Resin composition and laminate having layer comprising the resin composition

Abstract

To provide a resin composition having further improved adhesiveness with a substrate layer when used as an adhesive layer in a laminate, and to also provide a laminate with superior interlayer adhesive strength including a layer composed of the resin composition.SOLUTION: The present invention relates to a resin composition and a laminate that includes the resin composition layer, the resin composition containing a propylene-based polymer (A) in a range of 5 to 70 wt.%, a soft propylene-based polymer (B) in a range of 30 to 95 wt.%, a propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer, in a range of 0.1 to 20 wt.%, a polyethylene (D) in a range of 0 to 20 wt.%, and an ethylene / α-olefin random copolymer (E) in a range of 1 to 30 wt.%, provided that the total amount of (A), (B), (C), (D), and (E) is 100 wt.%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition having further improved adhesiveness to a base material layer when used as an adhesive layer in a laminate, and a laminate having excellent interlayer adhesive strength including a layer composed of the resin composition.

Background Art

[0002] Multilayer films made of resins such as polyethylene terephthalate (PET), polypropylene (PP), ethylene-vinyl acetate copolymer (EVOH), polyamide (PA), and polyester are used as packaging films to impart gas barrier properties, water vapor barrier properties, and oil resistance. As a method for forming a multilayer film, when all layers are composed of a thermoplastic resin, molding is easy and the obtained multilayer film has excellent interlayer adhesiveness, so coextrusion molding is common.

[0003] On the other hand, for applications that require higher rigidity as a packaging film, a biaxially or uniaxially stretched film is used as the base material layer (base film), and for applications that require light shielding properties and high barrier properties, aluminum (Al) foil, aluminum vapor-deposited film, or a transparent vapor-deposited film made of aluminum oxide or silicon oxide is used as a layer of the multilayer film.

[0004] As one method for obtaining such a multilayer film having a biaxially or uniaxially stretched film, or an Al foil, Al vapor-deposited film, or transparent vapor-deposited film, an adhesive is applied to the bonding surface of a layer such as a pre-formed stretched film, Al foil, or Al vapor-deposited film and a layer such as a heat-sealable film, and then the films are laminated by dry lamination (dry lami).

[0005] However, dry lamination has problems such as the toxicity of residual solvents contained in the adhesive and the complexity of the process, so multilayer formation by extrusion lamination molding without using an adhesive is also carried out.

[0006] On the one hand, in order to improve the adhesion strength between layers, in the extrusion lamination molding, a method of extruding and laminating a molten adhesive resin onto the surface of a preformed stretched film, Al foil, Al vapor-deposited film, etc. is adopted. However, the adhesion between the two layers is not necessarily high, and problems such as peeling occurring at the interface between the base material layer and the adhesive resin layer may occur in the obtained multilayer film.

[0007] As a composition with excellent adhesion strength, a modified polyolefin composition for adhesion composed of a propylene-based polymer, a tackifier, a graft-modified propylene-based polymer, polyethylene, and an ethylene·α-olefin random copolymer (Patent Document 1), or a resin composition composed of a propylene-based resin containing a modified polypropylene modified with an unsaturated carboxylic acid or its derivative, a propylene-based copolymer, an ethylene·α-olefin copolymer, and a polyethylene-based resin (Patent Document 2) has been proposed.

[0008] However, since the modified polyolefin composition for adhesion proposed in Patent Document 1 contains a tackifier, it may generate smoke during extrusion molding, and when a multilayer film containing a layer made of the modified polyolefin composition for adhesion is used as a packaging material for oily food and drink, there is a risk that the tackifier may leak into the food and drink. Although the resin composition proposed in Patent Document 2 does not contain a tackifier, the adhesion strength is still insufficient, and depending on the application, an adhesive resin composition with more excellent adhesion strength is required.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] An object of the present invention is to obtain a resin composition having further improved adhesiveness to a base material layer when used as an adhesive layer in a laminate, and a laminate having excellent interlayer adhesive strength including a layer made of the resin composition.

Means for Solving the Problems

[0011] The present invention relates to 5 to 70% by weight of the following propylene-based polymer (A), 95 to 30% by weight of the following soft propylene-based polymer (B), 0.1 to 20% by weight of a propylene-based polymer (C) graft-modified with the following ethylenically unsaturated monomer, 0 to 20% by weight of the following polyethylene (D), and 1 to 30% by weight of the following ethylene·α-olefin random copolymer (E) in the range [wherein, the total amount of (A), (B), (C), (D), and (E) is 100% by weight].

[0012] Propylene-based polymer (A): A propylene-based polymer in which the content of structural units derived from propylene is in the range of 80 to 100 mol%, and the content of structural units derived from α-olefins other than ethylene and / or propylene is 20 mol% or less (wherein, the sum of the content of structural units derived from propylene and the content of structural units derived from α-olefins other than ethylene and / or propylene is 100 mol%).

