DK166607B1 - PROCEDURE FOR THE PREPARATION OF AN AUTOCLAVIC RESISTANT LAMINATE FOR PACKAGING FOOD - Google Patents

Description

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DK 166607 B1

The present invention relates to a process for producing an autoclave-resistant laminate for food packaging.

5 With the diversification and improvement of the foods that have been witnessed in recent times, and the increasing use of ready-made foods, there has been an increased need for packaging packaging laminates for foods, and several are being used. In particular, there is an increased need for packaging foods in foods which allow for high temperature sterilization of the foods packed therein, and such packaged and sterilized foods are conveniently called "autoclave foods" or "ready meals".

15

It is generally required that laminates for food packaging have the following basic properties: (1) They must not be toxic but must be hygienically satisfactory as they have many opportunities for direct contact with food, (2) ) they must be satisfactorily impervious to gases or the like in order to allow the food packaged therein to retain their aroma and taste unchanged for a long time (such impermeability is hereinafter referred to as "barrier property"); "), (3) they must have satisfactory light retardant properties in order to prevent the food packaging therein from being degraded or denatured as a result of radiation in the form of ultraviolet light or the like, (4) they must have high mechanical strength and satisfactory-3 (5) they must have high resistance to water and chemicals, such as acids and bases, and (6) they must have good heat sealing ability. e and could be thermally bonded under pressure in a very short time. Furthermore, (7) it is necessary that they have a good heat resistance, and (8) the 3 5 · must not have their joint strength reduced when packaged foods are subjected to stereo 1 in an autoclave (e.g. they must not have their properties degraded when they come into contact with water, acids, bases, oils or the like at high temperatures), since they must be subjected to high temperature sterilization usually of 100-140eC for above ten 5 seconds to over ten minutes.

It is difficult for plastic films or the like alone to meet such stringent requirements. Therefore, composite films are used as packaging materials for food. The components of a food packaging laminate can be polyolefin, polyamide, polyester and aluminum, and in many cases combinations of an aluminum foil or aluminum sheet having particularly excellent barrier properties are used together with a hygienically excellent polyolefin nf as autoclave resistant. food packaging materials. Aluminum foils are generally used for laminating with polyester foils. Among the PClyolefin foils, polyethylene, polypropylene, ethylene-propylene copolymer, and high density polybutene are preferred because of their heat resistance as packaging material for foodstuffs.

E mb alien food laminates must have the following properties. When manufactured industrially, they must (1) be capable of being produced at a high production rate (i.e., they must be capable of being joined within 1/2 to several seconds), they must (2) have high bonding or adhesion strength before and after heating in an autoclave, even when they have been joined at high speed, and must not have diminished bond strength during storage after being loaded with food and heated in an autoclave, and (3) they must not form any excretions or materials that present hygienic problems.

The lamination process for producing conventional food packaging laminates is carried out at a lamination rate of 50-100 m / min, and it is desirable that the autoclave-resistant food packaging laminates be prepared by lamination at such a rate of feed.

3 DK 166607 B1

It is well known that polyethylene, polypropylene, ethylene-propylene copolymers, polybutene and other high-density polyolefins are useful as food packaging materials because of their superiority in hygiene 5 and the like, but are not readily applicable due to high crystallinity and unpolarity, which is why they hardly exhibit any adhesion to other materials. To eliminate these drawbacks, the above polyolefins are subjected to chemical and physical treatments or treated by ultraviolet light, electronic radiation or the like. (1) In particular, chemical treatments of polyolene veneers with sulfuric acid chromate or the like are quite effective if carried out at elevated temperatures, but in fact these treatments are not performed since they are of the wet type and corrode the reaction apparatus used as a result of the use of one or more acids. Therefore, these treatments are now performed only for basic studies in attempts to improve the adhesiveness of polyolefins. (2) Copolymers of polyolefins = α, β-ethylenically unsaturated carboxylic acids (such as acrylic acid, methacrylic acid and maleic anhydride) and their esters are treated to be used as a coating or film adhesive for bonding polyolefin to other materials . In this case, however, either only a very low bond strength is obtained, or it also takes time to heat and dry, and a pressure is also required if a satisfactory bond strength is to be obtained, and in many cases primers are further used for acceleration. of the adhesion. (3) Corona discharge treated polyolefin films are widely used for industrial purposes, but in this case the improvement of bond strength is limited and an additional adhesive is used. As mentioned above, a few industrial processes are carried out to modify or improve the polyolefin itself in order to make it very adhesive. In fact, polyurethane resins and the like are widely used as adhesives in cases where a very secure bond is required between polyolefin films and other materials.

Polyurethane resins are said to suffer from the following 5 drawbacks: (1) It is likely that unreacted diisocyanate and polyol as well as lower polymers remaining in the polyurethane resins are transferred to the foods packaged in the packaging materials utilizing the polyurethane resins used, hygienic problems. (2) 10 It lasts approx. 1 week at ambient temperature or at least 1 day at 50-60 ° C by aging to achieve a practically useful bond between packaging materials if they are metal films or plastic films (resinous). (3) Foaming is effected in an adhesive used between polyolefin and other materials for joining them, thereby forming a uniform bonding strength throughout the joined portion, reducing the commercial value of the resulting product. Although the polyurethane resins have the above disadvantages, they are still used since other materials are currently available which are useful as adhesives for a polyolefin. Efforts have therefore been made to find polyolefin resin packaging materials which do not pose hygienic problems and provide satisfactory bond strength in a short-term processing of food packaging materials using polyolefin resin-containing adhesives, such as to provide a secure bond between polyolefin and other material.

It is also known that with metal ions cross-linked polyolefin resins are used to laminate the materials together in the field of building materials or structures in ceramics in cereals and in packaging materials. The metal ions crosslinked po 1 yo 1 ef ΐ ri resins are considered as a kind of thermoplastic resin (ionomer), in which the long chain molecules are joined together by ion bonding. Structurally, the ionic bonds between the long chain molecules are produced by the monovalent or polyvalent meta 1cations and the carboxyl groups of the long chain molecules.

5

The compositions and uses of conventional polyolefin resins are discussed in the literature set forth below.

U.S.A. U.S. Patent No. 3,264,272 discloses ionic copolymer = 10 more obtained by reacting a copolymer of an α-olefin and an ethylenically unsaturated monocarboxylic acid with a monovalent to trivalent metal ion, and it also deals with ion-crosslinked copolymers obtained by reacting a copolymer of an α-ole = fine and an ethylenically unsaturated dicarboxylic acid with a monovalent metal ion. By the same U.S.A. patent specification further states that the ions crosslinked copolymers are useful as adhesives and that they can be laminated to paper, metal foils and plastics, and it is also evident that it is inappropriate to react the copolymer of α-olefin and α, β-ethylenically unsaturated dicarboxylic acid with the polyvalent metal ion.

Japanese Patent Gazette No. 18238/77 discloses that a resin material can be used as an adhesive for the manufacture of polyolefin laminates with a metal, the resin material being prepared by reacting a crystalline polyolefin with an unsaturated aliphatic carboxylic acid and / or an anhydride thereof and with the oxide and / or sulfate of a metal in the groups IIa, IIla and IVb of the periodic table at a temperature higher than the melting point of the polyolefin.

