Method for producing polar resin composition, method for producing laminate, and method for producing regrind material

Abstract

[Problem] To provide: a multilayer body which has a polar resin layer that has excellent transparency and mechanical strength (especially impact resistance); and a polar resin composition for forming a polar resin layer of a multilayer body, the polar resin layer having the above-described characteristics. [Solution] A polar resin composition which contains 5 to 30% by mass of an ethylene polymer (A), 40 to 85% by mass of a polar resin component (B), and 10 to 40% by mass of a modified ethylene / α-olefin copolymer (C) that is obtained by modifying an ethylene / α-olefin copolymer (C0) with an unsaturated carboxylic acid or a derivative thereof, the modified ethylene / α-olefin copolymer (C) having an MFR (at 190°C under a load of 2.16 kg) of 0.1 to 50 g / 10 minutes (provided that the total of the fractions (A), (B) and (C) is taken as 100% by mass).

Description

[Technical Field]

[0001] The present invention relates to a polar resin composition and a laminate, and more particularly to a polar resin composition containing a polar resin component and a laminate including a polar resin layer made of the polar resin composition. [Background technology]

[0002] Polyolefin resins, such as polyethylene and polypropylene, are used in a variety of fields because they require little energy to produce, are lightweight, and are highly recyclable.

[0003] However, because polyolefin resins generally do not contain polar groups in their molecules, they have poor compatibility with polar resins such as polyamides, polyesters, and ethylene-vinyl alcohol copolymers (EVOH), making it difficult to blend or laminate them with these materials.To improve the low compatibility between polyolefins and polar polymers, polyolefin graft polymers are sometimes added to these mixtures.

[0004] For example, Patent Document 1 discloses a laminate in which the regrind layer is laminated in the following order: polyolefin layer / regrind layer / ethylene-vinyl alcohol copolymer layer / regrind layer / polyolefin layer, and the regrind layer is made of a composition of (A) ethylene-vinyl alcohol copolymer, (B) polyolefin, and (C) a graft polymer using polyolefin, and describes that this laminate has excellent impact resistance, etc.

[0005] Patent Document 2 discloses a multilayer laminate having a recyclable layer composed of a composition (A) containing a modified polyethylene resin obtained by graft-modifying a polyethylene resin with an unsaturated carboxylic acid or the like, a polyolefin resin (B), and an easily recyclable resin composition (D) containing an ethylene-vinyl alcohol copolymer (C), and discloses a specific example of the modified polyethylene resin as a copolymer obtained by graft-modifying an ethylene-butene copolymer with maleic anhydride and a peroxide. Furthermore, it discloses that the modified polyethylene resin composition (A) has compatibilizing properties, which enhances the compatibility between the polyolefin resin (B) and the ethylene-vinyl alcohol copolymer (C), thereby providing the multilayer laminate with excellent mechanical strength such as impact strength and tensile elongation, as well as excellent appearance, and no yellowing.

[0006] Patent Document 3 also describes that the incorporation of a low-viscosity ethylene-α-olefin interpolymer modified with maleic anhydride or the like compatibilizes an ethylene-based polymer and a polar polymer, thereby improving the optical and tensile properties of films and the like obtained from compositions containing these. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 5-147177 [Patent Document 2] Japanese Patent Application Publication No. 9-302170 [Patent Document 3] Special Publication No. 2015-535311 Summary of the Invention [Problem to be solved by the invention]

[0008] However, conventional laminates having a layer containing a polar resin have room for further improvement in terms of transparency and mechanical strength (particularly impact resistance, or impact resistance and puncture resistance).

[0009] Therefore, an object of the present invention is to provide a laminate having a layer containing a polar resin that is excellent in transparency and mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance), and a polar resin composition for forming a polar resin layer of a laminate having such properties. [Means for solving the problem]

[0010] The present invention relates to, for example, the following [1] to [9]. [1] 5 to 30% by mass of an ethylene polymer (A), 40 to 85% by mass of a polar resin component (B), and 10 to 40% by mass of a modified ethylene-α-olefin copolymer (C) that satisfies the following requirement (C-1), which is obtained by modifying an ethylene-α-olefin copolymer (C0) with an unsaturated carboxylic acid or a derivative thereof (where the total proportion of the ethylene polymer (A), the polar resin component (B), and the copolymer (C) is 100% by mass). A polar resin composition containing Requirement (C-1): The melt flow rate (190°C, 2.16 kg load) is 0.1 to 50 g / 10 min.

