JP2009227790A - Polymer composition, easily peelable film formed from the same, and laminate having layer of the composition - Google Patents

Abstract

[PROBLEMS] To realize excellent sealant attributes substantially equivalent to those of an unstretched polypropylene (CPP) film layer, in particular, appropriate easy peelability and heat seal properties, but it can be used for extrusion peelable moldable sealant materials. Provided are a combined composition, an easily peelable film comprising the composition, and a laminate having the sealant layer.
(A) An ethylene / (meth) acrylic acid copolymer (a1), an ionomer (a2) of an ethylene / (meth) acrylic acid copolymer, and a copolymer (a1) and an ionomer (a2) 99 to 90 parts by mass of one polymer or polymer composition selected from the mixture (a3) and 1 to 10 parts by mass of (B) methylpentene polymer (however, the total amount of (A) and (B) A polymer composition capable of extrusion lamination molding.
[Selection] Figure 2

Description

  The present invention relates to a polymer composition, an easily peelable film comprising the polymer composition, and a laminate comprising the composition layer as an easily peelable heat sealing material layer (easy peelable heat sealant layer).

  Polypropylene films are broadly classified into unstretched films (CPP) and biaxially stretched films (OPP), and unstretched films are flexible, tough, and have good gloss and transparency. It is widely used as protective packaging materials for various packaging materials such as textiles and miscellaneous goods, small machines, and appliances such as batteries.

Polypropylene unstretched film (CPP) is also used as a single film, but recently, as the packaging film becomes more sophisticated and sophisticated, base films such as biaxially stretched polypropylene film (OPP) and polyethylene terephthalate film (PET) Laminating applications used as a heat seal material bonded together are rapidly increasing, and this has become the mainstream.
CPP has an appropriate heat-sealing strength as an easy-peelable sealant layer, and is therefore frequently used as a sealant material for snack confectionery and instant noodle packaging materials. It is a necessity as a packaging material for dry food.
Therefore, a number of inventions and devices have been proposed, including improvements, modifications, etc. for laminated films for packaging in which polypropylene unstretched film (CPP) is laminated on a base film such as OPP, PET, ONy (stretched nylon film). Has been.

  For example, in Patent Document 1, a barrier layer made of a vapor-deposited thin film of an inorganic oxide such as silicic acid is provided on one surface of a CPP film by plasma chemical vapor deposition, and an adhesive layer is further provided on the surface of the barrier layer. Thus, an invention of a laminate for packaging which is obtained by dry laminating a base film such as OPP and is useful for filling and packaging snack foods having excellent transparency, barrier properties against oxygen and water vapor is disclosed.

  Patent Document 2 discloses an invention of a container for long-term storage of cooked food prepared by heat-sealing an aluminum foil laminated film comprising a CPP outermost layer / Al intermediate layer / CPP innermost layer.

  Further, Patent Document 3 discloses a stretched nylon film base layer / boehmite-treated aluminum foil layer / isocyanate compound anchor coat layer / homo or random copolymer polypropylene resin adhesive layer / CPP sealant layer formed by a sandwich lamination method. An invention of an outer packaging material for a lithium ion battery comprising a laminate is disclosed.

As described above, a laminate having a CPP film layer as a sealant layer is extremely useful as a packaging material for food packaging and the like, but has a serious bottleneck in terms of productivity and manufacturing cost in manufacturing the laminate. Was.
That is, almost all of the laminates having the CPP film layer as an easy peel layer are called so-called sandwich lamination method or dry lamination method. The substrate and the CPP film are pressed through the adhesive layer, for example. It was manufactured by the manufacturing method to which it adhere | attaches. Therefore, it had the fault that productivity was bad and cost became high.
On the other hand, when an extrusion lamination method such as extrusion coating or coextrusion (coextrusion) of a polymer composition having an easy peel property is adopted instead of using a CPP film, for example, coextrusion High-speed continuous production is easy and extremely high productivity with an extrusion laminating machine that combines a series of machinery including an extruder equipped with a die and T-die, a cooling roll, a crimping roll, and a winding device. it can.

  Therefore, in this field, there has been a strong demand for the appearance of a resin composition capable of extrusion lamination in place of a CPP film and capable of obtaining a good quality product.

