JPS62278034A - Metal evaporated film and laminate thereof - Google Patents

Abstract

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

Description

[Detailed description of the invention] Detailed description of the invention The present invention relates to a film and a laminate thereof.

More specifically, the metal-deposited film has extremely little deterioration of the metal-deposited layer during heat-seal packaging, and the metal-deposited film is laminated with a specific film or sheet on the metal-deposited surface, which has high gas barrier properties and is particularly suitable for packaging. Regarding a laminate.

(Prior art and its problems) In recent years, metal-deposited films have been developed in which metals are deposited on plastic films under vacuum. It has been widely used in construction materials and packaging materials, and aluminum-deposited films in particular have come to be used in large quantities mainly for packaging.

In addition, crystalline ethylene-propylene random copolymer whose main component is propylene, crystalline propylene-butene-
Crystalline propylene-based random copolymers such as 1 random copolymer and crystalline ethylene-propylene-butene-13 random copolymer have excellent transparency, impact resistance, and heat sealability. It is widely used for general packaging, laminated films, and sheets.

However, a metal-deposited film in which metal is deposited on a film made only of crystalline propylene-based random copolymers has weak adhesion between the film layer and the metal-deposited film layer, and the printability of the metal-deposited surface is poor. There is a problem that the adhesion with the material is extremely reduced.

In order to improve these shortcomings・Special Publications Showa 57-1, 43
Many proposals have been made, such as Publication No. 77 and Japanese Patent Application Laid-Open No. 59-25829.

However, when the metal-deposited film made only of the crystalline propylene random copolymer involved in the above-mentioned proposal is used for packaging, heat-sealing properties such as bag making and filling packaging are affected due to heating by the heat roll. It is still sufficient to solve problems such as the adhesive strength of the metal vapor deposited film in the sealing area decreasing, the metallic luster being lost, and the metal vapor depositing film peeling near the boundary between the heat sealed area and the non-sheet sealed area. Not.

The present inventor conducted extensive research to solve the above-mentioned problems with metal-deposited films using crystalline propylene-based random copolymers. As a result, a layer A consisting of a crystalline propylene polymer or a crystalline propylene random copolymer with a crystalline melting point exceeding 140°C and a crystalline melting point 5°C or more lower than that of the polymer or random copolymer used for the layer A were found. A metal vapor-deposited film in which metal is vapor-deposited on the four-layer surface of a laminated film obtained by co-extrusion with B layer consisting of a crystalline propylene-based random copolymer having Or, based on this knowledge, we have found that a laminate made by laminating plastic films with an equivalent amount of random copolymer and a plastic film having a crystalline melting point of -1 can solve the above-mentioned problems of metallized films. As a result, the present invention was completed.

As is clear from the above description, an object of the present invention is to provide a metal vapor-deposited film with excellent adhesion, printability in the vapor deposition direction, and adhesion with other films, and to ensure that the heat-sealed portion is excellent when heat-rolled. A metal-deposited film with no loss of metallic luster, peeling of the metal-deposited film, cracking of the film, unevenness of the film surface, etc. (hereinafter referred to as deterioration of the metal-deposited film), and a specific material on the deposition surface of the metal-deposited film. The object of the present invention is to provide a laminated film that is laminated with other plastic films and has high gas barrier properties and is particularly excellent for packaging.

(Means for solving problems) The present invention has the following configuration.

(1) Layer A consisting of a crystalline propylene polymer or crystalline propylene random copolymer with a crystalline melting point exceeding 140°C, and a crystalline melting point lower than that of the polymer or random copolymer used for layer A by 5°C or more. A metal vapor-deposited film obtained by vapor-depositing metal on four layer surfaces of a laminated film formed by laminating B layer made of a crystalline propylene-based random copolymer having

(2) Layer A consisting of a crystalline propylene polymer or crystalline propylene random copolymer with a crystalline melting point exceeding 140°C; and a crystalline melting point lower than that of the polymer or random copolymer used for layer A by 5°C or more. The metal-deposited surface of a metal-deposited film obtained by depositing a metal on the A-layer surface of a laminated film formed by laminating B-layer consisting of a crystalline propylene-based random copolymer having A laminate made by laminating plastic films or sheets that have a crystalline melting point equal to or higher than that of a random copolymer.