Japanese published patent Gazette No. 37494/73 discloses a polyolefin material prepared by reacting polyolefin with an unsaturated aliphatic carboxylic acid and / or anhydride thereof, and with the hydroxide or alcoholate of a metal of groups 1a, IIa, IIa and IVb thereof. periodic system at a temperature higher than the melting point of the polyolefin 6, and it is also mentioned that the polyolefin material thus produced exhibits particularly excellent adhesion to moldings of polyolefin, aluminum, iron, copper, zinc and the like, and it appears, the material can be used as an adhesive for laminating a synthetic resin with a metal.

Japanese Patent Gazette No. 17971/72 discloses a process for producing a usable thermoplastic monoolefin = 10 polymer by reacting a thermoplastic monoolefin copolymer with (a) a radically polymerizable carboxylic acid, (b) a radical initiator and (c) the oxide, hydroxide or carbohydrate of lithium, potassium, sodium, magnesium, calcium, zinc, aluminum or silicon at an elevated temperature in the near-T5 room or absence of a solvent. The usable thermoplastic monoolefin polymer thus obtained can be used to make injection molded articles, vacuum shaped articles and the like without any reduction in impact strength and creep or surface performance.

Japanese Patent Gazette No. 27580/74 discloses laminates in which the metal and ethylene copolymer surround an intermediate metal-containing copolymer, the ethylenic copolymer being a copolymer of ethylene, an α, β-25 ethylenically unsaturated carboxylic acid, an α, β ethylenically unsaturated carboxylic acid metal salt and, if desired, an α, β-ethylenically unsaturated carboxylic acid ester. The laminates thus provided are used in communication cables.

30 From Japanese published patent Gazette No. 74583/73, packaging materials which can be sterilized at a high temperature under pressure are known, which materials such as the inner layer have a film made of a high density polyethylene material and an ionomer. From the 35 gazette it also appears that "Surlyn" (ionomer manufactured by E. · I. Du Pont) can be used as an autoclave resistant food packaging material. The ionomer-containing film 7 DK 166607 B1, however, is laminated by dry lamination using an ethane-type adhesive.

The journal "Plastic Fairy", Vol. 4-6, Booklet 6, pages 244 - 249, 5 describes the preparation of an autoclave-resistant laminate for food packaging, in which an aluminum foil and at least one polyolefin film are adhered using an adhesive. Adhesives include plastic solutions in the broadest sense, plastic dispersions, partly also in admixture with path well sesiim, and also wax, and also in admixture with plastic.

The present invention aims to provide a process for producing autoclave-resistant laminates for packaging food which can be produced at a very high production rate and has excellent cohesive strength even when heated in an autoclave.

This is achieved according to the invention by a method 20 for producing an autoclave resistant laminate for food packaging in which at least one polyolefin film selected from high density polyethylene, polypropylene, ethylene propylene copolymer films is laminated to an aluminum foil or aluminum plate. and / or polybutene film using polyolefin resin as an adhesive, using as an adhesive an all-aluminum cross-linked polyolefin resin made by reacting (A), 100 parts by weight of high density polyethylene, polypropylene, an ethylene -propylene copolymer and / or polybutene, having (B), 0.01 to 30% by weight of maleic anhydride, and (C), 0.05 to 10% by weight of 1e aluminum hydroxide, which method is characterized by using a aluminum ions crosslinked polyolefin resin from which unreacted maleic anhydride (B) and maleic anhydride were removed during or after its manufacture low molecular weight rid homo polymer.

8 DK 166607 B1

Surprisingly, it has been found that special polyolefin resins, as described above, are very effective in producing autoclave-resistant packaging inputs for foods. In contrast, when a polyurethane adhesive is used, the lamination could be carried out at a somewhat higher lamination rate, but aging of the laminates is necessary after the lamination, whereby the method compared to the method of the present invention takes a considerable time to obtain packaging laminates. which will exhibit satisfactory bond strength when used. Such high-speed lamination and subsequent autoclave treatment (this term throughout the description means "after heating in an autoclave) cannot be obtained by using metal ion-free or cross-linked polyolefin polyolefin resins prepared by reacting 1 5 3 of polyolefin with maleic anhydride by reaction of polyolefin, an α, β-ethylenically unsaturated carboxylic acid which is not maleic anhydride, and alpha aluminum hydroxide, or by reaction of polyolefin, maleic anhydride and a metal compound which is not all aluminum hydroxide.

20

The polyolefin (A) which may be used in the process of the invention is a heat-resistant polyolefin and includes high density polyethylene produced by low pressure polymerization, an ethylene-propylene copolymer produced by low pressure polymerization, high polyethylene density produced by medium pressure polymerization, an ethylene-propylene copolymer prepared by medium pressure polymerization, a high crystalline polymer such as isotactic or syndiotactic polymer.

O U

tical polypropylene, or a low crystalline polymer such as atactic polypropylene. The polybutene of any crystallinity can also be used without regard to the fact that, depending on its tacticity, it varies from low to high crystallinity. Ethylene propylene copolymers can be further used, whether randomized or block copolymers.

9 DK 166607 B1

However, propylene-rich copolymers are preferred since the ethylene-propylene copolymers are required to be heat resistant. Either or both of these olefins (ethylene and propylene) may be polymerized with a third copolymerizable component to produce a copolymer or ter = 5 polymer which may also be used, and preferably selected depending on the purpose for which it is to be used. .

The α, β-ethylenically unsaturated carboxylic acid used in the process of the invention is maleic anhydride (B). Compared to other α, β-ethylenically unsaturated carboxylic acids, maleic anhydride can be readily copolymerized with the polyolefin (A). Furthermore, the specific polyolefin resins obtained from the graft copolymer thus prepared can be used to prepare packaging laminates having excellent adhesive properties after furnace treatment.

Maleic anhydride (B) is used in amounts of 0.01-30 parts by weight per day. 100 parts by weight of the polyolefin (A). The use of maleic anhydride in an amount of less than 0.01 parts by weight 20 will result in the preparation of a resin-bonded aluminum aluminum polyolef which, when used as an adhesive in a laminate packaging containing an edible oil, acetic acid or the like the laminate has some excellent bond strength after autoclave treatment, while use of maleic anhydride in an amount of more than 30 parts by weight will not result in further increased bond strength.

The metal compound (C) used in the process of the invention is aluminum hydroxide. Compound (C) 30 is used in an amount of 0.05 - 10 parts by weight per minute. 100 parts by weight of the heat-resistant polyolefin (A), which results in the production of a specific polyolefin resin which will exhibit high bond strength when subjected to heating for 0.3-5 seconds and which will not lose bond strength when some time has passed after an oven test. Use of less than 0.05% by weight of the metal compound (C) will make it difficult for the resulting specific polyolefin resin to achieve high bond strength by heat treatment for a short time as indicated above, while using more than 10 parts by weight of the compound (C) will not result in increased bond strength when the polyolefin resin is heat treated, and 10 will allow the resulting polyolefin resin to foam as it is heated and melted, making it impossible to apply the resin uniformly as a coating on a substrate.

