JPS6028658B2 - Method for manufacturing laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a laminate, and more specifically to manufacturing a sealed package for retort sterilization that has excellent flavor retention properties and delamination resistance after retort sterilization. The present invention relates to a method for manufacturing a laminate that can be advantageously used for.

Conventionally, for use in sealed packages for retort sterilization, a crystalline olefin resin layer for heat sealing is provided on one surface of an aluminum foil or sheet, and a heat-resistant resin layer such as polyethylene terephthalate is provided on the other surface. Laminated sheets are widely used.

These laminated sheets are stacked together and heat-sealed around the edges to form a bag, which is then filled with food and other contents, deaerated and sealed, and then heated and sterilized in a sterilizer called a retort. Packaged in a manner that can be stored. The crystalline olefin resin used as the sealant and inner surface material is generally inert, and since the package is subjected to severe heat sterilization, the olefin resin layer and aluminum foil or sheet are attached using only urethane adhesive ( This is done using thermosetting adhesives such as isocyanate adhesives and epoxy adhesives.

Although the above-mentioned thermosetting adhesives are generally satisfactory for the purpose of forming adhesive bonds with excellent heat resistance and hot water resistance, they are still unsatisfactory for the purpose of preserving the flavor of food contents after retort sterilization. It wasn't a kimono.

That is, thermosetting resins are complex resin compositions containing uncondensed monomers and relatively low molecular weight condensation polymers, and
In the above-mentioned package, the thermosetting adhesive layer is always located inside the impermeable metal aluminum layer, so harsh treatments such as retort sterilization can cause decondensation of the uncondensed substances and low molecules mentioned above. The coalescence tends to migrate into or interact with the food contents.

Further, the above-mentioned thermosetting adhesive is generally provided in a diluted form with an organic solvent such as toluene, ethyl acetate, or methyl ethyl ketone. When laminating aluminum foil and crystalline olefin resin film using such a thermosetting adhesive, the process of applying the adhesive to the aluminum foil, drying the solvent in a hot air oven, and then performing pressure bonding lamination is necessary. It will be done.
However, it is difficult to completely remove the organic solvent by oven drying, and this residual organic solvent may migrate into the food contents during retort sterilization treatment and may significantly impair the flavor of the food contents. Due to these reasons, although packages made of laminated sheets made by bonding a crystalline olefin resin layer and aluminum foil etc. with a thermosetting adhesive have excellent preservability, they have problems in retaining the flavor of the food contents. However, I was still not completely satisfied with it. The present inventors have found that among various thermoplastic adhesives, the degree of crystallinity is 15.
A modified olefin resin with a carbonyl group content of 1 to 95% and a carbonyl group content of 1 to 60 skin eq/100 polymer is selected, and this resin is layered between aluminum foil or the like and a crystalline olefin resin film. During melt extrusion, before bringing the modified olefin resin layer into contact with the aluminum foil or the like, or after contacting and temporarily bonding, the aluminum foil or the like is heated to a temperature higher than the Vicat softening point of the modified olefin resin, preferably at a melting point. When heated to a temperature above, it becomes possible to introduce an adhesive bond with excellent heat resistance, hot water resistance, impact resistance, etc. between the crystalline olefin resin layer and aluminum foil, etc., resulting in a laminate that can withstand retort sterilization. It has been found that when this laminate is used as a sealed package for retort sterilization, the flavor retention characteristics of the food contents can be significantly improved.

An object of the present invention is to provide a method for producing a laminate in which an impermeable aluminum foil or the like and a heat-sealable crystalline olefin resin layer are thermally bonded via a specific modified olefin resin layer.

Another object of the present invention is to form an adhesive bond between an aluminum foil or the like and a crystalline olefin resin layer that can withstand retort sterilization treatment, and furthermore, this adhesive layer can protect the contents when the package is sealed. To provide a method for obtaining a laminate that does not adversely affect flavor.

Still another object of the present invention is to provide a new method for firmly bonding a crystalline olefin resin layer and an aluminum foil or the like by a technique called so-called extrusion lamination.

According to the present invention, the degree of crystallinity is between 15 and 9 between the aluminum foil or sheet and the crystalline olefin resin film.
At 5%, the carbonyl group content is 1 to 60 eq/10
Melt-extrude a modified olefin resin in a layered manner at a polymer concentration of 0.0 and whose constituent olefin units are of the same type as the crystalline olefin resin, to form the aluminum foil or sheet,
There is provided a method for producing a laminate, which comprises maintaining the laminate at a temperature equal to or higher than the Vicat softening point of the modified olefin resin prior to bringing it into contact with the modified olefin resin.
According to the present invention, there is a crystallinity of 15 between the aluminum foil or sheet and the crystalline olefin resin film.
95% to 95%, carbonyl group content 1 to 60mhe
A laminate in which the modified olefin resin is temporarily adhered to an aluminum foil or sheet is prepared by melt-extruding a modified olefin resin in a layered manner at a concentration of q/100 polymer and whose constituent olefin units are the same type as the crystalline olefin resin. There is provided a method for producing a laminate, which comprises producing the modified olefin resin, and then heating the laminate to a temperature equal to or higher than the Vicat softening point of the modified olefin resin.

The invention will be explained in detail below.

In FIG. 1 showing the cross-sectional structure of a laminate produced by the method of the present invention, a laminate sheet 1 includes an aluminum foil or sheet 2, and a crystalline olefin resin layer 4 bonded to at least one surface of the aluminum foil or sheet 2 via a modified olefin resin layer 3. The other surface of the aluminum foil 1 may have a heat-resistant resin layer 6 bonded via an adhesive layer 5 if desired.

An important feature of the present invention is that the adhesive for bonding the aluminum foil 1 and the crystalline olefin resin layer 4 has a crystallinity of 15 to 95%, particularly 40 to 80%, and a carbonyl group content of 1. Select a modified olefin resin that is in the range of 60 to 60 heq/100 heq polymer, especially 10 to 30 heq/100 heq polymer, and whose constituent olefin units are the same type as that of the crystalline olefin resin. The purpose of the present invention is to bond the melt-extruded layer and aluminum foil or the like at a temperature equal to or higher than the Vikato softening point of the modified olefin resin. First, the crystallinity of the modified olefin resin is 1.
If it is 4% higher than 5%, it is extremely difficult to form an adhesive bond between the crystalline olefin resin layer and the aluminum foil that can withstand retort sterilization, and manufacturing using this laminate is difficult. In such a sealed package, delamination easily occurs in a retort atmosphere containing hot water or hot steam at a temperature higher than 100°C. In addition, the carbonyl group content is lme
It is difficult to form a sufficient adhesive bond with aluminum foil with a modified olefin resin whose carbonyl group content is lower than that of a polymer with a carbonyl group content of 60 haq/1.
If the modified olefin resin is higher than the 00 polymer, it will still be difficult to form a sufficient adhesive bond with the crystalline olefin resin layer. Furthermore, when the constituent olefin monomers of the modified olefin resin are different from those of the crystalline olefin resin, significant interlayer separation occurs during retort sterilization. Furthermore, when simply melt-extruding a modified olefin resin between a crystalline olefin resin layer and an aluminum foil, etc., and press-bonding the two through the modified olefin resin layer, there is still a strong bond between the two that has good hot water resistance, etc. This makes it difficult to form a good adhesive bond (see Comparative Example 3).

