JPS6179648A - Laminate and manufacture thereof - 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 [Industrial Field of Application] The present invention relates to a laminate comprising a metal layer and a polymer layer and a method for producing the same.

[Conventional technology]

Since polyolefin resin is non-polar, it has excellent chemical and electrical properties and is used in a variety of fields. However, on the other hand, it has very poor adhesive properties, so it is not suitable for adhesive purposes. could not be used at all.

Therefore, various improvement methods have been proposed in order to impart adhesive properties to polyolefin resins, and one of them is to replace polyolefin resin with γ-methacryloyl oxy7probyltrimethoxycidine.

A method has been proposed for improving the adhesiveness of polyolefin resins by modifying them with a type of modifier selected from glycidyl methacrylate and an organic peroxide.

[Problems to be Solved by the Invention] However, 10 to 80% by weight of the modified polyolefin obtained by graft modification under heating with the modified organosilane compound obtained by this method and 10 to 8% of the unmodified polyolefin resin. Weight and powdered inorganic substances 5~
The present invention relates to a laminate formed by laminating an adhesive polyolefin composition of 50% by weight (total ioo% by weight) with a uniform adhesive layer having a thickness of 1 μm or more interposed therebetween.

Furthermore, the present invention provides 10 to 80% by weight of a modified polyolefin obtained by graft-modifying a polyolefin resin with an organic silane compound having an ethylenically unsaturated bond under heating between a metal layer and a polymer layer. Polyolefin resin 10-80% by weight and powdered inorganic substance 5-5%
0% by weight (total 100% by weight) of an adhesive polyolefin composition, and heat-press bonding is performed so that the adhesive layer formed thereby has a thickness of 1μ or more. It is something.

In the present invention, the metal forming the metal layer is not particularly limited, and the adhesion of iron, aluminum, chromium, nickel, gold, silver, copper, zinc, tin, steel, and polyolefin has not yet been improved. It cannot be called a kimono. In particular, when this modified polyolefin is used as an adhesive for bonding metal plates such as 1-chrome plated steel plates and stainless steel plates, it is necessary to degrease the adhesive surface of the metal plates in advance, and the Even when metal plates are bonded together, the adhesive strength of the resulting laminate is still not satisfactory.

A laminate of a metal layer and a polymer layer using such a modified polyolefin as an adhesive layer does not have a satisfactory adhesive strength. For this reason, the range of use of conventional laminates has been largely limited.

[Failure to solve the problem]

The present inventors completed the present invention as a result of intensive research aimed at providing a laminate in which a metal layer and a polymer layer are firmly adhered to each other via an adhesive layer mainly composed of a polyolefin resin.

That is, one aspect of the present invention includes a metal layer and a polymer layer.

Examples of polyolefin resins with ethylenically unsaturated bonds include steel, galvanized iron, and tinplate, especially iron.

Steel, stainless steel and aluminum are preferred.

The above-mentioned metal may be plate-shaped, tubular, or rod-shaped; it is usually plate-shaped, and may or may not be degreased. In the case of a metal tube, either the inner or outer surface of the tube may be used.

In the present invention, the polymer forming the polymer layer is not particularly limited, and may be a polyolefin such as polypropylene (crystalline homopolymer).

crystalline random or block copolymers of propylene and ethylene or other α-olefins, such as butene-1, hexene, octene, etc.).

Polyethylene (ethylene alone x combination, x-f L/
y-hinyl acetate copolymer, ethylene and α-olefin.

For example, copolymers with butene-1, hexene, octene, etc.), natural rubber, elastomers (copolymers of ethylene-lene-butadiene-7, etc., polybutadiene), and unsaturated acids, acid esters, and metal salts thereof.

It is also possible to use those that have been addition-modified with derivatives such as imide or amide, or those that have been partially crosslinked. Known inorganic fillers for these polymers.

For example, calcium carbonate, Merck, carbon black, metal powder, fibrous materials or woven fabrics thereof, etc. can be added as necessary. The amount added is determined as appropriate depending on the use of the laminate. Further, the polymer layer may be a foam having closed cells or open cells. The thickness of the polymer layer is 0.01~20mm, especially 0.1~! A length of 5 m is preferred. Also conductive filler in the polymer layer (and adhesive).

For example, metal laminates are created by adding carbon fiber, metal fibers, flakes or powder, and filler metal plating (basic structure: metal layer - adhesive layer - polymer layer - adhesive layer - metal layer)
spot welding.