[0013] The density measured by ASTM D1505 is 0.89 g / cm 3 or more. Soft propylene-based polymer (B): A soft propylene-based polymer containing structural units derived from propylene in the range of 50 to 95 mol% and structural units derived from α-olefins other than ethylene and / or propylene in the range of 5 to 50 mol% (however, the total content of the structural units derived from propylene and the structural units derived from α-olefins other than ethylene and / or propylene is 100 mol%).

[0014] The density measured by ASTM D1505 is less than 0.89 g / cm 3 . A propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer: A modified propylene-based polymer obtained by graft-modifying a propylene-based polymer (c) having a content of structural units derived from propylene in the range of 50 to 100 mol% and a content of structural units derived from α-olefins other than ethylene and / or propylene of 50 mol% or less (however, the total amount of the structural units derived from ethylene and the structural units derived from α-olefins other than ethylene and / or propylene is 100 mol%) with an ethylenically unsaturated monomer.

[0015] Polyethylene (D): The content of structural units derived from ethylene is in the range of 90 to 100 mol%. The density measured by ASTM D1505 is in the range of 0.90 to 0.94 g / cm 3 .

[0016] Ethylene-α-olefin random copolymer (E): The content of structural units derived from ethylene is in the range of 50 to 88 mol%, and the content of structural units derived from α-olefins is in the range of 12 to 50 mol% (however, the total amount of the structural units derived from ethylene and the structural units derived from α-olefins is 100 mol%).

[0017] The density measured by ASTM D1505 is less than 0.90 g / cm 3 . [Effect of the Invention]

[0018] Since the resin composition of the present invention has good extrusion moldability and excellent adhesive strength to a substrate, there are provided a resin composition capable of maintaining good adhesiveness to a substrate layer, and a laminate including a layer made of the resin composition.

Mode for Carrying Out the Invention

[0019] <Propylene-based polymer (A)> The propylene-based polymer (A), which is one of the components contained in the resin composition of the present invention, is a propylene-based polymer in which the content of structural units derived from propylene is in the range of 80 to 100 mol%, preferably 81 to 99 mol%, more preferably 82 to 98 mol%, and the content of structural units derived from α-olefins other than ethylene and / or propylene is in the range of 0 to 20 mol%, preferably 1 to 19 mol%, more preferably 2 to 18 mol% (however, the total amount of the content of structural units derived from propylene and the content of structural units derived from α-olefins other than ethylene and / or propylene is 100 mol%).), and the density measured by ASTM D1505 is 0.89 g / cm 3 or more, preferably 0.89 to 0.92 g / cm 3 , more preferably 0.89 to 0.91 g / cm 3 within the range. The resin composition of the present invention containing the propylene-based copolymer (A) having a density within the above range is excellent in the balance between flexibility and mechanical strength and also has a high adhesive force to other layers.

[0020] Specific examples of the propylene-based polymer (A) according to the present invention include a propylene homopolymer or a copolymer of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms.

[0021] Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. As at least one olefin selected from ethylene and α-olefins, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene are particularly preferred, and ethylene and α-olefins may be used singly or in combination of two or more, for example, ethylene and 1-butene may be used.

[0022] The copolymer of propylene and these α-olefins may be a random copolymer or a block copolymer. The structural units derived from these α-olefins can be contained in the copolymer of α-olefin and propylene in a proportion of 0 to 20 mol%, preferably 1 to 19 mol%.

[0023] The propylene-based polymer (A) according to the present invention preferably satisfies the following requirement (a). (a) The melting point (Tm) measured using a differential scanning calorimeter (DSC) is in the range of 120°C or higher, more preferably 120 to 170°C, still more preferably 130 to 165°C.

[0024] The melt flow rate (MFR) of the propylene-based polymer (A) according to the present invention, measured at 230°C under a load of 2.16 kg in accordance with ASTM D 1238, is usually in the range of 0.01 to 1000 g / 10 min, preferably 0.05 to 100 g / 10 min.

[0025] As the propylene-based polymer (A) according to the present invention, there are a propylene homopolymer excellent in heat resistance, a block copolymer excellent in the balance between heat resistance and flexibility, for example, a block copolymer (block PP) having an n-decane elution rubber component of usually 3 to 30% by mass, and a random copolymer (random PP) excellent in the balance between flexibility and transparency, for example, a random copolymer (random PP) having a melting point (Tm) measured using a differential scanning calorimeter (DSC) of 120°C or higher, preferably in the range of 130 to 150°C. These can be appropriately selected from among them to obtain the desired physical properties, or two or more types of propylene-based polymers (A) having different melting points and rigidities may be used in combination.

[0026] The propylene-based polymer (A) according to the present invention can be produced by polymerizing propylene or copolymerizing propylene and another α-olefin using a Ziegler catalyst system composed of a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, an organoaluminum compound, and an electron donor, or a metallocene catalyst system using a metallocene compound as one component of the catalyst.

