 102 for 5 minutes. Pressed and pasted together.

The following tests were conducted using the same method as in section (6) above.

Example 1 Crystalline propylene-ethylene random copolymer powder having an ethylene content of 4 aS and a melt index of 7, 100 parts by weight, 0.7 parts by weight of maleic anhydride, and 0.2 parts by weight of t-butyl peroxylaurate. were mixed in a Henssier/L' mixer, and this mixture was melt-kneaded in a 120-meter twin-screw extruder at a temperature of 220° C. and an average residence time of 1 minute to obtain graft-modified polymer pellets.

The melt index of this modified polymer was 29, and the weight of the maleic anhydride-containing hawk was 0.25.

For 40 parts by weight of this graft modified polymer, the median diameter was 2.7 #1. 1.2 and 5 parts by weight of magnesium oxide powder with an iodine adsorption amount of 30"? 1/l MgO, respectively,
As an antioxidant, 0.1 part by weight of Irganox 101G (manufactured by Ciba Geigy), 1 part by weight of the crystalline propylene-ethylene random comonomer ao used in Example 1,
Add 10 parts by weight of low-density polyethylene with a melt index of 10, mix with a Henschel mixer, and then knead at 230°C with the above extruder trowel to obtain a melt index of 1.
A pellet of composition No. 2 was obtained. This composition was attached to a T die with 30
■ Extruded at 230℃ using a single screw extruder, width 200■
A composition sheet having a thickness of 0.4+wlI was obtained.

This composition sheet was used as an intermediate adhesive layer, and a steel plate and an A/L/minium plate were bonded to each other, and the adhesive strength thereof was measured.

The results of B are shown in Table 1.

Comparative Example 1 Modification was carried out under the same formulation conditions as in Example 1 except that 0.001 part of maleic anhydride was added when producing the graft-modified polymer, and the maleic anhydride content was 0.0005 parts by weight. A modified polymer with a melt index of 34 was obtained. Hereinafter, the method of Example 1 was repeated.

The results of B are shown in Table 1.

Comparative Examples 2 to 4 The method of Example 1 was repeated except that the amount of magnesium oxide added, the median diameter, and the amount of iodine adsorbed were changed as shown in Table 1. The results are shown in Table 1.

Example 2 In producing a graft modified polymer, a crystalline propylene-ethylene block copolymer containing 17% by weight of ethylene and a melt index of 2 was used, and 0% of maleic anhydride was used.
．． 111 parts, 0.2 parts of t-butyl peroxylaurate
Melt index 8 and maleic anhydride content 0.05 weight 1 were prepared by the method of Example 1, except that 1 part was added.
% modified polymer was obtained. Per 100 parts by weight of this modified polymer, median diameter 2.2μ, iodine adsorption amount 70η・17
The procedure of Example 1 was repeated again, except that 2 parts by weight of 1 Mg0 of magnesium oxide were added.

The results are shown in Table 1.

Comparative Example 5 The method of Example 2 was repeated except that the median diameter was 2.5 microns, the iodine adsorption amount was 7.about.I/F, and MgO magnesium oxide was added. The results are shown in Table 1.

Comparative Example 6 In Example 2, 1 part by weight of the modified polymer, 10 parts by weight of the crystalline propylene-ethylene block copolymer used in Example 2
The method of Example 2 was repeated, except that the adhesion test was conducted using a composition consisting of 0 parts by weight and 2 parts by weight of magnesium oxide. The results are shown in Table 1.

Example 3 In Example 1, when producing the graft modified polymer,
A melt index of 12 and a maleic anhydride content were prepared by the method of Example 1, except that a crystalline propylene-ethylene random copolymer with a melt index of 3 and an ethylene content of 2 was used, and 0.2 parts by weight of maleic anhydride was added. 0
．． A modified polymer of 0.06% by weight was obtained.

Ethylene content is 5 parts by weight per 100 parts by weight of this modified polymer.
0, Mooney viscosity (100°C) 35 ethylene-propylene copolymer rubber 10-layer plate part and median diameter 2.9
A composition consisting of 2 parts by volume of magnesium oxide with an iodine adsorption amount of 55° was prepared by the method of Example 1. Hereinafter, the method of Example 1 was repeated.

The results are shown in Table 1.

Comparative Example 7 In Example 3, the method of Example 3 was repeated except that a propylene homopolymer having a melt index of 3 was used in producing the graft modified polymer. The results are shown in Table 1.

