Resin composition, laminate, and packaging material

Abstract

The present invention addresses the problem of providing a resin composition capable of constituting a laminate or the like having excellent extrusion lamination processability, heat resistance, and flexibility. The solution is to provide a resin composition which contains the following four components at a prescribed content ratio: a propylene polymer (A) that satisfies the conditions (A-1) MFR of 0.1-60 g / 10 minutes, (A-2) density of 886-930 kg / m3, and (A-3) melting point of 130-170 DEG C, and a propylene polymer (B) that satisfies the conditions (A-3) MFR of 0.1-60 g / 10 minutes, (A-2) density of 886-930 kg / m3, and (A-3) melting point of 130-170 DEG C; a propylene-based polymer (B) that satisfies the following conditions (B-1): MFR of 0.1-60 g / 10 minutes, (B-2): density of 855-885 kg / m3, (B-3): melting point of 130-170 DEG C, and (B-4): Shore hardness A of 65-90; an ethylene-based polymer (C) having an MFR of 0.2 to 10 g / 10 minutes (C-1), a density of 855 to 913 kg / m3 (C-3), and a melting point of less than 130 DEG C (C-3); conditions (D-1) MFR of 0.1 to 50 g / 10 minutes and (D-2) a low density polyethylene (D) having a density of 914 to 935 kg / m3 are satisfied.

Description

Technical Field

[0001] The present invention relates to a resin composition, a laminate having a layer containing the above resin composition, and a packaging material. Background Art

[0002] Since the sealing film contained in the raw material of the packaging material needs to be given functions suitable for each use due to the diversity of its uses, the exploration of olefin resin compositions constituting the film has been actively promoted. Among them, the film using polypropylene is excellent in flexibility, heat resistance, etc. However, since the polypropylene film is poor in extrusion lamination processability, low-temperature sealability, anti-blocking property, etc., it needs to be improved. In particular, extrusion lamination, which is one of the methods for laminating the base material, is widely used as a technique for laminating a thin resin on a sheet-like base material, and improving the extrusion lamination processability in the polypropylene film is very important in the field of sealing films.

[0003] As a polypropylene film for packaging material use, for example, a resin composition containing polypropylene, an ethylene-based polymer, and low-density polyethylene is disclosed, and there are descriptions of various resin compositions having effects such as improving extrusion lamination processability (see Patent Document 1), exhibiting peelability (see Patent Document 2), and imparting low-temperature sealability (see Patent Document 3).

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Laid-Open No. 52-24553

[0007] Patent Document 2: Japanese Patent Laid-Open No. 2017-066305

[0008] Patent Document 3: Japanese Patent Laid-Open No. 56-40549 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] Generally, in order to impart extrusion lamination processability, a method of blending low-density polyethylene in polypropylene is often used. In Patent Document 1, a resin composition having improved extrusion lamination processability by further adding an ethylene-based polymer is disclosed, but it is difficult to maintain the heat resistance and flexibility, which are the characteristics of the polypropylene resin. In addition, the resin compositions described in Patent Documents 2 and 3 also have problems in heat resistance and flexibility.

[0011] An object of the present invention is to provide a resin composition that can form a laminate and a packaging material having excellent extrusion lamination processability and achieving an excellent balance in heat resistance and flexibility, focusing on the above problems of the polypropylene film.

[0012] Technical solutions for solving the problems

[0013] The present invention relates to, for example, the following [1] to [3].

[0014] [1] A resin composition containing:

[0015] An acrylic polymer (A) satisfying the following conditions (A-1) to (A-3),

[0016] An acrylic polymer (B) satisfying the following conditions (B-1) to (B-4),

[0017] An ethylene polymer (C) satisfying the following conditions (C-1) to (C-3), and

[0018] A low-density polyethylene (D) satisfying the following conditions (D-1) and (D-2),

[0019] wherein

[0020] The content of the above polymer (A) is in the range of 30.0% by mass or more and 95.0% by mass or less,

[0021] The content of the above polymer (B) is in the range of 2.0% by mass or more and 50.0% by mass or less,

[0022] The content of the above polymer (C) is in the range of 1.0% by mass or more and 20.0% by mass or less,

[0023] The content of the above low-density polyethylene (D) is in the range of 1.0% by mass or more and 20.0% by mass or less (wherein, the total content of the above polymer (A), the above polymer (B), the above polymer (C) and the above low-density polyethylene (D) is set to 100% by mass.).

[0024] (A-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.1 to 60 g / 10 min;

[0025] (A-2) The density measured according to JIS K 7112 is 886 to 930 kg / m 3 ;

[0026] (A-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is 130 to 170 °C;

[0027] (B-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.1 to 60 g / 10 min;

[0028] (B-2) The density measured according to JIS K 7112 is 855 to 885 kg / m 3 ;

[0029] (B-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is 130 to 170 °C;

[0030] (B-4) The Shore hardness A measured according to ASTM D2240 is 65 to 90;

[0031] (C-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.2 to 10 g / 10 min;

[0032] (C-2) The density measured according to JIS K 7112 is 855 to 913 kg / m 3 ;

[0033] (C-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is lower than 130 °C;

[0034] (D-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 190 °C and a load of 2.16 kg is 0.1 to 50 g / 10 min;

[0035] (D-2) The density measured according to JIS K 7112 is 914 to 935 kg / m 3 .

[0036] [2] A laminate having a layer containing the resin composition described in [1].