[0027] <Soft propylene-based polymer (B)> The soft propylene-based polymer (B), which is one of the components contained in the resin composition of the present invention, contains a structural unit derived from propylene in an amount of 50 to 95 mol%, preferably 60 to 94 mol%, more preferably 70 to 93 mol%, and an α-olefin excluding ethylene and / or propylene, preferably an α-olefin having 4 to 20 carbon atoms, in an amount of 5 to 50 mol%, preferably 6 to 40 mol%, more preferably 7 to 30 mol% (provided that the total amount of the structural unit derived from propylene and the structural unit derived from the α-olefin excluding ethylene and / or propylene is 100 mol%). It is a soft propylene-based polymer having a density measured by ASTM D1505 of less than 0.89 g / cm 3 Preferably, it is 0.85 to 0.89 g / cm 3 More preferably, it is 0.86 to 0.88 g / cm 3It is within the range. The resin composition of the present invention containing the soft polypropylene-based polymer (B) with the density within the above range is excellent in the balance between flexibility and mechanical strength and also has a high adhesive force with other layers.

[0028] Examples of the α-olefin having 4 to 20 carbon atoms include 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.

[0029] As at least one olefin selected from ethylene and α-olefin, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are particularly preferable. Ethylene and α-olefin may be used alone or in combination of two or more, for example, ethylene and 1-butene may be used.

[0030] The soft polypropylene-based polymer (B) according to the present invention preferably satisfies the following requirement (b). (b) The melting point (Tm) measured using a differential scanning calorimeter (DSC) is 110°C or lower, preferably in the range of 40 to 110°C, more preferably in the range of 45 to 108°C, or no melting point is observed.

[0031] Here, the fact that no melting point is observed means that no crystal melting peak with a crystal melting heat of 1 J / g or more is observed in the range of -150 to 200°C in differential scanning calorimetry. When the melting point (Tm) satisfies the above conditions, it is preferable in terms of the compatibility and transparency with the polypropylene-based polymer.

[0032] Details of the melting point measurement conditions are as described in the Examples section below. The soft polypropylene-based polymer (B) according to the present invention usually has an MFR measured at 230°C and a load of 2.16 kg in accordance with ASTM D1238 in the range of 0.01 to 100 g / 10 min, preferably 0.01 to 30 g / 10 min.

[0033] The soft propylene-based polymer (B) according to the present invention preferably has a single glass transition temperature, and the glass transition temperature (Tg) measured using a differential scanning calorimeter (DSC) is usually in the range of -50 to 10°C, preferably -45 to 0°C, more preferably -40 to 0°C.

[0034] When the soft propylene-based polymer (B) has a glass transition temperature (Tg) within the above range, the packaging material having the resulting resin composition is preferable because it has excellent cold resistance, low-temperature characteristics, and exhibits stress absorption performance.

[0035] <Propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer> It is a propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer, which is one of the components contained in the resin composition of the present invention [hereinafter, may be abbreviated as "modified propylene-based polymer (C)"].

[0036] The modified propylene-based polymer (C) according to the present invention is a modified propylene-based polymer obtained by graft-modifying a propylene-based polymer (c) in which the content of structural units derived from propylene is 50 to 100 mol% and the content of structural units derived from α-olefins excluding ethylene and / or propylene is 50 mol% or less (however, the total amount of the content of structural units derived from ethylene and the content of structural units derived from α-olefins excluding ethylene and / or propylene is 100 mol%) with an ethylenically unsaturated monomer.

[0037] The propylene-based polymer (c) according to the present invention is a homopolymer of propylene and / or a propylene-α-olefin copolymer. Examples of the α-olefin include, but are not limited to, preferably ethylene and α-olefins having 4 to 20 carbon atoms, and these α-olefins may be used alone or in combination of two or more. Preferred α-olefins are ethylene and α-olefins having 4 to 10 carbon atoms, and particularly preferably ethylene and α-olefins having 4 to 8 carbon atoms. Here, in the propylene-α-olefin copolymer, the content of the structural unit derived from propylene is in the range of 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and the content of the structural unit derived from α-olefins excluding ethylene and / or propylene is in the range of 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol% (however, the total amount of the content of the structural unit derived from ethylene and the content of the structural unit derived from α-olefins excluding ethylene and / or propylene is 100 mol%).

[0038] The method for producing the propylene-based polymer (c) according to the present invention is not particularly limited, and examples thereof include well-known methods using well-known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0039] Examples of the ethylenically unsaturated monomer for graft-modifying the propylene-based polymer (c) according to the present invention, preferably an unsaturated carboxylic acid and / or its derivative, include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having a carboxylic acid group and an alkyl alcohol, unsaturated compounds having one or more anhydrous carboxylic acid groups, and the like.

[0040] Examples of the unsaturated group possessed by the unsaturated compound include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. The unsaturated carboxylic acid and / or its derivative can be used alone or in combination of two or more. Among these ethylenically unsaturated monomers, an unsaturated dicarboxylic acid or its acid anhydride is preferred, and maleic acid, nadic acid or their acid anhydrides are particularly preferred.