[0011] [2] The polar resin composition of [1] above, wherein the modified ethylene-α-olefin copolymer (C) satisfies the following requirement (C-2): Requirement (C-2): Density is 850 to 930 kg / m 3 is.

[0012] [3] The resin component (B) 50 to 90 mass% of an ethylene polymer (BA), 5 to 49.5 mass% of polar resin (BB), and Modified ethylene-α-olefin copolymer (BC) 0.5 to 5 mass% (wherein the total proportion of the ethylene polymer (BA), the polar resin (BB), and the modified ethylene-α-olefin copolymer (BC) is 100 mass %). The polar resin composition according to [1] or [2], which is a mixture comprising:

[0013] [4] The polar resin composition according to any one of [1] to [3] above, wherein the polar resin component (B) comprises a polar resin (BB) selected from the group consisting of polyamide resins, polyester resins, ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, and combinations thereof.

[0014] [5] The polar resin composition according to [4] above, wherein the polyamide resin is an aliphatic polyamide resin. [6] A laminate comprising a polyethylene layer, a polar resin layer formed from the polar resin composition of any one of the above [1] to [5], and a polyethylene layer laminated in this order.

[0015] [7] The laminate of [6] above, which has a film impact strength of 20 kJ / m or more as measured in accordance with JIS P8134.

[0016] [8] The laminate of [6] or [7] above, wherein the internal haze measured in accordance with JIS K7136 is 10% or less.

[0017] [9] A regrind material obtained by pulverizing a molded article of the polar resin composition of any one of [1] to [5] above. [Effects of the Invention]

[0018] A laminate having a layer containing the polar resin composition of the present invention is excellent in transparency and mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance). Furthermore, the polar resin composition of the present invention can form a polar resin layer of a laminate having such properties. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will now be described in further detail. [Polar resin composition] The polar resin composition according to the present invention contains an ethylene polymer (A), a polar resin component (B), and a modified ethylene-α-olefin copolymer (C).

[0020] <Ethylene polymer (A)> Examples of the ethylene polymer (A) include high density polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ethylene-α-olefin (having 3 or more carbon atoms) copolymers.

[0021] The MFR (190°C, 2.16 kg load) of the ethylene polymer (A) is preferably 0.5 to 50 g / 10 min, more preferably 0.5 to 25 g / 10 min, still more preferably 0.5 to 10 g / 10 min, and particularly preferably 1 to 10 g / 10 min. When the MFR (190°C, 2.16 kg load) of the ethylene polymer (A) is within this range, the moldability is excellent.

[0022] The density of the ethylene polymer (A) is preferably 860 to 960 kg / m 3 , more preferably 880 to 950 kg / m 3 , and more preferably 900 to 945 kg / m 3 , preferably 920 to 940 kg / m 3 When the density of the ethylene polymer (A) is within this range, the moldability and rigidity are excellent.

[0023] The content of the ethylene polymer (A) (excluding the ethylene polymer (BA) contained in the polar resin component (B) described below) in the polar resin composition of the present invention is 5 to 30% by mass. The lower limit of the proportion of the ethylene polymer (A) in the polar resin composition of the present invention is preferably 5 mass %, more preferably 6 mass %, and even more preferably 8 mass %. When the proportion of the ethylene polymer (A) is equal to or greater than the above lower limit, the composition has excellent moldability and mechanical strength.

[0024] On the other hand, the upper limit of the proportion of the ethylene polymer (A) in the polar resin composition of the present invention is preferably 29% by mass, more preferably 28% by mass, and even more preferably 25% by mass.

[0025] <Polar resin component (B)> The polar resin component (B) is a component containing a polar resin (BB). The polar resin (BB) is preferably selected from the group consisting of polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, and combinations thereof, more preferably selected from the group consisting of polyamide, ethylene-vinyl alcohol copolymer, and combinations thereof, and even more preferably contains a polyamide resin.

[0026] Among the polyamide resins, aliphatic polyamide resins are preferred, with nylon 6, nylon 6,6, nylon 11, and nylon 12 being more preferred. The melting point of the polyamide resin is preferably 150 to 330°C, more preferably 150 to 270°C.

[0027] In the present invention, a blend of two or more polyamides, such as a mixture of nylon 6 and nylon 6,6, can also be used as the polyamide resin. The ethylene-vinyl alcohol copolymer is not particularly limited and is a copolymer mainly having structural units derived from ethylene and structural units derived from vinyl alcohol. For example, an ethylene-vinyl alcohol copolymer can be obtained by saponifying a copolymer of ethylene and a vinyl ester using an alkali catalyst. A typical example of the vinyl ester is vinyl acetate, but other fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate) can also be used.