[0037] [3] A packaging material having a layer containing the resin composition described in [1].

[0038] Advantages of the Invention

[0039] In the resin composition of the present invention, by adding an ethylene-based polymer (C) and a propylene-based polymer (B) (different from the above-mentioned polypropylene resin) to the polypropylene resin (propylene-based polymer (A)) and low-density polyethylene (D), the compatibility between the above-mentioned polypropylene resin and low-density polyethylene can be improved, and the extrusion lamination processability of the laminate using this resin composition can be greatly improved. In addition, the laminate using the above resin composition can be an extrusion lamination with excellent balance in extrusion lamination processability, flexibility and heat resistance without significantly impairing the heat resistance of the properties derived from the propylene resin. Detailed Description of the Invention

[0040] Hereinafter, the resin composition of the present invention and the like will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of its gist. It should be noted that in the present invention, "~" includes the values at both ends. For example, "0.1 to 60 g / 10 min" includes the values of both 0.1 g / 10 min and 60 g / 10 min, indicating a range of "0.1 g / 10 min or more and 60 g / 10 min or less".

[0041] [Resin composition]

[0042] The resin composition of the present invention comprises an acrylic polymer (A), an acrylic polymer (B), an ethylene polymer (C), and a low-density polyethylene (D). The content of the above polymer (A) is 30.0% by mass or more and 95.0% by mass or less, the content of the above polymer (B) is 2.0% by mass or more and 50.0% by mass or less, the content of the above polymer (C) is 1.0% by mass or more and 20.0% by mass or less, and the content of the above low-density polyethylene (D) is 1.0% by mass or more and 20.0% by mass or less (wherein, the total content of the above polymer (A), the above polymer (B), the above polymer (C), and the above low-density polyethylene (D) is set to 100% by mass).

[0043] In addition, each of the above four components satisfies the following conditions.

[0044] (A) An acrylic polymer satisfying the following conditions (A-1) to (A-3)

[0045] (A-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.1 to 60 g / 10 min.

[0046] (A-2) The density measured according to JIS K 7112 is 886 to 930 kg / m 3 .

[0047] (A-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is 130 to 170 °C.

[0048] (B) An acrylic polymer satisfying the following conditions (B-1) to (B-4)

[0049] (B-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.1 to 60 g / 10 min.

[0050] (B-2) The density measured according to JIS K 7112 is 855 to 885 kg / m 3 .

[0051] (B-3) The melting point (Tm) determined by differential scanning calorimetry (DSC) is 130 to 170 °C.

[0052] (B-4) The Shore hardness A measured according to ASTM D2240 is 65 to 90.

[0053] (C) An ethylene-based polymer satisfying the following conditions (C-1) to (C-3)

[0054] (C-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.2 to 10 g / 10 min.

[0055] (C-2) The density measured according to JIS K 7112 is 855 to 913 kg / m 3 .

[0056] (C-3) The melting point (Tm) determined by differential scanning calorimetry (DSC) is lower than 130 °C.

[0057] (D) Low-density polyethylene satisfying the following conditions (D-1) and (D-2)

[0058] (D-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 190 °C and a load of 2.16 kg is 0.1 to 50 g / 10 min.

[0059] (D-2) The density measured according to JIS K 7112 is 914 to 935 kg / m 3 .

[0060] <Propylene-based polymer (A)>

[0061] The resin composition of the present invention contains a propylene-based polymer (A) satisfying the above conditions (A-1) to (A-3). Examples of the polymer (A) include, for example, a homopolymer of propylene, a random copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms, and a propylene block copolymer. A homopolymer of propylene or a random copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms is preferred. The polymer (A) used in the present invention may be one (co)polymer or two or more (co)polymers.

[0062] In the resin composition of the present invention, from the viewpoint of being able to impart heat resistance and stiffness to the sealing film, a homopolymer of propylene is particularly preferably used. On the other hand, from the viewpoint of being able to impart flexibility and transparency to the sealing film, a random copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms is particularly preferably used.

[0063] Examples of the α-olefin having 2 carbon atoms or 4 to 20 carbon atoms copolymerized with propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.

[0064] Among them, ethylene, 1-butene, 1-hexene, and 1-octene are preferred, and ethylene and 1-butene are more preferred.

[0065] (Condition (A-1))

[0066] The melt flow rate (MFR) of the above-mentioned polymer (A) measured under the conditions of a temperature of 230 °C and a load of 2.16 kg according to JIS K 7210 is 0.1 to 60 g / 10 min, preferably 0.2 to 55 g / 10 min, and more preferably 0.3 to 50 g / 10 min. By using the polymer (A) with an MFR within the above range, the extrusion lamination processability of the resin composition can be improved.

[0067] (Condition (A-2))

[0068] The density of the above-mentioned polymer (A) measured according to JIS K 7112 is 886 to 930 kg / m 3 , preferably 890 to 920 kg / m 3 , more preferably 900 to 915 kg / m 3 . By using the polymer (A) with a density within the above range, heat resistance and flexibility can be imparted to the film using the resin composition. It should be noted that the densities in the present invention are all values obtained by rounding the measured values to one decimal place.

[0069] (Condition (A-3))

[0070] The melting point (Tm) of the above-mentioned polymer (A) measured by differential scanning calorimetry (DSC) is 130 °C or higher and 170 °C or lower, preferably 131 °C or higher and 165 °C or lower, and more preferably 132 °C or higher and 160 °C or lower. By using the polymer (A) with a Tm within the above range, heat resistance and flexibility can be imparted to the film using the resin composition.