In the present invention, modified polyolefin 10 to 80 is obtained by graft-modifying a polyolefin resin with an organic silane compound having an ethylenically unsaturated bond under heating.
10-80% by weight of unmodified polyolefin resin and 5-50% by weight of powdered inorganic material (total IOO% by weight)
It is necessary to use a uniform adhesive layer made of a polyolefin composition with a thickness of 1μ or more, preferably 10 to 80μ, thereby firmly bonding the metal layer and the polymer layer through the adhesive layer. Can be glued to.

Also, various combinations of polymer layers and adhesive layers are possible.

The above-mentioned modified polyolefin can be obtained by graft-modifying the polyolefin resin by heating in the presence of a polyolefin resin, an organic silane compound having an ethylenically unsaturated bond, and preferably an organic peroxide.

The polyolefin resin mentioned above is a crystalline homopolymer of propylene, a copolymer with propylene, and the content thereof is about 1
Crystalline propylene polymers such as binary or more block or random copolymers with 5% by weight or less of other α-olefins (flu is ethylene, phthene, pentene, hexene, heptene, etc.), or crystalline propylene polymers with a density of 0.93 ? Other α-olefins (propylene, phthene, pentene, hexene, heptene, etc.) whose content in the ethylene homopolymer or ethylene copolymer is about 15% by weight or less
Examples include ethylene polymers such as block or random copolymers of two or more elements. Among these, random or block copolymers of ethylene and propylene with an ethylene content of 2 to 15% by weight, or this copolymer with a density of 0.93? It is preferable to mix up to 50% by weight, particularly up to 25% by weight, of an ethylene polymer having a molecular weight of /- or more. In addition, the melt flow rate (MFR) of polyolefin resin is 0;01~20 f/10
Minutes.

Especially 0. /~10P/10 minutes is preferable. A stabilizer or the like may be added to the polyolefin resin.

In addition, the above-mentioned organic silane compounds having ethylenically unsaturated bonds (hereinafter also simply referred to as modifiers) include:
Vinyltriethquinsilane, methacryloyloxytrimethoxysilane 1 γ-methacryloyloxyglopyltrimethoxy 7rane, methacryloyloxy/cyclohexyltrimethoxysilane, γ-methacryloyloxypropyltriacetyloxinrane, methacryloyloxytriethoxy Examples include silane, γ-methacryloyloxyglobiltriethoxy 7rane, and the like. In the present invention, other modifiers may be used in combination with the organosilane compound having an ethylenically unsaturated bond. There are no particular limitations on such modifiers, and examples include allylgly7dyl ether, 2-methyl-allylgly/dyl ether, sodium acrylate, sodium methacrylate, calcium acrylate, calcium methacrylate, and magnesium/um acrylate. .

Magnesium methacrylate, zinc acrylate.

Zinc methacrylate, aluminum acrylate.

Aluminum methacrylate, iron acrylate (■).

Metal salt compounds of (meth)acrylic acid such as iron(II[) methacrylate, triallylcyanurate, tri(2-
methylallyl) cyanurate, 1.3.5-triacryloylhexahydro-5-)lyazine.

1,3,5-trimethacryloylhexahydro-8-
triazine, 4-acryloyloxyphenol, 4-
(acryloyloxymethyl)phenol, 4-7ri'
) Royloxybenzyl alcohol.

4-methacryloyloxyphenol, 4-meth:jZ
Examples include 7-(+)loyloxybenzyl alcohol, 4-(methacryloyloxymethyl)benzyl alcohol, and the like.

Furthermore, the organic peroxide mentioned above is preferably one having a 1-minute half-life temperature of about 160 to 260°C, such as tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisopropyl carbonate, etc. Tri-butyl civa-oxyphthalate, tert-butyl peroxy acetate, 2.
5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-6, tert-butylperoxylaurate.

Tertiary butyl peroxymaleic acid, tertiary butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide.

Examples include cyclohexano/peroxide, tert-butylcumyl peroxide, 2,5-dimethylhexanone 2,5-cybidroba-oxide, and the like. These organic peroxides may be used alone or in combination of two or more.

The blending ratio of the above-mentioned polyolefin resin, the modifying agent, an organic silane compound having an ethylenically unsaturated bond, and an organic peroxide varies depending on the desired MFR of the modified polyolefin, etc. For 100 parts by weight of resin, the modifier is 0.01 to 5 parts by weight, especially 0.1 to 3 parts by weight, and the organic peroxide is 0.01 to 5 parts by weight.
Parts by weight, particularly preferably in the range of 0.1 to 2 parts by weight. What is the mixing ratio of modifier and organic peroxide?

The amount of organic peroxide is preferably in the range of 5 to 80 parts by weight per 100 parts by weight of the modifier.