The metal vapor deposited film and the laminate thereof of the present invention are a metal vapor deposited film formed by vapor depositing a metal only on the high crystal melting point layer of a specific laminated film consisting of two layers A/B having different crystal melting points, and a metal vapor deposited film of the metal vapor deposited film. It is a laminate made by laminating plastic films or sheets of the same type or different types having a specific crystal melting point on the vapor deposition surface, and its structure will be described in detail below.

The crystalline propylene polymer or crystalline propylene random copolymer used in the A layer and B layer of the present invention is usually obtained by polymerizing propylene using a known α-onfin stereoregular catalyst such as a Ziegler-Natsuta catalyst. A propylene homopolymer obtained by
It is a crystalline random copolymer with 1-beptene-1, octene-1, etc., specifically crystalline propylene-butene homopolymer, crystalline ethylene-a-pyrene random copolymer, crystalline propylene-butene-1 Random copolymer! , f
Examples include ethylene-propylene-butene-13-element random copolymer.

In addition, in the present invention, it is necessary that the crystal melting point of the polymer or random copolymer used for the A layer exceeds 140°C, and if the crystal melting point is 140°C or lower, the metal vapor deposited film obtained is This is undesirable because wrinkles, curls, etc. are likely to occur in the film, the appearance of the vapor-deposited film is poor, and when the obtained metal-deposited film is heat-sealed, the quality of the metal-deposited film in the heat-sealed portion is increased. In addition, the crystalline propylene random copolymer used for layer B may be the same type as the random copolymer used for layer A, but its crystal melting point is that of the polymer or random copolymer used for layer A. It must be at least 5°C lower, preferably at least 8°C lower than the crystalline melting point of.

If the difference in crystal melting point between the crystal melting point of the polymer or random copolymer used for layer A and the crystal melting point of the random copolymer used for layer B is less than 5°C, the obtained metallized film When heat-sealing, it is not preferable because deterioration and cracking of the vapor-deposited film in the heat-sealed portion occur. Therefore, in the present invention, the A layer has a crystal melting point of 145°C or higher,
Preferably, a propylene polymer or a propylene random copolymer with a temperature of 150°C or higher is used, and when a propylene random copolymer with a crystal melting point of 140°C or lower is used for layer B, it has particularly excellent metallic luster and good adhesion. A particularly excellent metal vapor deposited film can be obtained which has strong strength and shows no deterioration in quality of the vapor deposited film in the heat sealed portion when heat sealed.

In addition, crystalline ethylene, which has excellent impact resistance at low temperatures,
When a propylene block copolymer is used in layer A, the metallic luster of the metallized film obtained is significantly reduced and the decorative appearance is lost.
If it is used in the layer, the heat sealability of the metallized film obtained is undesirably reduced.

Polymer or random copolymer used for layer A and B
It is desirable to add very specific antioxidants, inorganic fillers, and limited additions of other polymers to the random copolymer used in the layer. In other words, fatty acids and The derivatives migrate to the surface of the laminated film over time and float to the surface of the film on the side where the metal is deposited, resulting in a decrease in the metal deposition power, or on the side opposite to the metal deposited layer. When the metallized film is rolled up, the substance floating on the back side of the film layer adheres to the metallized film surface, lowering the wettability index of the metallized film surface, and as a result, the printability of the metallized film surface decreases. This is not preferable because it causes problems such as deterioration of the adhesive strength and a decrease in adhesive strength when laminating other films.

Therefore, preferable additives to be added to the polymers and random copolymers used in layers A and B include heat stabilizers and antioxidants with a molecular weight of 500 or more, and inorganic fillers such as phosphorus, zeolite, and carbonate. , polyethylene that does not contain additives such as the above-mentioned fatty acids or derivatives thereof, ethylene-α-olefin co-%i Combined: l'
Polymer additives such as mana may be mentioned.

The addition ratio of the above-mentioned additives added to the polymer and random copolymer used for layer A and B is: 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 phosphorus of a phenol-based or phosphorus-based heat stabilizer and antioxidant with a molecular weight of 500 or more. 0.3% by weight, 0.01 to 0.5% by weight of one or more inorganic fillers such as phosphorus, zeolite, etc.
In addition, if necessary (2) low-density polyethylene, linear ethylene containing only the above-mentioned additives in one or both of the polymer or random copolymer used for the A layer and the random copolymer used for the B layer, α-olefin copolymer, high-density polyethylene or ethylene-α-olefin copolymer rubber, and mixtures of two or more of these
It is possible to add up to 15% by weight.