[0071] The melting point (Tm) of the above-mentioned polymer (A) is, for example, measured using a differential scanning calorimeter. Under a nitrogen atmosphere (20 mL / min), approximately 5 mg of the sample is heated to 200°C, held for 10 minutes, then cooled to -30°C at a rate of 10°C / min and held for 5 minutes. Subsequently, the temperature at the peak apex of the crystal melting peak when heating to 200°C at a rate of 10°C / min is taken as the melting point (Tm) of the polymer. It should be noted that in the case where multiple peaks are detected, the peak detected on the highest temperature side is adopted.

[0072] (Method for manufacturing polymer (A))

[0073] The above-mentioned polymer (A) can be manufactured by polymerizing a monomer through a known polymerization method such as gas phase method, bulk method, or slurry method in the presence of a known catalyst such as Ziegler-Natta catalyst or metallocene catalyst.

[0074] The above-mentioned polymer (A) is not particularly limited as long as it can satisfy the above conditions (A-1) to (A-3), and it can also be a commercially available product. As commercially available products, for example, the "Prime Polypro (registered trademark)" series manufactured by Prime Polymer Co., Ltd. can be cited.

[0075] <Propylene-based polymer (B)>

[0076] The resin composition of the present invention contains a propylene-based polymer (B) that satisfies the above conditions (B-1) to (B-4). As the above polymer (B), the same specific examples as the above polymer (A) can be cited, and preferably it is a homopolymer of propylene or a random copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms. The copolymer (B) used in the present invention can be one copolymer or two or more copolymers.

[0077] In the resin composition of the present invention, from the viewpoint of being able to impart heat resistance and stiffness to the sealing film, it is particularly preferred to use a homopolymer of propylene. On the other hand, from the viewpoint of being able to impart flexibility and transparency to the sealing film, it is particularly preferred to use a random copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms.

[0078] As the α-olefin having 2 or 4 to 20 carbon atoms copolymerized with propylene, the same α-olefins as those listed in the above polymer (A) can be cited, among which ethylene, 1-butene, 1-hexene, and 1-octene are preferred, and ethylene and 1-butene are more preferred.

[0079] (Condition (B-1))

[0080] The melt flow rate (MFR) of the above-mentioned polymer (B) measured according to JIS K 7210 at a temperature of 230°C and a load of 2.16 kg is 0.1 to 60 g / 10 min, preferably 0.2 to 55 g / 10 min, and more preferably 0.3 to 50 g / 10 min. By using the polymer (B) with an MFR within the above range, the extrusion lamination processability of the resin composition can be improved.

[0081] (Condition (B-2))

[0082] The density of the above-mentioned polymer (B) measured according to JIS K 7112 is 855 to 885 kg / m 3 , preferably 858 to 880 kg / m 3 , more preferably 860 to 875 kg / m 3 . By using the polymer (B) with a density within the above range, heat resistance and flexibility can be imparted to the film using the resin composition.

[0083] (Condition (B-3))

[0084] The melting point (Tm) of the above-mentioned polymer (B) measured by differential scanning calorimetry (DSC) is 130 to 170°C, preferably 131 to 165°C, and more preferably 132 to 160°C. By using the polymer (B) with a Tm within the above range, heat resistance and flexibility can be imparted to the film using the resin composition. It should be noted that the melting point (Tm) of the above-mentioned polymer (B) can be measured by the same method as the measurement method described in the above polymer (A).

[0085] (Condition (B-4))

[0086] The Shore hardness A of the above-mentioned polymer (B) measured according to ASTM D2240 is 65 to 90, preferably 67 to 89, and more preferably 70 to 88. By using the polymer (B) with a Shore hardness A within the above range, heat resistance and flexibility can be imparted to the film using the resin composition. It should be noted that the test method for the above Shore hardness A is as follows. After heating the sample to melt at 190 to 230°C, a test sample obtained by compression molding at a cooling temperature of 15 to 25°C is stored in an environment of 23 ± 2°C for more than 72 hours. Using a Type A tester, the value obtained when reading the scale immediately after the indenter contacts is taken as the Shore hardness A.

[0087] (Manufacturing method of polymer (B))

[0088] The above-mentioned polymer (B) can be produced by polymerizing a monomer by a known polymerization method such as gas phase method, bulk method, or slurry method in the presence of a known catalyst such as Ziegler-Natta catalyst or metallocene catalyst.

[0089] The above-mentioned polymer (B) is not particularly limited as long as it can satisfy the above conditions (B-1) to (B-4), and it can also be a commercially available product. As commercially available products, for example, "Tafmer (registered trademark) PN" series manufactured by Mitsui Chemicals, Inc. can be cited.

[0090] <Ethylene-based polymer (C)>

[0091] The resin composition of the present invention contains an ethylene-based polymer (C) that satisfies the above conditions (C-1) to (C-3). As the above polymer (C), for example, homopolymers of ethylene, random copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, and ethylene block copolymers can be cited. Preferably, homopolymers of ethylene or random copolymers of ethylene and α-olefins having 3 to 20 carbon atoms are used. The copolymer (C) used in the present invention can be one kind of copolymer or two or more kinds of copolymers.

