Laminate and molded article

Abstract

To provide a laminate having a layer containing 4-methyl-1-pentene based polymer and a layer containing propylene-based copolymer, which has excellent adhesive strength between layers.SOLUTION: A laminate has a layer (I) containing 4-methyl-1-pentene based polymer (A), a layer (II) containing 4-methyl-1-pentene based polymer (B1) and propylene-based copolymer (B2), and a layer (III) containing propylene homopolymer (C) in this order in a thickness direction.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a laminate and a molded article. [Background technology]

[0002] Conventionally, containers made of propylene-based polymers, which are lightweight, strong, and have excellent scratch resistance, have been widely used. However, depending on the type of contents contained in the container, it may be difficult to wash off the contents adhering to the container. 4-methyl-1-pentene-based polymers have excellent releasability and are therefore used as materials constituting containers (see, for example, Patent Document 1). Contents adhering to the container can be easily washed off from containers made of 4-methyl-1-pentene-based polymers. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 11-198314 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have investigated the production of a container composed of a laminate having a layer containing a 4-methyl-1-pentene polymer and a layer containing a propylene polymer. However, in such a laminate, the adhesive strength between the layer containing the 4-methyl-1-pentene polymer and the layer containing the propylene polymer is not high, and delamination is likely to occur.

[0005] One aspect of the present disclosure aims to provide a laminate having a layer containing a 4-methyl-1-pentene polymer and a layer containing a propylene polymer, the laminate having excellent adhesive strength between the layers. [Means for solving the problem]

[0006] In one aspect, the laminate of the present disclosure has, in the thickness direction, a layer (I) containing a 4-methyl-1-pentene polymer (A), a layer (II) containing a 4-methyl-1-pentene polymer (B1) and a propylene copolymer (B2), and a layer (III) containing a propylene homopolymer (C) in this order. [Advantages of the Invention]

[0007] According to the present disclosure, it is possible to provide a laminate having a layer containing a 4-methyl-1-pentene polymer and a layer containing a propylene polymer, the laminate having excellent adhesive strength between the layers. [Brief Description of the Drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view of an embodiment of the laminate. [Embodiments for Carrying Out the Invention]

[0009] Hereinafter, embodiments of the present disclosure will be described in detail. Each component described in this specification can be used alone or in combination of two or more. In this specification, the term "polymer" may be used without particularly distinguishing between homopolymers and copolymers. That is, the term "polymer" is used to mean either a homopolymer or a copolymer.

[0010] In this specification, the numerical range n1 to n2 means n1 or more and n2 or less. Here, n1 and n2 are any numbers satisfying n1 < n2. In this specification, when a lower limit value and an upper limit value are each described for a certain element in plural, a numerical range formed by combining a value arbitrarily selected from the described lower limit values and a value arbitrarily selected from the described upper limit values is also regarded as being described. In addition, various monomers in the present disclosure may be derived from fossil raw materials or may be derived from biomass.

[0011] [Laminate] The laminate of the present disclosure comprises: A layer (I) containing a 4-methyl-1-pentene polymer (A); A layer (II) containing a 4-methyl-1-pentene polymer (B1) and a propylene copolymer (B2); a layer (III) containing a propylene homopolymer (C); in this order in the thickness direction.

[0012] Fig. 1 shows a schematic cross-sectional view of one embodiment of a laminate of the present disclosure. The laminate 1 of Fig. 1 has a layer (I) 10, a layer (II) 20, and a layer (III) 30 in this order in the thickness direction. The layer (II) 20 has a first surface 21 and a second surface 22 opposing the first surface 21. The layer (I) 10 is provided in contact with the first surface 21 of the layer (II) 20, and the layer (III) 30 is provided in contact with the second surface 22 of the layer (II) 20.

[0013] <Layer (I)> The layer (I) contains a 4-methyl-1-pentene polymer (A). The layer (I) containing the 4-methyl-1-pentene polymer (A) can effectively suppress adhesion of contents to the layer (I). In addition, the contents attached to the layer (I) can be effectively washed off. In one embodiment, the layer (I) is excellent in various physical properties such as heat resistance, chemical resistance, and transparency.