A polymer or random copolymer with such an addition ratio is
By using it for layer and B layer, rigidity, slip property,
A metal-deposited film with excellent heat-on-roll strength can be obtained.

The two layers A and B of the present invention are laminated in a molten state by a known method such as melt kneading extrusion, feed block method, or coextrusion multilayer die method using two extruders.
Examples include a coextrusion lamination method in which the laminated film is wound up after cooling with a cooling roll or the like. Other lamination methods, such as extrusion lamination in which one film is melt-extruded and laminated on the other, lamination methods in which two layers of films A and B are bonded and laminated using an adhesive, etc. are A,
Since the B2 layer film is thin, it has poor slip properties and is flexible and stretches easily, so when laminating these two types of films, wrinkles tend to appear in the two types of films, making it difficult to obtain a uniform laminated film. However, it is difficult to put it into practical use, and even if it could be put into practical use, the yield of a good laminated film would be low and the cost would be high, so it is not preferred.

The thickness ratio of the A%B layer of the present invention is such that the thickness of the B layer is preferably 30 to 95 inches of the total thickness, particularly 40 to 80 inches.
% is desirable.

If the total thickness of layer B is less than 30 inches, the resulting metal vapor deposited film will lack heat roll strength, and if it exceeds 95 inches, the quality of the metal vapor deposited film will increase during heat roll, which is undesirable.

A obtained in this way, A of a laminated film consisting of 82 layers
After surface-treating the layer surface, a metal is deposited under vacuum to obtain the desired metal-deposited film of the present invention.

At this time, as a surface treatment method, any treatment method such as acid treatment, flame treatment, plasma treatment, or corona discharge treatment may be used, but if the laminated film can be treated continuously and the laminated film is Corona discharge treatment, which can be easily treated, is preferred because it is simple.

In addition, the degree of surface treatment is such that the wettability index measured by the method of JIS K6768 is 35 dynes/crn or more, especially 38
Preferably, the treatment is performed so that the dynes/crn is ~43 dynes/crn. In addition, in order to strengthen the adhesion between the film and the metal vapor-deposited film, it is possible to anchor coat the surface-treated surface of the film with an adhesive such as polyester, polyurethane, or Evokin resin, and then vapor-deposit the metal. good.

Any known method such as a vacuum evaporation method, a sputtering method, or an ion beam method can be used to deposit the metal. Using an oil pump and a diffusion pump in combination, reduce the pressure inside the device to about 10-' ttrxHt, and heat the container containing the desired metal such as aluminum, nickel, gold, or silver, or the filament to which the desired metal is attached. A common method is to melt and evaporate the metal, continuously or intermittently deposit the metal on the surface of layer A of the laminated film, and then wind it up. The metal used is preferably aluminum from the point of view of workability and economy.
The thickness of the layer is from several 10 to several 100 mm from the viewpoint of adhesion of the deposited film.
A thickness of approximately angstrom (A) is desirable.

The metallized film of the present invention thus obtained is
Although it is useful as such, it is also useful as a material for packaging by taking advantage of the excellent adhesive properties of the metal-deposited surface, such as preventing scratches on the metal-deposited surface. , After applying an anchor coat of adhesive to the vapor deposition surface, thermoplastic polyester resin, nylon resin,
By laminating a stretched or unstretched film or sheet having a crystal melting point equal to or higher than that of layer A, such as crystalline polypropylene resin, rigidity, strength, and gas barrier properties can be achieved while maintaining the characteristics of the metallized film of the present invention. A laminate with improved wearability can be obtained.

It is also possible to print on the metal vapor-deposited surface before laminating the unstretched film or sheet described above on the metal vapor-deposited surface to obtain a laminate with improved decorativeness and product image. For printing and laminating on the metal vapor deposited surface, commonly used methods can be used. The above-mentioned stretched or unstretched film or sheet used for the lamination may be the polymer or random film used for layer A. It must have a crystal melting point equal to or higher than that of the copolymer. If a film or sheet with a crystal melting point lower than that of layer A is used, when the resulting laminate is heat-rolled, the film or sheet will soften or melt, causing the heat-sealed portion to shrink or become thinner. This is undesirable because it may cause a change in the metallic luster and deteriorate the wearability and appearance.