[0092] In the resin composition of the present invention, from the viewpoint of being able to impart heat resistance and stiffness to the sealing film, it is particularly preferred to use homopolymers of ethylene. On the other hand, from the viewpoint of being able to impart flexibility and transparency to the sealing film, it is particularly preferred to use random copolymers of ethylene and α-olefins having 3 to 20 carbon atoms.

[0093] As the α-olefins having 3 to 20 carbon atoms copolymerized with ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. can be cited.

[0094] Among them, α-olefins having 3 to 10 carbon atoms are preferred, and α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene are more preferred.

[0095] (Condition (C-1))

[0096] The melt flow rate (MFR) of the above polymer (C) measured under the conditions of a temperature of 230 °C and a load of 2.16 kg according to JIS K 7210 is 0.2 to 10 g / 10 min, preferably 0.3 to 9 g / 10 min, and more preferably 0.4 to 8.5 g / 10 min. By using the polymer (B) with an MFR within the above range, the extrusion lamination processability of the resin composition can be improved.

[0097] (Condition (C-2))

[0098] The density of the above polymer (C) measured according to JIS K 7112 is 855 to 913 kg / m3 , preferably 856 to 910 kg / m 3 , more preferably 857 to 905 kg / m 3 . By using the polymer (C) having a density within the above range, the extrusion lamination processability of the resin composition can be improved.

[0099] (Condition (C-3))

[0100] The melting point (Tm) of the above polymer (C) measured by differential scanning calorimetry (DSC) is lower than 130 °C, preferably lower than 120 °C, and more preferably lower than 110 °C. By using the polymer (C) having a Tm within the above range, flexibility can be imparted to the film using the resin composition. It should be noted that the melting point (Tm) of the above polymer (C) can be measured by the same method as the measurement method described in the above polymer (A).

[0101] (Method for producing polymer (C))

[0102] The above polymer (C) can be produced by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.

[0103] The above polymer (C) is not particularly limited as long as it satisfies the above conditions (C-1) to (C-3), but it can also be a commercially available product. Examples of commercially available products include the "Tafmer P" series, "Tafmer (registered trademark) A" series manufactured by Mitsui Chemicals, Inc., the "EVOLUE (registered trademark)" series manufactured by Prime Polymer Co., Ltd., and the "SABIC (registered trademark) COHERE S" series manufactured by Saudi Basic Industries Corporation.

[0104] The above copolymer (C) can be produced by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. As a method for making the melting point, for example, lower than 120 °C, as an example, a method of controlling polymerization conditions such as the monomer feed amount can be cited, and by this method, a copolymer having a target melting point can be obtained.

[0105] <Low-density polyethylene (D)>

[0106] The resin composition of the present invention contains low-density polyethylene (D) that satisfies the above conditions (D-1) and (D-2). As the above low-density polyethylene (D), for example, homopolymers of ethylene, random copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, and ethylene block copolymers can be mentioned. A homopolymer of ethylene or a random copolymer of ethylene and α-olefins having 3 to 20 carbon atoms is preferred. The low-density polyethylene (D) used in the present invention may be one copolymer or two or more copolymers.

[0107] In the resin composition of the present invention, from the viewpoint of being able to impart heat resistance and stiffness to the sealing film, it is particularly preferred to use a homopolymer of ethylene. On the other hand, from the viewpoint of being able to impart flexibility and transparency to the sealing film, it is particularly preferred to use a random copolymer of ethylene and α-olefins having 3 to 20 carbon atoms.

[0108] As the α-olefins having 3 to 20 carbon atoms copolymerized with ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. can be mentioned.

[0109] Among them, ethylene, 1-butene, 1-hexene, and 1-octene are preferred, and ethylene, 1-butene, and 1-hexene are more preferred.

[0110] (Condition (D-1))

[0111] The melt flow rate (MFR) of the above low-density polyethylene (D) measured under the conditions of a temperature of 190 °C and a load of 2.16 kg according to JIS K 7210 is 0.1 to 50 g / 10 min, preferably 0.2 to 45 g / 10 min, and more preferably 0.3 to 40 g / 10 min. By using low-density polyethylene (D) with an MFR within the above range, the extrusion lamination processability of the resin composition can be improved.

[0112] (Condition (D-2))

[0113] The density of the above low-density polyethylene (D) measured according to JIS K 7112 is 914 to 935 kg / m 3 , preferably 915 to 933 kg / m 3 , more preferably 916 to 930 kg / m 3 . By using low-density polyethylene (D) with a density within the above range, the extrusion lamination processability of the resin composition can be improved.

[0114] (Manufacturing method of low-density polyethylene (D))

[0115] Generally speaking, polyethylene with a density within the above range is called low-density polyethylene. In the present invention, for example, high-pressure low-density polyethylene can be used. The high-pressure method refers to a method of polymerizing ethylene under the conditions of 1000-4000 atmospheres and about 100-350 °C using oxygen or a free radical initiator as a catalyst.

[0116] The above polymer (D) is not particularly limited as long as it is a polymer that satisfies the above conditions (D-1) and (D-2), but it can also be a commercially available product. As commercially available products, for example, the "Mirason (registered trademark)" series manufactured by DOW-MITSUIPOLYCHEMICALS can be cited.