JP 2000-355069 A JP 2006-137494 A JP-A-2005-203294

  As a result of intensive studies to meet the above-mentioned demands, the present inventors have obtained ethylene / (meth) acrylic acid copolymer or ethylene / (meth) acrylic acid / (meth) acrylic acid ester copolymer, or ethylene / A relatively small amount of polymethylpentene resin in (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid / (meth) acrylic ester copolymer ionomer, or a mixture of the copolymer and the ionomer. It was found that the polymer composition blended in a specific amount was suitable for the above purpose, and the present invention was completed based on this finding.

Accordingly, an object of the present invention is to realize an excellent sealant attribute substantially equivalent to that of the CPP layer, in particular, an appropriate easy-peeling heat-seal characteristic, and yet a polymer composition for an easily-peelable sealant material that can be extrusion laminated. To provide.
Another object of the present invention is to provide an easily peelable film comprising the above polymer composition.
Furthermore, another object of the present invention is to provide an easily peelable laminate obtained by extrusion laminating the above composition on a substrate.

  According to the present invention, (A) an ethylene / (meth) acrylic acid copolymer (a1), an ionomer (a2) of an ethylene / (meth) acrylic acid copolymer, and a copolymer (a1) and an ionomer (a2) 99 to 90 parts by mass of one polymer or polymer composition selected from the mixture (a3) and 1 to 10 parts by mass of (B) methylpentene polymer (however, the sum of (A) and (B) A polymer composition capable of extrusion lamination molding is provided.

  In the polymerization composition of the present invention, the ethylene / (meth) acrylic acid copolymer (a1) further contains (meth) acrylic acid ester as a copolymerization component. A terpolymer is preferred.

  The base resin constituting the ionomer (a2) is an ethylene / (meth) acrylic acid / (meth) acrylic acid ester ternary copolymer further containing a (meth) acrylic acid ester as a copolymerization component. preferable.

  Further, the mixture (a3) is an ethylene / (meth) acrylic acid binary copolymer and / or an ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer (i) and an ethylene / (meta ) Acrylic acid / (meth) acrylic acid ester terpolymer ionomer (ii) and its composition is in the range of (i) 60 to 95% by mass and (ii) 5 to 40% by mass. Those are particularly preferred.

  In the polymerization composition of the present invention, the (B) methylpentene polymer is preferably a 4-methyl-1-pentene polymer.

  Further, (A) comprises 65 to 85 parts by mass of ethylene / (meth) acrylic acid copolymer (a1) and 5 to 34 parts by mass of ethylene / (meth) acrylic acid copolymer ionomer (a2). A polymer composition in which B) is composed of 1 to 10 parts by mass of a methylpentene polymer (however, the total amount of (A) and (B) is 100 parts by mass) is particularly preferred.

  Moreover, according to this invention, the easily peelable film formed by shape | molding the said polymer composition is provided.

  Furthermore, according to this invention, the easily peelable laminated body formed by extrusion-laminating the said polymer composition to a base material is provided.

  Furthermore, according to the present invention, there is provided an easily peelable laminate obtained by coextrusion lamination molding of the polymer composition with a substrate.

  It is preferable that the base material used for the easily peelable laminate is one selected from a polyester film, a stretched polypropylene film, and a nylon film.

The polymer composition of the present invention is excellent in easy peel sealability (easy peelable sealability), suitable as a heat sealant material and excellent in molding processability, and can be easily formed into a film or a laminate. High-speed continuous extrusion lamination to film and co-extrusion lamination with base resin are possible. For this reason, it is generally composed of an unstretched polypropylene (CPP) sealant layer produced by a non-extrusion lamination method such as a sandwich lamination method or a dry lamination method. Compared with the laminated body, extremely high productivity can be retained, and thus the manufacturing cost can be greatly reduced in this respect.
However, the obtained laminate exhibits excellent heat seal characteristics equivalent to or better than a laminate comprising an unstretched polypropylene (CPP) easy-peelable sealant layer, and also has excellent low-temperature seal characteristics.

Embodiments according to the present invention will be described in detail and specifically below.
As already mentioned, the polymer composition of the present invention comprises (A) an ethylene / (meth) acrylic acid copolymer (a1), an ethylene / (meth) acrylic acid copolymer ionomer (a2), It is an invention of a polymer composition comprising 1 to 10 parts by weight of (B) methylpentene polymer blended with 60 to 99 parts by weight of a mixture of the union (a1) and the ionomer (a2).