On the other hand, according to the present invention, a modified olefin resin whose type, crystallinity and carbonyl group content of constituent olefins are within the above-mentioned ranges is selected as the modified olefin resin, and a melt extruded product of this modified olefin resin is and an aluminum foil, etc. which has been previously maintained at a temperature equal to or higher than the Vicat transformation point of the modified olefin resin, or a laminate in which the modified olefin resin is temporarily bonded to the aluminum foil, etc. is bonded to the modified olefin resin. By maintaining the temperature above the Vicat softening point of the resin, we succeeded in creating a strong adhesive bond between the crystalline olefin resin layer and aluminum foil, etc. that can withstand hot water and hot steam. be.

In the present invention, the exact reason why the adhesive strength and the retort resistance of the adhesive interface are improved by preheating the aluminum foil, etc. mentioned above or after heating the temporary adhesive is unknown, but the preheating of the aluminum foil, etc. By heating or post-heating the temporary adhesive,
It is presumed that the main reason is that the interfacial adhesive strength is increased due to the interaction between the aluminum metal and the carbonyl group, which is a functional group of the modified olefin resin.

In this specification, crystallinity refers to
Polymer Science (J.Pol m.Sci.) Volume 18, pp. 17-26, 1955 (S.L.Ag.
walandG. D. It means the degree of crystallinity determined by the x-ray diffraction method described in J.D. Tilley).

In the present invention, as the modified olefin resin, a known carbonyl group-containing ethylenic lower saturated monomer is used to modify the main chain or side of the olefin resin by graft copolymerization, block copolymerization, random copolymerization, or terminal treatment. Among those introduced into the chain, those that satisfy the above conditions are used.

As the carbonyl group-containing ethylenically unsaturated monomer, a carbonyl group based on a carboxylic acid, a carboxylic acid salt, a carboxylic acid anhydride, a carboxylic acid ester, a carboxylic acid amide or imide, an aldehyde, a ketone, etc. alone, Or a cyano (1C2N) group; hydro.

One type or a combination of two or more types of ethylene unsaturated monomers having a combination with an xy group, an ether group, an oxirane ring, etc. can be used, and suitable examples thereof are as follows.

A. Ethylenically unsaturated carboxylic acids: acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid.

B Ethylenically unsaturated hydroruboxic acid anhydride: maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride.

C Ethylenically unsaturated ester: ethyl acrylate, methyl methacrylate, acrylic acid 2
-Ethylhexyl, mono- or di-ethyl maleate, vinyl acetate, vinyl propionate, propyl y-hydroxymethacrylate, ethyl 8-hydroxyacrylate, glycidyl acrylate, glycidyl methacrylate, 8
-N-ethylaminoethyl acrylate.

D Ethylenically unsaturated amide or imide: acrylamide, methacrylamide, maleimide.

E. Ethylenically unsaturated aldehydes or ketones: acrolein, methacrolein, vinyl methyl ketone, vinyl butyl ketone.

In the present invention, among the above-mentioned monomers, ethylenically unsaturated carboxylic acids and ethylenically unsaturated anhydrous carboxylic acids are particularly preferred, and these monomers may be used alone or in combination with other monomers. Used in combination with to modify olefin resins.

These carbonyl group-containing monomers are bonded to the main chain or side chain of the olefin resin so that the concentration of polar groups is within the above range and the crystallinity of the modified olefin resin is at least 15%.

Olefins include ethylene, propylene, and butene.
Examples include one or a combination of two or more of 1, bentene-1, 4-methylbentene-1, etc., which satisfy the above-mentioned conditions.

In order to modify an olefin resin so as to satisfy the above-mentioned conditions, for example, in the case of graft treatment, an olefin resin with a degree of crystallinity higher than 15% is selected as the raw material olefin resin, and the olefin resin is It is necessary to carry out the grafting treatment under conditions such that the degree of crystallinity does not fall below 15%.

For this purpose, high-crystalline materials such as high-density polyethylene, isotactic polypropylene, or ethylene-propylene copolymers are preferably used as the backbone polymer, and furthermore, there is virtually no decrease in crystallinity. Under such mild grafting conditions, medium density polyethylene or low density polyethylene with a crystallinity higher than 15% may also be used. The above-mentioned grafting process can be carried out under conditions known per se, except for the above-mentioned limitations.

For example, a modified olefin resin can be easily produced by bringing a backbone polymer consisting of an olefin resin into contact with a carbonyl group-containing ethylenically unsaturated monomer in the presence of a radical initiator or radical initiation means. The backbone polymer and the monomer can be contacted in a homogeneous solution system, a solid-liquid or solid-liquid heterogeneous system, or a molten homogeneous system. Examples of initiators include organic peroxides such as dicumyl peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, and dilauroyl peroxide, and azonitrile such as azobisisobutyronitrile and azobisisopropionitrile. etc. are used in catalytic amounts known per se. Radical initiation means include ionizing radiation such as x-rays, y-rays, and electron beams; ultraviolet rays or a combination of ultraviolet rays and a sensitizer; mechanical radical initiation means such as kneading (mastication) and ultrasonic irradiation. is used. For example, in a homogeneous solution reaction, the olefin resin, monomer, and initiator are mixed with toluene,
Grafting is performed by dissolving the resin in an aromatic solvent such as xylene or tetralin, and the resulting modified olefin resin is recovered as a precipitate.

In addition, in a heterogeneous reaction, grafting is carried out by bringing the olefin resin powder into contact with the monomer or a diluted solution of the monomer under irradiation with ionizing radiation. Furthermore, in a homogeneous melt system reaction, a blend of an olefin resin, a monomer, or an initiator is melted and kneaded using an extruder or kneader,
Use modified olefin resin. In any of these cases, the resulting modified olefin resin can be subjected to purification treatments such as bran washing and extraction in order to remove the monomers, homopolymers, initiator residues, etc. of the polymerization. Furthermore, the particle size of the resulting modified olefin resin can be adjusted by subjecting it to the recrystallization operation in the aromatic solvent described above and changing the crystallization conditions at that time. In this way, the modified olefin resin used in the present invention can be easily obtained.

Another example of the modified olefin resin having the above-mentioned carbonyl group content concentration is polyethylene oxide.

As the oxidized polyethylene used in the present invention, so-called oxidized polyethylene that satisfies the above-mentioned requirements is used, which is obtained by oxidizing polyethylene or a copolymer mainly composed of ethylene in a melt or solution state, if desired. be done.

The molecular weight of the modified olefin resin used may be one sufficient to form a film, and generally has a melt index (MI) of 0.2 to 30 minutes, particularly 2 to 2 minutes.
0 evening/10 minutes is preferably used. Still other examples of modified olefin resins include polymers obtained by neutralizing ionomers, that is, copolymers of olefins and ethylenically unsaturated carboxylic acids, with metal ions such as Na, Zn, Ca, and amines. Examples include copolymers of olefins and ethylenically unsaturated carboxylic acids or their esters or vinyl esters.