[0117] In the polymers (A)-(C) and low-density polyethylene (D) used in the present invention, the α-olefins constituting these polymers can contain α-olefins derived from biomass. That is, the α-olefins constituting the polymer can be α-olefins only derived from biomass, or can contain both α-olefins derived from biomass and α-olefins derived from fossil fuels. The α-olefins derived from biomass refer to α-olefins formed from various renewable natural raw materials and their residues such as plant sources and animal sources including fungi, yeasts, algae, and bacteria, and contain 14C isotopes at a ratio of about 10 -12 and the biomass carbon concentration (unit: pMC) measured according to ASTM D 6866 is about 100 pMC. The α-olefins derived from biomass can be obtained by known methods.

[0118] From the viewpoint of being able to reduce the environmental burden (mainly able to cut greenhouse gases), it is preferable that the α-olefins constituting (A)-(C) and low-density polyethylene (D) used in the present invention contain α-olefins derived from biomass. If the polymer manufacturing conditions such as the polymerization catalyst, polymerization process, and polymerization temperature are the same, even if the raw material α-olefins contain α-olefins derived from biomass, except for containing 14C isotopes at a ratio of about 10 -12 -10 -14 and the molecular structure is the same as that of the propylene-based polymer formed from α-olefins derived from fossil fuels. Therefore, it can be considered that the performance is also not different.

[0119] In the polymers (A)-(C) and low-density polyethylene (D) used in the present invention, α-olefins derived from chemical recycling can also be contained in the α-olefins constituting the polymer. That is, the α-olefins constituting the polymer can contain only α-olefins derived from chemical recycling, or can contain α-olefins derived from chemical recycling and α-olefins derived from fossil fuels and / or α-olefins derived from biomass. The α-olefins derived from chemical recycling can be obtained by known methods.

[0120] From the viewpoint of reducing the environmental burden (mainly reducing waste), it is preferable that the propylene-based polymer according to the present invention contains α-olefins derived from chemical recycling. Even if the raw material monomers contain monomers derived from chemical recycling, the monomers derived from chemical recycling are monomers obtained by depolymerizing and thermally decomposing polymers such as waste plastics to restore them to monomer units such as propylene, and monomers produced using such monomers as raw materials. Therefore, if the polymer production conditions such as the polymerization catalyst, polymerization process, and polymerization temperature are the same, the molecular structure is the same as that of the polymer formed from monomers derived from fossil fuels. Therefore, it can be considered that the performance is also not different.

[0121] <Resin composition>

[0122] The resin composition of the present invention contains the above polymer (A), the above polymer (B), the above polymer (C), and the above low-density polyethylene (D). The content of each component will be described below, but the total content of the above four components is 100% by mass.

[0123] The content of the above polymer (A) is 30.0% by mass or more and 95.0% by mass or less, preferably 40.0% by mass or more and 93.0% by mass or less, more preferably 45.0% by mass or more and 90.0% by mass or less. When the content of polymer (A) is within the above range, the processability and heat resistance of the film are excellent.

[0124] The content of the above polymer (B) is 2.0% by mass or more and 50.0% by mass or less, preferably 3.0% by mass or more and 40.0% by mass or less, more preferably 4.0% by mass or more and 30.0% by mass or less. When the content of polymer (B) is within the above range, the flexibility and heat resistance of the film are excellent.

[0125] The content of the above polymer (C) is 1.0% by mass or more and 20.0% by mass or less, preferably 1.0% by mass or more and 15.0% by mass or less, more preferably 1.0% by mass or more and 10.0% by mass or less. When the content of polymer (C) is within the above range, the extrusion lamination processability of the resin composition and the heat resistance of the film are excellent.

[0126] The content of the above low-density polyethylene (D) is 1.0% by mass or more and 20.0% by mass or less, preferably 2.0% by mass or more and 15.0% by mass or less, more preferably 3.0% by mass or more and 10.0% by mass or less. When the content of low-density polyethylene (D) is within the above range, the extrusion lamination processability of the resin composition and the heat resistance of the film are excellent.

[0127] The melt flow rate (MFR) of the above resin composition measured according to JIS K 7210 under the conditions of a temperature of 230°C and a load of 2.16 kg is preferably 1.0 to 20 g / 10 min, more preferably 3.0 to 15 g / 10 min. The MFR of the resin composition within the above range means that the extrusion lamination processability of the resin composition is sufficient. Containing the above four components or more within the above range can increase the compatibility of each component and greatly improve the extrusion lamination processability.

[0128] The resin composition of the present invention can be produced by any method, and it is preferred to produce the above components by melt-kneading or the like. Specifically, for example, a method can be cited in which the above four components are charged into a drum mixer, a V-type mixer, a ribbon mixer, a Henschel mixer, etc. for kneading, and then melt-kneaded using a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc.

[0129] The resin composition of the present invention is useful as a sealing film, and a film can be produced by extrusion molding the resin composition of the present invention. In the present invention, the film refers to a sheet-shaped molded product having a thickness of 800 μm or less. The thickness of the film is preferably 1 to 300 μm, more preferably 3 to 200 μm.

[0130] Within the range not impairing the object of the present invention, the above sealing film may also contain resins other than the above polymers (A) to (C) and low-density polyethylene (D), tackifiers, weather stabilizers, heat stabilizers, antistatic agents, antislip agents, antiblocking agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants, nucleating agents, and other additives as needed.

[0131] [Laminate]

[0132] The laminate of the present invention is a layer containing the above resin composition. That is, in the laminate of the present invention, the above sealing film is used as a sealing layer. The laminate refers to a structure in which multiple layers are laminated. The laminate of the present invention has a structure in which the above sealing layer and a base material layer are laminated.

