Polar resin composition and laminate

Abstract

The present invention provides a laminate having a polar resin layer, which is excellent in transparency and mechanical strength (particularly, impact resistance), and a polar resin composition for forming a polar resin layer of a laminate having such characteristics. The present invention is a polar resin composition containing: 5 to 30 mass% of an ethylene-based polymer (A); 40 to 85 mass% of a polar resin component (B); and 10 to 40 mass% of a modified ethylene-α-olefin copolymer (C) obtained by modifying an ethylene-α-olefin copolymer (C0) with an unsaturated carboxylic acid or a derivative thereof, and MFR (190°C, 2.16 kg load) = 0.1 to 50 g / 10 minutes (wherein the total of the proportions of (A), B), and (C) is 100 mass%).

Description

TECHNICAL FIELD

[0001] The present application 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 containing a polar resin layer formed from the aforementioned polar resin composition. BACKGROUND

[0002] Polyolefin resins represented by polyethylene and polypropylene are used in various fields because they are produced with less energy, are lightweight, and have excellent recyclability.

[0003] However, polyolefin resins generally do not contain polar groups in the molecules, and thus lack compatibility with polar resins such as polyamides, polyesters, and ethylene-vinyl alcohol copolymers (EVOH), and there are problems in that it is difficult to utilize them by blending with these materials or by laminating them. In order to improve the low compatibility of polyolefins with polar polymers, a polyolefin-based graft polymer is sometimes further compounded in their mixture.

[0004] For example, in Patent Literature 1, a laminate is disclosed in which, in a laminate layered in the order of a polyolefin layer / a regrind layer / an ethylene-vinyl alcohol copolymer layer / a regrind layer / a polyolefin layer, the regrind layer is formed of a composition of (A) an ethylene-vinyl alcohol copolymer, (B) a polyolefin, and (C) a graft polymer using a polyolefin, and it is described that the laminate has excellent impact resistance and the like.

[0005] In Patent Literature 2, a multilayer laminate is disclosed which has a recycling layer formed of a recyclable resin composition (D) containing: 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 ethylene-vinyl alcohol copolymer (C), as a specific example of the modified polyethylene resin, a copolymer obtained by graft-modifying an ethylene-butene copolymer with maleic anhydride and a peroxide is disclosed. Further, it is described that the modified polyethylene resin composition (A) has compatibilizing properties, and thus the compatibility of the polyolefin resin (B) with the ethylene-vinyl alcohol copolymer (C) is increased, and thus the multilayer laminate has excellent mechanical strength such as impact strength and tensile elongation, and appearance, and also has no yellowing property.

[0006] In addition, in Patent Literature 3, it is described that a low-viscosity ethylene-a-olefin interpolymer obtained by modification with maleic anhydride or the like is compounded, thereby compatibilizing an ethylene-based polymer and a polar polymer, and improving optical properties and tensile properties of a film or the like obtained from a composition containing them.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT LITERATURE

[0009] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 5-147177

[0010] Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 9-302170

[0011] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 2015-535311 SUMMARY

[0012] PROBLEMS TO BE SOLVED BY THE INVENTION

[0013] However, in the existing laminate having a layer containing a polar resin, there is room for further improvement from the viewpoint of transparency and mechanical strength (particularly, impact resistance, or impact resistance and puncture resistance).

[0014] Therefore, an object of the present application is to provide a laminate having a layer containing a polar resin, which 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.

[0015] MEANS FOR SOLVING THE PROBLEMS

[0016] The present application relates to, for example, [1] to [9] below. [1]

[0018] A polar resin composition containing:

[0019] 5 to 30 mass% of an ethylene-based polymer (A) ;

[0020] 40 to 85 mass% of a polar resin component (B) ; and

[0021] 10 to 40 mass% of a modified ethylene-a-olefin copolymer (C) obtained by modifying an ethylene-a-olefin copolymer (CO) with an unsaturated carboxylic acid or a derivative thereof, and satisfying the following requirement (C-1) (wherein the total of the proportions of the aforementioned ethylene-based polymer (A), the aforementioned polar resin component (B), and the aforementioned copolymer (C) is taken as 100 mass%).

[0022] Requirement (C-1) : Melt flow rate (190°C, 2.16 kg load) is 0.1 to 50 g / 10 minutes. [2]

[0024] The polar resin composition of the aforementioned [1], wherein the aforementioned modified ethylene-a-olefin copolymer (C) satisfies the following requirement (C-2).