In the present invention, the above-mentioned modified olefin resins can be used alone or in the form of a blend of two or more types.

In addition, this modified olefin resin may be used in the form of a blend with a crystalline olefin resin or in the form of an elastomer as described below.
It can also be used in the form of a blend with. In any of these cases, the point is that the final resin composition should have a degree of crystallinity, a carbonyl group content, and a main composition of olefinic monostars within the range specified in the present invention. Aluminum foils or sheets with a thickness of 6 to 80 microns are generally used for flexible sealed packaging such as bag-shaped containers, while those with a thickness of 6 to 80 microns are used for flexible sealed packaging such as bag-shaped containers, while those with a thickness of 6 to 80 microns are used for flexible sealed packaging such as bag-shaped containers. In the case of hard containers, the thickness is 9 to 50 mm.
A 0 micron foil or sheet is used.

Even if the surface of the aluminum foil or sheet is untreated,
Alternatively, it may be subjected to a known surface treatment. For the purpose of the present invention, it is desirable to use an aluminum foil or sheet having a layer of alumina hydrate of 10 to 00 millimicrons, and a modified olefin resin layer is provided in a positional relationship adjacent to this alumina hydrate layer. It is better. A crystalline olefin resin layer can be provided on both surfaces of aluminum foil, etc. via a modified olefin resin layer, or a crystalline olefin resin layer can be provided on only one surface of aluminum foil, etc., and the other surface, A heat-resistant resin layer can be provided for protection.

This heat-resistant resin layer can be applied in advance to aluminum foil or the like prior to laminating the olefin resin layer.

As the heat-resistant resin layer, a thermoplastic resin or a thermosetting resin having a higher melting temperature or decomposition temperature than the above-mentioned crystalline olefin resin is used.

Examples of heat-resistant thermoplastic resins include polyesters such as polyethylene terephthalate, polyamides such as nylon-6 and nylon-6.6, polycarbonates, cellulose esters, fluororesins, etc., and examples of thermosetting resins include: For example, a heat-resistant polymer containing a heterocyclic ring such as an imide ring, imidazopyrrolone ring, imidazole ring, oxazole ring, oxadiazole ring, or thiazole ring in its molecular chain, such as polyimide, polyamideimide, polyesterimide, polyamideimide ester , polyesteramideimide, polyimideimidazopyrrolone, etc. can be used.

Or in addition, epoxy/phenolic resin paint, phenolic resin paint, unsaturated polyester resin paint,
Oleogenous paints and the like can also be used. Heat-resistant thermoplastic resins are readily available as unoriented or biaxially oriented films, and these films can be used with epoxy adhesives,
The aluminum foil or sheet is laminated with a known adhesive such as a polyurethane adhesive, while the heat-insoluble heat-resistant resin is laminated onto the foil or sheet after a solution of a precursor polymer of these resins is applied. Formed by baking.

As the crystalline olefin resin, known olefin resins that can be heat-sealed and can withstand retort sterilization, such as low, medium to high density polyethylene, isotactic polypropylene, polybutene-1,4-methylbentene-1, Polyolefins such as ethylene-propylene copolymers or blends thereof are used. In order to improve the impact resistance and, in some cases, the blocking property of the polyolefin, a small amount of elastomer such as polyisobutylene, butyl rubber, styrene-butadiene rubber, ethylene propylene rubber, etc. is added to the crystalline olefin resin, i.e., 1 to 3 elastomers per crystalline olefin resin. Amounts of % by weight can be included. These crystalline olefin resin films are
For example, they can be easily obtained by film forming methods known per se, such as the T-die method and the inflation film forming method, and these may be unstretched or stretched appropriately in two directions without adversely affecting heat sealing. Good too.

The thickness of this film is 10 to 10
0 micron, especially in the range of 30 to 70 micron. In one embodiment of the present invention, the above-mentioned modified olefin resin is melt-extruded between the aluminum foil, etc. and the crystalline olefin resin, and at this time, prior to lamination, the aluminum foil, etc. is preliminarily attached to the modified olefin resin. The temperature should be kept above the Vicat softening point.

For this purpose, aluminum foil or the like is generally preheated by a heating mechanism known per se, and immediately before it comes into contact with the modified olefin resin layer to be extruded, the aluminum foil or the like is heated to a temperature equal to or higher than the Vicat softening point (Tw) of the modified olefin resin, particularly preferably. The temperature should be between TM+loo○ and TM1100qo.

As the heating mechanism, mechanisms such as a heat roll, an infrared heater, various heating furnaces, direct flame heating, hot air blowing, and high frequency induction heating may be used alone or in combination. In FIG. 2 for explaining the operation of this aspect of the invention, aluminum foil 2 is fed onto drive roller 2 by a heating device 11, such as induction heating.

On the other hand, the crystalline olefin resin film 4 is supplied onto a driving roller 13 that is paired with the roller 12. A die 14 of the extruder is located above the nip position of the rollers 12 and 13, and the die 14 of the extruder is located above the nip position of the rollers 12 and 13.
is supplied between the aluminum sheet 2 and the crystalline olefin resin film 4 through the die 14. In this way, the aluminum foil or the like 2 and the olefin resin film 4 are pressed together via the modified olefin resin 3 by the pressing rollers 12 and 13, and a laminated sheet is obtained. According to this aspect of the present invention, the aluminum foil, etc. 2 is heated to a temperature equal to or higher than the softening point of the modified olefin resin prior to contact with the modified olefin resin 3, so that the olefin resin that comes into contact with the aluminum foil, etc. 2 Rapid cooling of the layer 3 is prevented, and as a result, the mechanical properties of the modified olefin resin layer 3 itself and the adhesive strength with the aluminum foil or the like 2 can be maintained at a high level.

In the present invention, the thickness of the modified olefin resin layer 3 is preferably in the range of 5 to 50 microns, particularly 10 to 20 microns, from the viewpoint of adhesion.

In order to maintain the temperature of the aluminum foil or the like 2 at the above-mentioned temperature, the pair of pressure rollers 2 and 13 desirably maintain the surface temperature at a temperature equal to or higher than the Vicat softening point of the modified olefin resin.

The produced laminate is passed over a cooling roller or allowed to cool naturally to form a laminate for packaging.

In another aspect of the present invention, the modified olefin resin described above is melt-extruded between the aluminum foil or the like and the crystalline olefin resin film to produce a laminate in which the modified olefin resin is temporarily adhered to the aluminum foil or the like, Next, this laminate is heated to a temperature equal to or higher than the Vicat softening point of the modified olefin resin to form a product.

In FIG. 3 for explaining the operation of this alternative embodiment of the invention, aluminum foil 2 is fed onto drive roller 12, crystalline olefin resin film 4 is fed onto drive roller 3,
The modified olefin resin 3 is supplied between the aluminum foil 2 and the olefin resin film 4 through the die 14 located on these roller pairs 12 and 13, and
3, these are pressed together to form a laminate 1' in which the modified olefin resin 3 is temporarily bonded to the aluminum foil 2.

This temporarily bonded laminate 1' is then placed in a heating mechanism 11' and heated to a temperature equal to or higher than the softening point of the modified olefin resin to obtain the final laminate product 1. As the heating mechanism 11', a heating mechanism similar to that used for heating aluminum foil or the like can be used.