[0041] The method for grafting the propylene-based polymer (c) according to the present invention with an ethylenically unsaturated monomer is not particularly limited, and a conventionally known graft polymerization method such as a solution method or a melt kneading method can be employed. For example, a method of melting the propylene-based polymer (c), adding an ethylenically unsaturated monomer and subjecting it to a graft reaction, or a method of dissolving the propylene-based polymer (c) in a solvent to form a solution, adding an ethylenically unsaturated monomer thereto and subjecting it to a graft reaction, etc. are available.

[0042] Preferably, in the modified propylene-based polymer (C) according to the present invention, the amount of the structural unit derived from the ethylenically unsaturated monomer is preferably 0.01 to 5% by mass or 0.01 to 5.0% by mass in terms of the structural unit derived from maleic anhydride, and more preferably 0.05 to 3.5% by mass.

[0043] A resin composition containing the modified propylene-based polymer (C) in which the amount of the structural unit derived from the ethylenically unsaturated monomer is within the above range can provide a resin composition excellent in the balance between moldability and adhesiveness.

[0044] <Polyethylene (D)> Polyethylene (D), which is one of the components contained in the resin composition of the present invention, has a content of the structural unit derived from ethylene of 90 to 100 mol% and a density measured by ASTM D1505 of 0.90 to 0.94 g / cm 3 , preferably in the range of 0.91 to 0.93 g / cm 3 .

[0045] The polyethylene (D) according to the present invention is a homopolymer of ethylene or a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, which is manufactured and sold as high-pressure low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), or high-density polyethylene (HDPE), and is an ethylene-based polymer mainly composed of ethylene.

[0046] Examples of the α-olefins having 3 to 20 carbon atoms include propylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins may be used alone or in combination of two or more.

[0047] The MFR of the polyethylene (D) according to the present invention, measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238, is usually in the range of 0.1 to 10 g / 10 min, preferably 0.5 to 8 g / 10 min, and more preferably 1 to 6 g / 10 min. The resin composition of the present invention containing the polyethylene (D) having the MFR in the above range is excellent in the balance between flexibility and mechanical strength and also has high adhesion to other layers.

[0048] The production method of the polyethylene (D) according to the present invention is not particularly limited, and it can be produced by a well-known method using a well-known catalyst such as a high-pressure method, a Ziegler-Natta catalyst, or a metallocene-based catalyst. Furthermore, as long as it satisfies the moldability and has a strength sufficient to withstand use as a molded article, there are no particular restrictions on the stereoregularity or molecular weight. It is also possible to directly use commercially available resins.

[0049] <Ethylene-α-olefin random copolymer (E)> One of the components contained in the resin composition of the present invention, the ethylene·α-olefin random copolymer (E), has a content of structural units derived from ethylene in the range of 50 to 88 mol%, and a content of structural units derived from α-olefin in the range of 12 to 50 mol% (provided that the total amount of the content of structural units derived from ethylene and the content of structural units derived from α-olefin is 100 mol%). The density measured by ASTM D1505 is 0.90 g / cm 3 less than.

[0050] The α-olefin copolymerized with ethylene is preferably an α-olefin having 3 to 20 carbon atoms. Specifically, propylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. may be mentioned. These α-olefins may be used alone or in combination of two or more.

[0051] In the ethylene·α-olefin random copolymer (E) according to the present invention, the content of structural units derived from ethylene is preferably in the range of 50 to 88 mol%, more preferably in the range of 60 to 86 mol%, and even more preferably in the range of 60 to 85 mol%. The content of structural units derived from α-olefin is preferably in the range of 12 to 50 mol%, more preferably in the range of 14 to 40 mol%, and even more preferably in the range of 15 to 40 mol%.

[0052] The ethylene·α-olefin random copolymer (E) according to the present invention preferably has a density in the range of 0.85 to 0.90 g / cm 3 more preferably in the range of 0.86 to 0.90 g / cm 3 of the range.

[0053] The ethylene-α-olefin random copolymer (E) according to the present invention usually has an MFR measured at 190 °C under a load of 2.16 kg in accordance with ASTM D 1238 in the range of 0.1 to 100 g / 10 min, preferably in the range of 0.5 to 50 g / 10 min. The resin composition of the present invention containing the ethylene-α-olefin random copolymer (E) having an MFR in the above range is excellent in the balance between flexibility and mechanical strength and also has high adhesion to other layers.

[0054] The ethylene-α-olefin random copolymer (E) according to the present invention preferably satisfies the following requirement (e). (e) The melting point (Tm) measured using a differential scanning calorimeter (DSC) is 110 °C or lower, preferably in the range of 40 to 85 °C, more preferably in the range of 40 to 60 °C, or no melting point is observed.