[0014] Examples of the 4-methyl-1-pentene polymer (A) include a homopolymer of 4-methyl-1-pentene and a copolymer (4-methyl-1-pentene copolymer) of 4-methyl-1-pentene and α-olefin (excluding 4-methyl-1-pentene). Among these, copolymers are preferred, and random copolymers are more preferred, that is, random copolymers of 4-methyl-1-pentene and α-olefin (excluding 4-methyl-1-pentene) are more preferred. The 4-methyl-1-pentene polymer (A) is also referred to as "component (A)".

[0015] Examples of α-olefins other than 4-methyl-1-pentene include α-olefins having 2 to 20 carbon atoms, such as linear α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene; and branched α-olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. Among these, from the viewpoint of copolymerizability with 4-methyl-1-pentene, linear α-olefins are preferred, and propylene, 1-decene, 1-hexadecene, and 1-octadecene are more preferred. The copolymer may have one or more types of structural units derived from α-olefins other than 4-methyl-1-pentene.

[0016] In the above copolymer as component (A), when the total of the content of the structural units derived from 4-methyl-1-pentene and the content of the structural units derived from α-olefins other than 4-methyl-1-pentene is taken as 100 mol%, the content of the structural units derived from 4-methyl-1-pentene is preferably 80 to 99.9 mol%, more preferably 85 to 99 mol%, and even more preferably 90 to 98 mol%, and the content of the structural units derived from α-olefins other than 4-methyl-1-pentene is preferably 0.1 to 20 mol%, more preferably 1 to 15 mol%, and even more preferably 2 to 10 mol%. Such a copolymer tends to be able to improve adhesion inhibition of contents and mechanical properties of the laminate. In this specification, the content of each structural unit in the copolymer is as follows: 13 It is measured by C-NMR.

[0017] Component (A) may further have a structural unit derived from a polymerizable compound other than 4-methyl-1-pentene and α-olefin (hereinafter also referred to as "other polymerizable compound"). Examples of the other polymerizable compound include cyclic olefins, aromatic vinyl compounds, functionalized vinyl compounds, non-conjugated polyenes, and conjugated dienes.

[0018] The number of carbon atoms in the cyclic olefin is preferably 3 to 20, more preferably 5 to 15. Examples of the cyclic olefin include cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.

[0019] Examples of aromatic vinyl compounds include mono- or polyalkylstyrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene.

[0020] Examples of functionalized vinyl compounds include hydroxyl group-containing olefins; unsaturated carboxylic acids such as (meth)acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, and 10-undecenoic acid; unsaturated amines such as allylamine, 5-hexenamine, and 6-heptenamine; (2,7-octadienyl)succinic anhydride, pentapropenylsuccinic anhydride, and anhydrides obtained from the above unsaturated carboxylic acids. unsaturated carboxylic acid anhydrides such as those mentioned above; unsaturated epoxy compounds such as 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, and 11-epoxy-1-undecene; and ethylenically unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane.

[0021] Examples of hydroxyl-containing olefins include terminally hydroxylated olefins. Examples of terminally hydroxylated olefins include linear hydroxylated α-olefins having preferably 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, such as vinyl alcohol, allyl alcohol, 1-butene hydroxide, 1-pentene hydroxide, 1-hexene hydroxide, 1-octene hydroxide, 1-decene hydroxide, 1-undecene hydroxide, 1-dodecene hydroxide, 1-tetradecene hydroxide, 1-hexadecene hydroxide, 1-octadecene hydroxide, and 1-eicosene hydroxide. and branched hydroxylated α-olefins preferably having 5 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, such as 3-methyl-1-butene hydroxide, 3-methyl-1-pentene hydroxide, 4-methyl-1-pentene hydroxide, 3-ethyl-1-pentene hydroxide, 4,4-dimethyl-1-pentene hydroxide, 4-methyl-1-hexene hydroxide, 4,4-dimethyl-1-hexene hydroxide, 4-ethyl-1-hexene hydroxide, and 3-ethyl-1-hexene hydroxide.

[0022] The number of carbon atoms of the non-conjugated polyene is preferably 5 to 20, more preferably 5 to 10. Examples of the non-conjugated polyene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene, and dicyclopentadiene. Dienes include, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinylidene-2-norbornene, 5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

[0023] The number of carbon atoms of the conjugated diene is preferably 4 to 20, more preferably 4 to 10. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene.