In still another embodiment of the present invention, the laminate 1 obtained by the operation shown in FIG. A laminate is obtained. The present invention can be modified in many ways without departing from the spirit of the invention described above. for example,
The modified olefin resin layer can be extruded as a multilayer coextrudate. As shown in the examples described below, the modified olefin resin layer was formed in a portion adjacent to the aluminum foil or sheet with a carbonyl group content of loo to 60 h.
A highly modified olefin resin layer having a carbonyl group content of 1 to 2 meq/100 polymer in a portion adjacent to the crystalline olefin resin layer. By coextruding the laminate as a laminate with a multilayer structure, the adhesive strength of the laminate product can be further improved.

In this embodiment of the invention in which simultaneous multilayer extrudates are used for lamination, the low modified olefin resin layer may be a highly modified olefin resin blended with a crystalline olefin resin to adjust the carbonyl group concentration. In addition, by creating a three-layer structure with two layers of modified olefin resin and a polyamide resin (nylon) layer interposed between them, the seal part will be resistant to impact when the final laminate is used as a retort sterilization package. can improve sex. The laminate according to the invention is particularly useful in the production of sealed packages for retort sterilization.

The invention is illustrated by the following example.

Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 12 strands and an aluminum foil having a thickness of 9 strands were laminated using a urethane adhesive.

Also, isotactic polypropylene with a melting point of 16,500, a density of 0.91 m/m, and a melt index of 7.0 m/h is 5 mm in diameter? Melt extrusion was carried out from a single layer die using an extruder having a screw of 1.5 mm, and a film with a thickness of 50 mm was obtained by an inflation method.

Next, the laminated aluminum sheet is heated and held at 20,000 ℃ by heating open and high frequency induction heating equipment,
Between this laminated sheet and the polypropylene film, an average concentration of carbonyl groups of isotactic polypropylene grafted with maleic anhydride is 14.
q/100 polymer, crystallinity 65%, melting point 159
Modified polypropylene with a Vicat softening point of 14r0 and a melt index of 10.0r/1 plate was extruded using an extruder having a screw with a diameter of 65rl under the condition that the resin temperature at the die part was 260qo. Melt extrusion is performed through a T-die on the cape, and after crimping with a pair of pressure rolls with a diameter of 400 mm and 20 mm, the temperature is maintained at 180 qo, and then cooled to room temperature using a cooling roll with a diameter of 40 ㎜. A laminated sheet having a structure of 12 polyethylene terephthalate layers/9 real aluminum foil/20 polypropylene layers/50 polypropylene layers was obtained.

The peel strength between the aluminum foil and the polypropylene layer of this fin layer sheet was measured and was 980/1. & It was pine. Next, this laminated sheet was immersed in boiling water for 120 minutes, and then its peel strength was measured, and no decrease in strength was observed.

Furthermore, when this laminated sheet was treated in heated steam at 135q0 for 10 minutes, no peeling between the layers was observed.
No decrease in adhesive strength was observed.

Example 2 A double-stretched polyethylene terephthalate film having a thickness of 12 mm and an aluminum foil having a thickness of 9 mm were laminated using a urethane adhesive.

In addition, an ethylene-propylene floc copolymer with a melting point of 158°C, a density of 0.90 m/h, a melt index of 8.0 m/h, and an ethylene content of 5 mol % was used. Melt extrusion was carried out from a single layer die using an extruder with a screw of the same type as the above, and a film with a thickness of 50 layers was obtained by the inflation method.

Next, the laminated aluminum sheet is heated and maintained at 170 CO using a heating oven and a high frequency induction heating device,
Between this laminated sheet and the propylene copolymer film, maleic anhydride and itaconic anhydride were grafted onto an ethylene-propylene flock copolymer having an ethylene content of 5 mol% in a molar ratio of 3:1. Modified propylene copolymer with a carbonyl group concentration of 31 eq/100 in, crystallinity 60%, melting point 150, softening point 139 in, melt index 12.0 eq/1 in. Combined with an ethylene-propylene floc copolymer having a melting point of 15,400, a density of 0.90 mm/hin, a melt index of 10.0 m/hin, and an ethylene content of 5 mol%. The blended mixture at a weight ratio of 1:1 was melt-extruded through an extruder having a screw with a diameter of 65 mm under conditions where the resin temperature at the die part was 250 qo, and the temperature was After crimping with a pair of crimping rolls with a diameter of 40 mm and 20 mm held at a temperature of 16,000, the temperature is further crimped with a pair of crimping rolls with a diameter of 20 mm and a temperature of 20,000 ℃. By cooling it to room temperature with a 40mm cooling roll, the structure changes to 12r polyethylene terephthalate layer/
A laminated sheet of 9 aluminum foil/20 French-modified propylene copolymer blend layer/50 polypropylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1050 tano 1.
& It was pine. Further, when the same machine as in Example 1 was subjected to boiling water treatment and heated steam treatment, no decrease in adhesive strength was observed, but rather an increase in adhesive strength.

Comparative Example 1 In Example 1, when unmodified polypropylene was used instead of maleic anhydride-modified polypropylene, the adhesion to aluminum foil was poor and a laminate for retort sterilization packaging could not be obtained.

Comparative Example 2 In Example 1, when a maleic anhydride-modified polypropylene having an average levonyl group concentration of 80 eq/100 polymer was used as the modified polypropylene, the adhesion between the modified polypropylene layer and the polypropylene layer was poor. Ta.

Comparative Example 3 In Example 1, when the laminated aluminum sheet and the pressure roll were laminated at a heating temperature of 100 qo, the adhesion was poor and a laminate for retort sterilization packaging could not be obtained.

Comparative Example 4 In Example 2, when a maleic anhydride- and itaconic anhydride-modified propylene copolymer with a carbonyl group concentration of 0.8 heq/100 polymers was used as the modified propylene copolymer, the adhesion to aluminum foil was improved. It was not possible to obtain a laminate for retort sterilization packaging due to poor quality.

Example 3 A biaxially stretched polyethylene terephthalate film with a thickness of 12 mm and an aluminum foil with a thickness of 18 mm and whose surface was treated with boehmite were laminated using a urethane adhesive.

In addition, isotactic polypropylene with a melting point of 165 qo, a density of 0.91 m/hjn, and a melt index of 7.0 m/hjn is made into a single layer by using an extruder having a screw with a diameter of 5 mm. A film with a thickness of 55 cm was obtained by melt extrusion from the film and by an inflation method.

Next, the laminated aluminum sheet is heated and maintained at 200° C. using a heating oven and high-frequency induction heating, and an average carbonyl group of isotactic polypropylene grafted with maleic anhydride is placed between the laminated sheet and the polypropylene film. Concentration is 12meq/10
Polymer, crystallinity 67%, melting point 160mm, softening point 14mm, melt index 10mm.
Modified polypropylene of 0 evening/1 hour was melt-extruded through an extruder having a screw with a diameter of 65 mm and a T-die of 65 mm diameter under conditions where the resin temperature at the die part was 250 °C. was held at 170qo and crimped with a pair of crimping rolls with a diameter of 40mm and 20mm, and then cooled to room temperature with a cooling roll with a diameter of 400mm, and the composition was 12-polyethylene terephthalate layer/1
8 Aluminum foil / 15 μm modified polypropylene layer / 5
A laminated sheet having five polypropylene layers was obtained.