  In the polymer composition of the present invention, the ethylene / (meth) acrylic acid copolymer (a1) which is one of the components (A) includes only an ethylene / (meth) acrylic acid binary copolymer. Also included are copolymers of ethylene and (meth) acrylic acid / (meth) acrylic acid ester terpolymers, which contain ethylene and a (meth) acrylic acid component as essential polymerization components. The

More specifically, ethylene / acrylic acid binary copolymer, ethylene / methacrylic acid binary copolymer, ethylene / acrylic acid / methacrylic acid ternary copolymer, ethylene / acrylic acid / acrylic acid ester ternary copolymer. Polymer, ethylene / methacrylic acid / acrylic acid ester terpolymer, ethylene / methacrylic acid / methacrylic acid ester terpolymer, ethylene / methacrylic acid / acrylic acid / acrylic acid ester copolymer, ethylene / methacrylic acid -Acrylic acid, a methacrylic acid ester copolymer, etc. can be illustrated.
Among these, it is more preferable to use an ethylene / acrylic acid binary copolymer, an ethylene / methacrylic acid binary copolymer, and a ternary or higher copolymer further including a (meth) acrylic acid ester component, An ethylene / methacrylic acid / acrylic acid ester terpolymer is preferred.

Moreover, when the said copolymer contains (meth) acrylic acid ester, C1-C20 alkylester of (meth) acrylic acid can be mentioned as a suitable example as ester, More specifically, And alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, and isooctyl.
Of these, methyl, ethyl and isobutyl esters are preferred.

As for the content rate of the (meth) acrylic acid unit in the said copolymer (a1), 2-30 mass% is preferable.
Moreover, in the copolymer containing an ester component, that whose content of this ester unit is 0-30 mass% is preferable.
The melt flow rate (MFR) of the copolymer (according to JIS K-7210, measured at 190 ° C. under a load of 2160 g) is 0.05 to 500 g / 10 minutes, particularly 0.2 to 300 g / 10 minutes. It is preferable that

The ethylene / (meth) acrylic acid copolymer ionomer (a2) which is another one of the component (A) in the present invention includes the ethylene / (meth) acrylic acid copolymer mentioned in the above (a1). And metal ion ionomers having the same copolymer as the base resin.
Further, in the case of a copolymer containing MFR and (meth) acrylic acid component content of the base resin, and further a (meth) acrylic acid alkyl ester, the ester content is preferably in the same range as described above.
Examples of the metal ion species include alkali metal ions such as Li, Na, and K, alkaline earth metal ions such as Be, Mg, Ca, Sr, and Ba, and zinc ions.
In these, the ionomer of Zn ion is preferable.
The degree of neutralization of the ionomer is preferably about 1 to 95%, particularly preferably 4 to 85%.
Further, as the ionomer (a2) of the present invention, an ionomer having an MFR (based on JIS K-7210, measured at 190 ° C. under a load of 2160 g) in the range of 0.01 to 100 g / 10 min is used. It is preferable.

As the component (A) of the present invention, a mixture (a3) obtained by mixing the above (a1) and (a2) is also used.
In this case, the mixing ratio of (a1) and (a2) is not particularly limited, and can be blended at an arbitrary ratio. However, when component (A) is in the form of mixture (a3), ethylene (meta ) Acrylic acid binary copolymer or ethylene / (meth) acrylic acid / (meth) acrylic acid ester ternary copolymer or both (i) and ethylene / (meth) acrylic acid / (meth) acrylic acid ester ternary Copolymer ionomer (ii) mixed with (i) 60 to 95% by mass and (ii) 5 to 40% by mass has a wide range of seal strength-seal temperature relationships as an easy peel sealant. This is particularly preferred because it approximates that of a CPP sealant.

  In the polymer composition of the present invention, the methylpentene polymer constituting the component (B) is a methylpentene monomer such as 3-methyl-1-pentene or 4-methyl-1-pentene, or a methylpentene monomer. Is a polymer obtained by copolymerizing a small amount of other monomers, for example, methylpentene homopolymer (3-methyl-1-pentene homopolymer, 4-methyl-1-pentene homopolymer). In addition to (polymer), it also includes copolymers of methylpentene and other compounds copolymerizable therewith, and is typically a so-called TPX resin.