The modified polyolefin used in the present invention is prepared from a polyolefin resin, a modifier and preferably an organic peroxide by a method known per se, preferably under conditions in which the organic peroxide does not decompose.

A polyolefin resin, a modifier, and an organic peroxide are mixed by applying a known suitable mixing method, and the resulting mixture is heated to a temperature at which the polyolefin resin melts but does not decompose, preferably about 180 to 260°C.

In particular, it can be obtained by heating and reacting at a temperature of 220 to 250°C. The simplest heat treatment operation is to melt and heat the mixture in an extruder at the above temperature for about 2 to 5 minutes.

The modified polyolefin obtained in the above manner is MF
R is 1 to +50?710 minutes, especially 10 to 50? /10 minutes is preferable.

As the powdered inorganic substance used in the present invention, calcium carbonate (heavy or light), talc, and particularly calcium carbonate are preferably used. The inorganic substance has an average particle size of 0.05 to 10
[mu], particularly preferred is O,OS~2[mu]. Although the inorganic substance may be surface-treated, it is preferable that the inorganic substance is not surface-treated.

Furthermore, examples of the unmodified polyolefin resin used in this invention include the polyolefin resins described above. Does unmodified polyolefin resin have an MFR of 0.1 to 10L? /
10 minutes, particularly preferably 0.3 to 5p/10 minutes,
The same type of polyolefin used to obtain the modified polyolefin is preferably used. In particular, the above-mentioned crystalline propylene polymer is preferably used as the unmodified polyolefin resin. Conventionally known additives (antioxidants, ultraviolet absorbers, etc.) may be blended with the unmodified polyolefin resin. The powdered inorganic substance and modified polyolefin may each be used in the form of a master batch of unmodified polyolefin resin.

The adhesive polyolefin composition used in the present invention includes the modified polyolefin, powdered inorganic substance, and unmodified polyolefin resin in a blending ratio of each component in one composition.
(a): 10 to 80% by weight of modified polyolefin,
(b): Powdered inorganic substance 5 to 50 parts by weight, preferably 10 to 500 to 50 parts by weight (C): Unmodified polyolefin resin 10 to 80 weight fL% (total 100 weight%) mixed You can get it by doing this. During mixing, various additives 9 such as weathering (thermal) stabilizers,
Molding aid.

Other inorganic or organic fillers, conductive fillers, etc. may be added. The simplest mixing operation is to mix each of the above components at a temperature of about 180 to 260°C, especially 220 to 250°C.
Melt and mix in a ratio machine for about 10 minutes. Examples of the extruder include a single-screw or twin-screw extruder, and a Conte 4 neutral mixer such as FCM. The effect of the present invention is further improved by performing a deaeration operation (venting) during melt-mixing. This is because there is moisture attached to the surface of the powdered inorganic substance.

The laminate of the present invention has the modified polyoff 4 film 10 to 80%
Weight ratio and unmodified polyolefin resin 10-80% by weight
and powdered inorganic substances 5-50% by weight (total 100% by weight)
This includes all materials in which a metal layer and a polymer layer are present via an adhesive layer made of an adhesive polyolefin composition and having a thickness of /μ or more. For example, laminates such as metal layer/adhesive layer/polymer layer, polymer layer/adhesive layer/metal layer/adhesive layer/polymer layer, metal layer/adhesive layer/polymer layer/adhesive layer/metal layer, etc. are suitable.

The laminate of the present invention has high adhesion strength even when not only degreased metals but also non-degreased metals 9 such as undegreased chrome, matte plated steel sheets, stainless steel, etc. are used as the metal layer, and conventionally known This is industrially extremely advantageous compared to adhesives based on polyolefin resins.

In the laminate of the present invention, the adhesive polyolefin/composition described above is interposed between the metal layer and the polymer layer.

The thickness of the adhesive layer formed by this is 1μ or more.

Preferably, it can be manufactured by heat-pressing so that the thickness is 10 to 80μ. Preferably.

Adhesive layer and polymer layer (preferably thickness 0.1 to 20 fI)
aIt) and a composite resin layer (the structure is preferably an adhesive layer/polymer layer or an adhesive layer/polymer layer/adhesive layer), and this composite resin layer and a metal layer (for example, a metal plate,
In the case of a metal plate, the thickness is preferably 0.1 to 20 strands. ) can be heat-welded using a press, roll, etc. to produce a laminate.