The peel strength between the aluminum foil and the polypropylene layer of this laminated sheet was measured and found to be 1570/1.5 skin. Further, when boiling water treatment and heated steam treatment were performed in the same manner as in Example 1, no decrease in adhesive strength and no peeling between the layers was observed. Example 4 A double-stretched polyethylene terephthalate film with a thickness of 12 and a thickness of 9 with gravure printing on one surface.
aluminum foil and were laminated using a urethane adhesive so that the printed side was on the inside.

In addition, an ethylene-propylene block copolymer with a melting point of 158 qo, a density of 0.90 q/kg, a melt index of 8.0 q/IQhin, and an ethylene content of 5 mol% was made into a screw with a diameter of 5 mm. Melt extrusion was carried out from a single layer die using an extruder having the following properties, and a film with a thickness of 60 mm was obtained by an inflation method.

Next, the laminated aluminum sheet is heated and held at a temperature of 20 mm using a high frequency induction heating device, and an ethylene-propylene flock having an ethylene content of 5 mol% is placed between the laminated sheet and the propylene copolymer film. Maleic anhydride and citraconic anhydride were grafted onto the copolymer at a molar ratio of 2:1, and the carbonyl group concentration was 49 heq/h.
100 polymer, crystallinity 52%, melting point 1470,
Vikatsu softening point is 137℃, melt index is 12
．． A highly modified propylene copolymer of 0 evening/1 hour was processed using a first extruder having a screw with a diameter of 5 m◇, and an ethylene-propylene copolymer with an ethylene content of 5 mol% was used.
Maleic anhydride and citraconic anhydride are grafted to the block copolymer at a molar ratio of 2:1.The carbonyl group concentration is 11 heq/100, the crystallinity is 62%, the melting point is 153 qo, and the Vicat softening point is 14ro, a low modified propylene copolymer with a melt index of 12.0 evening/1 hour was heated to a resin temperature of 260q in the die using a second extruder with a diameter of 65 mm screw.
Co-extrusion was carried out from a double T-die for two layers with a diameter of 65 m and a diameter of 40 m and a temperature of 180 °C under conditions of 20 m. After crimping, it was cooled to room temperature using a cooling roll with a diameter of 40 mm, and the composition was 12 M polyethylene terephthalate layer / 9 M aluminum foil / 5 French high modified propylene copolymer layers / 10 French low modified propylene copolymer layer. A laminated sheet of layer/60-propylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1470/1.
It was 5 skin. Moreover, when the same boiling water treatment and heated CK steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength were observed.

Example 5 A biaxially stretched polyethylene terephthalate film with a thickness of 12 mm and an aluminum foil with a thickness of 9 mm were laminated using a urethane adhesive.

In addition, it has a melting point of 157 o0, a density of 0.90 m/m, a melt index of 7.0 m/1 min, and an ethylene-propylene random copolymer with an ethylene content of 3 mol% and an average of 9 3% by weight. Ethylene-propylene copolymer rubber (EP) with a molecular weight of 10 and a propylene content of 35 mol%
R) 50 legs of 7% by weight blend in diameter? Melt extrusion was carried out from a single layer die using an extruder having a screw of 1.5 mm, and a film with a thickness of 50K was obtained by the inflation method.

Next, the laminated aluminum sheet is heated and maintained at 220°C using a heating oven and an infrared heater, and between this laminated sheet and the propylene copolymer film,
Maleic anhydride and fumaric acid were grafted at a molar ratio of 3:1 to an ethylene-propylene random copolymer with an ethylene content of 3 mol%, and the carbonyl group concentration was 24 eq.
/100 polymer, crystallinity 51%, melting point 14 o
, a modified propylene copolymer with a Vicat softening point of 136 mm and a melt index of 13.0 m/1 plate was prepared using a first extruder having a screw with a diameter of 5 mm, and the above-mentioned The weight percent of modified propylene copolymer 4 and the melting point are 15
1°C, density 0.90 m/s, melt index 1
A blend of 6% by weight of ethylene-propylene random copolymer 6 having an ethylene content of 3% by mole at a ratio of 2.0 m/1 ratio was dipped using a second extruder with a screw having a diameter of 65 mm. Co-extrusion was carried out from a double T-die for two layers with a diameter of 65 m and a diameter of 40 m and a diameter of 20 m. After crimping with a pair of crimping rolls, the diameter is 40 mm.
Cooled to room temperature by the cooling roll of the cape, and the composition was 12.
〃Polyethylene terephthalate layer / 9mm aluminum foil / 5mm modified propylene copolymer layer / 15mm modified propylene copolymer blend layer / 50mm propylene copolymer-E
A laminated sheet of PR blend layers was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and found to be 94M/1.5 skin. Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed. Example 6 A biaxially stretched polyethylene terephthalate film with a thickness of 12 mm and an aluminum foil with a thickness of 9 mm were laminated using a urethane adhesive.

In addition, 92% by weight of high-density polyethylene has a melting point of 13 ro, a density of 0.955 polyethylene, a melt index of 0.9 m/h, an average molecular weight of 80 molar, and a density of 0.9.
2 evenings: A blend of 8% by weight of Sakaki's polyisobutylene rubber was melt-extruded from a single-layer die using an extruder with a screw with a diameter of 5 mm, and a film with a thickness of 60 mm was obtained by the inflation method. .

Next, the laminated aluminum sheet is heated and held at 16,000 ℃ using a heating oven and a high frequency induction heating device,
Between this laminated sheet and the high-density polyethylene film, an average carbonyl group concentration of maleic anhydride grafted to high-density polyethylene is 13 heq/100
Polymer, crystallinity 68%, melting point 128°, Vicat softening point 9°, melt index 5.0°/
The modified polyethylene of No. 1 Hin was melt-extruded from a T-die with a diameter of 65 mm using an extruder having a screw with a diameter of 65 mm and the resin temperature at the die part was 290 oo, and the temperature was maintained at 14,000 ℃. Diameter is 40
After crimping with a pair of crimping rolls facing 0 side and 20 degrees upwards, it was cooled to room temperature with a cooling roll with a diameter of 40 degrees, and the composition was 12 polyethylene terephthalate layer / 9 real aluminum foil / 15 French modified polyethylene layer. A laminated sheet having a layer of high-density polyethylene of /60 French was obtained.

The peel strength between the aluminum foil and the high-density polyethylene layer of this laminated sheet was measured and was 1360/1.
It was 5 arcs. In addition, this laminated sheet was placed in boiling water for 12 hours.
When soaked for 0 minutes, no peeling between the layers and no decrease in adhesive strength was observed.

Example 7 A two-dimensional stretched polyethylene terephthalate film having a thickness of 12 strands and an aluminum foil having a thickness of 9 strands were laminated using a urethane adhesive.

In addition, low-density polyethylene with a melting point of 12 RO, a density of 0.925 mm/base, and a melt index of 4.0 mm/1 skin is extruded from a single-layer die using an extruder with a screw with a diameter of 5 mm. Melt extrusion was performed to obtain a film with a thickness of 55 mm by an inflation method.