[0025] (C-2) The density is 850 to 930 kg / m 3 . [3]

[0027] The polar resin composition of the foregoing [1] or [2], wherein the aforementioned resin component (B) is a mixture comprising:

[0028] 50 to 90 mass% of an ethylene-based polymer (BA);

[0029] 5 to 49.5 mass% of a polar resin (BB); and

[0030] 0.5 to 5 mass% of a modified ethylene-a-olefin copolymer (BC)

[0031] (wherein the total of the proportions of the aforementioned ethylene-based polymer (BA), the aforementioned polar resin (BB), and the aforementioned modified ethylene-a-olefin copolymer (BC) is taken to be 100 mass%). [4]

[0033] The polar resin composition of any one of the foregoing [1] to [3], wherein the aforementioned polar resin component (B) comprises a polar resin (BB) selected from the group consisting of a polyamide resin, a polyester resin, an ethylene-vinyl alcohol copolymer, and an ethylene-vinyl acetate copolymer, and combinations thereof. [5]

[0035] The polar resin composition of the foregoing [4], wherein the aforementioned polyamide resin is an aliphatic polyamide resin. [6]

[0037] A laminate which is a polyethylene layer, a polar resin layer formed of the polar resin composition of any one of the foregoing [1] to [5], and a polyethylene layer, which are sequentially laminated. [7]

[0039] The laminate of the foregoing [6], wherein the film impact strength measured in accordance with JIS P8134 is 20 kJ / m or more. [8]

[0041] The laminate of the foregoing [6] or [7], wherein the internal haze measured in accordance with JIS K7136 is 10% or less. [9]

[0043] A plastic regrind material which is obtained by pulverizing a molded article of the polar resin composition of any one of the foregoing [1] to [5].

[0044] Effects of the Invention

[0045] The laminate having a layer containing the polar resin composition of the present application is excellent in transparency and mechanical strength (particularly impact resistance, preferably impact resistance and puncture resistance). In addition, according to the polar resin composition of the present application, a polar resin layer of a laminate having such properties can be formed. DETAILED DESCRIPTION

[0046] Hereinafter, the present application will be described in more detail.

[0047] [Polar resin composition]

[0048] The polar resin composition according to the present application contains an ethylene-based polymer (A), a polar resin component (B), and a modified ethylene-α-olefin copolymer (C).

[0049] <Ethylene-based polymer (A)>

[0050] As the aforementioned ethylene-based polymer (A), high-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene-α-olefin (carbon number 3 or more) copolymer, and the like can be given.

[0051] The MFR (190°C, 2.16 kg load) of the aforementioned ethylene-based polymer (A) is preferably 0.5 to 50 g / 10 minutes, more preferably 0.5 to 25 g / 10 minutes, further preferably 0.5 to 10 g / 10 minutes, and particularly preferably 1 to 10 g / 10 minutes. If the MFR (190°C, 2.16 kg load) of the aforementioned ethylene-based polymer (A) is within this range, the moldability is excellent.

[0052] The density of the aforementioned ethylene-based polymer (A) is preferably 860 to 960 kg / m 3 , more preferably 880 to 950 kg / m 3 , further preferably 900 to 945 kg / m 3 , and preferably 920 to 940 kg / m 3 . If the density of the aforementioned ethylene-based polymer (A) is within this range, the moldability and rigidity are excellent.

[0053] The proportion of the aforementioned ethylene-based polymer (A) in the polar resin composition of the present application (excluding the ethylene-based polymer (BA) contained in the polar resin component (B) described later) is 5 to 30 mass%.

[0054] The lower limit value of the proportion of the aforementioned ethylene-based polymer (A) in the polar resin composition of the present application is preferably 5 mass%, more preferably 6 mass%, and further preferably 8 mass%. If the proportion of the aforementioned ethylene-based polymer (A) is 5 mass% or more, the moldability and mechanical strength are excellent.

[0055] On the other hand, the upper limit value of the proportion of the aforementioned ethylene-based polymer (A) in the polar resin composition of the present application is preferably 29% by mass, more preferably 28% by mass, and further preferably 25% by mass.

[0056] <Polar resin component (B)>

[0057] The aforementioned polar resin component (B) is a component containing a polar resin (BB).

[0058] The aforementioned polar resin (BB) is preferably selected from the group consisting of a polyamide resin, a polyester resin, an ethylene-vinyl alcohol copolymer, and an ethylene-vinyl acetate copolymer, and combinations thereof, more preferably from the group consisting of a polyamide and an ethylene-vinyl alcohol copolymer, and combinations thereof, and further preferably contains a polyamide resin.

[0059] Among the aforementioned polyamide resins, an aliphatic polyamide resin is preferable, and nylon 6, nylon 6,6, nylon 11, and nylon 12 are more preferable.