At this time, the temperature is preferably equal to or higher than the softening point of the modified polyolefin, and the pressure is preferably 1 to 100 Kg/(yA.The composite resin layer of the adhesive layer and the polymer layer is formed by coextruding the adhesive polyolefin composition with the polymer layer. A method of laminating an adhesive layer on the surface of a polymer layer in advance, a method of laminating an adhesive film made of an adhesive polyolefin composition (an extruded film may also be used) with a preformed sheet for forming a polymer layer, and Alternatively, it can be suitably obtained by a method of laminating a polymer layer extruded into a sheet shape with a pre-formed adhesive film.

Various laminates can be continuously produced by the method of the present invention. For example, a method for continuously producing a laminate of metal plate/adhesive layer/polymer layer/adhesive layer/metal plate is as follows. can be mentioned. That is, different or similar metal plates (which may be degreased in advance by a method known per se) are preheated using a preheating device such as an oven or a roll (preferably preheated to a temperature equal to or higher than the melting temperature of the modified polyolefin). These are then fed to a heating and pressing device such as a roll or steel belt.

On the other hand, an adhesive film and a polymer sheet, which serve as an intermediate layer, are supplied between two metal plates as a laminated sheet that is laminated separately or in advance and integrated. The adhesive film may be preliminarily adhered to the surface of the metal plate. Metal plate-
It is preferable that five layers (adhesive film, polymer sheet, adhesive film, metal plate) are stacked one on top of the other, and heated and pressed using a heating and pressing device so that at least the surface portions of the adhesive film and the polymer sheet are melted. When using a crystalline propylene polymer as the polyolefin resin (for adhesive film or polymer sheet), the heating temperature is preferably about 170 to 270°C, particularly 180 to 240°C, and the pressing pressure is generally 1 to 100 kg/ cA, especially 3~
At 100Kq/CrA, stay in this state for about 5 seconds to 10
A laminated plate (metal composite plate) is produced by holding for a minute.

The thus produced laminate is cooled under pressure using a roll or the like.

The temperature at this time is preferably a temperature equal to or lower than the crystallization temperature of the modified polyolefin. For example, crystallized polypropylene resin (
(for adhesive film) is used.

Cooling under pressure is preferred to a temperature of about 110°C or less. After being cooled under pressure to a temperature below the crystallization temperature of the modified polyolefin, it is cooled to room temperature. The laminate is then edged with a slitter if necessary, and then
It is straightened by a leveler, and then cut to an appropriate length in a cutting or winding process, or rolled up seven times to form a product laminate.

The laminate obtained by the method of the present invention generally has a thickness of 0.2 to 20 cm, has a high adhesive strength between metal plates,
It is lighter than metal plates of the same thickness, has excellent sound insulation and heat insulation properties, can be cut into various shapes, and has excellent cold workability such as drilling, bending, and drawing.

The laminate of the present invention can be used as automobile interior and exterior materials, building materials, industrial materials, and packaging materials.

〔Example〕

Next, examples will be shown. In the following description, parts indicate parts by weight, and melt flow rate (MFR) is based on ASTM D
1238, the T-peel strength to indicate adhesion is JI
Measured according to SK6854.

Example 1 Ethylene-propylene block copolymer (MFRl, 0
Si'/10 min, ethylene content 8% by weight, melting temperature approx. 1
60°C) [resin (I)] to 100 parts of powder.

As antioxidants, 0.1 part of Ganox 1010 (Musashino Geigy) and Antiox S (Nippon Oil & Fats) were used.
0.2 parts of calcium stearate, 0.05 parts of calcium stearate, 0.7 parts of γ-methacryloyloxyglopyltrimethoxysilane as a modifier, and 0.35 parts of tert-butyl peroxybenzoate as an organic peroxide, After mixing for 10 minutes in a Henschel mixer.

2 minutes at 240°C (residence time) using a 50mm single screw extruder
Melt and heat to react, MFR of about 2maX3mm+
A pellet of modified polypropylene of 25P/10 minutes was obtained. This pellet and calcium carbonate (Whiten SSB red, average particle size 1.25 μ, specific surface area 1.85 rr?/
t, Shiraishi calcium) (Charcoal carbon ■ and pellets of ethylene-propylene block copolymer (MFRl, OP/10 min, ethylene content 8% by weight, melting temperature 160°C) (contains a known antioxidant, calcium stearate) ).

After mixing 40 parts of modified polypropylene, 20 parts of calcium carbonate, and 40 parts of unmodified polypropylene in a blender, 50 Wr! Melt kneaded for 2 minutes at 250°C using a r1JZf vented-shaft extruder, and then molded to a thickness of 8 mm using a film forming machine.
It was molded into a film (adhesive film) of a 0 μ adhesive polyolefin composition.