[0133] <Base material layer>

[0134] The resin composition constituting the above base material layer is preferably polypropylene. As the above polypropylene, homopolymers of propylene and copolymers having propylene as the main monomer can be cited. In the case of a copolymer, it can be a random copolymer or a block copolymer. As the monomer copolymerized with propylene, α-olefins having 2 or 4 to 20 carbon atoms, diene compounds, etc. can be listed. The above polypropylene contains 85 to 100 mol%, preferably 90 to 99.5 mol%, of structural units derived from propylene, and 0 to 15 mol%, preferably 0.5 to 10 mol%, of structural units derived from other monomers (wherein the total of the structural units derived from propylene and the structural units derived from other monomers is 100 mol%).

[0135] As the α-olefin having 2 or 4 to 20 carbon atoms copolymerized with propylene, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc. can be exemplified.

[0136] The polypropylene constituting the above base material layer can be produced by polymerizing monomers by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. The polypropylene contained in the above base material layer can be the same as or different from the polymer (A) or (B) contained in the resin composition constituting the above sealing layer.

[0137] The above base material layer can be composed of one layer or multiple layers.

[0138] Within the range not impairing the object of the present invention, the above base material layer can also contain additives such as resins other than polypropylene, tackifiers, weather stabilizers, heat stabilizers, antistatic agents, antislip agents, antiblocking agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants, nucleating agents, etc. as needed.

[0139] When the above sealing film is used as the sealing layer in the laminate of the present invention, its thickness is usually 3 to 30 μm, preferably 5 to 25 μm, and the thickness of the base material layer is usually 10 to 100 μm, preferably 20 to 50 μm. In the case of multiple sealing layers, it is preferable that the thickness of each sealing layer falls within the above range. In addition, the overall thickness of the laminate of the present invention is usually 20 to 100 μm, preferably 25 to 70 μm.

[0140] The laminate of the present invention can be produced by laminating the sealing layer and the base material layer by dry lamination, solventless lamination, sandwich lamination, etc., or by laminating the sealing layer and the base material layer by melt extrusion lamination. Since the extrusion lamination processability of the resin composition of the present invention is excellent, the laminate of the present invention is suitable for the method of laminating by melt extrusion lamination.

[0141] <Packaging material>

[0142] The layer containing the resin composition of the present invention can be well applied to packaging materials. The packaging material of the present invention has a layer containing the resin composition of the present invention, and the packaging material is excellent in processability, heat resistance, and flexibility.

[0143] The above-mentioned packaging material can be formed, for example, by a laminate having a layer containing the resin composition of the present invention. Specifically, the sealing layers of the above-mentioned laminate are arranged opposite to each other, or the sealing layer of the laminate is arranged opposite to another film, and then at least a part of the periphery of the laminate is heat-sealed from the outer surface side so as to form a desired container shape, whereby a packaging material can be manufactured. In addition, by heat-sealing the entire periphery, a sealed packaging material can be manufactured. This packaging material can be used in automatic packaging devices for solid components such as puffed snacks or bread, powders, or liquid materials.

[0144] In addition, the laminate or sheet is formed into a bowl-shaped container by pre-vacuum forming or pressure forming, etc., a container obtained by injection molding, etc., or a container formed from a paper substrate, etc., and then the laminate of the present invention is used as a lid material to cover it, and the upper part to the side part of the container is heat-sealed to obtain a container packaging the content. This container can be well applied to the packaging of instant noodles, sauces, jellies, puddings, puffed snacks, etc.

[0145] Examples

[0146] Examples for the laminate of the present invention are shown below and described in detail, but the present invention is not limited to these examples.

[0147] The materials used in the examples and comparative examples are as follows.

[0148] ): 6 g / 10 min, density (according to JIS K 7112): 868 g / m 3 , melting point: 160 °C, Shore hardness A (according to ASTM D2240): 84)

[0149] (b-2) Propylene-based elastomer: Tafmer (registered trademark) PN-2070 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 7 g / 10 min, density (according to JIS K 7112): 868 g / m 3 , melting point: 140 °C, Shore hardness A (according to ASTM D2240): 75)

[0150] (A) Propylene-based polymer

[0151] (a-1) Polypropylene resin: Prime Polypro (registered trademark) F113A (manufactured by Prime Polymer Co., Ltd., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 3 g / 10 min, density (according to JIS K 7112): 910 kg / m 3 , melting point: 159)

[0152] (a-2) Polypropylene resin: Prime Polypro (registered trademark) F327 (manufactured by Prime Polymer Co., Ltd., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 7 g / 10 min, density (according to JIS K 7112): 910 kg / m 3 , melting point: 137)

[0153] (a-3) Polypropylene resin: Prime Polypro (registered trademark) F-744NP (manufactured by Prime Polymer Co., Ltd., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 7 g / 10 min, density (according to JIS K 7112): 910 kg / m 3 , melting point: 134)

[0154] (B) Polypropylene-based polymer

[0155] (b-1) Polypropylene-based elastomer: Tafmer (registered trademark) PN-2060 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 6 g / 10 min, density (according to JIS K 7112): 868 kg / m 3 , melting point: 160, Shore hardness A (according to ASTM D2240): 84)