Examples of other compounds copolymerizable with methylpentene include 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. Α-olefins and the like.
One or more of these may be contained in the methylpentene polymer.

The content of methylpentene in the methylpentene polymer is usually 85 mol% or more, preferably 90 mol% or more.
The melt flow rate (MFR) of this methylpentene polymer is usually 0.05 to 500 g / 10 min (ASTM D1238, load: 5 Kg, temperature: measured at 260 ° C.), preferably 0.1 to 300 g / 10. Minutes.

The polymer composition of the present invention comprises (A) an ethylene / (meth) acrylic acid copolymer (a1), an ethylene / (meth) acrylic acid copolymer ionomer (a2), and a copolymer (a1) and an ionomer. 99 to 90 parts by mass, more preferably 98 to 92 parts by mass of one polymer or polymer composition selected from the mixture (a3) with (a2) and 1 to 10 parts by mass of (B) methylpentene polymer. Part, more preferably 2 to 8 parts by mass (provided that the total amount of (A) and (B) is 100 parts by mass).
When the blending amount of the component (A) is lower than the above lower limit, the sealing strength is too low, and it peels off due to an extremely light impact or the like.
On the other hand, when the component (A) is higher than the above upper limit, the sealing strength is too high and the easy peeling property is impaired, which is not preferable.

Further, in the polymer composition of the present invention, a three-resin blending mode in which the component (A) is blended with up to 34 parts by mass (relative to the total amount) of ethylene / (meth) acrylic acid copolymer ionomer component (a2). As described above, the ((a3) embodiment) is particularly preferable because the seal strength-seal temperature relationship substantially matches that of the CPP.
Further, the ionomer is particularly preferably an ionomer of ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer. When the amount of the ionomer component exceeds 34 parts by mass, the CPP The divergence from that becomes slightly larger.
That is, in the present invention, the ethylene / (meth) acrylic acid copolymer (a1) constituting the (A) is 65 to 85 parts by mass, more preferably 68 to 82 parts by mass, and ethylene / (meth). Acrylic acid copolymer ionomer (a2) 5 to 34 parts by mass, more preferably 10 to 30 parts by mass, and 1 to 10 parts by mass of the methylpentene polymer constituting the (B), more preferably 2 to 8 parts by mass. A polymer composition comprising parts (however, (A) {(a1) + (a2)}, total amount of 100 parts by weight of (B)) can be mentioned as a preferred embodiment.

  The above copolymer component and ionomer component do not necessarily need to be of one type, but two or more types may be mixed. Rather, the melt viscoelastic behavior during extrusion film formation can be easily adjusted, and the seal strength is finely adjusted. Therefore, it is preferable from the viewpoint that it can be more optimized.

In the polymer composition of the present invention, in addition to the essential resin components (A) and (B), saturated or unsaturated fatty acid amide, saturated or unsaturated fatty acid bisamide, polyethylene glycol, hydrogenated castor oil and Additives such as silica may be added.
These specific additives prevent blocking when the sealant composition of the present invention is pelletized, etc., and also prevent blocking between films or stake with metal rolls during extrusion and coating. Furthermore, the workability is improved when a post-process such as rewinding, slitting, bag making, punching, filling, etc. is required.

As the saturated or unsaturated fatty acid amide, amides of C8 to C22 saturated linear fatty acids and monounsaturated fatty acids are preferable, specifically, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, Examples include erucic amide and a mixture thereof.
Furthermore, secondary amides such as oleyl palmitoamide and stearyl erucamide can also be used as the fatty acid amide.
The saturated or unsaturated fatty acid bisamide is mainly composed of C8 to C22 N, N'-methylenebisamide or N, N'-ethylenebisamide, and among them, stearic acid, behenic acid, olein Methylene bisamides such as acid and erucic acid and ethylene bisamides such as stearic acid, behenic acid, oleic acid and erucic acid are preferred.

  The compounding amount of these additives is suitably 300 ppm to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin components (A) and (B), and in particular, saturated or unsaturated fatty acid amide, saturated or unsaturated fatty acid bisamide. In the case of polyethylene glycol and hydrogenated castor oil, 300 to 10000 ppm is preferable, and in the case of silica, 0.1 to 3 parts by mass is preferable. Moreover, in this invention, even if it mix | blends polyolefins, such as polyethylene and a polypropylene, and well-known tackifier to the said resin component (A) and (B) as long as the characteristic of the composition of this invention is not impaired. good.