[0055] Here, the fact that no melting point is observed means that no crystal melting peak with a crystal melting heat of 1 J / g or more is observed in the range of -150 to 200 °C in the differential scanning calorimetry. The resin composition of the present invention containing the ethylene-α-olefin random copolymer (E) having the melting point (Tm) satisfying the above conditions is excellent in the balance between flexibility and mechanical strength and also has high adhesion to other layers.

[0056] Details of the melting point measurement conditions are as described in the Examples section below. The production method of the ethylene-α-olefin random copolymer (E) according to the present invention is not particularly limited, and examples include well-known methods using well-known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0057] 《Resin Composition》 The resin composition of the present invention contains 5 to 70% by weight, preferably 5 to 50% by weight, more preferably 5 to 30% by weight of the above propylene-based polymer (A), and 30 to 95% by weight, preferably 35 to 95% by weight, more preferably 40 to 95% by weight of the above soft propylene-based polymer (B). 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, of the propylene-based polymer (C) graft-modified with the above ethylene unsaturated monomer, 0 to 20% by weight, preferably 1 to 20% by weight, more preferably 1 to 19% by weight, still more preferably 2 to 18% by weight, particularly preferably 10 to 18% by weight of the above polyethylene (D), and 1 to 30% by weight, preferably 2 to 29% by weight, more preferably 3 to 28% by weight of the above ethylene-α-olefin random copolymer (E) in the range [provided that the total amount of (A), (B), (C), (D), and (E) is 100% by weight].

[0058] By containing the above components (A), component (B), component (C), and component (E) within the above ranges, the resin composition of the present invention can obtain a resin composition excellent in the balance between moldability and adhesiveness.

[0059] By containing the above components (A), component (B), component (C), component (D) and component (E) within the above ranges, the resin composition of the present invention can obtain a resin composition excellent in the balance between moldability and adhesiveness.

[0060] Since the resin composition of the present invention is excellent in adhesiveness to other materials, it can also be used as a resin composition for adhesives, for example, a resin composition for hot melt adhesives. The resin composition of the present invention usually has an MFR measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238 in the range of 1 to 50 g / 10 min, preferably 5 to 30 g / 10 min. A resin composition having an MFR within the above range is excellent in the balance between moldability and adhesiveness.

[0061] The resin composition of the present invention may contain other thermoplastic resins such as other polyolefin resins, and resin additives (for example, stabilizers such as heat stabilizers and weather stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, fillers, mineral oil-based softeners, petroleum resins, waxes, etc.) as long as the object of the present invention is not impaired.

[0062] However, in the resin composition of the present invention, the content of the tackifier is preferably 0% by weight or more and less than 1% by weight, more preferably 0% by weight. Here, the content of the tackifier being 0% by weight means that the tackifier is not contained.

[0063] Examples of the tackifier include aliphatic hydrocarbon resins mainly made from C4 fractions, C5 fractions, mixtures thereof or any fractions thereof obtained by decomposition of petroleum, naphtha, etc., such as isoprene and 1,3-pentadiene in the C5 fraction; aromatic hydrocarbon resins mainly made from styrene derivatives and indenes in the C9 fraction obtained by decomposition of petroleum, naphtha, etc.; aliphatic-aromatic copolymerized hydrocarbon resins obtained by copolymerizing any fraction of C4·C5 fractions and C9 fractions; alicyclic hydrocarbon resins obtained by hydrogenating aromatic hydrocarbon resins; synthetic terpene hydrocarbon resins having a structure containing aliphatic, alicyclic and aromatic groups; terpene hydrocarbon resins made from α,β-pinene in turpentine oil; coumarone-indene hydrocarbon resins made from indene and styrenes in coal tar naphtha; low molecular weight styrene resins; and rosin hydrocarbon resins.

[0064] 《Method for Producing Resin Composition》 The olefin polymer composition of the present invention can be produced by melt-kneading and dry-blending the above-mentioned propylene polymer (A), the above-mentioned soft propylene polymer (B), the propylene polymer (C) graft-modified with the above-mentioned ethylenically unsaturated monomer, the above-mentioned polyethylene (D), and the above-mentioned ethylene-α-olefin random copolymer (E) in the amounts within the above ranges by various known methods.

[0065] 《Laminate》 The laminate of the present invention is a laminate including a layer made of the resin composition of the present invention. For example, it is a laminate in which a layer made of the resin composition of the present invention is laminated on at least one surface of a base material layer.

[0066] The laminate of the present invention is not particularly limited in the form of the base material layer, and may be in any form such as a film, a container, a tube, etc. As the base material used in the present invention, any polymer having a film-forming ability or paper, aluminum foil (aluminum foil), cellophane, etc. can be used. Examples of such polymers include high-density polyethylene, medium- and low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionomer, polypropylene, poly-1-butene, poly-4-methyl-1-pentene and other olefin copolymers, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile and other vinyl copolymers, nylon 6, nylon 66, nylon 7, nylon 10, nylon 1, nylon 12, nylon 610, polyamide such as polymetaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate and other polyesters, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate and the like.