[0024] When component (A) has a structural unit derived from another polymerizable compound, component (A) may have one type of structural unit derived from another polymerizable compound, or may have two or more types. In component (A), the content of the structural unit derived from another polymerizable compound is preferably 10 mass % or less, more preferably 5 mass % or less, and even more preferably 3 mass % or less.

[0025] The melting point of the component (A) is preferably from 200 to 260° C., more preferably from 210 to 250° C., and further preferably from 220 to 240° C. The layer (I) containing such a component (A) tends to have excellent heat resistance.

[0026] In this specification, the melting point of a polymer is the melting peak temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K 7121:2012 (measuring the melting point after conditioning of a test piece according to 3.(2), cooling rate: 10°C / min, heating rate: 10°C / min). When multiple melting peaks are detected, the one with the maximum temperature is regarded as the melting point.

[0027] The melt flow rate (MFR) of component (A) is preferably 0.1 to 200 g / 10 min, more preferably 1 to 150 g / 10 min, even more preferably 3 to 100 g / 10 min, even more preferably 5 to 50 g / 10 min, and particularly preferably 10 to 30 g / 10 min. When the MFR is within the above range, the resin fluidity when forming the layer (I) containing component (A) and the strength and impact resistance of the laminate tend to be improved. The MFR of component (A) can be adjusted, for example, by allowing hydrogen to coexist in the reactor during the polymerization reaction. The MFR of component (A) is measured in accordance with JIS K 7210-1:2014 under conditions of a load of 5.0 kg and a temperature of 260°C.

[0028] The method for producing component (A) can be, for example, the method described in WO 2001 / 027124 and WO 2014 / 050817, etc. In the method for producing component (A), a conventionally known polymerization catalyst can be used. The layer (I) may contain one type of component (A) or two or more types of component (A).

[0029] The layer (I) may further contain a polymer other than the component (A). The layer (I) may contain an additive. Examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a slip agent, an antiblocking agent, a silane coupling agent, a nucleating agent, an antistatic agent, a dispersant, a foaming agent, a plasticizer, a flame retardant, a dye, and a pigment. The layer (I) may contain one type of additive, or two or more types of additives.

[0030] The content of component (A) in layer (I) is preferably more than 50 mass%, more preferably 60 mass% or more, even more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more or 95 mass% or more, based on the mass of layer (I).

[0031] The layer (I) can be formed, for example, using the component (A) or a composition thereof.

[0032] The thickness of the layer (I) is preferably 3 to 200 μm, more preferably 5 to 150 μm, even more preferably 10 to 100 μm, still more preferably 20 to 80 μm, and particularly preferably 30 to 70 μm. The ratio of the thickness of layer (I) to the thickness of the laminate of the present disclosure is preferably 10 to 55%, more preferably 15 to 50%, further preferably 20 to 45%, and particularly preferably 25 to 40%.

[0033] <Layer (II)> The layer (II) contains a 4-methyl-1-pentene polymer (B1) and a propylene copolymer (B2). The layer (II) is present between the layer (I) and the layer (III) and functions as an adhesive resin layer that bonds the layer (I) and the layer (III).

[0034] A layer made of a 4-methyl-1-pentene polymer tends to have low adhesive strength with a layer made of a propylene homopolymer, and interlayer delamination is likely to occur in a laminate having these layers. It is generally known that a certain adhesive strength can be obtained by providing a layer containing resin A and resin B between a layer made of a certain resin A and a layer made of a certain resin B. However, according to the study by the present inventors, it was found that sufficient adhesive strength cannot be obtained when a layer containing only 4-methyl-1-pentene polymer and propylene homopolymer is provided as an adhesive resin layer between a layer made of a 4-methyl-1-pentene polymer and a layer made of a propylene homopolymer.

[0035] The present inventors have studied the polymers constituting the adhesive resin layer and found that a layer containing a 4-methyl-1-pentene polymer and a propylene copolymer has excellent adhesion strength not only to a layer made of a propylene homopolymer but also to a layer made of a 4-methyl-1-pentene polymer. That is, in the laminate of the present disclosure, the layer (II) containing a 4-methyl-1-pentene polymer (B1) and a propylene copolymer (B2) has excellent adhesion strength to a layer (I) containing a 4-methyl-1-pentene polymer (A) and to a layer (III) containing a propylene homopolymer (C). Therefore, the occurrence of delamination is suppressed in the laminate of the present disclosure.