In order to obtain the polymer composition of the present invention, the fatty acid amide and other additives are blended with the above components (A) and (B) as desired, and mixed simultaneously or sequentially.
As the mixing method, a method of melt mixing using a single screw extruder, a twin screw extruder, a Banbury mixer or various kneaders is preferable, and there is no particular limitation on the mixing order.
The polymer composition of the present invention preferably has a melt flow rate (MFR) in the range of 0.1 to 500 (g / 10 minutes) after mixing and kneading the above components.
When the MFR of the composition is 0.1 or less, the viscosity is too high and the resin pressure is increased, and the motor load is increased, resulting in difficulty in extrusion moldability and coating workability.
Further, when the polymer composition of the present invention is extrusion coated, the MFR is preferably in the range of 1 to 300 from the viewpoint of moldability, and in particular, MFR (based on JIS K-7210, 190 Measured at 2 ° C. at 2 ° C.) is preferably in the range of 2-50.

In order to form the polymer composition of the present invention into a film, not only can a method similar to the T-die casting method normally used for forming a CPP single film be used, but also an inflation method can be used. A layer film can be formed.
In this case, the thickness of the single layer film is preferably 5 to 300 μm, particularly preferably 10 to 100 μm.
The layer of the polymer composition of the present invention is laminated with a base material such as aluminum foil, cellophane, paper, polyester resin (PET), stretched polypropylene (OPP) resin, stretched nylon resin (ONy) and used as a laminate. can do. In order to laminate the layer of the polymer composition of the present invention on these substrates, it is of course possible to apply and laminate by a high viscosity coater such as dry lamination, sandwich lamination, gravure roll coating, cast coating, etc. as in CPP. The polymer composition of the present invention is characterized in that it can be subjected to extrusion (extrusion) lamination by T-die casting or the like, whereby the production efficiency of the laminated film can be remarkably improved.
Further, the polymer composition of the present invention is formed by coextrusion inflation molding with polyethylene, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer or its appropriate ionomer, nylon, polyester, polystyrene and the like. Or it can also be set as a coextrusion laminated film by coextrusion cast molding.

  The single film thus obtained can be used as it is as a packaging material or a sealing material for a molded body, and in the case of an extruded laminated film or a coextruded laminated film, the polymer composition layer of the present invention is heat sealed. The layer is used as a sealing laminate container or a sealing lid.

As a laminated structure example of the laminated body or lid, for example,
Base material layer of paper, PET, ONy, etc./invention composition sealant layer,
Base material layer / polyethylene layer (intermediate layer) / the sealant layer of the composition of the present invention,
Sealant layer / base material layer / invention composition sealant layer,
Sealant layer / intermediate layer / base material layer / polyethylene layer (intermediate layer) / the sealant layer of the composition of the present invention,
Examples thereof include a thermoplastic resin layer / a polymer composition sealant layer of the present invention.

In the laminate having the above layer structure, examples of the base material layer include paper, stretched polyester resin film (OPET), stretched nylon resin film (ONy), stretched film such as stretched polypropylene film (OPP), and the like. Examples of materials that can be used for the intermediate layer include aluminum, polyethylene, ethylene / α-olefin copolymers, ethylene / vinyl ester copolymers, and ethylene / unsaturated carboxylic acid ester copolymers.
Further, in the laminate having the above layer structure, the thermoplastic resin layer may be a high-, medium- or low-density polyethylene, a polyethylene such as linear low-density polyethylene obtained by using a metallocene catalyst, or an ethylene / vinyl acetate copolymer. Examples thereof include ethylene (co) polymers such as ethylene / methacrylic acid copolymers and ionomers thereof, polyamides (such as nylon), polyesters, polystyrenes and the like. In the laminate of the present invention, the thickness of the base material layer is preferably 5 to 300 μm, particularly preferably 10 to 100 μm, the thickness of the composition sealant layer of the present invention is preferably 3 to 100 μm, particularly preferably 5 to 50 μm, and the thickness of the intermediate layer is 3-50 micrometers is preferable. The thickness of the thermoplastic resin layer is preferably 3 to 100 μm, particularly preferably 5 to 50 μm.
As described above, the polymer composition of the present invention is formed into a single film or a laminated film, and mainly used as a sealant (heat seal) layer in various packaging forms such as containers, container lids, bags, etc. It can be suitably used as a packaging material for goods.
In particular, it is suitable as a packaging material for snacks, instant ramen, retort food, bread and the like.