[0067] The base material according to the present invention preferably has an inorganic compound vapor deposition layer or a metal layer on at least one side of the base material, because the resulting laminate is excellent in appearance and gas barrier properties. When using a base material having an inorganic vapor deposition layer or a metal layer on at least one side, the layer of the resin composition of the present invention may be in contact with the inorganic vapor deposition layer or the metal layer of the base material (that is, the surface of the base material layer on which the resin composition is laminated may have an inorganic vapor deposition layer or a metal layer), or may be in contact with the opposite side. However, when the inorganic vapor deposition layer is disposed on the outside, one or more protective layers can also be laminated.

[0068] As the protective layer, the polymers, paper, aluminum foil (aluminum foil), cellophane, etc. that can be used for the base material layer can be used, and for example, polyethylene terephthalate can be used.

[0069] The base material according to the present invention can be appropriately selected according to the purpose. For example, in the case of foods that are prone to corrosion of the packaged items, resins excellent in transparency, rigidity, and gas permeation resistance, such as polyamide, polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and polyester, are selected. For confectionery, fiber packaging, etc., polypropylene with good transparency, rigidity, and water permeation resistance can be selected as the outer layer. Further, if the base material is a polymer, it may be uniaxially or biaxially stretched. Further, the base material may contain a printing surface or a primer.

[0070] Examples of the inorganic compound used for inorganic compound vapor deposition include metals such as aluminum (Al), gold, and silver, and oxides such as aluminum oxide (aluminum oxide), silicon oxide, magnesium oxide, and indium-zinc oxide. Among them, aluminum, aluminum oxide, and silicon oxide are preferable in terms of price and gas barrier properties.

[0071] The thickness of the vapor deposition layer is not particularly limited, but is preferably in the range of 50 to 5000 Å, more preferably in the range of 300 to 2000 Å. As a method for obtaining a laminate using the resin composition of the present invention, for example, the resin composition of the present invention and one or two or more other resins constituting the laminate are melted in separate extruders in a pre-formed base material, and after melting, they are separately supplied to a die having a two-layer or three-layer or more structure, and co-extrusion laminated on the base material so that the resin composition of the present invention comes to the base material side, or a so-called sandwich lamination method in which the composition is melt-extruded between two pre-formed base materials can be mentioned. The die used here is a so-called flat die, and either a single-manifold type or a multi-manifold type using a black box may be used.

[0072] The thickness of the layer using the resin composition of the present invention is not particularly limited, but is preferably in the range of 0.1 to 1000 μm. The resin composition of the present invention exhibits excellent adhesion performance to a metal layer and a resin. Therefore, the laminate of the present invention can be suitably used for food packaging such as snacks and dry hoods.

Example

[0073] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The polymers and the like used in the examples and comparative examples are shown below. [Propylene-based polymer (A)] As the propylene-based polymer (A), a propylene / ethylene / 1-butene random copolymer (PP) was used.

[0074] Propylene content = 87 mol%, ethylene content = 7 mol%, 1-butene content = 6 mol%, MFR (230 °C, 2.16 kg load) = 7 g / 10 min, density = 0.90 g / cm 3 , melting point (Tm) = 141 °C. [Soft propylene-based polymer (B)] As the soft propylene-based polymer (B), a propylene / ethylene random copolymer (PER) was used.

[0075] Propylene content = 79 mol%, ethylene content = 21 mol%, MFR (230 °C, 2.16 kg load) = 20 g / 10 min, density = 0.86 g / cm 3 , melting point (Tm) = 109 °C, glass transition temperature (Tg) = -33 °C. [Propylene-based polymer graft-modified with ethylenically unsaturated monomer (C)] As the modified propylene-based polymer (C), maleic anhydride-modified propylene homopolymer (modified PP) was used.

[0076] MFR (230 °C, 2.16 kg load) = 100 g / 10 min, density = 0.90 g / cm 3 , maleic anhydride graft modification amount = 3.0 mass%. [Polyethylene (D)] As the polyethylene (D), the following high-pressure low-density polyethylene was used.

[0077] High-pressure low-density polyethylene (LDPE-1) MFR (at 190 °C, 2.16 kg load) = 4 g / 10 min, density = 0.92 g / cm 3 . High-pressure low-density polyethylene (LDPE-2) MFR (at 190 °C, 2.16 kg load) = 7 g / 10 min, density = 0.92 g / cm 3 . [Ethylene·α-olefin random copolymer (E)] As the ethylene·α-olefin random copolymer (E), the following ethylene·1-butene copolymers etc. were used.

[0078] Ethylene·1-butene copolymer (EBR-1) MFR (at 230 °C, 2.16 kg load) = 7 g / 10 min, density = 0.87 g / cm 3 , ethylene content = 85 mol%, 1-butene content = 15 mol%.

[0079] Ethylene·1-butene copolymer (EBR-2) MFR (at 230 °C, 2.16 kg load) = 70 g / 10 min, density = 0.87 g / cm 3 , ethylene content = 85 mol%, 1-butene content = 15 mol%.