[0060] The melting point of the aforementioned polyamide resin is preferably 150°C to 330°C, and more preferably 150°C to 270°C.

[0061] In the present application, as the aforementioned polyamide resin, a blend obtained by compounding two or more polyamides, such as a mixture of nylon 6 and nylon 6,6, can also be used.

[0062] The aforementioned ethylene-vinyl alcohol copolymer is not particularly limited, and is a copolymer mainly having a structural unit derived from ethylene and a structural unit derived from vinyl alcohol. The ethylene-vinyl alcohol copolymer is obtained, for example, by saponifying a copolymer formed from ethylene and a vinyl ester using an alkali catalyst or the like. As the vinyl ester, vinyl acetate is given as a representative, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used.

[0063] The aforementioned ethylene-vinyl alcohol copolymer can also have, as a copolymerization component, for example, a vinyl silane compound, propylene, butene, an unsaturated carboxylic acid or an ester thereof, and vinyl pyrrolidone, etc.

[0064] The structural unit derived from ethylene of the aforementioned ethylene-vinyl alcohol copolymer is preferably 20 to 60 mol%, and more preferably 25 to 50 mol%.

[0065] The MFR (190°C, 2.16 kg load) of the aforementioned ethylene-vinyl alcohol copolymer is preferably 0.1 to 50 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes, and further preferably 0.7 to 10 g / 10 minutes.

[0066] The proportion of the aforementioned polar resin (BB) in the aforementioned polar resin component (B) is preferably 5 to 49.5% by mass, more preferably 10 to 39.5% by mass.

[0067] The aforementioned polar resin component (B) can further contain an ethylene-based polymer (BA). Specific examples of the aforementioned ethylene-based polymer (BA) include the specific examples of the aforementioned ethylene-based polymer (A). The aforementioned ethylene-based polymer (BA) can be the same as or different from the aforementioned ethylene-based polymer (A).

[0068] The proportion of the aforementioned ethylene-based polymer (BA) in the aforementioned polar resin component (B) is preferably 50 to 90% by mass, more preferably 60 to 80% by mass.

[0069] The aforementioned polar resin component (B) can further contain a modified ethylene-α-olefin copolymer (BC). Specific examples of the aforementioned modified ethylene-α-olefin copolymer (BC) include the specific examples of the modified ethylene-α-olefin copolymer (C) described later. The aforementioned modified ethylene-α-olefin copolymer (BC) can be the same as or different from the modified ethylene-α-olefin copolymer (C) described later.

[0070] The proportion of the aforementioned modified ethylene-α-olefin copolymer (BC) in the aforementioned polar resin component (B) is preferably 0.5 to 5% by mass, more preferably 0.5 to 1.5% by mass.

[0071] The aforementioned polar resin component (B) can contain various additives that are sometimes contained in resin molded bodies containing the aforementioned polar resin, in addition to the aforementioned components.

[0072] The proportion of the aforementioned polar resin component (B) in the polar resin composition of the present application is 40 to 85% by mass.

[0073] The lower limit value of the proportion of the aforementioned polar resin component (B) in the polar resin composition of the present application is preferably 42% by mass, more preferably 45% by mass, and further preferably 50% by mass.

[0074] On the other hand, the upper limit value of the proportion of the aforementioned polar resin component (B) in the polar resin composition of the present application is preferably 83% by mass, more preferably 80% by mass, and further preferably 70% by mass. If the proportion of the aforementioned polar resin component (B) is the aforementioned upper limit value or less, the moldability, mechanical strength, and transparency of the laminate of the present application are excellent.

[0075] The aforementioned polar resin component (B) is produced by mixing the aforementioned polar resin (BB), the aforementioned ethylene-based polymer (BA), the aforementioned modified ethylene-α-olefin copolymer (BC), and optional additives, preferably melt-kneading, and then pelletizing.

[0076] <Modified ethylene-α-olefin copolymer (C)>

[0077] The aforementioned modified ethylene-α-olefin copolymer (C) is obtained by modifying an ethylene-α-olefin copolymer (C0) that meets the following requirements (C0-1) and (C0-2) using unsaturated carboxylic acids or their derivatives (C0-1) or a combination of two or more ethylene-α-olefin copolymers.

[0078] It is believed that the aforementioned modified ethylene-α-olefin copolymer (C) functions as a compatibilizer, that is, it compatibilizes the aforementioned ethylene polymer (A) and the aforementioned polar resin component (B).

[0079] Ethylene-α-olefin copolymer (C0)

[0080] The aforementioned α-olefin preferably has 3 to 10 carbon atoms, more preferably 3 to 8.