A high-speed process can be achieved by using aluminum hydroxide as the metal compound.

The specific polyolefin resin (in which aluminum hydroxide is used) can be melt-laminated securely on an aluminum foil 20 at 180-220 ° C for one second.

An example of an industrial process for the production of autoclave-resistant packaging slurries in foods for food is as follows:

A specific molten polyolefin resin is extruded between an aluminum foil and a heat-resistant polyolefin film, and it is all passed between heating rollers for heat treatment thereof to produce an oven-safe food packaging laminate. In this case, the use of the specific polyolefin enables the production of such packaging laminates at a high production rate.

If metal compounds other than aluminum hydroxide, such as alumina, aluminum sulfate, aluminum acetate, sodium hydroxide, about 1 c of aluminum hydroxide, iron hydroxides and zinc hydroxide, are used to produce a polyolefin resin, the polyolefin resin thus obtained will not exhibit bond strength after autoclave treatment, even though it exhibits satisfactory bond strength prior to autoclave treatment (this term throughout the description should mean "before heating in an autoclave").

Such heat-treated polyolefin resins are disadvantageous in that they will not exhibit satisfactory bond strength when tested under stringent furnace conditions. and they will have the bond strength diminished when used to prepare a packaging laminate, and the laminate thus produced is subjected to a long-term preservation experiment after packaging some material in the laminate.

Some metal compounds other than aluminum hydroxide which have been reacted with compounds (A) and (B) to produce a polyolefin resin will allow the polyolefin resin thus obtained to obtain satisfactory bond strength after furnace treatment if the resin is heat treated for a long time, but they will not result in this if the resin is only heat-treated for a short time, so the use of these other metal compounds is very disadvantageous from a manufacturing speed point of view. In other words, the rate of production would have to be reduced in the case of a metal compound other than aluminum hydroxide if, in this case, the same bond strength which can be obtained by using aluminum hydroxide is desired, and furthermore, the heat treatment can have a long-term adverse effect (such as degradation and denaturalization) on the polyolefin resin, depending on the nature of the starting polyol = fin (A).

35 12 DK 166607 B1

In the preparation of a specific polyolefin resin in accordance with the process of the invention using compounds (A), (B) and (C) together, a third component such as polybutadiene may be used. In this case, the third component must be selected so that it has no detrimental effects on the hygienic aspect, heat resistance, adhesion and the like of the resulting specific resin.

The specific polyolefin resin used in the process of the invention can be prepared by a few methods which include heating, mixing and other steps. The preferred methods are as illustrated below.

(1) A process comprises adding the compound (C) to a heated mixture of the compounds (A) and (B), (2) A process comprising adding the compound (B) to a heated mixture of the compounds (A) and ( C), 20 (3) A process comprises adding a heated mixture of the compounds (B) and (C) to the compound (A) in the heated state, and 25 (4) A process comprising mixing the compounds (A), (B). ) and (C) together and heating the resulting mixture.

The order in which compounds (A), (B) and (C) are added and mixed is not limited to the above and, in addition to these additions and mixtures, reactions using other energy sources may be used.

Using one of the above methods, the specific polyolefin resins which can. used in the process of the present invention is readily obtainable. Further, the above four methods can be carried out using sufficient heat to melt the pre-adjuvants or using a solvent to dissolve the compounds therein.

Eg. the process (1) employing sufficient heat to melt the compounds comprises melt blending the heat-resistant polyolefin (A) with maleic anhydride (B) at a temperature 10-1000 ° C higher than polyole = fin (A) melting point, using heating rollers or an extruder and then incorporating aluminum = 10 hydroxide (C) into the resulting molten mixture to obtain a specific polyolefin resin. In the above process, the melt mixture can usually be carried out for 5-90 minutes, and the aluminum hydroxide (C) may preferably have a fine particle size (less than, for example, approx.

15 ly) for addition as present, the compound (C), if it has a larger particle size, should otherwise be mixed with the other compounds by suitable means to obtain a uniform mixture.

On the other hand, the above-mentioned methods which employ a solvent are advantageous in removing the unreacted materials and staining of the product resin to be obtained should be avoided. The solvents used herein generally include aromatic hydrocarbons such as toluene, xylene and "Solvesso" (manufactured by Esso

Company). Eg. xylene is incorporated into the respective predetermined amounts of the polyolefin (A) and the maleic anhydride (B) and then grafted in the presence of benzyl peroxide (BPO).

In the case where compounds (A) and (B) are to be mixed, the maleic anhydride (B) may be added to compound (A) at once or added dropwise thereto. The latter is advantageous in that by-products will be formed in smaller amounts and the specific polyol-fine resin to be eventually obtained will have a more satisfactory adhesion ability. The mixture under heat supply can be carried out at 130-134 ° C for 30 minutes to 3 hours.

It is desirable that the graft copolymer of compounds (A) and (B) be thoroughly washed.

The aluminum hydroxide (C) is then incorporated into the inoculated copolymer and heated for 15-60 minutes. In this case, it is desirable that the aluminum hydroxide (C) be swelled and dispersed in a small amount of methanol, acetone, water or the like to form a dispersion which is then uniformly mixed with a solution of the resin (grafted copolymer).

It is strictly necessary that the special polyolefin resin is hygienically safe for use as an adhesive in food packaging laminates. Thus, the specific polyolefin resin desired to be obtained can be thoroughly washed with acetone, methyl ethyl ketone, ethyl acetate or the like during and after its preparation. The specific polyol-ephine resin thus obtained is hygienically safe and has excellent adhesion ability.

20

When using polyolefin resin as an adhesive, the entire amount of aluminum hydroxide (C) used has not necessarily been crosslinked with the potted maleic anhydride.

The special polyolefin resins thus prepared can be used in the following different ways. They can be dissolved or dispersed in xylene, "Solvesso" (manufactured by Esso Company), kerosene or other organic solvents, water alone or in a mixed solvent prior to their use. They can be extruded onto a substrate using an extruder to coat the substrate therewith, or they can be formed into films which are then laminated to a substrate or inserted between two substrates. They can be applied as a coating on a substrate to form a coating which is then laminated with a different substrate, or they can be formed into films which are each laminated to a film and then laminated with a different substrate. They can also be applied as a coating in powder form 15 DK 166607 B1. The special polyphone resins are used as an adhesive layer or in the form of a plastic film.