[0080] Ethylene·1-butene copolymer (EBR-3) MFR (at 230 °C, 2.16 kg load) = 7 g / 10 min, density = 0.89 g / cm 3 , ethylene content = 90 mol% (82 wt%), 1-butene content = 10 mol% (18 wt%).

[0081] Ethylene·propylene copolymer (EPR) MFR (at 230 °C, 2.16 kg load) = 8 g / 10 min, density = 0.87 g / cm 3 , ethylene content = 80 mol%, propylene content = 20 mol%.

[0082] The physical properties of the polymers and resin compositions used in the examples and comparative examples were measured by the following methods. [Measurement method of physical properties] [Melt Flow Rate (MFR)] The MFR was measured in accordance with ASTM D1238. The propylene-based polymer (A), the soft propylene-based polymer (B), the propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer, the ethylene / α-olefin copolymer (E), and the resin composition were measured under a load of 2.16 kg at 230°C, and the polyethylene (D) was measured under a load of 2.16 kg at 190°C.

[0083] <Density> The density was measured in accordance with ASTM D1505 (density gradient column method). <Composition of the polymer> The contents of the structural units derived from ethylene and the structural units derived from α-olefin in the copolymer were 13 determined by C-NMR using the following apparatus and conditions.

[0084] The quantification of the ethylene and α-olefin contents was carried out using a JECX400P type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., with a mixed solvent of deuterated ortho-dichlorobenzene / deuterated benzene (80 / 20% by volume) as the solvent, a sample concentration of 60 mg / 0.6 mL, a measurement temperature of 120°C, and the observed nucleus was 13 C (100 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.62 μs (45° pulse), the repetition time was 5.5 s, the number of integrations was 8000 times, and the measurement was carried out under the condition that 29.73 ppm was used as the reference value of the chemical shift.

[0085] <Amount of structural units derived from ethylenically unsaturated monomer (graft modification amount)> The amount of structural units derived from the ethylenically unsaturated monomer (graft modification amount) was measured by an infrared absorption analyzer for the peak derived from the structural unit (1790 cm when maleic anhydride was used -1 ), and quantified using a calibration curve prepared in advance.

[0086] <Melting point (Tm), glass transition temperature (Tg)> The Tm and Tg of the raw materials of the following adhesives were measured by differential scanning calorimetry (DSC) using the following method.

[0087] Approximately 5 mg of the sample was sealed in an aluminum pan, and using a DSCRDC220 manufactured by Seiko Instruments Inc., the temperature was raised from room temperature to 200 °C at 10 °C / min, held at 200 °C for 5 minutes, then cooled from 200 °C to -100 °C at 10 °C / min, held at -100 °C for an additional 5 minutes, and then the melting point (Tm) and glass transition temperature (Tg) were determined from the endothermic curve when heating from -100 °C to 200 °C at 10 °C / min.

[0088] When multiple peaks were detected during the measurement, the peak temperature detected on the highest temperature side was defined as the melting point (Tm). [Example 1] [Manufacture of Resin Composition] Propylene-based polymer (A) PP: 26% by weight, soft propylene-based polymer (B) PER: 45% by weight, propylene-based polymer (C) modified PP graft-modified with an ethylenically unsaturated monomer: 4% by weight, and ethylene·α-olefin random copolymer (E) EBR-1: 25% by weight were melt-kneaded at 230 °C using a single-screw extruder to obtain a resin composition. The MFR of the obtained resin composition was 14 g / 10 min, and the density was 0.88 g / cm 3 It was.

[0089] [Manufacture of Laminate] Commercially available polypropylene (F329RA manufactured by Prime Polymer Co., Ltd., MFR (230°C): 27 g / 10 min) and the above resin composition were co-extruded at 230°C using a co-extrusion film forming machine having a screw with a diameter of 50 mm and an effective length L / D = 28 onto a T-die with a die temperature of 310°C. The extruded polypropylene and resin composition were laminated in the feed block of the T-die such that the polypropylene formed the outer layer and the resin composition formed the inner layer, and a film-like laminate with a thickness of approximately 40 μm where both the outer layer and the inner layer were 20 μm was brought into contact with the aluminum side of an aluminum PET film (aluminum layer: 20 μm / polyethylene terephthalate layer: 12 μm) in a molten state (extrusion lamination), and while cooling with a chill roll equipped with pinch rolls, it was drawn at a speed of 25 m / min to obtain a multilayer film for evaluating adhesive strength (polypropylene layer: 20 μm / resin composition layer: 20 μm / aluminum layer: 20 μm / polyethylene terephthalate layer 12 μm).

[0090] [Formability] During the formation of the laminate by the above co-extrusion coating molding, the presence or absence of ear flutter at the end of the molten film was evaluated.

[0091] [Interlayer Adhesion of Multilayer Film] After storing the laminate composed of the obtained multilayer film at room temperature for one week, the laminate was cut into 15 mm widths, and the interlayer adhesion between the aluminum layer and the resin composition layer was evaluated by the T-peel method. The evaluation was performed using a tensile testing machine in an atmosphere of 23°C. The crosshead speed was set at 300 mm / min.