[0081] Examples of the aforementioned α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene, with 1-butene being the most preferred.

[0082] The aforementioned α-olefins can be used alone or in combination with two or more.

[0083] Specific examples of (unmodified) ethylene-α-olefin copolymers include ethylene-propylene polymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-1-octene copolymers, with ethylene-1-butene copolymers being preferred. The aforementioned ethylene-α-olefin copolymers are generally random copolymers. It should be noted that LLDPE is also included among the aforementioned ethylene-α-olefin copolymers.

[0084] The aforementioned ethylene-α-olefin copolymer contains structural units derived from ethylene as the main component (more than 50% by mass relative to all structural units).

[0085] Condition (C0-1):

[0086] The melt flow rate (190°C, 2.16 kg load) of the aforementioned ethylene-α-olefin copolymer (CO) 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.

[0087] If the melt flow rate is above the aforementioned lower limit, the formability of the laminate of the present invention is excellent.

[0088] Condition (C0-2):

[0089] The density of the aforementioned ethylene-α-olefin copolymer (CO) is preferably 850–930 kg / m³. 3 More preferably, it is 855–925 kg / m³. 3 A further preferred value is 860–890 kg / m³. 3 The preferred value is 865-875 kg / m³. 3 Since the density is above the aforementioned lower limit, the laminate of the present invention has excellent formability and rigidity; since the density is below the aforementioned upper limit, the laminate of the present invention has excellent mechanical strength (especially impact resistance, preferably impact resistance and puncture resistance).

[0090] Modified ethylene-α-olefin copolymer (C)

[0091] Examples of unsaturated carboxylic acids mentioned above include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.

[0092] Examples of the aforementioned derivatives include:

[0093] Maleic anhydride, Nadic anhydride (cis-5-norbornene-endo-2,3-dicarboxylic anhydride), itaconic anhydride, citraconic anhydride and other anhydrides;

[0094] 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.

[0095] 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, fumaric acid-N,N-dibutylamide, etc.

[0096] maleimide, N-butylmaleimide, N-phenylmaleimide and other imides;

[0097] Sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and other metal salts.

[0098] Among these unsaturated carboxylic acids and their derivatives, maleic acid and maleic anhydride are preferred, and maleic anhydride is more preferred.

[0099] The aforementioned modified ethylene-α-olefin copolymer (C) can be used alone or in combination with two or more types.

[0100] Modification of ethylene-α-olefin copolymers based on unsaturated carboxylic acids or their derivatives can be carried out using methods known in the past, such as those described in International Publication No. 2012 / 133008

[0016] .

[0101] Defined by the following formula, and based on the wavenumber 1780 cm⁻¹ attributable to the carbonyl group as determined by Fourier transform infrared spectroscopy. -1 The degree of modification of the modified ethylene-α-olefin copolymer (C), calculated from the peak intensity, is, for example, 0.1 to 20% by mass, preferably 0.2 to 10% by mass, and more preferably 0.3 to 5% by mass. If the aforementioned degree of modification of the modified ethylene-α-olefin copolymer (C) is within this range, the laminate of the present invention exhibits excellent formability, mechanical strength, and transparency.

[0102] Degree of modification (grafting amount) (mass%) = (total mass of structural units having a structure derived from monomers containing olefinic unsaturated groups and groups derived from unsaturated carboxylic acids or their derivatives) / (mass of modified ethylene-α-olefin copolymer (C)) × 100

[0103] Condition (C-1):

[0104] The melt flow rate (according to ASTM D1238, 190°C, 2.16 kg load) of the aforementioned modified ethylene-α-olefin copolymer (C) 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.

[0105] When the melt flow rate is above or above the aforementioned lower limit, the laminate of the present invention exhibits excellent formability. Furthermore, when the melt flow rate is below or above the aforementioned upper limit, the laminate of the present invention exhibits excellent mechanical strength (especially impact resistance, preferably impact resistance and puncture resistance).

[0106] Furthermore, since the melt flow rate is below the aforementioned upper limit, the mechanical strength (especially impact resistance, preferably impact resistance and puncture resistance) of the laminate of the present invention is excellent. This is presumably due to increased entanglement of the molecular chains of the polar resin (BB), the ethylene polymer (A), and the modified ethylene-α-olefin copolymer (C) present at the interface with the ethylene polymer (BA) in the polar resin component (B).

[0107] Condition (C-2):

[0108] The density of the aforementioned modified ethylene-α-olefin copolymer (C) is, for example, 850–930 kg / m³. 3The preferred value is 855–925 kg / m³. 3 More preferably, it is 860–890 kg / m³. 3 A further preferred value is 863–887 kg / m³. 3 The preferred value is 865-875 kg / m³. 3 .