[0028] The ethylene-vinyl alcohol copolymer may also be copolymerized with copolymer components such as vinylsilane compounds, propylene, butylene, unsaturated carboxylic acids or esters thereof, and vinylpyrrolidone.

[0029] The ethylene-vinyl alcohol copolymer preferably contains 20 to 60 mol %, more preferably 25 to 50 mol %, of structural units derived from ethylene. The MFR (190°C, 2.16 kg load) of the ethylene-vinyl alcohol copolymer is preferably 0.1 to 50 g / 10 min, more preferably 0.5 to 20 g / 10 min, and even more preferably 0.7 to 10 g / 10 min.

[0030] The proportion of the polar resin (BB) in the polar resin component (B) is preferably 5 to 49.5 mass %, more preferably 10 to 39.5 mass %. The polar resin component (B) may further contain an ethylene polymer (BA). Specific examples of the ethylene polymer (BA) include the specific examples of the ethylene polymer (A). The ethylene polymer (BA) may be the same as or different from the ethylene polymer (A).

[0031] The proportion of the ethylene polymer (BA) in the polar resin component (B) is preferably 50 to 90% by mass, more preferably 60 to 80% by mass. The polar resin component (B) may further contain a modified ethylene-α-olefin copolymer (BC). Specific examples of the modified ethylene-α-olefin copolymer (BC) include the specific examples of the modified ethylene-α-olefin copolymer (C) described below. The modified ethylene-α-olefin copolymer (BC) may be the same as or different from the modified ethylene-α-olefin copolymer (C) described below.

[0032] The content of the modified ethylene-α-olefin copolymer (BC) in the polar resin component (B) is preferably 0.5 to 5% by mass, more preferably 0.5 to 1.5% by mass. The polar resin component (B) may contain, in addition to the above-mentioned components, various additives that may be contained in a resin molded product containing the polar resin.

[0033] The content of the polar resin component (B) in the polar resin composition of the present invention is 40 to 85 mass %. The lower limit of the proportion of the polar resin component (B) in the polar resin composition of the present invention is preferably 42 mass %, more preferably 45 mass %, and even more preferably 50 mass %.

[0034] On the other hand, the upper limit of the proportion of the polar resin component (B) in the polar resin composition of the present invention is preferably 83 mass %, more preferably 80 mass %, and even more preferably 70 mass %. When the proportion of the polar resin component (B) is the upper limit or less, the laminate of the present invention is excellent in moldability, mechanical strength, and transparency.

[0035] The polar resin component (B) is prepared by mixing the polar resin (BB), the ethylene polymer (BA), the modified ethylene-α-olefin copolymer (BC) and optional additives, preferably by melt-kneading the mixture, followed by pelletizing.

[0036] <Modified ethylene-α-olefin copolymer (C)> The modified ethylene-α-olefin copolymer (C) is obtained by modifying an ethylene-α-olefin copolymer (C0) (which may be a composition of two or more ethylene-α-olefin copolymers) that satisfies the following requirements (C0-1) and (C0-2) with an unsaturated carboxylic acid or a derivative thereof:

[0037] The modified ethylene-α-olefin copolymer (C) is thought to function as a compatibilizer, that is, to make the ethylene polymer (A) and the polar resin component (B) compatible with each other.

[0038] Ethylene-α-olefin copolymer (C0) The α-olefin preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms.

[0039] Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene, with 1-butene being preferred.

[0040] The α-olefins may be used alone or in combination of two or more. Specific examples of ethylene-α-olefin copolymers (before modification) include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-1-octene copolymers, among which ethylene-1-butene copolymers are preferred. The ethylene-α-olefin copolymers are usually random copolymers. Incidentally, the ethylene-α-olefin copolymers also include LLDPE.

[0041] The ethylene-α-olefin copolymer contains ethylene-derived structural units as the main component (50% by mass or more of all structural units). Requirements (C0-1): The melt flow rate (190°C, 2.16 kg load) of the ethylene-α-olefin copolymer (C0) is preferably 0.1 to 50 g / 10 min, more preferably 0.2 to 45 g / 10 min, even more preferably 0.5 to 30 g / 10 min, and particularly preferably 0.5 to 20 g / 10 min.