"Sample preparation raw materials (polymers, ionomers)"
Ethylene / (meth) acrylic acid copolymer:
NCL1 = ethylene (E) / methacrylic acid (MAA) / isobutyl acrylate (IBA) terpolymer; E unit content: 81.0% by mass, MAA unit content: 11.0% by mass, IBA unit content: 8 0.0% by mass, MFR 10.0 g / 10 min NCL2 = ethylene (E) / methacrylic acid (MAA) / isobutyl acrylate (IBA) terpolymer; E unit content: 80.0% by mass, MAA unit content: 10.0% by mass, IBA unit content: 10.0% by mass, MFR 36.0 g / 10 min NCL3 = ethylene (E) / methacrylic acid (MAA) / isobutyl acrylate (IBA) terpolymer; E unit content : 80.0% by mass, MAA unit content: 10.0% by mass, IBA unit content: 10.0% by mass, MFR 37 g / 10 min NCL4 = ethylene (E) · methacrylic acid ( AA) 2 terpolymer; E unit content: 91.3 mass%, MAA unit content: 8.7 wt%, MFR10.5g / 10 min ionomer:
HM1 = zinc (Zn) ionomer based on NCL3: 70% neutralization; MFR 1.0 g / 10 min HM2 = zinc (Zn) ionomer based on NCL4: 17% neutralization; MFR 5.0 g / 10 minutes Methylpentene polymer:
TPX1 = 4-methylpentene-1 polymer; DX820 manufactured by Mitsui Chemicals; density 833 kg / m ³ , melting point 238 ° C., MFR 180 g / min

Example 1
97 parts by mass of ethylene / methacrylic acid / isobutyl acrylate terpolymer (NCL1) and 3 parts by mass of methylpentene resin (TPX1) are mixed and melt-kneaded under the following compound conditions using a twin-screw extruder. A coalescence composition (Sample No. 1) was obtained.
The MFR of this composition was 8.6 g / 10 minutes.
Compound conditions: 30 mmφ twin screw extruder, screw rotation speed 200 rpm, feeder discharge setting 4.0% (manual), set temperature, C1 = 140 ° C., C2 = 220 ° C., C3-C7 = 260 ° C., C8-C9 = 200 ° C. AD−D = 180 ° C.

Subsequently, the polymer composition (Sample No. 1) was subjected to continuous extrusion laminate film molding (single layer) under the following conditions, and its drawdown performance (D · Down;) was evaluated (workability evaluation).
Extrusion laminate film molding process conditions: Extrusion device; 65 mmφ laminator, screw; 3-stage type, screw cooling; ON, AG = 110 mm
Evaluation item, workability (D · Down (Q = 1)) ... Extrusion amount (reference value; 80 m / min × extrusion amount when forming 20 μm film) Take-off rate when film breakage was evaluated at a constant; m / min (LipH ( 6 Amp))
The results are shown in Table 1.

Further, a laminate in which the polymer composition (sample sample-1) layer (20 μm) is extrusion laminated onto the PE layer of a base material obtained by laminating a polyethylene layer (PE) (15 μm) on a polyester (PET) film (12 μm). A body sample (PET (12 μm) / PE (15 μm) / real-1 composition (20 μm) was prepared (laminated body real-1 sample).
Then, this laminate sample (laminate 1 sample) was heat-sealed from 100 ° C. to 210 ° C. at intervals of 10 ° C. under the following heat seal conditions, and the seal strength was measured under the following conditions.
Heat sealing condition: A laminate sample of the laminate layer surface is sandwiched between Teflon sheets and a heat sealer is used, and the sealing pressure is 0.2 MPa, the sealing time is 0.5 seconds, and every 10 ° C. from 100 to 210 ° C. Heat seal at each temperature (TD direction face-to-face seal).
Strength measurement conditions: Peel test sample width 15 mm, peel angle 90 °, tensile speed 300 mm / min Table 2 shows the results.