[0109] When the density is above the aforementioned lower limit, the laminate of the present invention exhibits excellent formability and rigidity. When the density is below the aforementioned upper limit, the laminate of the present invention exhibits excellent mechanical strength (especially impact resistance, preferably impact resistance and puncture resistance).

[0110] The proportion of the aforementioned modified ethylene-α-olefin copolymer (C) in the polar resin composition involved in this invention is 10 to 40% by mass.

[0111] The lower limit of the proportion of the aforementioned 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 aforementioned 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. If the proportion of the modified ethylene-α-olefin copolymer (C) is within the aforementioned range, the laminate of the present invention exhibits excellent transparency and rigidity.

[0112] [Layered body]

[0113] The laminate of the present invention is characterized in that it is a laminate obtained by sequentially stacking a polyethylene layer, a polar resin layer and another polyethylene layer, wherein the aforementioned polar resin layer is formed from the polar resin composition of the present invention.

[0114] <Polyethylene layer>

[0115] A polyethylene layer is a layer made of polyethylene. Examples of polyethylene include high-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ethylene-α-olefin (carbon atoms 3 or more) copolymers, etc.

[0116] The thickness of each of the two aforementioned polyethylene layers is typically 3 to 50 μm, preferably 3 to 50 μm, more preferably 4 to 40 μm, even more preferably 5 to 20 μm, and particularly preferably 6 to 15 μm.

[0117] <Polar resin layer>

[0118] The aforementioned polar resin layer is a layer formed from the polar resin composition involved in this invention.

[0119] The aforementioned polar resin layer can be formed by melt-kneading the polar resin composition involved in this invention using, for example, an extruder, and then molding it.

[0120] The thickness of the aforementioned polar resin layer is typically 4–300 μm, preferably 15–150 μm, more preferably 25–90 μm, even more preferably 30–70 μm, and particularly preferably 40–60 μm.

[0121] <Arbitrary layer>

[0122] The laminate of the present invention may also have layers other than the two polyethylene layers and the polar resin layer (hereinafter also referred to as "arbitrary layers"). There are no particular limitations on the type, thickness, number, or position of the arbitrary layers in the laminate, and they can be suitably set with reference to conventionally known laminates.

[0123] (Layered body)

[0124] The laminates involved in this invention are typically in the form of films or sheets, with a thickness typically ranging from 10 to 360 μm, preferably from 20 to 300 μm, more preferably from 30 to 190 μm, even more preferably from 40 to 110 μm, and particularly preferably from 50 to 90 μm.

[0125] In each layer constituting the laminate of the present invention, additives such as fillers, stabilizers, nucleating agents, antistatic agents, flame retardants, and foaming agents may be added without impairing the effects of the present invention.

[0126] The membrane impact strength of the laminate of the present invention, as measured according to JIS K7136, is preferably 14 kJ / m or more, more preferably 16 kJ / m or more, even more preferably 18 kJ / m or more, particularly preferably 20 kJ / m or more, and its upper limit may be, for example, 40 kJ / m.

[0127] The internal haze of the laminated body according to JIS K7136 is preferably 10% or less, more preferably 6% or less, and the lower limit may be, for example, 0.1%.

[0128] (Method for manufacturing layered body)

[0129] The laminates involved in this invention can be manufactured using conventionally known methods, except that the polar resin layer is formed from the polar resin composition of this invention as described above. Examples of manufacturing methods include: feeding raw materials for a polyethylene layer, raw materials for a polar resin layer (i.e., the polar resin composition of this invention), and another raw material for a polyethylene layer to different extruders, melting them separately, merging them, and laminating them, then extruding them in sheet form from a T-die (co-extrusion).

[0130] (Layered body)

[0131] As examples of applications of the laminated body according to the present invention, it can be used in packaging materials, particularly for packaging food, pharmaceuticals, industrial components, and electronic materials. Furthermore, this laminated body can be applied, for example, to packaging films for inner bags of boxes containing highly fluid substances such as liquids, or as packaging films for pillow-type packaging, vacuum-formed packaging, etc., used for packaging processed meat, seafood, and electronic materials. In particular, this laminated body can be suitably used as packaging films for electronic components such as capacitors with hard corners, or for packaging films for irregularly shaped foods with hard parts, such as meat with bones, foods containing a large amount of spices, and shellfish.

[0132] Example

[0133] The present invention will be described below using examples, but the present invention is not limited to the examples.

[0134] [Measurement method or evaluation method]

[0135] "raw material"

[0136] The properties of the raw materials (polymers) used in the examples were determined as described below.