[0042] When the melt flow rate is equal to or higher than the lower limit, the laminate of the present invention has excellent moldability. Requirements (C0-2): The density of the ethylene-α-olefin copolymer (C0) is preferably 850 to 930 kg / m 3 and more preferably 855 to 925 kg / m 3 and more preferably 860 to 890 kg / m 3 and particularly preferably 865 to 875 kg / m 3Since the density is equal to or greater than the lower limit, the laminate of the present invention is excellent in formability and rigidity, and since the density is equal to or less than the upper limit, the laminate of the present invention is excellent in mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance).

[0043] Modified ethylene-α-olefin copolymer (C) Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.

[0044] Examples of the derivatives include acid anhydrides such as maleic anhydride, endic anhydride (cis-5-norbornene-endo-2,3-dicarboxylic anhydride), itaconic anhydride, and citraconic anhydride; Esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconic acid, and diethyl itaconic acid; amides such as acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid N-monoethylamide, maleic acid N,N-diethylamide, maleic acid N-monobutylamide, maleic acid N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid N-monobutylamide, and fumaric acid N,N-dibutylamide; Imides such as maleimide, N-butylmaleimide, and N-phenylmaleimide; Examples of the metal salts include sodium acrylate, sodium methacrylate, potassium acrylate, and potassium methacrylate.

[0045] Among these unsaturated carboxylic acids and their derivatives, maleic acid and maleic anhydride are preferred, with maleic anhydride being more preferred. The modified ethylene-α-olefin copolymer (C) may be used alone or in combination of two or more.

[0046] The modification of the ethylene-α-olefin copolymer with the unsaturated carboxylic acid or its derivative can be carried out by a conventionally known method, for example, the method described in paragraph

[0016] of WO 2012 / 133008.

[0047] The wave number assigned to the carbonyl group as defined by the following formula and measured by Fourier transform infrared spectroscopy is 1780 cm -1 The degree of modification of the modified ethylene-α-olefin copolymer (C), calculated based on the peak intensity of (a), is, for example, 0.1 to 20 mass%, preferably 0.2 to 10 mass%, and more preferably 0.3 to 5 mass%. When the degree of modification of the modified ethylene-α-olefin copolymer (C) is within this range, the laminate of the present invention is excellent in formability, mechanical strength, and transparency.

[0048] Degree of modification (graft amount) (mass%) = (total mass of structural units having a structure derived from a monomer having an ethylenically unsaturated group and a group derived from an unsaturated carboxylic acid or its derivative in one molecule) / (mass of modified ethylene-α-olefin copolymer (C)) × 100 Requirement (C-1): The melt flow rate of the modified ethylene-α-olefin copolymer (C) (according to ASTM D1238, 190°C, 2.16 kg load) is 0.1 to 50 g / 10 min, preferably 0.2 to 45 g / 10 min, more preferably 0.3 to 43 g / 10 min, even more preferably 0.5 to 30 g / 10 min, and particularly preferably 0.5 to 20 g / 10 min.

[0049] When the melt flow rate is equal to or higher than the lower limit, the laminate of the present invention has excellent moldability, and when the melt flow rate is equal to or lower than the upper limit, the laminate of the present invention has excellent mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance).

[0050] Furthermore, since the melt flow rate is equal to or less than the upper limit, the laminate of the present invention has excellent mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance). This is presumably due to increased entanglement of molecular chains of the polar resin (BB) contained in the polar resin component (B), the ethylene polymer (A), and the modified ethylene-α-olefin copolymer (C) present at the interface between the ethylene polymer (BA).

[0051] Requirement (C-2): The density of the modified ethylene-α-olefin copolymer (C) is, for example, 850 to 930 kg / m 3 and preferably 855 to 925 kg / m 3 and more preferably 860 to 890 kg / m 3 and more preferably 863 to 887 kg / m 3 and particularly preferably 865 to 875 kg / m 3 is.

[0052] When the density is equal to or greater than the lower limit, the laminate of the present invention has excellent moldability and rigidity, and when the density is equal to or less than the upper limit, the laminate of the present invention has excellent mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance).

[0053] The content of the modified ethylene-α-olefin copolymer (C) in the polar resin composition according to the present invention is 10 to 40% by mass. The lower limit of the proportion of the modified ethylene-α-olefin copolymer (C) in the polar resin composition of the present invention is preferably 11% by mass, more preferably 12% by mass, and even more preferably 15% by mass. On the other hand, the upper limit of the proportion of the modified ethylene-α-olefin copolymer (C) in the polar resin composition of the present invention is preferably 39% by mass, more preferably 38% by mass, and even more preferably 35% by mass. When the proportion of the modified ethylene-α-olefin copolymer (C) is within the above range, the laminate of the present invention has excellent transparency and rigidity.