[0036] Examples of the 4-methyl-1-pentene polymer (B1) include a homopolymer of 4-methyl-1-pentene and a copolymer of 4-methyl-1-pentene and an α-olefin (excluding 4-methyl-1-pentene). The details of these are the same as those of the 4-methyl-1-pentene polymer (A), and the explanation will be omitted here. From the viewpoint of the adhesiveness of the layer (II), it is preferable that the component (B1) is a copolymer. The 4-methyl-1-pentene polymer (B1) is also referred to as "component (B1)".

[0037] The 4-methyl-1-pentene polymer (B1) contained in the layer (II) may be the same as or different from the 4-methyl-1-pentene polymer (A) contained in the layer (I).

[0038] Examples of the propylene copolymer (B2) include copolymers of propylene and α-olefins (excluding propylene). Examples of the α-olefins other than propylene include linear α-olefins such as ethylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 1-hexadecene, 1-heptadecene, 1-octadecene and 1-eicosene; branched α-olefins such as 4-methyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene and 3-ethyl-1-hexene, and other α-olefins having 2 to 20 carbon atoms. Among these, ethylene, 1-butene and 4-methyl-1-pentene are more preferable, and ethylene is further preferable. The copolymer may have one type or two or more types of structural units derived from α-olefins other than propylene. The propylene copolymer (B2) is also referred to as "component (B2)".

[0039] Component (B2) may be a propylene-based random copolymer or a propylene-based block copolymer, and specific examples of component (B2) include a propylene-ethylene copolymer, a propylene-1-butene copolymer, and a propylene-ethylene-1-butene copolymer.

[0040] In component (B2), when the sum of the content of the propylene-derived structural units and the content of the structural units derived from α-olefins other than propylene is taken as 100 mol%, the content of the propylene-derived structural units is preferably more than 50 mol%, more preferably 60 mol% or more, even more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 85 mol% or more or 90 mol% or more, and is preferably less than 100 mol%, more preferably 99.9 mol% or less, even more preferably 98 mol% or less, for example, more than 50 mol% and less than 100 mol%.

[0041] In component (B2), when the sum of the content of the structural units derived from propylene and the content of the structural units derived from α-olefins other than propylene is taken as 100 mol%, the content of the structural units derived from α-olefins other than propylene is preferably less than 50 mol%, more preferably 40 mol% or less, even more preferably 30 mol% or less, still more preferably 20 mol% or less, particularly preferably 15 mol% or less or 10 mol% or less, and is preferably more than 0 mol%, more preferably 0.1 mol% or more, even more preferably 2 mol% or more, for example more than 0 mol% and less than 50 mol%.

[0042] Component (B2) may further have the above-mentioned structural units derived from other polymerizable compounds. When component (B2) has structural units derived from other polymerizable compounds, component (B2) may have one type of structural unit derived from other polymerizable compounds, or may have two or more types. In component (B2), the content of structural units derived from other polymerizable compounds is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0043] The melting point of the component (B2) is preferably from 100 to 165°C, more preferably from 110 to 155°C, and even more preferably from 120 to 145°C.

[0044] The MFR of component (B2) is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 50 g / 10 min, even more preferably 0.5 to 30 g / 10 min, even more preferably 1 to 20 g / 10 min, and particularly preferably 2 to 10 g / 10 min. Such component (B2) has excellent miscibility with component (B1), and the layer (II) tends to exhibit high adhesiveness. The MFR of component (B2) is measured in accordance with JIS K 7210-1:2014 under conditions of a load of 2.16 kg and a temperature of 230°C.

[0045] The layer (II) may contain one type of component (B1), or two or more types. The layer (II) may contain one type or two or more types of the component (B2). The layer (II) may further contain a polymer other than the components (B1) and (B2). Layer (II) may further contain one or more of the above-mentioned additives.

[0046] The layer (II) can be formed, for example, by using an adhesive resin composition containing the components (B1) and (B2). The adhesive resin composition can be prepared, for example, by mixing the components (B1) and (B2) by a conventionally known method, and then melt-kneading. Specifically, the adhesive resin composition can be prepared by mixing the components (B1) and (B2) with a V blender, ribbon blender, Henschel mixer, tumbler blender, or the like, and then melt-kneading and granulating with a single-screw extruder, twin-screw extruder, or melt-kneading and pulverizing with a kneader, Banbury mixer, or the like.