[0137] (Degree of modification)

[0138] Based on the wavenumber of 1780 cm⁻¹ attributable to carbonyl groups determined using FT-IR. -1 The peak intensity is obtained from a separately prepared standard curve, and the degree of modification of the compatibilizer (maleic anhydride content) is expressed by the following formula.

[0139] Degree of modification (mass%) = (Total mass of structural units having a structure derived from monomers containing olefinic unsaturated groups and groups derived from maleic anhydride in one molecule) / Mass of compatibilizer) × 100

[0140] (Mel flow rate)

[0141] According to ASTM D1238, the melt flow rate (MFR) was determined at 190°C and a load of 2.16 kg.

[0142] (density)

[0143] Density was determined according to ASTM D1505.

[0144] Laminated Membranes

[0145] The properties of the laminated films manufactured in the examples, etc., are measured or evaluated as described below.

[0146] (Tensive properties)

[0147] Test pieces with a width of 15 mm and a length of 150 mm were cut from the 70 μm thick film obtained in the examples, etc. Next, according to JIS K7127, using the Shimadzu Corporation's universal testing machine "AG-X-5", the tensile modulus of elasticity (YM) (unit: MPa), elongation at break (EL) (unit: %), and tensile strength at break (TS) (unit: MPa) of the test pieces were measured under the conditions of a chuck distance of 50 mm, a tensile speed of 300 mm / min, and a temperature of 23°C.

[0148] (Puncture Energy (Puncture Resistance))

[0149] Using the Shimadzu Corporation's universal testing machine "AG-5kNX", in accordance with JIS Z1707, at -20°C, a needle with a tip shape of 1mmφ was pierced into the membrane sample at a speed of 50mm / min, and the energy required to penetrate until complete penetration was measured (hereinafter referred to as "piercing energy").

[0150] (Membrane impact strength (impact resistance))

[0151] The membrane impact strength at -20°C was determined using a membrane impact tester manufactured by Toyo Seiki Co., Ltd., in accordance with JIS P8134, under the condition that the spherical shape of the impact head is 1 inch φ.

[0152] (Internal haze (transparency))

[0153] Using a haze meter “HM-150” manufactured by Murakami Color Technology Research Institute Co., Ltd., in accordance with JIS K7136, the internal haze of the film (70 μm thick) prepared in the examples was measured in cyclohexanol and calculated by the following formula.

[0154] Internal haze (%) = 100 × (diffuse transmitted light) / (total transmitted light)

[0155] 〔raw material〕

[0156] The polymers used as raw materials in the examples are described below.

[0157] ·LLDPE-1:

[0158] Commercially available linear low-density polyethylene (MFR (190℃, 2.16kg load) 15g / 10min, density 914kg / m³ 3 )

[0159] LLDPE-2:

[0160] Commercially available linear low-density polyethylene (MFR (190℃, 2.16kg load) 19g / 10min, density 918kg / m³ 3 )

[0161] LLDPE-3:

[0162] Commercially available linear low-density polyethylene (MFR (190℃, 2.16kg load)) 3.4g / 10min, density 923kg / m³ 3 )

[0163] EBR-1:

[0164] Commercially available ethylene-1-butene copolymer (MFR (190℃, 2.16kg load) 0.5g / 10min, density 870kg / m³) 3 )

[0165] EBR-2:

[0166] Commercially available ethylene-1-butene copolymer (MFR (190℃, 2.16kg load) 35g / 10min, density 870kg / m³ 3 )

[0167] EBR-3:

[0168] Commercially available ethylene-1-butene copolymer (MFR (190℃, 2.16kg load) 3.6g / 10min, density 870kg / m³) 3 )

[0169] PA6:

[0170] Polyamide resin (Nylon 6) (Toray Corporation, AMILAN (registered trademark) CM1021XF, melting point 225°C)

[0171] ·EVOH:

[0172] Ethylene-vinyl alcohol resin (manufactured by KURARAY Co., Ltd., EVAL (registered trademark) F101A, structural unit content from ethylene 32 mol%, MFR (190℃, 2.16 kg load): 1.6 g / 10 min)

[0173] [Preparation of compatibilizer]

[0174] The following shows the preparation methods of the compatibilizers (Q-1) to (Q-5) used in the embodiments disclosed below.