[0054] [Laminate] The laminate of the present invention is a laminate comprising a polyethylene layer, a polar resin layer and a polyethylene layer laminated in this order, and is characterized in that the polar resin layer is formed from the polar resin composition of the present invention described above.

[0055] <Polyethylene layer> The polyethylene layer is a layer made of polyethylene, and examples of polyethylene include ethylene-based polymers such as high-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ethylene-α-olefin (having 3 or more carbon atoms) copolymers.

[0056] The thickness of each of the two polyethylene layers is, independently, usually 3 to 50 μm, preferably 3 to 50 μm, more preferably 4 to 40 μm, still more preferably 5 to 20 μm, and particularly preferably 6 to 15 μm.

[0057] <Polar resin layer> The polar resin layer is a layer formed from the polar resin composition according to the present invention. The polar resin layer can be formed by melt-kneading the polar resin composition according to the present invention using an extruder or the like, and molding the composition.

[0058] The thickness of the polar resin layer is usually 4 to 300 μm, preferably 15 to 150 μm, more preferably 25 to 90 μm, still more preferably 30 to 70 μm, and particularly preferably 40 to 60 μm.

[0059] <any layer> The laminate of the present invention may further include layers other than the two polyethylene layers and the polar resin layer (hereinafter also referred to as "optional layers"). The type, thickness, number, position in the laminate, etc. of the optional layers are not particularly limited and can be appropriately determined with reference to conventionally known laminates.

[0060] (Laminate) The laminate according to the present invention is usually in the form of a film or sheet, and its thickness is usually 10 to 360 μm, preferably 20 to 300 μm, more preferably 30 to 190 μm, still more preferably 40 to 110 μm, and particularly preferably 50 to 90 μm.

[0061] Each layer constituting the laminate according to the present invention may contain additives such as fillers, stabilizers, nucleating agents, antistatic agents, flame retardants, and foaming agents, as long as the effects of the present invention are not impaired. The film impact strength of the laminate according to the present invention, measured in accordance with JIS K7136, is preferably 14 kJ / m or more, more preferably 16 kJ / m or more, even more preferably 18 kJ / m or more, and particularly preferably 20 kJ / m or more, and the upper limit thereof may be, for example, 40 kJ / m.

[0062] The internal haze of the laminate according to the present invention, measured in accordance with JIS K7136, is preferably 10% or less, more preferably 6% or less, and the lower limit thereof may be, for example, 0.1%.

[0063] (Method of manufacturing laminate) The laminate of the present invention can be produced by a conventionally known method, except that the polar resin layer is formed from the polar resin composition of the present invention. An example of the production method is a method in which the raw materials for the polyethylene layer, the raw materials for the polar resin layer (i.e., the polar resin composition of the present invention), and the raw materials for the other polyethylene layer are fed into separate extruders, melted, merged, laminated, and extruded into a sheet from a T-die (co-extrusion method).

[0064] (Laminate) Examples of uses for the laminate of the present invention include packaging materials, particularly materials for packaging food products, pharmaceuticals, industrial parts, electronic materials, etc. Furthermore, this laminate can be used, for example, as packaging films for inner bags of bag-in-boxes, which are often filled with highly fluid materials such as liquids, or as packaging films for pillow packaging and vacuum-formed packaging used to package processed meats, processed seafood products, and electronic materials. In particular, this laminate can be suitably used as a packaging film for electronic components with hard corners, such as capacitors, or for foods with irregular, hard parts, such as bone-in meat, foods containing a lot of spices, and shells. [Example]

[0065] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. [Measurement method or evaluation method] 《Raw materials》 The properties of the raw materials (polymers) used in the examples were measured as follows.

[0066] (Degree of denaturation) The degree of modification of the compatibilizer (maleic anhydride content) expressed by the following formula was measured by FT-IR at a wave number of 1780 cm attributed to the carbonyl group. -1 The peak intensity was calculated from a separately prepared calibration curve.

[0067] Degree of modification (mass%) = (total mass of structural units having a structure derived from a monomer having an ethylenically unsaturated group and a group derived from maleic anhydride in one molecule) / mass of compatibilizer) × 100 (Melt Flow Rate) The melt flow rate (MFR) was measured in accordance with ASTM D1238 under conditions of 190°C and a load of 2.16 kg.

[0068] (density) The density was measured according to ASTM D1505. Laminated film The properties of the laminated films produced in the examples were measured and evaluated as follows.