The autoclave resistant packaging materials for food prepared according to the invention consist mainly of (1) an aluminum foil or aluminum sheet, (2) a polyethylene film, polypropylene film, ethylene-propylene copolymer film or high density polybutene film and (3) the specific polyolefin resin used in the process of the invention in the form of an adhesive in the form of a coating or foil. The laminates can be illustrated as aluminum foil (outer layer) / specific polyol = fine resin / polypropylene (inner layer), aluminum foil (outer layer) / specific polyolefin resin / high density polyethylene film (inner layer), polyamide film (outer layer) / aluminum foil / specific polyolefin resin / polypropylene film (inner layer), poly = lamide film (outer layer) / aluminum foil / specific polyolefin resin / high density polyethylene (inner layer), poly = ester film (outer layer) / aluminum foil / specific polyolefin resin / polypropylene film (inner layer) , polyester film (outer layer) / aluminum foil / specific high density polyolefin resin / polyethylene (inner layer), polyester film (outer layer) / aluminum = aluminum foil / specific polyolefin resin / ethylene-propylene copolymer (inner layer), polyester film ( outer film) / aluminum = foil / specific polyolefin resin / polybutene film (inner film), and polyester film (outer layer) / aluminum foil / specific polyole = fine resin / polypropylene suspension coating (inner layer).

Food packaging laminates obtained using the polyolefin foil as an adhesive in the process of the present invention include autoclave resistant, soft packaging laminates comprising at least one plastic film and an aluminum foil as well as autoclave resistant, rigid packaging laminates comprising an aluminum plate or the like. The present invention is preferably applicable to the manufacture of the autoclave-resistant soft packaging laminates which must have high bond strength under more stringent conditions, and in fact the invention enables the production of such excellent soft packaging laminates.

16 DK 166607 B1

Furthermore, for the sake of adhesion, it is desirable for the packaging laminates that polypropylene film, ethylene-propylene copolymer film and polybutene film be used as the component film of the laminate in the case where the specific polyolefin resin is polypropylene, while high density polyethylene film can be used as a high density polyethylene film. the case where the specific polyolefin resin is high density polyethylene.

The component materials used in the process of the invention can be laminated together in the following different ways. As an example of lamination, an aluminum foil or aluminum sheet is coated with the specific molten polyolefin resin and then laminated to the poly = 15 olefin resin layer with a heat-resistant polyolefin film. In this lamination of the heat-resistant polyolefin film, it is not always necessary to melt the specific polyol = fine resin. As another example of lamination, the specific polyolefin resin is laminated with a heat-resistant poly = 20 olefin film and then melt laminated on the molten resin side with an aluminum foil or aluminum sheet. As a further example, the specific polyolefin resin is inserted between a heat-resistant polyolefin film and an aluminum foil or aluminum sheet, after which the three layers of 25 are laminated together.

Packing lambs in high bond strength nats are not obtained solely by coating or placing the specific polyolefin resin on an aluminum foil or aluminum plate. Therefore, in any lamination method, a composition of an aluminum foil or aluminum sheet and the specific or coated specific polyolefin resin or composition thereof, or a composition of an aluminum foil or aluminum sheet, a heat-resistant polyolefin film, and the specific interleaved polyolefin resin interposed, will be subjected to specific resin, thereby increasing the bond strength of the resulting laminate. The term "composition" as used herein is intended to mean "component materials (such as an aluminum foil or aluminum sheet, plastic film, a specific polyolefin resin and the like) which are simply superimposed on one another and not laminated to one another in the absence of a heat treatment ". The heat treatment can be carried out by contact with heating rollers or heating plates, by radiation with infrared light or by using a heating furnace. In the case where such a composition is obtained using an extruder or the like, it is useful in terms of operation and heat efficiency to heat treat the composition immediately after it is obtained.

Heat treatment with heating rolls or plates is most effective as it enables high operating speed, ie. a short-term melt adhesion, and also since such heating rolls or plates can be easily incorporated into an industrial manufacturing system. Furthermore, heating by contact with heating rolls or plates is excellent in terms of heat efficiency and can be easily kept constant, thereby avoiding adverse effects caused by temperature variation. The contact with the heating rolls or plates should cause the specific polyolefin resin to melt adhesive to the second component material. The composition is contacted with the heating apparatus on the side where the specific polyolefin resin is located, or on the side where the other component material is located, preferably the aluminum foil or aluminum sheet. In a method of contacting the heater with the specific polyolefin resin, since this resin is softened or melted, care must be taken to ensure that the specific resin is not transferred to the heating rollers or plates. In carrying out the process according to the invention, it is not always necessary to completely melt the specific polyolefin resin, although the term "melt" is used in the discussion 5 of the lamination in the specification. The heating rollers or plates are preferably of the rotary or circular type, but they may also be of stationary type. They may be cylindrical, semi-cylindrical, flat or have a curved surface shape, but their shape is not very limited and is merely designed to contact the component materials (including the specific polyolefin resin) for a sufficient period of time. The preferred heating rollers are rotatable and cylindrical. The heating rollers can be rotated by means of a propellant, by frictional contact with the component materials or by a railless belt system.

The heating rolls or plates may be heated by a hot medium, an electric heater, an induction heater, a flame or the like. Any heat source which heats the heating rolls or plates may be used so that their surface is maintained at a certain appropriate temperature. The surface temperature of the heating rolls or plates may vary mainly according to the nature of the specific polyolefin resin, line speed and contact time.

The surface temperature may be approx. 150 to 220 ° C for the specific polyolefin resin in which the polyolefin unit is derived from high density polyethylene or polybutene, and the temperature may be approx. 180 to 250 ° C for the resin in which the polyolefin unit is derived from polypropylene or ethylene propylene copolymers.

The heating rolls or plates may be made of any satisfactory heat-resistant material, preferably a metal, and they may also be made of a metal / heat-resistant polymer laminate. In cases where the specific polyolefin resin or other component materials tend to be partially transferred to the heating rolls or plates, it is preferred that the surface of the rollers or plates be "Teflon" treated.

The methods by which the heating rolls or plates are brought into contact with the component materials in laminates to be made will be explained in the following with reference to the drawing, in which: FIG. 1-4 each are cross-sections showing an embodiment of the method according to the invention; 5 is a cross-sectional view showing a sandwich lamination obtained by extruding a specific polyolefin resin between an aluminum foil and a polyolefin film; 6 is a cross section showing melt adhesion and irradiation 15 with infrared light; and FIG. 7 is a cross-sectional view showing heating by an electric heater.

FIG. 1 and 4 illustrate a method using a heating roller, while FIG. Figure 2 shows a method using a heating plate. FIG. 3 shows a method using a tape type heating plate. Reference numeral 1 denotes an aluminum foil or aluminum sheet (also an aluminum foil or aluminum sheet which is laminated with a polyester resin or the like, although not shown in the drawing), a heat-resistant polyole = fine film is designated 2, a specific polyolefin resin is designated 3, an apparatus for coating or laminating the specific polyolefin resin with 4, a heating roller or plate of 5, a heat source of 6 and a rubber roller 30 of 7. The heat source 6 is shown in FIG. 1, a heating medium in the roller is shown in FIGS. 3, 5 and 6; a flame is shown in FIG. 2, and an electric heater is shown in FIG. 4th

Rapid heating can be done using the heating roller or plate 5 due to heat conduction. This is an effective heating method. If necessary, the heating roller or plate 5 capable of rapid heating can be used in combination with the infrared light radiation apparatus and a heater 8. The infrared light beam apparatus and / or heater 8 may be used simultaneously with or after the use of the heating roller or plate 10 for melting and adhesion. The combined use of the heating roller or plate 5, the infrared light beam apparatus and / or the heater 8 is effective in forming a coating of specific high-density polyolefin resin. FIG. 6 and 7 both show a cross section, and fig. 6 illustrates a method of using the heating roller 5 as well as the infrared light beam apparatus 8 in combination for melting and adhesion. FIG. 7 illustrates a method of using the heater 8 immediately after using the heating band 5 for melting and adhesion. FIG. 6 illustrates an effective method of forming a specific large-thickness polyolefin resin, while it is more difficult to achieve safe adhesion using conventional methods.