[0156] (b-2) Polypropylene-based elastomer: Tafmer (registered trademark) PN-2070 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 7 g / 10 min, density (according to JIS K 7112): 868 kg / m 3 , melting point: 140, Shore hardness A (according to ASTM D2240): 75)

[0157] (C) Ethylene-based polymer

[0158] (c-1) Ethylene-propylene random copolymer: Tafmer (registered trademark) P-0375 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 3 g / 10 min, density (according to JIS K 7112): 859 kg / m 3 ), melting point (Tm): 29 °C)

[0159] (c-2) Ethylene-propylene random copolymer: Tafmer (registered trademark) P-0775 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 0.6 g / 10 min, density (according to JIS K 7112): 858 kg / m 3 ), melting point: 43 °C)

[0160] (c-3) Ethylene-propylene random copolymer: Tafmer (registered trademark) P-0480 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 1.8 g / 10 min, density (according to JIS K 7112): 869 kg / m 3 , melting point (Tm): 43 °C)

[0161] (c-4) Ethylene-propylene random copolymer: Tafmer (registered trademark) P-0680 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 0.8 g / 10 min, density (according to JIS K 7112): 869 kg / m 3 , melting point (Tm): 44 °C)

[0162] (c-5) Ethylene-butene copolymer: Tafmer (registered trademark) A-0550S (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 0.9 g / 10 min, density (according to JIS K 7112): 861 kg / m 3 , melting point (Tm): below 50 °C)

[0163] (c-6) Ethylene-based polymer: Tafmer (registered trademark) A-0585X (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 0.9 g / 10 min, density (according to JIS K 7112): 885 kg / m 3 , melting point (Tm): 68 °C)

[0164] (c-7) Ethylene-butene copolymer: Tafmer (registered trademark) A-0250S (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 0.5 g / 10 min, density (according to JIS K 7112): 861 kg / m 3 , melting point (Tm): below 50 °C)

[0165] (c-8) Linear low-density polyethylene: EVOLUE (registered trademark) SP0510 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 2.3 g / 10 min, density (according to JIS K 7112): 904 kg / m 3 , melting point (Tm): 98 °C)

[0166] (c-9) Linear low-density polyethylene: SABIC (registered trademark) COHERE S100 (manufactured by Saudi Basic Industries Corporation, MFR (230 °C, 2.16 kg load, according to JIS K 7210): 1.8 g / 10 min, density (according to JIS K 7112): 900 kg / m 3 , melting point (Tm): 107 °C)

[0167] (c'-1) Ethylene-butene copolymer: Tafmer (registered trademark) A-6050 (manufactured by Mitsui Chemicals, Inc., MFR (230 °C, 2.16 kg load, according to JIS K 7210): 12 g / 10 min, density (according to JIS K 7112): 864 kg / m 3 , melting point (Tm): 68 °C)

[0168] (D) Low-density polyethylene

[0169] (d-1) Mirason (registered trademark) 11P (manufactured by DOW-MITSUIPOLYCHEMICALS, MFR (190 °C, 2.16 kg load, according to JIS K 7210): 7.2 g / 10 min, density (according to JIS K 7112): 917 kg / m 3 )

[0170] (d-2) Mirason (registered trademark) 16P (manufactured by DOW-MITSUIPOLYCHEMICALS, MFR (190 °C, 2.16 kg load, according to JIS K 7210): 3.7 g / 10 min, density (according to JIS K 7112): 923 kg / m 3 )

[0171] The melting point (Tm) of the polymer, and the processability, heat resistance, and flexibility of the film were measured by the following measurement methods.

[0172] [Melting point (Tm)]

[0173] Using a differential scanning calorimeter (DSC Pyris 1 manufactured by PerkinElmer), in a nitrogen atmosphere (20 mL / min), approximately 5 mg of the sample (polymer) was heated to 200 °C, held for 10 minutes, then cooled to -30 °C at 10 °C / min, held for 5 minutes, and then heated to 200 °C at 10 °C / min again. The temperature indicated by the peak apex of the crystallization melting peak at this time was taken as the melting point (Tm) of polymers (A) to (C).

[0174] [Processability]

[0175] From the die lip The temperature of the resin composition extruded from the T-die of an extruder with a certain diameter was set to 270 °C in a coating device, and a film was produced under the conditions of a cooling roll surface temperature of 60 °C, a die width of 680 mm, a die lip opening of 0.8 mm, and an air gap of 80 mm. The screw rotation speed was slowly increased, and the processing speed when either end of the molten film was sent about 5 mm and shaken was taken as the maximum pulling speed. It should be noted that when increasing the processing speed, the screw rotation speed was slowly increased, and the extrusion amount was adjusted while ensuring that the film thickness always reached 20 μm.

[0176] The processability during extrusion lamination was evaluated based on the following criteria.

[0177] ○: The maximum pulling speed is higher than 40 m / min.

[0178] ×: The maximum pulling speed is 40 m / min or less.

[0179] [Heat resistance]

[0180] Two 20-μm-thick films produced by the film-making method described in the above [Processability] were sealed at each temperature of 0.2 MPa, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 150 °C, 160 °C, or 170 °C for 1 second using a heat sealer to produce test pieces. For each test piece, a tensile testing machine (RTG-1310, manufactured by A&D Co., Ltd.) was used to measure the peel strength when peeling the heat-sealed part at a speed of 300 mm / min in the 180° direction with respect to the film surface, which was taken as the heat-seal strength at each temperature.