[0047] The MFR of the adhesive resin composition is preferably 0.1 to 200 g / 10 min, more preferably 1 to 100 g / 10 min. The MFR of the adhesive resin composition is measured in accordance with JIS K 7210-1:2014 under conditions of a load of 5.0 kg and a temperature of 260° C. Such an adhesive resin composition tends to exhibit high adhesion to both the layer (I) and the layer (III).

[0048] In the layer (II) or adhesive resin composition, when the total content of the components (B1) and (B2) is 100 parts by mass, the content of the component (B1) is preferably 30 to 70 parts by mass, the content of the component (B2) is preferably 30 to 70 parts by mass, the content of the component (B1) is more preferably 35 to 65 parts by mass, the content of the component (B2) is more preferably 35 to 65 parts by mass, the content of the component (B1) is further preferably 40 to 60 parts by mass, the content of the component (B2) is further preferably 40 to 60 parts by mass, the content of the component (B1) is particularly preferably 45 to 55 parts by mass, and the content of the component (B2) is particularly preferably 45 to 55 parts by mass. Such a layer (II) and adhesive resin composition tend to be able to exhibit high adhesion to both the layer (I) and the layer (III).

[0049] In layer (II) or the adhesive resin composition, the total content of component (B1) and component (B2) is preferably more than 50 mass%, more preferably 60 mass% or more, even more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more or 95 mass% or more, based on the mass of layer (II) or the adhesive resin composition.

[0050] The thickness of the layer (II) is preferably 3 to 200 μm, more preferably 5 to 150 μm, even more preferably 10 to 100 μm, still more preferably 20 to 80 μm, and particularly preferably 30 to 70 μm. The ratio of the thickness of the layer (II) to the thickness of the laminate of the present disclosure is preferably 10 to 55%, more preferably 15 to 50%, further preferably 20 to 45%, and particularly preferably 25 to 40%.

[0051] <Layer (III)> The layer (III) contains a propylene homopolymer (C). The laminate having the layer (III) containing the propylene homopolymer (C) has excellent heat resistance and rigidity. Therefore, by using the laminate of the present disclosure, for example, a molded article having excellent heat resistance and rigidity can be produced.

[0052] The propylene homopolymer (C) is also referred to as "component (C)".

[0053] The melting point of component (C) is preferably 140° C. or higher, more preferably 145° C. or higher, even more preferably 150° C. or higher, and particularly preferably 155° C. or higher, and may be, for example, 175° C. or lower, or may be 170° C. or lower. Layer (III) containing such component (C) tends to have excellent heat resistance.

[0054] The MFR of component (C) is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 50 g / 10 min, even more preferably 0.5 to 30 g / 10 min, even more preferably 1 to 20 g / 10 min, and particularly preferably 2 to 10 g / 10 min. When the MFR is within the above range, the resin flowability when forming the layer (III) containing component (C) and the strength and impact resistance of the laminate tend to be improved. The MFR of component (C) is measured in accordance with JIS K 7210-1:2014 under conditions of a load of 2.16 kg and a temperature of 230°C.

[0055] The layer (III) may contain one type or two or more types of the component (C). The layer (III) may further contain a polymer other than the component (C). Layer (III) may further contain one or more of the above-mentioned additives.

[0056] The content of component (C) in layer (III) is preferably more than 50 mass%, more preferably 60 mass% or more, even more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more or 95 mass% or more, based on the mass of layer (III).

[0057] The layer (III) can be formed, for example, using the component (C) or a composition thereof.

[0058] The thickness of the layer (III) is preferably 3 to 200 μm, more preferably 5 to 150 μm, even more preferably 10 to 100 μm, still more preferably 20 to 80 μm, and particularly preferably 30 to 70 μm. The ratio of the thickness of the layer (III) to the thickness of the laminate of the present disclosure is preferably 10 to 55%, more preferably 15 to 50%, further preferably 20 to 45%, and particularly preferably 25 to 40%.