The heat treatment has been explained mainly with reference to the heating roller or plate shown in the drawing, but it can also be performed using infrared light radiation alone or use of the heater alone.

The invention is further explained in the following examples, in which parts and percentages are by weight and percentages, respectively, unless otherwise stated.

Example 1.

100 parts of polypropylene (M.I. 10), 20 parts of maleic anhydride and 375 parts of xylene were charged to a 1 liter three-neck flask equipped with nitrogen conduit, thermometer and stirrer. The resulting mixture was heated to 130 ° C with stirring in a nitrogen gas atmosphere, and a solution of 0.1 part benzoyl ylperoxide in 40 parts xylene was then added dropwise over 90 minutes, after which it was all heated to 130 ° C. and kept at this temperature with stirring for 60 mi. The reaction mixture thus obtained was cooled to room temperature to obtain a suspension. The suspension obtained was filtered to remove xylene therefrom, washed repeatedly with methyl ethyl ketone until unreacted maleic anhydride and low molecular weight maleic anhydride homopolymers could hardly be detected in the methyl ethyl ketone wash liquids by liquid chromatography, thereby obtaining a polypropylene anhydride maleic anhydride maleic anhydride graft ratio: 0.6%) which was then air dried. The air-dried copolymer resin was added 6.5 parts of aluminum hydroxide to form a mixture which was melted at 180 ° C in an extruder and extruded to obtain a specific polyolefin resin in pelletized form. The obtained specific polyolefin resin pellets were extruded on the aluminum foil surface of a 15 µ thick aluminum foil / polyester film laminate using an extruder (matrix temperature 240 ° C, 25 resin temperature 210 ° C) to form a 10 µ thick coating of the specific polyolefin resin. After the whole was heat treated at 180 ° C for 5 seconds, a 70 µm thick corona discharge treated polypropylene film was laminated to the layer of specific polyolefin resin and the resulting laminate passed through a heated roller to a speed of 180 ° C. of 40 m / min to obtain a packaging laminate.

The bond strength (adhesion strength) between the polypropylene film 22 DK 166607 B1 and the aluminum foil of the packaging laminate thus obtained was at least 1230 g / 15 mm without internal separation of the layers, although the polypropylene film was extended when a 90 ° peel test was performed at a peel rate 5 of 100 mm / min. Containers or bags were made from the packaging laminate thus obtained. Water, a salad oil / water mixture (1: 1), and a 3% aqueous solution of acetic acid were each charged to the containers thus prepared, which were then subjected to an oven test at 10 120 ° C for 30 minutes with the results obtained. which is shown in the following Table 1.

Table 1.

; "Ri" ^ - ,,, ... i

Content in Water Salad oil / water 3% aqueous solution J (1: 1) of vinegar 15._I ___ acid_

Bond strength j after furnace treatment 1220 1140 1020; length (g / 15 mm) _j

A 4% aqueous solution of acetic acid as well as a spice for 20 Chinese food were then packaged in containers or bags, respectively, made from the above packaging laminate and then subjected to a preservation test at 66 ° C. The above spice, which contained soy, soybean oil, soybean paste, rice wine, garlic, ginger and the like, was such that it was subjected to a powerful oven treatment compared to various other spices, such as curry and meat sauce. The acetic acid solution container was tested for its bonding or adhesion strength 1 week after the start of the experiment and the spice container 30 was tested for its bonding or adhesion strength two weeks thereafter. The results are shown in the following Table 2.

Table 2.

23 DK 166607 B1

Contents 4% acetic acid- Spice for chemical __ solution__nesic food_

Bond strength 5 (g / 15 mm) 970 1100

t I

Example 2.

Samples of the packaging laminate obtained according to Example 1 were subjected to an oven test at 140 ° C for 20 minutes with the results shown in the following Table 3.

Table 3.

Content Water Salad oil / water 3% aqueous acetic acid solution Bond strength 15 after oven treatment (g / 15 mm) 1040 1250 1090 i__i_j_i

From the above results, it was confirmed that the packaging laminate prepared by the method of the invention was satisfactorily resistant to the oven test at 140 ° C.

Example 3.

The procedure of Example 1 was followed except that a specific polyolefin resin was prepared by reacting maleic anhydride, benzoyl peroxide and aluminum hydroxide at once in a polypropylene xylene solution to obtain a packaging laminate. The packaging laminate thus obtained was tested in the same manner as in Example 1 and approximately the same results as in Example 1 were obtained.

Example 4

24 DK 166607 B1

The furnace test procedure of Example 1 was followed except that a heat treatment at 180 ° C for 1 second was used instead of the heat treatment at 180 ° C 5 for 5 seconds, obtaining the results shown in the following Table 4.

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Example 5

26 DK 166607 B1

The procedure of Example 1 was followed except that the specific polyolefin resin obtained in Example 1 was used and that the heat treatment was carried out by contacting a heating roller having a surface temperature of 220 ° C at 0.3 and 0, respectively. 5 seconds. The results obtained are shown in the following Table 5.

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Example 6

28 DK 166607 B1

The procedure of Example 1 was followed except that high density polyethylene (MI 6.0) or a propylene-ethylene copolymer (propylene / ethylene = 95/5) was used instead of the polypropylene to obtain a specific polyolefin resin. Using each of the specific polyolefin resins thus obtained, the same experiments as in Example 1 were performed with the results shown in the following Table 6.

In the laminates mentioned below, a high density polyethylene film was used in place of the polypropylene film when the polyolefin in the specific polyolefin resin used was high density polyethylene.

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Saxon Equation Example 1.

The polypropylene-maleic anhydride copolymer (not reacted with aluminum hydroxide) was coated to a thickness of 10 µ using an extruder to obtain a laminate in the same manner as in Example 1. Samples of the laminate thus obtained were heat treated. at 180 ° C for 1 second, at 180 ° C for 5 seconds, and at 220 ° C for 20 seconds, after which the heat-treated samples were each laminated with a 70µm thick polypropylene film on the copolymer coating, and the whole was then coated with a speed of 40 m / min. passed over a 180 ° C hot heating roller to obtain a product laminate. The bond strength of the polypropylene / aluminum foil for each of the product laminates thus obtained was not higher than 100 g / 15 mm.

Comparative Examples 2—6.