"Example 2"
A polymer composition (Sample Sample-2) was prepared in the same manner as in Example 1 except that 95 parts by mass of the same copolymer sample (NCL1) as in Example 1 and 5 parts by mass of methylpentene resin (TPX1) were mixed. Obtained.
The MFR of this composition was 7.7 g / 10 min.
Next, the above polymer composition (Sample No. 2) was continuously formed into an extruded film under the same conditions as in Example 1, and the drawdown performance (D · Down;) was evaluated.
The results are shown in Table 1.

Furthermore, a laminate sample (PET (12 μm) / PE (15 μm) / actual-2 composition (20 μm)) having the same layer structure as in Example 1 was produced (laminate actual-2 sample).
And this laminated sample (laminated body sample-2) is heat-sealed at a temperature interval of every 10 ° C. from 100 ° C. to 210 ° C. (however, the heat sealing time is 0.5 seconds and 1.0 seconds, respectively) Implementation), the heat seal strength was measured under the same conditions as in Example 1.
The results are shown in Table 2.

"Comparative Example 1"
A layered product (layered product) in which the layer structure is (ONy (15 μm) / PE (20 μm) / ratio-1 copolymer layer (30 μm)) using only the NCL1 copolymer sample (hereinafter referred to as sample ratio-1). Ratio-1 sample).
And this laminated body (laminate ratio-1 sample) was heat-sealed in the same manner as in Example 1 at a temperature interval of 10 ° C. from 90 ° C. to 160 ° C., and the heat seal strength was measured almost in the same manner as in Example 1. (Heat seal time 0.5 seconds)
The results are shown in Table 2.

"Example 3"
Zinc ionomer of two types of ethylene / methacrylic acid / isobutyl acrylate terpolymer (NCL1 = 25 parts by mass, NCL2 = 50 parts by mass) and 75 parts by mass of ethylene / methacrylic acid / isobutyl acrylate terpolymer (HM1) 20 parts by mass and methylpentene resin (TPX1) 5 parts by mass are mixed under different compound conditions of the following two types [i) and ii)] using two types of single-screw and twin-screw extruders. Two types of polymer compositions (sample -3A, i) biaxial) and sample -3B, ii) uniaxial) were obtained by melt-kneading.
The MFR of this composition was 11.5 g / 10 min for Sample No. 3A and 6.4 g / 10 min for Sample No. 3B.
Compound conditions:
i) (30 mmφ twin screw extruder) Screw rotation speed 200 rpm, feeder discharge setting 4.0% (manual), set temperature, C1 = 140 ° C., C2 = 220 ° C., C3-C7 = 260 ° C., C8-C9 = 200 ° C. , AD-D = 180 ° C
ii) (40 mmφ single screw extruder) Screw rotation speed 50 rpm, screw tip D, set temperature, C1 = 140 ° C., C2 = 240 ° C., C3-C4 = 260 ° C., AD-D = 180 ° C.

Subsequently, the above polymer composition (Sample No. 3A, Sample No. 3B) was subjected to continuous extrusion film molding (single layer) under the same conditions as in Example 1, and its drawdown performance (D · Down;) Evaluated.
The results are shown in Table 1.

Further, a laminate sample (PET (12 μm) / PE (15 μm) / actual-3A or 3B composition (20 μm) was prepared by extrusion lamination in the same manner as in Example 1 (laminate actual-3A, laminate actual- 3B sample).
And this laminated body sample was heat-sealed on the following heat-sealing conditions by the temperature interval for every 10 degreeC from 100 degreeC to 210 degreeC, and the heat-sealing intensity | strength was measured on the following conditions.
Heat sealing condition: A laminate sample of the laminate layer surface is sandwiched between Teflon sheets and a heat sealer is used, and the sealing pressure is 0.2 MPa and the sealing time is 0.5 seconds or 1.0 seconds. Heat sealing is performed at each temperature of 10 ° C. up to 210 ° C. (sealing in the TD direction).
Strength measurement conditions: Peel test sample width 15 mm, peel angle 90 °, tensile speed 300 mm / min Table 3 shows the results.