[0175] [Preparation Example 1]

[0176] (Preparation of compatibilizer (Q-1))

[0177] A solution obtained by dissolving 150g of maleic anhydride (MAH) and 6g of PERHEXA (registered trademark) 25B (manufactured by Nippon Yushi Co., Ltd.) in acetone was mixed with 10kg of LL DPE-1 to obtain blend 1. Blend 1 was then fed into the feed hopper of a twin-screw extruder with a screw diameter of 32mm and an L / D ratio of 42, and extruded in a wire bundle at a resin temperature of 200°C, a screw speed of 240rpm, and a discharge rate of 12kg / hr. After the resulting wire bundle was thoroughly cooled, it was granulated to obtain compatibilizer (Q-1). The physical properties of compatibilizer (Q-1) are shown in Table 1.

[0178] (Preparation of compatibilizer (Q-2))

[0179] A solution obtained by dissolving 60 g of MAH and 2 g of PERHEXA 25B in acetone was mixed with 10 kg of the aforementioned LLDPE-2 to obtain blend 2. Blend 1 was then replaced with blend 2, and the same procedure as for compatibilizer (Q-1) was followed to obtain compatibilizer (Q-2). The properties of compatibilizer (Q-2) are shown in Table 1.

[0180] (Preparation of compatibilizer (Q-3))

[0181] A solution obtained by dissolving 50 g of MAH and 2 g of PERHEXA 25B in acetone was mixed with 10 kg of EBR-1 to obtain blend 3. Blend 1 was then replaced with blend 3, and the same procedure as for compatibilizer (Q-1) was followed to obtain compatibilizer (Q-3). The properties of compatibilizer (Q-3) are shown in Table 1.

[0182] (Preparation of compatibilizer (Q-4))

[0183] A solution obtained by dissolving 50 g of MAH and 2 g of PERHEXA 25B in acetone was mixed with 10 kg of EBR-2 to obtain blend 4. Blend 1 was then replaced with blend 4, and the same procedure as for compatibilizer (Q-1) was followed to obtain compatibilizer (Q-4). The properties of compatibilizer (Q-4) are shown in Table 1.

[0184] (Preparation of compatibilizer (Q-5))

[0185] A solution obtained by dissolving 50 g of MAH and 2 g of PERHEXA 25B in acetone was mixed with 10 kg of EBR-3 to obtain blend 5. Blend 1 was then replaced with blend 5, and the same procedure as for compatibilizer (Q-1) was followed to obtain compatibilizer (Q-5). The properties of compatibilizer (Q-5) are shown in Table 1.

[0186] [Table 1]

[0187] Table 1

[0188]

[0189] [Preparation of polar resin components]

[0190] The following shows the preparation method of the polar resin components (B-1) to (B-3) used in the embodiments disclosed below.

[0191] [Preparation of polar resin component (B-1)]

[0192] LLDPE-3, PA6, and compatibilizer (Q-1) were blended at a mass ratio of 70 / 29 / 1 as described in Table 2, and then fed into a single-screw extruder (L / D = 26, 40 mm φ) set to 250°C to prepare granules of the polar resin component (B-1). The obtained granules of the polar resin component (B-1) were dried at 80°C for 24 hours.

[0193] [Preparation of polar resin component (B-2)]

[0194] Instead of blending LLDPE-3, PA6, and compatibilizer (Q-1), LLDPE-3, E VOH, and compatibilizer (Q-1) were blended in a mass ratio of 90 / 8 / 2 as described in Table 2. Otherwise, the process was the same as for polar resin component (B-1) to obtain polar resin component (B-2).

[0195] [Preparation of polar resin component (B-3)]

[0196] Instead of blending 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 as described in Table 2. Otherwise, the process was the same as that for polar resin component (B-1) to obtain polar resin component (B-3).

[0197] [Table 2]

[0198] Table 2

[0199]

[0200] [Example 1]

[0201] (Manufacturing of laminated films)

[0202] The resin for the outer skin layer (polyethylene layer) and the polar resin composition for the intermediate layer (polar resin layer) shown below are supplied to each extruder. A casting die (die width 350 mm φ, die lip gap 1 mm) is used, and the resin temperature is set to 250°C. The extrusion rate of each extruder is set so that the thicknesses of the outer skin layer, intermediate layer, and outer skin layer are 10 μm / 50 μm / 10 μm respectively. A multilayer film with a thickness of 70 μm is obtained by co-extrusion molding. The molding speed is 4 m / min.

[0203] • Resin used in the epidermis;

[0204] LLDPE-3

[0205] • Polar resin composition for the intermediate layer;

[0206] A resin composition is obtained by blending LLDPE-3, polar resin component (R-1), and compatibilizer (Q-1) in a mass ratio of 20 / 60 / 20.