In accordance with the procedure of Comparative Example 1, a polyolefin-α, β-ethylenically unsaturated carboxylic acid copolymer was prepared, and then polyester film (outer layer) / aluminum foil / polyolefin-α, β-ethylenically unsaturated carboxylic acid copolymer / polypropylene film was prepared. (inner layer) - laminates. The laminates thus prepared were subjected to an oven test at 120 ° C for 30 minutes with the results set forth in the following Table 7. The laminates obtained by the heat treatment at 180 ° C for 1 second 25 or for 5 seconds. had a bond strength prior to furnace treatment less than 100 g / 15 mm.

In Comparative Example 6, the laminate used was a polyester film (outer layer) / aluminum foil / polyethylene-maleine = high density acid anhydride copolymer / high density polyethylene film.

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Comparative Examples 7-20.

32 DK 166607 B1

The procedure of Example 1 was followed except that to obtain laminates other polyolefin resins than the polyolefin resins used in the process of the invention were prepared. The laminates thus obtained were tested as set forth in Example 1 with the results shown in the following Table 8.

In the above laminates, a high density polyethylene film was used in place of the polypropylene film when the polyolefin in the specific polyolefin resin was high density polyethylene.

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Furthermore, the packaging laminates obtained according to Comparative Examples 7-20 were treated and subjected to the same preservation experiment as in Example 1 with the result that both the containers containing a 4% aqueous acetic acid solution and the containers containing a spice for Chinese food made by Company A were exposed. for delamination.

The containers or bags made of laminates containing magnesium- and calcium-containing polyolefin = resin, respectively, were subjected to blistering when they contained a 3% aqueous acetic acid solution. The containers made according to the comparative examples showed very low bond strength as shown in Table 9, after being subjected to a furnace treatment and then a preservation experiment at 40 ° C for 30 days (which pre serving experiment is a very mild experiment compared to the experiment in Example 1 ). Thus, the comparison vessels failed in the preservation experiment and were further inferior in terms of bond strength after oven treatment compared to the containers made according to the examples.

Table 9.

Content in 3% aqueous "Water Salad oil / acetic acid equation" xv ^ water (1: 1) solution __example_ ___ 25 7 310 210 160

Bonding ----- strength 11 340 300 105 (g / 15 mm) ---- 12 290 280! 120 i -! - i-!

The procedure of each of Comparative Examples 10, 30, 12, 15 and 20 was followed except that a polyolefin resin was heat treated at 180 ° C for 1 second instead of the heat treatment at 180 ° C for 5 seconds to obtain containers. which were tested for bond strength with the results shown in the subsequent Table 10. Furthermore, the containers containing a 4% aqueous acetic acid solution and a condiment for Chinese food made by Company A were subjected to delamination when was subjected to the same preservation experiment as that of Example 1.

Table 10.

K "---: - 1

Contents Binding _After oven testing_j

Water Salad oil / I 3% aqueous 1 10 Treat water (1: 1) equilibrium re-dissolve Example 10 620590480460j «: i> i» -, -ji 12 670 480 I 480 j 430 j __; _i_j 15 15 620 530! 440 380 i -, -! - i 20 700 610; 450 | 430 i __i_i _! _ I

The use of a heat treatment at 180 ° C for 1 second instead of the heat treatment at 180 ° C for 5 seconds hardly caused any reduction in the bond strength in the examples, but a significant decrease in the bond strength in the comparative examples.

Examples 7-8 and Comparative Examples 21-28.

Polyolefin resins (containing metal) as listed in Table 11 were prepared and polyester film 25 (outer layer) / aluminum foil / polyolefin resin / polypropylene = film (inner layer) packaging laminates. The packaging laminates thus prepared were subjected to an oven test at 120 ° C for 30 minutes. Furthermore, containers made from the laminates were filled with a 4% aqueous 30 acetic acid solution and a Chinese food seasoning, respectively, prepared by Company A, and subjected to a test of the bond strength after a preservation test at 37 ° C for 1 week, respectively. 2 weeks. The results are shown in the following Table 11.

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Example 9

40 DK 166607 B1

The polypropylene-maleic acid anhydride copolymer obtained according to Example 1 (maleic anhydride graft ratio: 0.6%) was reacted with 6.5 parts of aluminum hydroxide in xylene at 130 ° C for 1 hour to obtain a specific polyolefin resin. The polyolefin resin thus obtained was washed, dried, dispersed in xylene (dry matter content: 15%) and applied as a coating on the same aluminum foil as in Example 1 to form a 5y thick coating which was then dried at 180 ° C for 10 minutes. 5 seconds. The aluminum foil coated with the specific polyolefin resin was laminated on the resin coating with a 70 y thick corona discharge treated polypropylene film and thus at a rate of 40 m / min. passed over a heating roller at 180 ° C. The packaging laminates thus obtained had a polypropylene film / aluminum foil bond strength of at least 1150 g / 15 mm when subjected to a peeling test.

The packaging laminates were processed into containers which were filled with water, lettuce oil / water (1: 1) 20 and a 3% aqueous acetic acid solution, respectively, after which they were subjected to an oven test at 120 ° C for 30 minutes. Then, the packaging laminates of the tested containers were measured for bond strength with the results shown in the following Table 12.

Table 12.

Content Water Salad oil / 3% aqueous vinegar ___ water (1: 1) acid solution

Bond strength after furnace treatment 1190 1090 1040 30 length (g / 15 mm) I___

Example 10.

41 DK 166607 B1

The specific polyolefin resin pellets obtained in Example 1 were formed into 70y thick films at 190 ° C using a blow extruder. The 5 film thus prepared was laid on a 15y thick aluminum foil and heated under pressure on a heating roller at 180 ° C for 3 seconds to obtain a laminate of specific polyolefin resin / aluminum foil. The laminate thus obtained was tested for bond strength and found to have a bond strength 10 of 1160 g / 15 mm. The laminate was formed into containers which were filled with water, lettuce oil / water (1: 1) and a 3% aqueous acetic acid solution, respectively, after which they were subjected to an oven test at 140 ° C for 20 minutes. After the oven test, the tested containers were measured for bond strength with the result that they exhibited 1120 g / 15 mm, 1010 g / 15 mm and 1050 g / 15 mm in bond strength, respectively. The containers showed satisfactory results when subjected to the same preservation experiment as that of Example 1.

Example 11.

The specific polyolefin resin obtained in Example 1 was melt extruded at a thickness of 10y between a 15µ thick aluminum foil / polyester laminate and a 70y thick polypropylene film using an extruder, and it was then sandwiched by a method such as that shown in FIG. . 5 to obtain a packaging laminate. The lamination was carried out at a lamination speed of 60 m / min. by contacting the materials for lamination with a heating roller having a surface temperature of 220 ° C for 1 second. The packaging laminate 30 thus obtained exhibited satisfactory laminate strength, bond strength after oven treatment and results in preservation experiments as in Example 1.

Example 12.

42 DK 166607 B1

The specific polyolefin resin obtained from Example 1 as well as polypropylene was coextruded to obtain a laminate of a 10y thick layer of specific polyolefin resin with a 50y thick layer of polypropylene. The laminate thus obtained was then applied to a 15y thick aluminum foil / polyester laminate side consisting of the specific polyolefin resin facing the aluminum foil side, and the whole was then contacted with a heating roller having a surface temperature of 220 ° C for 1 second. thereby producing a packaging laminate. The laminate thus produced exhibited satisfactory bond strength, as in Example 1.