[0181] When the heat seal strength exceeds 1.5 N / m, heat-induced adhesion occurs. Therefore, the maximum temperature at a heat seal strength of 1.5 N / m or less is defined as the heat resistance temperature, and the heat resistance of the film was evaluated based on the following criteria.

[0182] ○: The heat resistance temperature is 120 °C or higher.

[0183] ×: The heat resistance temperature is lower than 120 °C.

[0184] [Flexibility]

[0185] Using the film with a thickness of 20 μm produced by the film-forming method described in the above [Processability], a short strip test piece was produced in accordance with JIS K 7161. Using a tensile testing machine (RTG-1310, manufactured by A&D Company, Limited), the elastic modulus of the film was measured in each direction at a speed of 300 mm / min at 180° to the film surface in the resin flow direction (MD) or the perpendicular direction (TD).

[0186] Based on the following criteria, the flexibility of the film was evaluated.

[0187] ○: The elastic modulus in each direction is less than 1200 MPa.

[0188] ×: The elastic modulus in each direction is 1200 MPa or more.

[0189] [Example 1]

[0190] After mixing various raw materials used in the amounts shown in Table 1-1 using a mixer (Henschel mixer FM-150, manufactured by Mitsui Miike Manufacturing Co., Ltd.), a 65 mm single-screw extruder (manufactured by TOMI Machinery Industry Co., Ltd.) was used to melt-knead the mixture at 200 °C at a discharge rate of 50 kg / h. The molten resin extruded from the strip die was pulled while being cooled and solidified using a water bath, and cut using a pelletizer to prepare a resin composition in the form of pellets with a diameter of approximately 3 mm.

[0191] Using the above resin composition, a film was produced by the film-forming method described in the above [Processability], and the processability, heat resistance, and flexibility were obtained by the above measurement methods. The results are shown in Table 1-1.

[0192] [Examples 2 to 13, Comparative Examples 1 to 4]

[0193] Except for changing the amounts of various raw materials used in the resin composition to the amounts shown in Table 1-1 or Table 1-2, pellet-shaped resin compositions were produced in the same manner as in Example 1. Using these resin compositions respectively, the processability, heat resistance, and flexibility were obtained by the above measurement methods. The results are shown in Table 1-1 or Table 1-2.

[0194] [Example 14]

[0195] After mixing various raw materials used in the compounding amounts shown in Table 1-2 using a mixer (Henschel mixer FM-150, manufactured by Mitsui Miike Co., Ltd.), melt-kneading was performed at 200 °C at a discharge rate of 50 kg / h using a twin-screw extruder (manufactured by Ikegai Corporation). The molten resin extruded from the strip die was drawn while being cooled and solidified using a water bath, and cut using a pelletizer to prepare a resin composition in the form of pellets with a diameter of approximately 3 mm.

[0196] Using the above resin composition, a film was produced by the film-forming method described in the above [Processability], and the processability, heat resistance, and flexibility were determined by the above measurement methods. The results are shown in Table 1-2.

[0197] [Example 15, Comparative Example 5]

[0198] A laminate was produced in the same manner as in Example 14, except that the various raw materials used in the resin composition were changed to the compounding amounts shown in Table 1-2. Using these laminates respectively, the processability, heat resistance, and flexibility were determined by the above measurement methods. The results are shown in Table 1-2.

[0199] [Table 1-1]

[0200] Table 1-1

[0201]

[0202] [Table 1-2]

[0203] Table 1-2

[0204]

Claims

1. A resin composition, characterized in that, Comprising: An acrylic polymer (A) satisfying the following conditions (A-1) to (A-3), An acrylic polymer (B) satisfying the following conditions (B-1) to (B-4), An ethylene polymer (C) satisfying the following conditions (C-1) to (C-3), and A low-density polyethylene (D) satisfying the following conditions (D-1) and (D-2), wherein, The content of the polymer (A) is in the range of 30.0% by mass or more and 95.0% by mass or less, The content of the polymer (B) is in the range of 2.0% by mass or more and 50.0% by mass or less, The content of the polymer (C) is in the range of 1.0% by mass or more and 20.0% by mass or less, The content of the low-density polyethylene (D) is in the range of 1.0% by mass or more and 20.0% by mass or less, wherein, the total content of the polymer (A), the polymer (B), the polymer (C) and the low-density polyethylene (D) is set to 100% by mass, (A-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.1 to 60 g / 10 min; (A-2) The density measured according to JIS K 7112 is 886 to 930 kg / m 3 ; (A-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is 130 to 170 °C; (B-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.1 to 60 g / 10 min; (B-2) The density measured according to JIS K 7112 is 855 to 885 kg / m 3 ; (B-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is 130 to 170 °C; (B-4) The Shore hardness A measured according to ASTM D2240 is 65 to 90; (C-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg is 0.2 to 10 g / 10 min; (C-2) The density measured according to JIS K 7112 is 855 to 913 kg / m 3 ; (C-3) The melting point (Tm) obtained by differential scanning calorimetry (DSC) is lower than 130 °C; (D-1) The melt flow rate measured according to JIS K 7210 under the conditions of a temperature of 190 °C and a load of 2.16 kg is 0.1 to 50 g / 10 min; (D-2) The density measured according to JIS K 7112 is 914 to 935 kg / m 3 .

2. A laminate, characterized in that It has a layer containing the resin composition according to claim 1.

3. A packaging material, characterized in that It has a layer containing the resin composition according to claim 1.

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