Next, the laminated aluminum sheet is heated to 150 oo by a heating oven and an infrared heater, and between the laminated sheet and the low density polyethylene film, a mixture of low density polyethylene, maleic anhydride and acrylic acid in a ratio of 3:1 is placed. Modified carbonyl group concentration grafted with a molar ratio of 90 heq/100 Yugumo coalescence, crystallinity 57%, melting point 11800, Vicat softening point 9 or 0, melt index 7.0 tano monovalent in Polyethylene was melt-extruded through a T-die with a diameter of 65 mm and a resin temperature of 300 oo in the die section using an extruder having a screw with a diameter of 65 mm. After crimping with a pair of pressure rolls with a diameter of 20mm, the material was cooled to room temperature with a cooling roll with a diameter of 40mm, and the composition was 12mm polyethylene terephthalate layer / 9mm aluminum foil / 15mm modified polyethylene layer. A laminated sheet having a /55 French low density polyethylene layer was obtained.

The peel strength between the aluminum foil and the low density polyethylene layer of this laminated sheet was measured and was 1270/1.
It was a 5-game. In addition, this laminated sheet was placed in boiling water for 12 hours.
When soaked for 0 minutes, no peeling between the layers and no decrease in adhesive strength was observed.

Example 8 Biaxially stretched extruded nylon-6 film with a thickness of 15 mm and a thickness of 7
It was laminated with French aluminum foil using urethane adhesive.

In addition, 60% by weight of low-density polyethylene has a melting point of 12RO, a density of 0.925 mm/hin, and a melt index of 4.0 mm/hin, and a melting point of 105 dos and a density of 0.92 mm.
Evening/earth, melt index is 8.0 evening/1 hin,
A blend of 4% by weight of ethylene-vinyl acetate copolymer with a vinyl acetate content of 4% by weight was prepared with a diameter of 5 mm. Melt extrusion was carried out from a single layer die using an extruder having a screw of 1.5 mm, and a film with a thickness of 55 r was obtained by an inflation method.

Next, the laminated aluminum sheet is heated and maintained at 90 qo using an infrared heater, and Zn of ethylene methacrylic acid copolymer is placed between the laminated sheet and the low density polyethylene blend film.
A partial salt carbonyl group concentration of 21 eq/10M polymer, a melting point of 99 qo, a Vicat softening point of 8000, a melt index of 5.0 eq/1 hin, and a melting point of 97°C, The density is 0.93 ta',
A blend of 4% by weight of ethylene-pinyl acetate copolymer with a melt index of 12.0 min/1 h and a vinyl acetate content of 8% by weight was produced by an extruder having a screw with a diameter of 65 legs. Melt extrusion was performed from a T-die with a medium diameter of 650 mm under the condition that the resin temperature at the die part was 300 qo, and the diameter was 40 mm while the temperature was maintained at 9000 qo. After crimping with a pair of crimping rolls on the 200 side, the diameter is 4
Cooled to room temperature with a cooling roll of 0.00 mm, and the composition was
A laminated sheet containing 5 layers of nylon, 6 layers, 7 layers of aluminum foil, 15 layers of ionomer blend, and 55 layers of low-density polyethylene blend was obtained.

The peel strength between the aluminum foil and the low density polyethylene blend layer of this laminated sheet was measured and was 580.
It was a packaging material with an excellent heat sealability and impact resistance. Example 9 Melting point is 158 qo,
An ethylene-propylene floc copolymer with a density of 0.90 mm, a melt index of 80 mm, and an ethylene content of 5 mol% was produced using an extruder with a screw of 5 mm in diameter. Melt extrusion was performed from a single layer die, and a film with a thickness of 50 peaks was obtained by an inflation method.

Next, a loom-thick aluminum sheet with a protective film made of eboxy resin on one surface was heated and held at 220 o'clock in a heating oven and a high frequency induction heating device, and the aluminum sheet and the propylene were heated and held at 220 o'clock. Between the polymer film and the ethylene-propylene random copolymer with an ethylene content of 4 mol%, a carbonyl group concentration of 18 heq. /100 polymer, crystallinity 49%, melting point 145oo, Vikato softening point 13400, melt index 13. M/1 plate in
The weight percent of modified propylene copolymer 7 and the melting point are 1620
, the density is 0.91 pm/earth, and the melt index is 12.
A blend of 3% by weight of isotactic polypropylene with a diameter of 65 ribs at a ratio of 0/1 ratio? An extruder with a screw of
Melt extrusion was carried out through a T-die with 650 ribs under the condition of 50°C, and the diameter was 40° while the temperature was maintained at 200°.After being crimped with a pair of pressure rolls of 20°, the diameter was 4
0 enemy? It is cooled to room temperature using a cooling roll, and the composition is epoxy resin protective film / 100 real aluminum sheet /
A laminated sheet of 15 French modified propylene copolymer blend layers/50 French propylene copolymer layers was obtained. The peel strength between the aluminum sheet and the propylene copolymer layer of this laminated sheet was measured and was 1430#/1. & was young. Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

This laminated sheet is suitable as a material for draw-molded containers.

Example 10 A two-rut stretched polyethylene terephthalate film with a thickness of 12 ridges, a biaxially oriented nylon-6 film with a thickness of 15 ridges, and an aluminum foil with a thickness of 9 strands were laminated using a urethane adhesive.

Also, an ethylene tape with a melting point of 15,800, a density of 0.90 m/lump, a melt index of 8.0 m/1 skin, and an ethylene content of 5 mol%.

Pyreso block copolymer 95% by weight and average molecular weight 10
10,000, ethylene content 62 mol%, plastic. Pyrene content 3
Ethylene-propylene-diene copolymer rubber (EPD) with 5 mol% and 1,4-hexadiene content of 3 mol%.
M) A blend of 5% by weight with a diameter of 5 mm? Melt extrusion was carried out from a single layer die using an extruder having a screw of 100 mm, and a film with a thickness of 45# was obtained by the inflation method. Next, the laminated aluminum sheet was heated and maintained at 180°C using a heating oven and a high-frequency heating device, and a film with an ethylene content of 5 mol % was placed between the laminated sheet and the propylene copolymer blend film. Maleic anhydride and itaconic anhydride are grafted onto the ethylene-propylene floc copolymer at a molar ratio of 3:1.The carbonyl group concentration is 31 eq/100, the crystallinity is 60%, and the melting point is 1520, Vicat softening point is 1
39qo, melt index is 12.0 evening/15 hi
60% by weight of a modified propylene copolymer of n and a melting point of 154
°C, density is 0.90 m/m, melt index is 10
．． 0 evening/1 hour, 35% by weight of an ethylene-propylene block copolymer with an ethylene content of 5 mol% and 5% by weight of the ethylene-propylene-gene copolymer rubber.
The resin temperature in the die part was increased to 26,000 by using an extruder having a screw with a diameter of 65 feet.
Under these conditions, 650 pigs? Melt extrusion is carried out from a T-die, and the diameter is maintained at 180 qo. After being crimped with a pair of bonding rolls with a diameter of 400 and a side J and 20 mm, the diameter is 400
It was cooled to room temperature using a small cooling roll, and the composition was 12 polyethylene terephthalate layers / 15 French nylon and 16 layers / 9 real aluminum foil / 15 French modified propylene copolymer blend layer / 45 French polypropylene copolymer blend layer. A laminated sheet was obtained.