In addition, it is desirable to apply the above-mentioned surface treatment to the laminated surface of the above-mentioned film or sheet used for lamination in order to improve adhesion.Also, two or more types of films or sheets to be laminated are stacked on the metal-deposited surface. I don't mind if you do.

(Effects of the Invention) The metallized film of the present invention has a vapor-deposited film that adheres firmly to the base film, has excellent printability on the vapor-deposited surface and adhesion to other films, and has excellent adhesive properties when heat-sealed. The heat causes loss of metallic luster, peeling, and
It is a metal vapor deposited film that has excellent heat sealability without any change in metal Yonezawa or film cracking. In addition to the above-mentioned characteristics of the present invention and the metal-deposited film, the laminate of the present invention obtained by simulating a film or a laminate having a specific crystalline melting point has superior rigidity, strength, and high gas barrier properties. This laminate is not only particularly suitable for packaging, but can also be suitably used in many other fields.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Note that the evaluation method used in the present invention was as follows.

1) Melt flow rate) (MFR): 721 to JI8
0-1976 test conditions 14. (230℃, 2.16K
f load).

2) Crystal melting point (Tm) 1 under nitrogen atmosphere using a scanning differential calorimeter (DSC)
The peak temperature of the endothermic curve (
Unit: °C).

3) Wetting index: Measured on both the film surface and the metal-deposited surface in accordance with JISK 676B (unit: 2 dynes/2).

4) Film roll appearance: A film roll obtained by continuously winding a certain length of metal-deposited film is visually observed, and those with a flat surface and no wrinkles or thickening (rolling bumps) are judged to be good. Those with thickening and uneven rolling appearance were evaluated as poor.

5) Adhesion of the vapor deposited film: Apply cellophane adhesive tape (Sekisui Cellotape■) with a width of 18 mm to the vapor deposited film side of the metal vapor deposited film.
) was attached to a length of 7Qzx, and then quickly peeled off by hand to determine the area percentage of the deposited film remaining on the sample film surface without adhering to the adhesive tape, and ranked based on the following criteria.

6) Suitability for printing and laminating on vapor-deposited surfaces Using a film with metal vapor-deposited on two sides, overlap the vapor-deposited surface (metallic surface) and non-vapor-deposited surface (back side of the vapor-deposited surface), and apply a load of 1b/1ood to heat the film. After leaving it in an atmosphere of 40°C and relative humidity of 95 cm for 72 hours, the overlapping film was peeled off and the wettability index (dyne/6n) of the vapor-deposited surface was measured, and the wettability index was 35 dynes/c.
rn or higher was evaluated as having good suitability for printing and lamination.

7) Stability of vapor deposited film: 2.
Axially stretched polypropylene films are laminated, and the laminated film surfaces are heat-rolled using a parr type heat roller to give a heat seal strength of 0.5 to 1. o
The condition of the heat-sealed portion at a heat-sealing temperature at which a width of Kf/15 mm was obtained was evaluated by visual observation using the following criteria.

○: Almost no change is observed between the heat rolled part and the non-heated rolled part.

×: Metallic luster is lost only in the heat-sealed portion, and film cracks and pinholes are observed at the boundary between the heat-sealed portion and the non-heat-sealed portion.

However, the heat seal temperature and seal strength were measured as follows.