[0059] <Adhesion strength> In the laminate of the present disclosure, the adhesive strength between the layer (I) and the layer (II) is preferably 1.2 N / 15 mm or more, more preferably 1.5 N / 15 mm or more, and even more preferably 2.0 N / 15 mm or more. The upper limit of the adhesive strength is not particularly limited, but may be, for example, 30 N / 15 mm, 20 N / 15 mm, or 10 N / 15 mm. The adhesive strength is measured by a T-peel test under the conditions of a test speed of 300 mm / min, a peel width of 15 mm, and a temperature of 23°C. In one embodiment of the laminate of the present disclosure, the adhesive strength between the layer (II) and the layer (III) is higher than the adhesive strength between the layer (I) and the layer (II).

[0060] <Laminate thickness, manufacturing method, etc.> The thickness of the laminate of the present disclosure can be appropriately selected depending on its shape, size and application, and is, for example, 0.01 to 2.0 mm, preferably 0.02 to 1.0 mm, and more preferably 0.03 to 0.5 mm.

[0061] The laminate of the present disclosure can be produced, for example, by co-extrusion molding component (A) or a composition thereof, an adhesive resin composition, and component (C) or a composition thereof by a co-extrusion processing method such as a T-die casting method or an inflation method. The laminate of the present disclosure can be produced, for example, by bonding a film formed from component (A) or a composition thereof and a film formed from component (C) or a composition thereof by extrusion lamination using an adhesive resin composition. The laminate of the present disclosure can be produced, for example, by laminating films formed in advance from each polymer or composition thereof and press molding them.

[0062] [Molded body] The molded article of the present disclosure is composed of the above-described laminate of the present disclosure. Examples of the molded article include containers and tableware.

[0063] Examples of containers include containers for food and drink, storage containers, medical containers, cooler boxes, flower boxes, and transport containers. Examples of containers for food and drink include outdoor containers, lunch boxes, cups for instant food, food containers or food trays for fresh fish, meat, vegetables, tofu, side dishes, and lunch boxes, fish boxes for fish used in fresh fish markets, containers for dairy products such as milk, yogurt, and lactic acid bacteria drinks, containers for carbonated drinks and soft drinks, containers for alcoholic drinks such as beer and whiskey, and containers for eating and drinking for infants. Examples of containers for eating and drinking for infants include baby bottles, breast pump containers, mug bottles for infants, and containers for weaning food. Examples of containers for storage include containers for storing cosmetics, shampoos, rinses, conditioners, hand soaps, body soaps, detergents, fabric softeners, air fresheners, bleaches, deodorants, deodorants, insect repellents, medicines, pesticides, or blood. Examples of medical containers include medical syringes and measuring instruments. Examples of tableware include plates other than the above-mentioned food and drink containers.

[0064] In one embodiment, the container has a layer (I), a layer (II) and a layer (III) in this order from the inner layer facing the storage space of the container to the outer layer. In one embodiment, the layer in contact with the storage space of the container is layer (I). In one embodiment, the tableware has a layer (I), a layer (II) and a layer (III) in this order from the inner layer, which is the surface on which food or the like is placed, to the outer layer. In one embodiment, the surface on which food or the like is placed in the tableware is layer (I). Therefore, the contents or the like are less likely to adhere to the container. Therefore, even if the container contains highly sticky or adhesive contents or the like, the contents are less likely to adhere to the container. The same is true for tableware. In addition, the container of the present disclosure also has excellent interlayer adhesion in the laminate constituting the container. In the tableware of the present disclosure, the tableware also has excellent interlayer adhesion in the laminate constituting the tableware.

[0065] The molded body of the present disclosure can be produced, for example, by thermoforming the above-mentioned laminate using a mold having a predetermined shape. The molded body can be produced, for example, by heating the above-mentioned laminate to soften it, and then thermoforming it into the shape of the mold. Thermoforming methods include, for example, vacuum molding, pressure molding, and press molding. The molding temperature is not particularly limited as long as it is a temperature at which the resin can be softened sufficiently to mold the laminate.

[0066] The molded article of the present disclosure can be produced, for example, by blow molding the above-mentioned laminate using a mold having a predetermined shape. The molded article can be produced, for example, by blowing the co-extruded molten laminate into the shape of the mold. Examples of the blow molding method include direct blow molding.