The peel strength between the aluminum foil and the propylene copolymer blend layer of this laminated sheet was measured and found to be 970/1.5. Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 11 A double-stretched polyethylene terephthalate film with a thickness of 12 mm and an aluminum foil with a thickness of 9 mm were laminated using a urethane adhesive.

In addition, the weight percent of poly-4-methylbentene-19 having a melting point of 235 qo, a density of 0.84 q/h, and a melt index of 8.0 q/h and an average molecular weight of 100,000,
Ethylene content is 62 mol%, propylene content is 35
Ethylene propylene diene copolymer rubber (EPDM) with a mol%, 1.4 hexadiene content of 3 mol% 1
The blended product with 0% by weight was melt-extruded through a single-layer T-die using an extruder having a screw with a diameter of 50 mm to obtain a film with a thickness of 60 r.

Next, the laminated aluminum sheet is heated and maintained at 250 oo by a heating oven and a high frequency induction heating device,
Between this laminated sheet and the poly-4-methylbentene-1 film, a polymer having a carbonyl group concentration of 12 heq/100% and a crystallinity of poly-4-methylbentene-1 to which maleic anhydride is grafted. 63%, melting point 2
A blend of 7% by weight of modified poly-4-methylbentene-1 and 3% by weight of the poly-4-methylbentene-1 was prepared at 31°C with a melt index of 12.0 m/1 plate. Using an extruder with a screw on the 65th side, the resin temperature at the die part was 320 °C,
Middle 65 revenge? Melt extrusion is performed from a T-die at a temperature of 2.
After crimping with a pair of bonding rolls with diameters of 40 and 20 degrees held at 50 qo, it was cooled to room temperature with a cooling roll with a diameter of 40W, and the composition was 12〃Polyethylene terephthalate layer/9F aluminum foil. A laminate of 15r modified poly-4-methylbentene-1 layer/60 poly-4-methylbentene-1 blend layer was obtained.

Furthermore, this laminated sheet was left in a heating furnace maintained at 180° C. for 6 hours.

The peel strength between the aluminum foil and the poly-4-methylbentene-1 blend layer of this laminated sheet was measured and found to be 815 mm/1.5 mm. Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed. Example 12 A double-stretched polyethylene terephthalate film with a thickness of 12 cm and an aluminum foil with a thickness of 9 r were laminated using a urethane adhesive.

In addition, an ethylene-propylene floc copolymer with a melting point of 1 °C, a density of 0.90 °C, a melt index of 8.0 °C / 1 °C, and an ethylene content of 5 mol % was prepared with a diameter of 5 °C. Melt extrusion was carried out through a single layer die using an extruder with a double screw, and a film with a thickness of 50 cm was obtained by the inflation method.

Next, the laminated aluminum sheet is heated and maintained at 170 oo by a heating oven and a high frequency induction heating device,
Between this laminated sheet and the propylene copolymer film, a carbonyl group concentration of Na partial salt of a copolymer in which acrylic acid is grafted to isotactic polypropylene is 27 heq/100%. is 14
At 3°C, a blend of weight % of ionomer 6 with a picatto softening point of 120 min and a melt index of 12.0 min/min and the weight % of the ethylene-propylene block copolymer 4 was prepared. Using an extruder with a ◇ screw on the 65 side, melt extrusion is performed from a T-die with a 650 mm diameter under the condition that the resin temperature at the die part is 26 mm.
After being crimped with a pair of pressure bonding rolls with a diameter of 400° and 200°, which were kept at a temperature of 160°C, it was cooled to room temperature using a cooling roll with a diameter of 400°, and the composition was 12 M polyethylene terephthalate layer/ A laminate of 9 aluminum foil/20 ionomer blend layer/50 ribropylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1150/1.
It was 5 skin. Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 13 A biaxially stretched polyethylene terephthalate film with a thickness of 12 mm and an aluminum foil with a thickness of 9 peaks were formed into a fin layer using a urethane adhesive.

In addition, an ethylene-propylene block copolymer with a melting point of 1 degree Celsius, a density of 0.90 degrees Celsius, a melt index of 8.0 degrees Celsius, a melt index of 8.0 degrees Celsius, and an ethylene content of 5 mol% is 5 degrees Celsius in diameter. Melt extrusion was carried out from a single layer die using an extruder having a screw of 1.5 mm, and a film with a thickness of 40 mm was obtained by an inflation method.

Next, the laminated aluminum sheet is heated and maintained at 180 qo using a heating oven and a high frequency induction heating device,
Between this laminate sheet and the propylene copolymer film, an average strength carbonyl group concentration of 14% is produced by grafting maleic anhydride onto isotactic polypropylene.
q/100 multipolymer, crystallinity 65%, melting point 159
Modified polypropylene with a Vicat softening point of 141 q0 and a melt index of 10.0 m/h is used in both cases, having a screw with a diameter of 65 ribs and an adapter having a melt channel branched into two. An extruder was used for the outer layer, and the melting point was 211°C and the density was 1.14.
Using an extruder for intermediate layer having a screw with a diameter of 5 mm, coextrusion of nylon-6 with a T base is carried out through a triple T-die for three layers under the condition that the resin temperature at the die part is 240 qo. After crimping with a pair of crimping rolls with a diameter of 40 m and 20 m and kept at a temperature of 180 oo, it was cooled to room temperature with a cooling roll of 40 m in diameter, and the composition was 12 mpolyethylene. Terephthalate layer / 9 aluminum foil / 5 French modified polypropylene layer / 15 Renylon-6
A laminate of layers/5 French-modified polypropylene layers/40 polypropylene copolymer layers was obtained.

The peel strength between the aluminum foil and propylene copolymer layer of this laminated sheet was measured and was 824 mm/1. & It was pine. Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 14 A biaxially oriented polyethylene terephthalate film with a thickness of 12 mm and an aluminum foil with a thickness of 9 mm were laminated using a urethane adhesive.

In addition, ethylene-propylene block copolymer 9 has a melting point of 1°C, a density of 0.90 m/m, a melt index of 8.0 m/1 m, and an ethylene content of 5 mol%.
10% by weight of ethylene-propylene-diene copolymer rubber (EPDM) having an ethylene content of 62 mol%, a propylene content of 35 mol%, and a 1.4-hexadiene content of 3 mol%, with an average molecular weight of 100,000% by weight. % and a blend with a diameter of 5 cm? Using a first extruder with a screw of Melt extrusion was performed from a double die for two layers using a second extruder with a screw of
A layered coextruded film was obtained.