Seal conditions: Nurparo diameter 1011% J1300m,
Seal pressure 2 F4/cflG, 0.5 seconds Seal strength measurement: 15 times in the sample, tensile rate 300 sheets/min Example 11 Comparative Example I As the resin used for the A layer, the antioxidant tetrakis [methylene (3,5- 0.15% by weight of di-t-butyl-4-hydroxyphenyl)propionate comethane, 0.25% by weight of silica with an average particle size of 1μ as an antiblocking agent.
Melt flow rate (MFR) 7.5f/1 with added
0 minutes, Tm 150'C, ethylene content 2.0% by weight
A crystalline ethylene-propylene random copolymer of B
The resin used for the layer is MF containing the same type and amount of antioxidant and antiblocking agent as the random copolymer used for the A layer, of/10 min, Tm 140°C, and ethylene content! A 4.3wt% crystalline ethylene-propylene random copolymer was produced using two extruders and a two-layer T die connected to the extruders, so that the thickness ratio of layer A/layer B was 50+115.
0%, melt-kneaded at a melt-kneading temperature of 220°C, laminated in a molten state in a die, and quenched the extruded laminated film with a cooling roll at 30°C, followed by corona discharge treatment on the A layer surface. The film was then wound up to obtain a single-sided surface-treated coextruded laminated film having a wetting index of 40 dynes and 1 cm on the A-layer surface and a total S thickness of 30 μm.

Next, the laminated film was cut into a width of 60 crn using a slitter.
After cutting it into pieces, set it in a continuous vacuum evaporation device for s 10
While continuously unrolling the film under a vacuum maintained at MmHf, aluminum was deposited on the A-layer side of the laminated film and wound up, so that the thickness of the deposited film was 500 angstroms (5)) and the length was 10 mm.

A single-sided deposited film was obtained which was wound into a roll.

In addition, as Comparative Example 1, a crystalline ethylene-propylene random copolymer similar to that used for the B layer of Example 1 was
Using an extruder with a die, melt cross-wire extrusion was carried out at a melt cross-wire temperature of 210°C, and after quenching with a cooling roll at 30°C, one side was subjected to corona discharge treatment and rolled up, so that the wettability index of the treated surface was 3.
A single-sided treated film having a thickness of 9 dynes/cWI and a thickness of 30 μm was obtained. The obtained treated film was cut to a width of 60 m in accordance with Example 1, and then aluminum was vapor-deposited on the treated surface using a continuous vacuum evaporation device to form a roll having a thickness of 500 angstroms and a length of 1000 m. A single-sided vapor-deposited film was obtained.

Using the vapor-deposited films obtained in Examples and Comparative Examples, the winding form of the film, the adhesion of the vapor-deposited film, the suitability for printing and lamination of the vapor-deposited surface, and the stability of the vapor-deposited film were evaluated.

The results are shown in Table 1.

Table 1 Examples 2 to 6, Comparative Examples 2 to 5 As resins used for A layer and B layer - Various propylene homopolymers and copolymers shown in Table 2 below. 1,3.5-)limethyl- as an agent
0.1% by weight of 2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 0.05% by weight of silica as an antiblocking agent, and 0.1% of synthetic zeolite by weight. contains. ), using two extruders and a two-layer T-die connected to them, the extruded film was laminated in a molten state in the die while adjusting the thickness ratio to be uniform, and the extruded film was heated at 30°C. After quenching with a cooling roll, a coextruded laminated film consisting of two layers of %A/B was obtained, and then the A layer surface was subjected to corona discharge treatment and wound up.
A single-sided surface-treated laminated film having a wettability index of 40 dynes/3 on the A-layer surface and a total thickness of 28 μm was obtained.

The obtained treated laminated film was cut into 60mm thick pieces in accordance with Example 1, and aluminum was vapor-deposited on the treated surface using a continuous vacuum evaporation device, so that each deposited film had a thickness of 400 angstroms and a length of 1000 m. A single-sided vapor deposited film wound into a roll was obtained.

In addition, as Comparative Examples 2 to 5, various propylene homopolymers and copolymers listed in Table 2 below (all of the resins used had the same type and the same amount of oxidation as those used in Examples 2 to 6). In Examples 2 to 6, laminated films were obtained in which the surface of the λ layer was surface-treated in accordance with Examples 2 to 6.

The obtained treated laminated film was cut to a width of 60 crn according to Example 1, and then aluminum was vapor-deposited on the treated surface using a continuous vacuum evaporation device, and a roll having a thickness of 400 angstroms and a length of 1000 m was formed. A double-wound single-sided vapor deposition die □lume was obtained. The adhesion of the vapor deposited film and the stability of the vapor deposited film were evaluated using the vapor deposited films obtained on each experimental side and each comparative side.

The results are shown in Table 2.

26-1 Example 7 As the resin used for the A layer, MF R7, Or/l.