[0067] [Aspects of the present disclosure] The present disclosure relates to, for example, the following [1] to [8]. [1] A laminate having, in the thickness direction, a layer (I) containing a 4-methyl-1-pentene polymer (A), a layer (II) containing a 4-methyl-1-pentene polymer (B1) and a propylene copolymer (B2), and a layer (III) containing a propylene homopolymer (C) in this order. [2] The laminate according to [1], wherein the layer (II) has a first surface and a second surface, the layer (I) is provided in contact with the first surface of the layer (II), and the layer (III) is provided in contact with the second surface of the layer (II). [3] The laminate according to [1] or [2], wherein in the layer (II), the content of the 4-methyl-1-pentene polymer (B1) is 30 to 70 parts by mass, and the content of the propylene-based copolymer (B2) is 30 to 70 parts by mass, relative to 100 parts by mass of the total content of the 4-methyl-1-pentene polymer (B1) and the propylene-based copolymer (B2). [4] The laminate according to any one of [1] to [3], wherein the content of the 4-methyl-1-pentene polymer (A) in the layer (I) is more than 50 mass% based on the mass of the layer (I). [5] The laminate according to any one of [1] to [4], wherein the content of the propylene homopolymer (C) in the layer (III) is more than 50 mass% based on the mass of the layer (III). [6] The laminate according to any one of [1] to [5], wherein the adhesive strength between the layer (I) and the layer (II) measured by a T-peel test (test speed: 300 mm / min, temperature: 23°C) is 1.2 N / 15 mm or more. [7] A molded article comprising the laminate according to any one of the above [1] to [6]. [8] The molded article according to [7] above, which is a container or tableware. EXAMPLES

[0068] Hereinafter, the laminate of the present disclosure will be described in more detail based on examples, but the laminate of the present disclosure is not limited to the following examples. In the following examples and comparative examples, "parts" refers to "parts by mass".

[0069] [Polymer] 4-Methyl-1-pentene copolymer Product name: TPX, Grade: MX002O, manufactured by Mitsui Chemicals, Inc. MFR(5.0kg, 260℃):21g / 10min, Melting point:224℃ Propylene homopolymer Product name: Prime Polypro, Grade: F113G, Made by Prime Polymer Co., Ltd. MFR(2.16kg, 230℃): 3.0g / 10min, Melting point: 163℃ Propylene copolymer Product name: Prime Polypro, Grade: F-730NV, Made by Prime Polymer Co., Ltd. MFR(2.16kg, 230℃):6.2g / 10min, Melting point:139℃ Propylene-ethylene copolymer Butene copolymer Product name: Toughmer, Grade: BL3110, manufactured by Mitsui Chemicals, Inc. Butene Copolymer

[0070] [Example 1] An adhesive resin composition containing 50 parts of 4-methyl-1-pentene copolymer (MX002O) and 50 parts of propylene copolymer (F-730NV) was prepared. The 4-methyl-1-pentene copolymer (MX002O), the adhesive resin composition, and the propylene homopolymer (F113G) were molded using a film molding machine to obtain a laminate having a thickness of 150 μm. The die temperature was set to 280° C., and the die clearance was set to 0.5 mm. The extrusion temperature of the 4-methyl-1-pentene copolymer was set to 280° C., the extrusion temperature of the adhesive resin composition was set to 280° C., and the extrusion temperature of the propylene homopolymer was set to 220° C.

[0071] The obtained laminate had a 50 μm thick layer formed from a 4-methyl-1-pentene copolymer, a 50 μm thick adhesive resin layer formed from the adhesive resin composition, and a 50 μm thick layer formed from a propylene homopolymer.

[0072] [Comparative Example 1] A 4-methyl-1-pentene copolymer (MX002O) and a propylene homopolymer (F113G) were molded using a film molding machine to obtain a laminate having a thickness of 150 μm. The die temperature was set to 280° C., and the die clearance was set to 0.5 mm. The extrusion temperature of the 4-methyl-1-pentene copolymer was set to 280° C., and the extrusion temperature of the propylene homopolymer was set to 220° C.

[0073] The resulting laminate had a 75 μm thick layer formed from the 4-methyl-1-pentene copolymer and a 75 μm thick layer formed from the propylene homopolymer.