Next, between the laminated aluminum sheet and the two-layer coextruded film, an ethylene-propylene flock copolymer having an ethylene content of 5 mol % and a 2:1 molar ratio of maleic anhydride and citraconic anhydride are interposed. The grafted carbonyl group concentration is 49 heq/100 molar ratio polymer, the crystallinity is 52%, the melting point is 1470, and the Vicat softening point is 1.
370, melt index is 12.0 evening/1 hour
The weight percent of the modified propylene copolymer 7 is 154, the density is 0.90, the melt index is 10.
．． On 09/1, a blend of ethylene-propylene floc copolymer 3 with an ethylene content of 5 mol % by weight was prepared using a first extruder having a screw with a diameter of 5 mol %, and the above-mentioned 3% by weight of the modified propylene copolymer, 65% by weight of the propylene copolymer with a melt index of 10.0 minutes/1 hour, and 5% by weight of the EPDM.
Using a second extruder with a screw diameter of 65 mm, the resin temperature in the die section was 250 °C.
Co-extrusion was carried out from a double T-die for two layers with a medium 65-barrel under the following conditions, and temporary bonding was performed using a pair of pressure rolls with a diameter of 40 mm and 20 mm at room temperature. .

Next, this laminated sheet was kept at a temperature of 200 degrees and the diameter was 40 degrees. After doing the actual gluing with a pair of rolls of 20 J, the diameter was 40 mm? It is cooled to room temperature by a cooling roll of
Layer 9 Aluminum foil / 5 French-modified propylene copolymer binary blend layer / 15 French-modified propylene copolymer ternary blend layer / 40 Ribropylene copolymer binary blend layer / 10 isotactic polypropylene layer A laminated sheet was obtained. It was difficult to separate the aluminum foil from the polyolefin layer of this laminated sheet, and when the sheets were subjected to boiling water treatment and heated steam treatment in the same manner as in Example 1, no separation between the layers was observed. Example 15 A single layer of high-density polyethylene with a melting point of 130 oo, a density of 0.952 mm/base, and a melt index of 0.7 mm/1 mm was made into a single layer using an extruder having a screw with a diameter of 5 mm. Melt extrusion was performed from a die, and a film with a thickness of 100 mm was obtained by an inflation method.

Next, between the polyethylene film and the aluminum foil with a thickness of 150 mounds whose surface has been treated with boehmite, a polymer having a carbonyl group concentration of 7 heq/100 heq. , crystallinity is 54%, melting point is 11600, Vikatsu softening point is 90
00, 90% hydrolyzate of 40% by weight of modified polyethylene with a melt index of 8.0mm/1mm and ethylene-vinyl acetate copolymer with a vinyl acetate content of 3% by weight, maleic acid and acrylic. Acid-grafted carbonyl group concentration is 23 mheq/100 polymer, crystallinity is 58%, melting point is LOYO, Vicat softening point is 9〆0,
40% by weight of a modified ethylene copolymer with a melt index of 5.0 m/skin, a melting point of 129°C, and a density of 0.
955 evening/su, melt index is 5.5 evening/1 skin i
A blend of 2% by weight of high-density polyethylene with a diameter of 65 mm was prepared using an extruder with a screw of 65 mm in diameter and a resin temperature of 290 mm in the die section using a T die of 65 mm in diameter. Melt extrusion was performed, and temporary bonding was performed using a pair of pressure rolls with diameters of 40 mm and 20 mm maintained at a temperature of 80 mm.

Next, this laminated sheet was passed through a sand gap of 1 in a heating oven at a temperature of 14,000 to perform main adhesion, and the composition was 15.
0 French aluminum sheet / 20 French modified polyethylene
A laminated sheet having a blend layer/100 French high-density polyethylene layer was obtained. The peel strength between the aluminum sheet and the high-density polyethylene layer of this laminated sheet was measured.
It was 00/1.5. Example 16 95% by weight of an ethylene-propylene block copolymer with a melting point of 158 qo, a density of 0.90 ml/kg, a melt index of 8.0 ml/in, and an ethylene content of 5 mol% and vinyl acetate. Content is 5% by weight, melting point is 10○,
5% by weight of ethylene-vinyl acetate copolymer with a density of 0.939/hin and a melt index of 8.0 m/hin
The blend was melt-extruded through a single layer die using an extruder having a screw with a diameter of 5 mm, and a film with a thickness of 60 mm was obtained by the inflation method.

Next, maleic anhydride, fumaric acid, and vinyl acetate were grafted onto an ethylene-propylene floc copolymer with an ethylene content of 5 mol% between the 30r aluminum foil and the propylene copolymer blend film. Polymer with a carbonyl group concentration of 25 eq/100, a crystallinity of 56%, a melting point of 15r0, and a Vicat softening point of 13
8qo, melt index is 12.0 tano 1 hin
The weight percent of modified propylene copolymer 6 and the density are 0.90
9/earth, melting point is 154 0, melt index is 10
．． A blend of 4% by weight of an ethylene-propylene flock copolymer with an M/1 skin temperature and an ethylene content of 5 mol% was heated using an extruder equipped with a screw with a diameter of 65 mm, and the resin temperature in the die section was increased. Melt extrusion was performed through a T-die with a diameter of 65 mm under conditions of 250 qo, and the temperature was 100 qo.
Temporary adhesion was performed using a pair of pressure bonding rolls with a diameter of 40 mm and a temperature of 20 mm maintained at ℃.

Next, this laminated sheet was passed through a 1M sand gap in a heating oven at a temperature of 200°C to perform main adhesion, and the composition was 30 real aluminum foil/15 French modified propylene copolymer blend layer/60 ribropylene copolymer blend layer. A laminated sheet was obtained. The peel strength between the aluminum foil and the propylene copolymer blend layer of this laminated sheet was measured.2
It was 450/1.5. In addition, when the film was subjected to boiling water treatment and heated steam treatment in the same manner as in Example 1, no peeling between the layers was observed, and no decrease in adhesiveness was observed.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of an example of a laminated structure according to the present invention, FIG. 2 is an explanatory diagram for explaining the steps of one embodiment of the method of the present invention, and FIG. It is an explanatory diagram for explaining the process of the embodiment, and reference numeral 1 indicates a laminate;
2 is aluminum foil or the like, 3 is a modified olefin resin layer, 4 is a crystalline olefin resin film, 11, 11' is a heating mechanism,
12 and 13 are pressure rollers, and 14 is a die, respectively. Figure 1 Figure 2 Figure 3

Claims (1)

[Scope of Claims] 1. Between the aluminum foil or sheet and the crystalline olefin resin film, the crystallinity is 15 to 95%, the carbonyl group content is 1 to 600 meq/100 g of polymer, and the constituent olefin is Prior to melt-extruding a modified olefin resin whose units are the same as the crystalline olefin resin in a layered manner and bringing the aluminum foil or sheet into contact with the modified olefin resin, the temperature is higher than the Vikato softening point of the modified olefin resin. A method for manufacturing a laminate, characterized in that the laminate is maintained at 2. Between the aluminum foil or sheet and the crystalline olefin resin film, the crystallinity is 15 to 95%, the carbonyl group content is 1 to 600 meq/100 g polymer, and the constituent olefin units are of the above crystallinity. A modified olefin resin that is the same type as the olefin resin is melt-extruded in layers to produce a laminate in which the modified olefin resin is temporarily adhered to an aluminum foil or sheet, and then this laminate is heated to a temperature higher than the Vikato softening point of the modified olefin resin. A method for producing a laminate, the method comprising heating the laminate to a certain temperature.