Example 13

The specific polyol = fine resin / polypropylene laminate obtained according to Example 12 was laid on a 10-inch thick aluminum foil with the polyolefin resin side facing the aluminum foil, and the whole was contacted with a heating plate having a surface temperature of 250 ° C for 3 seconds to obtain 20 a packaging laminate. The packaging laminate thus obtained was tested as in Example 1 with the results shown in Table 13.

43 DK 166607 B1

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Comparative Example · 29.

44 DK 166607 B1 In a propylene acrylic acid copolymer (acrylic acid content: 3 mole%) per moles of acrylic acid incorporated 0.3 moles of aluminum hydroxide dispersed in methanol, and the whole was mixed on a kneading roller (190 ° C) for 30 minutes. The molten mixture thus obtained was dispersed in xylene and applied a 5µ thick coating to a 30µ thick aluminum foil. The aluminum foil thus coated was contacted with the aluminum foil side with a heating roller at 190 ° C (rotating at 10 rpm). Then, a 70y thick polypropylene film was applied to the polyolefin resin side at 180 ° C to form a laminate. The bond strength between the aluminum foil and the polypropylene film was 1030 g / 15 mm. The laminates thus obtained were subjected to an oven test in the same manner as in Example 1, and the results are shown in Table 14.

Table 14.

j

Content Water Salad oil / water 3% aqueous acetic acid: 1) Acetic acid solution 20 20 Binding strength according to oven condition. ! , „, N nnn \ ,. ,, 960 j 1210 990; action (g / i 15 mm) __ I__.

The same preservation experiment as in Example 1 was performed with the laminates with the result that they proved unsatisfactory for practical use, as shown in Table 15.

Table 15.

30 Content 4% van ^ i9 vinegar- Spice for succinic acid fresh food made ___from company Å_

Bond strength delamination 250 45 DK 166607 B1

Example 14.

100 parts of polypropylene, 0.4 parts of maleic anhydride and 0.1 parts of benzoyl peroxide were melted on a heating roller at 185 ° C for 10 minutes. After completion of the melting process, the materials were thoroughly extracted with acetone to remove the unreacted maleic anhydride and low molecular weight maleic anhydride homopolymer to obtain a polypropylene-maleic anhydride copolymer.

In the copolymer thus obtained, aluminum = 10 hydroxide was incorporated in an amount of 1.5 parts per liter. 100 parts of the polypropylene mesh to form a mixture which was mixed on a Hensche1 mixer.

The mixture thus obtained was melt blended and extruded with an extruder at 180 ° C. The pellets of specific polyolefin resin thus obtained were applied as an adhesive to a thickness of 10µ as an extrusion coating on a 15µ thick aluminum foil (an aluminum foil / polyester ester laminate) using an extruder (die temperature: 235 ° C) to forming a resin / aluminum laminate. Immediately after coating, the laminate thus formed on the opposite (polyester) side was contacted with a heating roller (surface temperature: 180 ° C) for 1 second as shown in FIG. 1, for heating (heat treatment equivalent to 60 m / min) of the laminate, whereby the surface-coated specific polyolefin resin is brought to adhere securely to the aluminum foil.

Furthermore, a 70µm thick polypropylene film was applied to the coating of specific polyolefin resin and the whole was passed over a heating roller (surface temperature: 180 ° C) at a speed of 60 m / min. In the packaging laminate thus obtained, the bond strength of the polypropylene film / aluminum foil was obtained. and it was found to be as high as 1020 g / 15 mm. The packaging laminate was formed into containers which were filled with water, salad oil / water (1: 1) and a 3% aqueous solution of acetic acid, respectively, after which they were subjected to an oven test at 120 ° C for 30 minutes. After the oven test, the packaging laminates were tested for bond strength with the results shown in the following Table 16.

Table 16.

Content Water Salad oil / water 3% aqueous vinegar ____ (1; 1) __ acid solution

Binding Strength Action ^ g / 1040 1110 990 15 mm)

j_ί_I

Furthermore, the packaging laminates were subjected to the same preservation experiment as in Example 1 with the results 15 shown in Table 17.

Table 17.

Content 4% aqueous vinegar- Spice for Chinese acid solution food made by ___ company Å_ 20 Binding strength (g / 15 mm)

Example 15

The packaging laminate obtained according to Example 14 was formed into containers, each of which was filled with the materials listed below as mentioned in Table 18 and then subjected to an oven test at 135 ° C for 20 minutes. The results are as shown in Table '18.

47 DK 166607 B1

Table 18.

Content Water Salad oil / water 3% aqueous vinegar- ___ (1; 1) __ acid solution_

Bond strength 5 kft ^ tOVnl? E ', 1010 980 960 action (g / 15 mm) _________

From the above results, it was confirmed that the specific polyolefin resin used in the process of the invention was satisfactorily resistant to the furnace test at 135 ° C.

Example 16.

The resin extrusion coated laminates (resin / aluminum laminates) obtained according to Example 14 were each heat treated as shown in Table 19 and then each laminated 15 with a 70µ thick polypropylene film to obtain packaging laminates. Each of the packaging laminates was then molded into containers / each filled with the materials shown in Table 19 as well as subjected to an oven test at 120 ° C for 30 minutes and then tested for bond strength. The results are shown in Table 19.

48 DK 166607 B1

Table 19.

Heat treatment Binding strength according to oven treatment conditions _ (g / 15 mm) _

Salad oil / water 3% aqueous acetic acid 5 __ (1: 1) __ re-solution_ 160 ° C for 20 sec. 1190 1180 180 ° C for 5 sec. 1110 980 200 ° C for 3 sec. 1140 1110 220 ° C for 3 sec. As shown in the above results, the packaging laminate containing resin / aluminum laminate, previously heat treated at 200 ° C for 3 seconds, exhibited high bond strength.

Examples 17 - 18 and Comparative Examples 30 - 35.

15 In the same way as in Example 14, specific polyolefin resins were prepared under the various conditions shown in Table 20. The resulting packaging laminates were a polyester film (outer layer) / aluminum foil / specific polyolefin resin / polypropylene film (inner layer) and subjected to an oven test at 120 ° C for 30 minutes with the results shown in Figs. Table 20. In the above packaging laminates, a polyethylene film was used as the inner layer instead of the polypropylene film when the polyolefin in the specific polyolefin resin was polyethylene.

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Example 19.

In the polypropylene-maleic acid anhydride copolymer obtained in Example 14, 1.5 parts of aluminum hydroxide and xylene (solid content: 15% by weight) were incorporated and heated to 5 to 130 ° C for 60 minutes, then the resulting mixture at a thickness of ca. . 5y was applied as a coating on a 15y thick aluminum foil (aluminum / polyester laminate).