Crystalline ethylene-propylene random copolymer with ethylene content of 2.7% by weight (antioxidant
-Hydroxyphenyl)propionate cometaf 0.1
5% by weight, 0 synthetic zeolite as anti-blocking agent
．． 1% by weight and density 0.955. MFl'L15f/
Contains 4.0% by weight of 10 minute high density polyethylene. ) is used as the resin for layer B, and the melt flow rate is 6.5.
t/10 min, Tm 137°C, ethylene content 3.
Crystalline ethylene-propylene-butene-13-element random copolymer with 3% by weight and butene-1 content of 2.7% by weight (
Contains the same type and amount of antioxidants, antiblocking agents, and high-density polyethylene as the resin used in the original. ), 2
Using a stand extruder and a two-layer T-die connected to it,
While adjusting the thickness ratio A/B to be 4/6, melt-kneading was carried out at a melt-kneading temperature of 210°C, lamination was carried out in a molten state in a die, and the extruded laminated film was kept at 25°C with an air knife. Roughening (20°puff finish)
After quenching with a cooling roll, the surface of the λ layer was subjected to a corona discharge treatment, and then wound up to obtain a single-sided surface-treated coextruded laminated film with a wetting index of 41 dynes/crn on the λ layer surface and a total thickness of 25 μm.

Next, the laminated film was prepared in accordance with Example 1 to a width of 60 cm.
After cutting into pieces, aluminum was vapor-deposited on the treated surface using a continuous vacuum evaporation apparatus to obtain a rolled single-sided vapor-deposited film with a thickness of 400 angstroms per vapor-deposited film and a length of 5000 m.

This vapor-deposited film has a good film roll, adhesion of the vapor-deposited film of 3, stability of the vapor-deposited film of 01, and suitability for printing and lamination on the vapor-deposited surface with a wettability index of 40 dynes/c! It was good at n.

Type M is printed on the vapor deposition surface of this vapor deposition film using a gravure printing machine.
After printing and drying using FG red ink (manufactured by Toyo Ink ■), anchor coat the printed surface with a two-component adhesive for dry lamination (type AD-330, manufactured by Toyo Morton), and biaxially stretch to a thickness of 25μ. A polypropylene film (OPP) and a 12μ thick polyethylene terephthalate film (P]13T) were laminated and heated at 40°C.
Two types of laminates were obtained: an OPP/printed/single-sided vapor-deposited film and a PET/printed/single-sided vapor-deposited film.

Heat rolling was performed using each of the two types of laminates obtained with the OPP surface and PIiIT surface facing outside.

The stability of the deposited film at this time was 0, with no film cracks or pinholes observed, and the metallic luster was the same as that of the non-heated roll part, with no change observed.

Patent applicant Chisso Co., Ltd. Company agent Patent attorney Yatabe Sasai Katsuhiko Nonaka

Claims (6)

[Claims] (1) Layer A consisting of a crystalline propylene polymer or crystalline propylene random copolymer with a crystalline melting point exceeding 140°C, and a crystalline melting point lower than that of the polymer or random copolymer used for layer A by 5°C or more. A metal vapor-deposited film obtained by vapor-depositing a metal on the A-layer surface of a laminated film formed by laminating B-layer consisting of a crystalline propylene-based random copolymer having (2) The metallized film according to claim 1, which uses a laminated film that does not substantially contain fatty acids or derivatives thereof. (3) The thickness of the B layer of the laminated film is 30 to 30% of the total thickness.
95% of the metallized film of claim 1. (4) Layer A consisting of a crystalline propylene polymer or crystalline propylene random copolymer with a crystalline melting point exceeding 140°C, and a crystalline melting point lower than that of the polymer or random copolymer used for layer A by 5°C or more. A layer B consisting of a crystalline propylene-based random copolymer having A laminate made by laminating plastic films or sheets with a crystal melting point equal to or higher than that of the copolymer. (5) The laminate according to claim 4, which uses a laminate film that does not substantially contain fatty acids or derivatives thereof. (6) As a plastic film or sheet,
Claim 4 uses a stretched or unstretched film or sheet of polyester resin, nylon resin, or crystalline polypropylene resin having a crystal melting point equal to or higher than that of the polymer or random copolymer used for layer A. laminate.