"Comparative Example 2"
Using only ionomer (HM2) (hereinafter referred to as sample ratio -2), the layer structure (ONy (15 μm) / PE (20 μm) / copolymer layer (ratio-2 sample) (30 μm)) A laminate ratio-2 sample) was produced.
And this laminated body (laminate ratio-2 sample) was heat-sealed in the same manner as in Example 1 from 90 ° C. to 160 ° C. at a temperature interval of 10 ° C., and the heat seal strength was measured under substantially the same conditions as in Example 1. (Heat seal time 0.5 seconds)
The results are shown in Table 3.

Reference example
Table of heat seal strength data for each 10 ° C temperature interval from 130 to 180 under conditions of actual pressure of 0.2 MPa and time of 1.0 second for a commercial CPP film (Tosero CP copoly type; standard GHC # 25). They are shown in 2 and 3, respectively.

For reference, the relationship between the heat seal temperature and the seal peel strength in Examples 1 and 2 and Comparative Examples 1 and 2 under the conditions of an actual heat seal pressure of 0.2 MPa and a time of 0.5 seconds is CPP ( However, it is shown as a diagram in FIG.
Further, the relationship between the heat seal temperature and the seal peel strength under the conditions of Example 3A, 3B and Example 2 under actual heat seal pressure of 0.2 MPa and time of 1.0 second is CPP (time of 1.0 second). It is shown in FIG.

From the results of Table 1, it can be seen that the polymer composition of the present invention has good film forming processability, can be continuously extruded and laminated at a high speed, and is remarkably excellent in productivity as compared with CPP.
Further, the sealant film obtained from the polymer composition of the present invention exhibits a heat seal temperature / seal peel strength behavior similar to that of CPP, and in particular, a sealant film (lamination) comprising a copolymer / ionomer / TPX3 resin blend composition. Solid 3A and Laminate 3B) exhibit almost the same heat seal temperature and seal peel strength behavior as CPP.
Therefore, it can be seen that the polymer of the present invention is extremely suitable as a substitute for the CPP sealant.

The diagram which showed the relationship between the heat seal temperature of Examples 1 and 2 and Comparative Examples 1 and 2 and seal peel strength (actual pressure 0.2 MPa, time 0.5 second). The diagram which showed the relationship between the heat seal temperature and seal peel strength in Example 3A, B and Example 2 (actual pressure 0.2MPa, time 1.0 second).

Claims (10)

  (A) Ethylene / (meth) acrylic acid copolymer (a1), ionomer (a2) of ethylene / (meth) acrylic acid copolymer and mixture (a3) of copolymer (a1) and ionomer (a2) 99 to 90 parts by mass of one polymer or polymer composition selected from 1 to 10 parts by mass of (B) methylpentene polymer (provided that the total amount of (A) and (B) is 100 parts by mass) A polymer composition capable of extrusion lamination molding.   The ethylene / (meth) acrylic acid copolymer (a1) is an ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer further comprising a (meth) acrylic acid ester as a copolymerization component. Item 2. The polymer composition according to Item 1.   The base resin constituting the ionomer (a2) is an ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer further comprising a (meth) acrylic acid ester as a copolymerization component. The polymer composition described.   The mixture (a3) is an ethylene / (meth) acrylic acid binary copolymer and / or an ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer (i) and an ethylene / (meth) acrylic. It is a mixture with an acid / (meth) acrylic acid ester terpolymer ionomer (ii), and its composition is in the range of (i) 60 to 95% by mass, (ii) 5 to 40% by mass. The polymer composition according to any one of 1 to 3.   The polymer composition according to any one of claims 1 to 4, wherein the methylpentene polymer is a 4-methyl-1-pentene polymer.   The (A) comprises 65 to 85 parts by mass of an ethylene / (meth) acrylic acid copolymer (a1) and 5 to 34 parts by mass of an ethylene / (meth) acrylic acid copolymer ionomer (a2), and the (B) The polymer composition according to any one of claims 1 to 5, wherein the polymer composition comprises 1 to 10 parts by mass of a methylpentene polymer (however, the total amount of (A) and (B) is 100 parts by mass).   The easily peelable film formed by shape | molding the polymer composition in any one of Claims 1-6.   The easily peelable laminated body formed by extrusion-laminating the polymer composition in any one of Claims 1-6 on a base material.   An easily peelable laminate obtained by coextrusion lamination molding of the polymer composition according to any one of claims 1 to 6 with a thermoplastic resin.   The laminate according to claim 8 or 9, wherein the substrate is one selected from a polyester film, a stretched polypropylene film, and a nylon film.

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