Example 4 Crystalline brepyrene-ethylene block copolymer powder 100 containing up to 15% ethylene and melt index 2
Parts by weight, 0.8 parts by weight of maleic anhydride, and 0.3 parts by weight of t-butyl peroxybenzoate were mixed in a Henschel mixer, and then the mixture was heated in a 30 mm single screw extruder at a temperature of 230°C for an average residence time. The mixture was melt-kneaded for 3 minutes to obtain a graft-modified polymer. The melt index of this modified polymer was 16, and the maleic anhydride content was 0.37 wt. To 30 parts by weight of this modified polymer, 70 parts by weight of crystalline propylene-ethylene propylene copolymer powder with an ethylene content of 15% by weight, a melt index of 1, a median diameter of 2.7#, and an oxidized iodine adsorption amount of 30% were added. The magnesium mixture was kneaded at 230° C. in a 30 md extruder to obtain a resin composition with a melt index of 4.

Hereinafter, the method of Example 1 was repeated. The results are shown in Table 1.

Comparative Example 8 The method of Example 4 was repeated except that magnesium oxide with a median diameter of 3.2μ and an iodine adsorption amount of 5I9·I/p-MgO was added. The results are shown in Table 1.

Comparative Example 9 In Example 4, median diameter was 21#, iodine adsorption amount was 3
The method of Example 4 was repeated except that magnesium oxide of 011W, I/p.MgO was added. The results are shown in Table 1.

! J) 11:5. ,. □1l151J1%, jlVh4
50 parts by weight of crystalline propylene-ethylene block copolymer powder of 7fx3 and ethylene content 2% by weight,
Using a mixture consisting of 50 parts by weight of a crystalline propylene-ethylene random copolymer having a melt index of 5, 0.5 parts by weight of maleic anhydride and 0.4 parts by weight of [-butyl peroxylaurate, the process was carried out under the conditions of Example 10. Graft denatured. As a result, a modified polymer having a melt index of 12 and a maleic anhydride content of 0.26% by weight was obtained.

Median diameter ass# for 20 parts by weight of modified polymer
A mixture consisting of 2 parts by weight of magnesium oxide with an iodine adsorption amount of 100 and 80 parts by weight of crystalline polypropylene with a melt index of 1 was mixed with a 30 m/J extruder number trowel at 220°C to obtain a composition pellet with a melt index of 3. Ta. This composition was heated at 230°C in a 30+m* extruder equipped with a T-die.
A sheet with a thickness of 0.6 cm was obtained by extrusion.

Ta. Hereinafter, an adhesion test with a steel plate was conducted in the same manner as in Example 1, and as a result, the adhesion strength was 104/rIa. In addition, the adhesive strength after heating at 100°C for 500 hours was 91';q
/cs.

Comparative Example 10 The method of Example 5 was repeated except that magnesium oxide with a median diameter of 2.8 # and a bonito adsorption amount of 3'9.17 g.MgO was used. As a result, the adhesive strength with the steel plate was 511/n. Also, 100℃, 5
The adhesive strength after heating for 00 hours was 4 Q/am.

Comparative Example 11 In Example 5, the median diameter was 25μ, the iodine adsorption amount was 2
1'9-1/P-MgO (D) The method of Example 5 was repeated except that magnesium oxide was used. As a result, the adhesive strength with the steel plate was 6 times.
The adhesive strength after heating for 00 hours was 4 instant/α. As shown in the examples above, the metal laminate of the present invention had an initial adhesive strength that was superior to each comparative example by -). It can be seen that it has.

In particular, the laminate of the present invention exhibits almost no decrease in strength even when heated at high temperatures for long periods of time, and has excellent durability.

Claims (1)

[Claims] (1) In a metal laminate formed by laminating metal plates of the same or different types via an intermediate adhesive layer, the intermediate adhesive layer is a crystalline propylene-ethylene random copolymer with an ethylene content of 0.5 to 7 ml. A crystalline propylene-ethylene block copolymer having a coalescence and/or ethylene content of 1 to 10 parts by weight is graft-modified with unsaturation power to ponic acid anhydride in the presence of a radical initiator by a melt-mixing method. Obtained unsaturated carboxylic anhydride content 110.001-2
Weight%, modified polymer with melt index 1-300^
), or a polymer consisting of a mixture of the modified polymer and an unmodified olefin polymer, in which the unsaturation power to the oxygen anhydride content in the mixture is 0.001 weight or more (BI100 polymer) A metal laminate characterized by using a resin composition consisting of magnesium oxide (C10,1 to 10 parts by weight) with a median diameter of 10μ or less and an iodine adsorption maximum of 20M9.1/f-MgO or more. .