The thus-coated aluminum foil was heat-treated at 180 ° C for 5 seconds, a 70y thick polypropylene film was applied thereto, and parts became at a rate of 60 m / min. passed over a heating roller at 180 ° C to produce a packaging laminate. The packaging laminate thus produced was found to have a high bond strength of 1160 g / 15 mm between the polypropylene film and the aluminum foil.

The packaging laminate was further molded into containers which were filled with lettuce oil / water (1: 1) and a 3% aqueous acetic acid solution, respectively, and then subjected to an oven test at 120 ° C for 30 minutes with the resultant binding strengths of 1140 and 1020 g / 20 15 mm. They also showed satisfactory results in the same preservation experiment mentioned earlier.

Example 20

100 parts of polypropylene (MI, 10), 16 parts of maleic acid anhydride, 10 parts of 1,2-polybutadiene (average molecular weight 150,000) and 375 parts of xylene were charged to a 1 liter three-neck flask equipped with nitrogen gas, thermometer and stirring. forming a mixture which was heated to 130 ° C with stirring in a nitrogen gas atmosphere to obtain a reaction mixture. To the thus obtained reaction mixture was added dropwise a solution of 1.5 parts of benzoyl peroxide in 40 parts of xylene over 90 minutes. Then, the reaction mixture was heated to 130 ° C with stirring for 30 minutes and the mixture was cooled to room temperature to give a suspension. The suspension thus obtained was filtered to remove xylene therefrom and repeatedly washed with acetone until unreacted maleic anhydride and low molecular weight maleic anhydride homopolymers could hardly be registered in the acetone wash liquids to obtain a powdered resin. The powdered resin was air dried, redissolved in xylene, added 1.0 part of aluminum = hydroxide and heated to 130 ° C with stirring for 30 minutes in a nitrogen atmosphere to obtain a specific poly = 10 lyolefin resin. After the heating was completed, the resin thus obtained in a ca. 5y thick layer applied to a 15y thick aluminum foil (aluminum / polyester laminate) while warm. The resin-applied aluminum foil was heated to 180 ° C for 5 seconds, a 70y thick polypropylene = 15 film was applied thereto, and the whole became at a rate of 20 m / min. (two second contact) passed over a heating roller at 180 ° C to obtain a packaging laminate. The polypropylene film / aluminum foil in the packaging laminate exhibited a high bond strength of 1360 g / 15 mm when a 90 ° peel test was performed at a peel rate of 100 mm / min. The packaging laminate was formed into containers, each filled with the materials listed in Table 21, and then each subjected to an oven test at 120 ° C for 30 minutes and a preservation test at 66 ° C. The measurement of the bond strength was performed as previously mentioned. The results are shown in Table 21.

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In addition, some of the packaging laminates in which the polyolefin resin is used as adhesive were tested in the Examples and Comparative Examples for their hygienic properties with the results shown in the following Table 22. Two measurements were taken for each of the experiments shown in Table 22.

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As can be seen in Table 22, the specific polyolefin resins used in the process of the present invention are excellent in terms of hygienic properties compared to the urethane type adhesive, and are also suitable for applications in which hygienic considerations should be made.

Experimental results showing the effect of the removal of unreacted maleic anhydride and its low molecular weight homopolymer, depending on the number of washes, are described below.

The test results for residual contaminants relate to the following polyolefin resins:

According to Example 1, a special polyolefin resin was prepared using a polypropylene maleic acid anhydride in d-copolymer resin which was washed five times with methyl ethyl ketone (about 30 times the amount).

In the case of the same polypropylene maleic anhydride copolymer resin which was washed only once or only three times, significant 2g amounts of low molecular weight maleic anhydride homopolymers could be detected.

The bond strength between polypropylene polypropylene in 1 men and the aluminum foil in the packaging laminate obtained as set forth in Example 1 using polypropylene-maleic anhydride, washed twice, three times and five times (as in Example 1), was determined. The results obtained are shown in the following Table 23.

35 DK 166607 Pg 57

Table 23.

Washed Washed Washed g once three times five times (bonding (bonding (bonding strength strength strength g / 15mm) g / 15mm) g / 15mm) Before autoclaving 150 1100 1230 10 After autoclaving, content

Water delamination 1080 1220

Saline oil / water (1: 1) delamination 1000 1140 3% aqueous acetic acid solution delamination 980 1020

Storage test (at 66 0 C), content 4¾ acetic acid solution (hatch) delamination 350 970

Seasoning for Chinese Law (2 weeks) Part Amines 450 1100 25 As can be seen from the above results, the five times washed polyethylene resin results in an excellent bond strength over a very short time (see Example 5), also retains its bond strength. after being subjected to a very rigorous treatment in autoclave and not losing its bonding strength after being subjected to a treatment in autoclave, so that the laminates prepared according to the present invention are apt to retain their contents undamaged for long periods of time.

Similarly, it could be shown by liquid chromatography that in the case of the polyolefin resin used (washed five times) in the polyolefin resin used, unreacted maleic anhydride and low molecular weight

Claims (4)

However, when unreacted maleic anhydride and low molecular weight maleic anhydride homopolymers remain in the polyvinyl resin, the bond strength of the laminate decreases extremely and delamination occurs after the autoclave treatment or after a longer shelf life. This shows that when using the e.g. JP-A 48-37,494 modified resin polyolef in adhesive as an adhesive, no autoclave resistant packaging material can be obtained. 15 Patent claims. A method of preparing an autoclave-resistant 1a-2q minate for food packaging wherein at least one polyolefin film selected from high density polyethylene, polypropylene, ethylene propylene copolymer and laminated films is laminated to an aluminum foil or aluminum plate. / or polybutylene film using polyethylene resin as an adhesive, using as an adhesive an aluminum ions crosslinked polyolefin resin made by reacting (A), 100 parts by weight of high density polyethylene, polypropylene, an ethylene copylene copolyene ymer and / or polybutene, with (B), 0.01 to 30 parts by weight of maleic anhydride, and (C), 0.05 to 20 parts by weight of aluminum hydroxide, characterized in that a polyolefin resin crosslinked with aluminum ions is used, from which or after its preparation, unreacted maleic anhydride (B) and low molecular weight maleic anhydride homopolymer have been removed. 35 Process according to Claim 1, characterized in that the compound (A) is graft copolymerized with the compound (B) to form a graft copolymer, so that the copolymer (C) thus formed (C) is heated. Process according to Claim 1 or 2, characterized in that the resin bonded with aluminum ions is applied to the aluminum foil or plate, contacting the two materials with a heating roller or plate having a surface temperature of 150-250 ° C. for melting together therewith, forming a resin-coated aluminum foil or sheet, and then laminating the resin-coated aluminum foil or sheet to the resin side with at least one film selected from high density polyethylene, polypropylene, ethylene-propylene copolymer films and the polybutene. Method according to claim 1 or 2, characterized in that the aluminum-bonded polyolefin resin is extruded between the aluminum foil or plate and at least one film selected from high density polyethylene, polypropylene, ethylene and propylene copolymer films. and the polybutene using an extruder to obtain a composite material and contacting the thus obtained composite material with a heating roller or plate having a surface temperature of 150-250 ° C to thereby obtain the autoclave resistant laminate. 25 30 35