[0069] (Tensile properties) Test pieces measuring 15 mm wide x 150 mm long were cut out from the 70 μm thick films obtained in the Examples, etc. The tensile modulus (YM) (unit: MPa), tensile elongation at break (EL) (unit: %), and tensile strength at break (TS) (unit: MPa) of the test pieces were measured in accordance with JIS K7127 using a universal material testing machine "AG-X-5" manufactured by Shimadzu Corporation under conditions of a chuck distance of 50 mm, a tensile speed of 300 mm / min, and a temperature of 23°C.

[0070] (Puncture energy (puncture resistance)) Using a universal material testing machine "AG-5kNX" manufactured by Shimadzu Corporation, a needle with a tip shape of 1 mmφ was pierced into a film sample at a speed of 50 mm / min at -20°C in accordance with JIS Z1707, and the energy required to penetrate (hereinafter referred to as "piercing energy") was measured.

[0071] (Film impact strength (impact resistance)) The film impact strength at −20° C. was measured using a film impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with JIS P8134, with an impact head spherical shape of 1 inch φ.

[0072] (Internal haze (transparency)) Using a haze meter "HM-150" manufactured by Murakami Color Research Laboratory Co., Ltd., measurements were carried out in cyclohexanol on the films (thickness 70 μm) produced in the examples in accordance with JIS K7136, and the internal haze was calculated using the following formula.

[0073] Internal haze (%) = 100 x (diffuse transmitted light amount) / (total transmitted light amount) [Raw materials] The polymers used as raw materials in the examples are as follows: LLDPE-1: Commercially available linear low-density polyethylene (MFR (190°C, 2.16 kg load) 15 g / 10 min, density 914 kg / m 3 ) LLDPE-2: Commercially available linear low-density polyethylene (MFR (190°C, 2.16 kg load) 19 g / 10 min, density 918 kg / m 3 ) LLDPE-3: Commercially available linear low-density polyethylene (MFR (190°C, 2.16 kg load) 3.4 g / 10 min, density 923 kg / m 3 ) EBR-1: A commercially available ethylene-1-butene copolymer (MFR (190°C, 2.16 kg load) 0.5 g / 10 min, density 870 kg / m 3 ) EBR-2: A commercially available ethylene-1-butene copolymer (MFR (190°C, 2.16 kg load) 35 g / 10 min, density 870 kg / m 3 ) EBR-3: A commercially available ethylene-1-butene copolymer (MFR (190°C, 2.16 kg load) 3.6 g / 10 min, density 870 kg / m 3 ) PA6: Polyamide resin (6 nylon) (Toray Industries, Inc., Amilan (registered trademark) CM1021XF, melting point 225°C) EVOH: Ethylene-vinyl alcohol resin (Kuraray Co., Ltd., EVAL (registered trademark) F101A, ethylene-derived structural unit content 32 mol%, MFR (190°C, 2.16 kg load): 1.6 g / 10 min) [Preparation of Compatibilizer] The methods for preparing the compatibilizers (Q-1) to (Q-5) used in the examples described later are as follows.

[0074] [Preparation Example 1] (Preparation of Compatibilizer (Q-1)) A solution of 150 g of maleic anhydride (MAH) and 6 g of Perhexa (registered trademark) 25B (manufactured by NOF Corporation) dissolved in acetone was blended with 10 kg of LLDPE-1 to obtain Blend 1. Blend 1 was then fed into the hopper of a twin-screw extruder with a screw diameter of 32 mm and an L / D ratio of 42 mm, and extruded into strands at a resin temperature of 200°C, a screw rotation speed of 240 rpm, and a throughput of 12 kg / hr. The resulting strands were thoroughly cooled and then granulated to obtain Compatibilizer (Q-1). The physical properties of Compatibilizer (Q-1) are shown in Table 1.

[0075] (Preparation of Compatibilizer (Q-2)) A solution of 60 g of MAH and 2 g of Perhexa 25B dissolved in acetone was blended with 10 kg of the LLDPE-2 to obtain Blend 2. Compatibilizer (Q-2) was obtained in the same manner as in the preparation of Compatibilizer (Q-1), except that Blend 1 was changed to Blend 2. The physical properties of Compatibilizer (Q-2) are shown in Table 1.

[0076] (Preparation of Compatibilizer (Q-3)) A solution of 50 g of MAH and 2 g of Perhexa 25B dissolved in acetone was blended with 10 kg of EBR-1 to obtain Blend 3. Compatibilizer (Q-3) was obtained in the same manner as compatibilizer (Q-1), except that Blend 1 was changed to Blend 3. The physical properties of compatibilizer (Q-3) are shown in Table 1.