This film was used as an adhesive layer, a sheet of resin (1) with a thickness of 0.47 cm was used as a polymer layer, and an undegreased chrome-plated steel plate (0.2 m thick x 300 @
IX 300) Using two sheets, by compression molding machine,
Preheat at 180-220℃ for 5 minutes, pressurize for 5 minutes (surface pressure 3 Kg/cA or more), then cool for 25 minutes (5 minutes).
A laminate with a five-layer structure was obtained by cooling slowly to 0°C.

A test piece (width 25 rrrm) was cut from this laminate and its adhesive strength was determined at a peeling rate of 20 cm/min. The results are summarized in Table 1.

Example 2 The adhesive layer in Example 1 was thinned from 80μ to 40μ,
The polymer layer was made thicker by that amount to obtain a laminate. The results are shown in Table 1.

Example 6 The type of metal plate was changed from steel plate to undegreased stainless steel plate (SUS
304. A laminate was obtained in the same manner as in Example 1 except that the thickness was changed to 0.15 mm). The results are shown in Table 1.

Example 4 Degreased chrome was used instead of an undegreased steel plate as a metal plate, which was immersed for 5 minutes in a 6% aqueous solution of Metasol H-400 [alkaline degreaser, Marubishi Yuka Kogyo ■] at 70 to 80°C, then washed with water and dried to degrease it. A laminate was obtained in the same manner as in Example 1 except that a plated steel plate was used. The results are shown in Table 1.

Example 5 80 parts of resin (1) and calcium carbonate (
A laminate was obtained in the same manner as in Example 1, except that 20 parts of charcoal (1) was mixed and formed into a sheet. The results are shown in Table 1.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1, except that a film made only of modified polypropylene was used in place of the adhesive polyolefin composition film (adhesive film). The results are shown in Table 1.

Example 6 A laminate was obtained in the same manner as in Example 1, except that a film of an adhesive polyolefin composition containing 20 parts of modified polypropylene, 25 parts of calcium carbonate, and 55 parts of unmodified polypropylene was used as the adhesive film. This laminate has excellent cold workability and has a T-peel strength of 13.7 Kq/Crr.
It was L.

Example 7 70 parts of each of the above components as an adhesive film.

Laminates were obtained in the same manner as in Example 1, except that films of adhesive polyolefin compositions of 10 parts and 20 parts were used. This laminate had excellent cold workability and a T-peel strength of 12.8 kg/cm.

Example 8 Each of the above components was used as an adhesive film in an amount of 10 parts.

A laminate was obtained in the same manner as in Example 1, except that a film of an adhesive polyolefin composition having tP-0 parts and tP-0 parts was used. This laminate had excellent cold workability and a T-peel strength of 1 s, sKy/α.

〔Effect of the invention〕

As described above, according to the present invention, a laminate with high adhesive strength can be obtained.

Claims (7)

[Claims] (1) The metal layer and the polymer layer are combined with 10 to 80% by weight of a modified polyolefin obtained by graft-modifying a polyolefin resin with an organic silane compound having an ethylenically unsaturated bond under heating and 10% by weight of an unmodified polyolefin resin.
~80% by weight and 5-50% by weight of powdered inorganic substances (total 1
A laminate formed by laminating an adhesive polyolefin composition (00% by weight) with a uniform adhesive layer having a thickness of 1 μ or more interposed therebetween. (2) The laminate according to claim 1, wherein the polyolefin resin is a crystalline propylene polymer. (3) The laminate according to claim 1, wherein the powdered inorganic substance is calcium carbonate. (4) Between the metal layer and the polymer layer, 10 to 80% by weight of a modified polyolefin obtained by graft-modifying a polyolefin resin with an organic silane compound having an ethylenically unsaturated bond under heating and 10% by weight of an unmodified polyolefin resin. An adhesive polyolefin composition of ~80% by weight and 5-50% by weight of a powdered inorganic material (total 100% by weight) is interposed, and the adhesive layer formed thereby is heat-pressed so that the thickness of the adhesive layer is 1μ or more. A method for producing a laminate, characterized by: (5) Production of a laminate according to claim 4, in which an adhesive layer is preliminarily laminated on the surface of the polymer layer by coextrusion molding the adhesive polyolefin composition with the polymer layer, and then the adhesive layer is bonded to the metal layer. Law. (6) The method for producing a laminate according to claim 4, wherein an adhesive film made of an adhesive polyolefin composition is laminated with a preformed polymer layer forming sheet and then bonded to a metal layer. (7) A method for producing a laminate according to claim 4, wherein the polymer layer extruded into a sheet is laminated with a pre-formed adhesive film and then bonded to a metal layer.