[0207] [Example 2]

[0208] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0209] [Example 3]

[0210] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0211] [Example 4]

[0212] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0213] [Example 5]

[0214] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0215] [Example 6]

[0216] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0217] [Example 7]

[0218] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0219] [Example 8]

[0220] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0221] [Example 9]

[0222] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0223] [Example 10]

[0224] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 3.

[0225] [Example 11]

[0226] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0227] [Example 12]

[0228] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0229] [Example 13]

[0230] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0231] [Example 14]

[0232] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0233] [Example 15]

[0234] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0235] [Example 16]

[0236] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0237] [Example 17]

[0238] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0239] [Example 18]

[0240] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0241] [Example 19]

[0242] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0243] [Example 20]

[0244] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 4.

[0245] [Example 21]

[0246] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 5.

[0247] [Example 22]

[0248] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 5.

[0249] [Example 23]

[0250] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 5.

[0251] [Example 24]

[0252] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 5.

[0253] [Example 25]

[0254] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 5.

[0255] [Comparative Example 1]

[0256] The polar resin composition used for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3 and polar resin component (B-1) at a mass ratio of 40 / 60. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 6.

[0257] [Comparative Example 2]

[0258] The polar resin composition used for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3 and polar resin component (B-2) at a mass ratio of 40 / 60. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 6.

[0259] [Comparative Example 3]

[0260] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 6.

[0261] [Comparative Example 4]

[0262] The polar resin composition used 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. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 6.

[0263] [Comparative Example 5]

[0264] The polar resin composition used for the intermediate layer was changed to a resin composition obtained by blending LLDPE-3 and polar resin component (B-3) at a mass ratio of 40 / 60. Otherwise, the procedure was the same as in Example 1 to obtain a multilayer film. The results are shown in Table 6.

[0265] [Comparative Example 6]

[0266] The polar resin composition used for the intermediate layer was changed to LLDPE-3, and otherwise the same procedure was followed as in Example 1 to obtain a multilayer film. The results are shown in Table 6.

[0267] [Table 3]

[0268]

[0269] [Table 4]

[0270]

[0271] [Table 5]

[0272] Table 5

[0273]

[0274] [Table 6]

[0275] Table 6

[0276]

Claims

1. A method for manufacturing a polar resin composition, wherein, The ethylene polymer (BA), polar resin (BB), modified ethylene-α-olefin copolymer (BC), and any additives are melt-blended and then granulated to prepare the polar resin (B). The total proportion of the ethylene polymer (BA), polar resin (BB), and modified ethylene-α-olefin copolymer (BC) is set to 100% by mass. 5-30% by weight of ethylene-based polymer (A), 40-85% by weight of polar resin component (B), and 10-40% by weight of modified ethylene-α-olefin copolymer (C) are blended. The modified ethylene-α-olefin copolymer (C) is obtained by modifying the ethylene-α-olefin copolymer (C0) with unsaturated carboxylic acids or their derivatives, and satisfies the following requirement (C-1), wherein the total proportion of the ethylene polymer (A), the polar resin component (B), and the copolymer (C) is set to 100% by mass. Requirement (C-1): The melt flow rate is 0.1~50 g / 10 min, and the melt flow rate is measured under conditions of 190℃ and 2.16 kg load. The ethylene-based polymer (BA) is selected from at least one of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ethylene-α-olefin copolymers with 3 or more carbon atoms. The ethylene-based polymer (A) is selected from at least one of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ethylene-α-olefin copolymers with 3 or more carbon atoms. The polar resin (BB) is at least one selected from the group consisting of polyamide resin and ethylene-vinyl alcohol copolymer.

2. The method for manufacturing the polar resin composition according to claim 1, wherein, The modified ethylene-α-olefin copolymer (C) satisfies the following requirement (C-2). Requirement (C-2): Density is 850~930 kg / m³ 3 .

3. The method for manufacturing the polar resin composition according to claim 1, wherein, The polyamide resin is an aliphatic polyamide resin.

4. A method for manufacturing laminated bodies, wherein, A polar resin composition is manufactured by the manufacturing method according to any one of claims 1 to 3, and then a polyethylene layer, a polar resin layer formed from the polar resin composition, and a polyethylene layer are sequentially stacked.

5. The method for manufacturing a laminate as described in claim 4, wherein, The membrane impact strength of the laminate, as measured according to JIS P8134, is above 20 kJ / m.

6. The method for manufacturing a laminate as described in claim 4, wherein, The internal haze of the laminate, as measured according to JIS K7136, is less than 10%.

7. A method for manufacturing recycled plastic materials, wherein, The polar resin composition is manufactured by the manufacturing method according to any one of claims 1 to 3, and the molded article of the polar resin composition is pulverized.

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