[0077] (Preparation of Compatibilizer (Q-4)) A solution of 50 g of MAH and 2 g of Perhexa 25B dissolved in acetone was blended with 10 kg of EBR-2 to obtain Blend 4. Compatibilizer (Q-4) was obtained in the same manner as compatibilizer (Q-1), except that Blend 1 was changed to Blend 4. The physical properties of compatibilizer (Q-4) are shown in Table 1.

[0078] (Preparation of Compatibilizer (Q-5)) A solution of 50 g of MAH and 2 g of Perhexa 25B dissolved in acetone was blended with 10 kg of EBR-3 to obtain Blend 5. Compatibilizer (Q-5) was obtained in the same manner as in the preparation of Compatibilizer (Q-1), except that Blend 1 was changed to Blend 5. The physical properties of Compatibilizer (Q-5) are shown in Table 1.

[0079] [Table 1] [Preparation of Polar Resin Component] The methods for preparing the polar resin components (B-1) to (B-3) used in the examples described later are as follows.

[0080] [Preparation of Polar Resin Component (B-1)] LLDPE-3, PA6, and compatibilizer (Q-1) were blended in a mass ratio of 70 / 29 / 1 as shown in Table 2, and then fed into a single-screw extruder (L / D=26, 40 mmφ) set at 250°C to prepare pellets of polar resin component (B-1). The resulting pellets of polar resin component (B-1) were dried overnight at 80°C.

[0081] [Preparation of Polar Resin Component (B-2)] Polar resin component (B-2) was obtained in the same manner as polar resin component (B-1), except that instead of the blend of LLDPE-3, PA6, and compatibilizer (Q-1), LLDPE-3, EVOH, and compatibilizer (Q-1) were blended in a mass ratio of 90 / 8 / 2, respectively, as shown in Table 2.

[0082] [Preparation of Polar Resin Component (B-3)] Polar resin component (B-3) was obtained in the same manner as polar resin component (B-1), except that instead of the blend of LLDPE-3, PA6, and compatibilizer (Q-1), LLDPE-3, PA6, EVOH, and compatibilizer (Q-1) were blended in a mass ratio of 64 / 25 / 10 / 1, respectively, as shown in Table 2.

[0083] [Table 2] Example 1 (Laminated film manufacturing) The resin for the skin layer (polyethylene layer) and the polar resin composition for the intermediate layer (polar resin layer) shown below were fed into each extruder, and a cast molding die (die width 350 mmφ, lip gap 1 mm) was used. The resin temperature was set to 250°C, and the extrusion rates of each extruder were set so that the thicknesses of the skin layer, intermediate layer, and skin layer were 10 μm / 50 μm / 10 μm, respectively, to obtain a 70 μm-thick multilayer film by co-extrusion molding at a molding speed of 4 m / min. Resin for the skin layer; LLDPE-3 Polar resin compositions for the intermediate layer; LLDPE-3, polar resin component ( B A resin composition obtained by blending the above-mentioned resin (Q-1) and the compatibilizer (Q-1) in a mass ratio of 20 / 60 / 20, respectively. Example 2 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-1) in a mass ratio of 10 / 60 / 30. The results are shown in Table 3.

[0084] Example 3 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-2) in a mass ratio of 20 / 60 / 20. The results are shown in Table 3.

[0085] Example 4 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-2) in a mass ratio of 10 / 60 / 30. The results are shown in Table 3.

[0086] Example 5 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-3) in a mass ratio of 20 / 60 / 20. The results are shown in Table 3.

[0087] Example 6 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-3) in a mass ratio of 10 / 60 / 30. The results are shown in Table 3.

[0088] Example 7 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-4) in a mass ratio of 20 / 60 / 20. The results are shown in Table 3.

[0089] Example 8 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-4) in a mass ratio of 10 / 60 / 30. The results are shown in Table 3.

[0090] Example 9 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-5) in a mass ratio of 20 / 60 / 20. The results are shown in Table 3.

[0091] Example 10 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-1), and compatibilizer (Q-5) in a mass ratio of 10 / 60 / 30. The results are shown in Table 3.

[0092] Example 11 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-1) in a mass ratio of 30 / 60 / 10. The results are shown in Table 4.

[0093] Example 12 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-1) in a mass ratio of 20 / 60 / 20. The results are shown in Table 4.

[0094] Example 13 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-2) in a mass ratio of 30 / 60 / 10. The results are shown in Table 4.

[0095] Example 14 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-2) in a mass ratio of 20 / 60 / 20. The results are shown in Table 4.