[0074] [Comparative Example 2] An adhesive resin composition containing 50 parts of 4-methyl-1-pentene copolymer (MX002O) and 50 parts of propylene homopolymer (F113G) was prepared. The 4-methyl-1-pentene copolymer (MX002O), the adhesive resin composition, and the propylene homopolymer (F113G) were molded using a film molding machine to obtain a laminate having a thickness of 150 μm. The die temperature was set to 280° C., and the die clearance was set to 0.5 mm. The extrusion temperature of the 4-methyl-1-pentene copolymer was set to 280° C., the extrusion temperature of the adhesive resin composition was set to 280° C., and the extrusion temperature of the propylene homopolymer was set to 220° C.

[0075] The obtained laminate had a 50 μm thick layer formed from a 4-methyl-1-pentene copolymer, a 50 μm thick adhesive resin layer formed from the adhesive resin composition, and a 50 μm thick layer formed from a propylene homopolymer.

[0076] [Comparative Example 3] An adhesive resin composition containing 50 parts of 4-methyl-1-pentene copolymer (MX002O) and 50 parts of butene copolymer (BL3110) was prepared. The 4-methyl-1-pentene copolymer (MX002O), the adhesive resin composition, and a propylene homopolymer (F113G) were molded using a film molding machine to obtain a laminate having a thickness of 150 μm. The die temperature was set to 280° C., and the die clearance was set to 0.5 mm. The extrusion temperature of the 4-methyl-1-pentene copolymer was set to 280° C., the extrusion temperature of the adhesive resin composition was set to 280° C., and the extrusion temperature of the propylene homopolymer was set to 220° C.

[0077] The obtained laminate had a 50 μm thick layer formed from a 4-methyl-1-pentene copolymer, a 50 μm thick adhesive resin layer formed from the adhesive resin composition, and a 50 μm thick layer formed from a propylene homopolymer.

[0078] [Adhesive strength] For each laminate obtained in the examples and comparative examples, the interlayer adhesive strength was measured in accordance with JIS K 6854-3:1999 as follows. A T-peel test was performed using a 200X universal testing machine manufactured by Intesco Co., Ltd. under the conditions of a test speed of 300 mm / min, a peel width of 15 mm, and a temperature of 23°C. In Example 1, Comparative Example 2, and Comparative Example 3, the T-peel test was performed so that the peel interface was the interface between the layer formed from the 4-methyl-1-pentene copolymer and the layer formed from the adhesive resin composition. In Example 1, Comparative Example 2, and Comparative Example 3, the adhesive strength obtained by performing the T-peel test so that the peel interface was the interface between the layer formed from the 4-methyl-1-pentene copolymer and the layer formed from the adhesive resin composition was lower than the adhesive strength obtained by performing the T-peel test so that the peel interface was the interface between the layer formed from the propylene homopolymer and the layer formed from the adhesive resin composition.

[0079] [Table 1] [Explanation of symbols]

[0080] 1...Laminate 10...Layer (I) 20...layer (II) 21...first surface of layer (II) 22...Second surface of layer (II) 30...layer (III)

Claims

1. a layer (I) containing a 4-methyl-1-pentene polymer (A); a layer (II) containing a 4-methyl-1-pentene polymer (B1) and a propylene copolymer (B2); a layer (III) containing a propylene homopolymer (C); A laminate having the above in this order in the thickness direction.

2. 2. The laminate according to claim 1, wherein the layer (II) has a first surface and a second surface, the layer (I) is provided in contact with the first surface of the layer (II), and the layer (III) is provided in contact with the second surface of the layer (II).

3. 2. The laminate according to claim 1, wherein, in the layer (II), the content of the 4-methyl-1-pentene polymer (B1) is 30 to 70 parts by mass, and the content of the propylene-based copolymer (B2) is 30 to 70 parts by mass, relative to 100 parts by mass of the total content of the 4-methyl-1-pentene polymer (B1) and the propylene-based copolymer (B2).

4. 2. The laminate according to claim 1, wherein the content of the 4-methyl-1-pentene polymer (A) in the layer (I) is more than 50% by mass based on the mass of the layer (I).

5. The laminate according to claim 1, wherein the content of the propylene homopolymer (C) in the layer (III) is more than 50 mass% based on the mass of the layer (III).

6. 2. The laminate according to claim 1, wherein the adhesive strength between the layer (I) and the layer (II) measured by a T-peel test (test speed: 300 mm / min, temperature: 23° C.) is 1.2 N / 15 mm or more.

7. A molded article comprising the laminate according to any one of claims 1 to 6.

8. The molded article according to claim 7, which is a container or tableware.

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