[0096] Example 15 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-3) in a mass ratio of 30 / 60 / 10. The results are shown in Table 4.

[0097] Example 16 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-3) in a mass ratio of 20 / 60 / 20. The results are shown in Table 4.

[0098] Example 17 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-4) in a mass ratio of 30 / 60 / 10. The results are shown in Table 4.

[0099] Example 18 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-4) in a mass ratio of 20 / 60 / 20. The results are shown in Table 4.

[0100] Example 19 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-5) in a mass ratio of 30 / 60 / 10. The results are shown in Table 4.

[0101] Example 20 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-5) in a mass ratio of 20 / 60 / 20. The results are shown in Table 4.

[0102] Example 21 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-3), and compatibilizer (Q-1) in a mass ratio of 30 / 60 / 10. The results are shown in Table 5.

[0103] Example 22 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-3), and compatibilizer (Q-1) in a mass ratio of 20 / 60 / 20. The results are shown in Table 5.

[0104] Example 23 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-3), and compatibilizer (Q-3) in a mass ratio of 30 / 60 / 10. The results are shown in Table 5.

[0105] Example 24 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-3), and compatibilizer (Q-4) in a mass ratio of 30 / 60 / 10. The results are shown in Table 5.

[0106] Example 25 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-3), and compatibilizer (Q-4) in a mass ratio of 20 / 60 / 20. The results are shown in Table 5.

[0107] Comparative Example 1 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3 and polar resin component (B-1) in a mass ratio of 40 / 60. The results are shown in Table 6.

[0108] Comparative Example 2 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3 and polar resin component (B-2) in a mass ratio of 40 / 60. The results are shown in Table 6.

[0109] Comparative Example 3 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-1) in a mass ratio of 35 / 60 / 5. The results are shown in Table 6.

[0110] Comparative Example 4 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3, polar resin component (B-2), and compatibilizer (Q-4) in a mass ratio of 35 / 60 / 5. The results are shown in Table 6.

[0111] Comparative Example 5 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3 and polar resin component (B-3) in a mass ratio of 40 / 60. The results are shown in Table 6.

[0112] Comparative Example 6 A multilayer film was obtained in the same manner as in Example 1, except that the polar resin composition for the intermediate layer was changed to LLDPE-3. The results are shown in Table 6.

[0113] [Table 3]

[0114] [Table 4]

[0115]

Table 5

[0116]

Table 6

Claims

1. 50 to 90% by mass of an ethylene polymer (BA), 5 to 49.5% by mass of polar resin (BB), 0.5 to 5 mass% of modified ethylene / α-olefin copolymer (BC) (where the total proportion of the ethylene polymer (BA), the polar resin (BB), and the modified ethylene-α-olefin copolymer (BC) is 100 mass %), and Optionally, additives These are melt-kneaded and pelletized to prepare a polar resin component (B), and then 5 to 30% by mass of an ethylene polymer (A), 40 to 85% by mass of the polar resin component (B), and 10 to 40% by mass of a modified ethylene / α-olefin copolymer (C) that satisfies the following requirement (C-1), which is obtained by modifying an ethylene / α-olefin copolymer (C0) with an unsaturated carboxylic acid or a derivative thereof (where the total proportion of the ethylene polymer (A), the polar resin component (B), and the copolymer (C) is taken as 100% by mass). Mixing A method for producing a polar resin composition, comprising: the polar resin (BB) is selected from the group consisting of polyamide, ethylene-vinyl alcohol copolymer, and combinations thereof, and the polyamide is nylon 6, nylon 6,6, nylon 11, nylon 12, or a blend thereof; the modified ethylene / α-olefin copolymer (BC) is a modified ethylene / α-olefin copolymer modified with maleic anhydride; A method for producing a polar resin composition. Requirement (C-1): The melt flow rate (190°C, 2.16 kg load) is 0.1 to 50 g / 10 min.

2. A polar resin composition is produced by the production method according to claim 1, and then laminating a polyethylene layer, a polar resin layer formed from the polar resin composition, and a polyethylene layer in this order; A method for manufacturing a laminate.

3. The method for producing a laminate according to claim 2, wherein the laminate has a film impact strength of 20 kJ / m or more as measured in accordance with JIS P8134.

4. 4. The method for producing a laminate according to claim 2, wherein the laminate has an internal haze of 10% or less as measured in accordance with JIS K7136.

5. A method for producing a regrind material, comprising producing a polar resin composition by the method according to claim 1 and pulverizing a molded article of the polar resin composition.

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