[0092] The physical properties of the obtained resin composition and laminate are shown in Table 1. [Examples 2 to 9] An adhesive was prepared in the same manner as in Example 1 except that the formulation shown in Table 1 was changed, and a laminate was produced in the same manner as in Example 1. The physical properties of the obtained adhesive and laminate are shown in Table 1.

[0093] [Comparative Examples 1 to 6] An adhesive was prepared in the same manner as in Example 1 except that the formulation shown in Table 1 was changed, and a laminate was produced in the same manner as in Example 1.

[0094] The physical properties of the obtained resin composition and laminate are shown in Table 2.

[0095] [Table 1]

[0096] [Table 2] [Example 10] A resin composition was prepared in the same manner as in Example 1, except that an aluminum-deposited PET film (12 μm) was used instead of the aluminum PET film as the adherend, and the formulation shown in Table 2 was changed. A laminate was produced in the same manner as in Example 1.

[0097] The physical properties of the obtained resin composition and laminate are shown in Table 3.

[0098] [Table 3]

Claims

1. 5 to 70% by weight of the following propylene polymer (A), 30 to 95% by weight of the following soft propylene polymer (B), 0.1 to 20% by weight of a propylene-based polymer (C) graft-modified with the following ethylenically unsaturated monomer, 0 to 20% by weight of the following polyethylene (D), and 1 to 30% by weight of the following ethylene / α-olefin random copolymer (E): (wherein the total amount of (A), (B), (C), (D), and (E) is 100% by weight). Propylene-based polymer (A): A propylene-based polymer having a content of structural units derived from propylene in the range of 80 to 100 mol % and a content of structural units derived from ethylene and / or an α-olefin other than propylene in the range of 20 mol % or less (wherein the total of the content of structural units derived from propylene and the content of structural units derived from ethylene and / or an α-olefin other than propylene is taken as 100 mol %). The density measured by ASTM D1505 is 0.89 g / cm 3 That's all. Soft propylene polymer (B): A flexible propylene-based polymer containing 50 to 95 mol % of structural units derived from propylene and 5 to 50 mol % of structural units derived from ethylene and / or an α-olefin other than propylene (wherein the total content of the structural units derived from propylene and the structural units derived from an α-olefin other than ethylene and / or propylene is 100 mol %). The density measured by ASTM D1505 is 0.89 g / cm 3 is less than. Propylene-based polymer (C) graft-modified with ethylenically unsaturated monomer: A modified propylene-based polymer obtained by graft-modifying a propylene-based polymer (c) having a content of structural units derived from propylene of 50 to 100 mol % and a content of structural units derived from ethylene and / or an α-olefin other than propylene of 50 mol % or less (wherein the total content of structural units derived from ethylene and the content of structural units derived from an α-olefin other than propylene is taken as 100 mol %) with an ethylenically unsaturated monomer. Polyethylene (D): The content of structural units derived from ethylene is 90 to 100 mol %. Density measured by ASTM D1505 is 0.90 to 0.94 g / cm 3 is in the range. Ethylene / α-olefin random copolymer (E): The content of structural units derived from ethylene is in the range of 50 to 88 mol %, and the content of structural units derived from an α-olefin is in the range of 12 to 50 mol % (wherein the total content of structural units derived from ethylene and the content of structural units derived from an α-olefin is taken as 100 mol %). Density measured by ASTM D1505 is 0.90 g / cm 3 is less than.

2. 2. The resin composition according to claim 1, wherein at least a part of the propylene-based polymer (C) graft-modified with the ethylenically unsaturated monomer is graft-modified with an unsaturated carboxylic acid or a derivative thereof.

3. The resin composition according to claim 1 or 2, wherein the ethylene / α-olefin random copolymer (E) is an α-olefin having 3 to 8 carbon atoms.

4. The resin composition according to any one of claims 1 to 3, wherein the soft propylene polymer (B) is a propylene-ethylene copolymer.

5. The resin composition according to any one of claims 1 to 4, wherein the propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer has a structural unit derived from the ethylenically unsaturated monomer in an amount of 0.01 to 5.0 mass%.

6. The resin composition according to any one of claims 1 to 5, wherein the propylene-based polymer (C) graft-modified with an ethylenically unsaturated monomer is a propylene-based polymer (C) graft-modified with maleic anhydride.

7. The resin composition according to any one of claims 1 to 6, characterized in that the polyethylene (D) is contained in a range of 1 to 20% by weight (wherein the total amount of (A), (B), (C), (D), and (E) is taken as 100% by weight).

8. The resin composition according to any one of claims 1 to 7, which is a resin composition containing no tackifier.

9. The resin composition according to any one of claims 1 to 8, which is used as an adhesive.

10. A laminate comprising a layer made of the resin composition according to any one of claims 1 to 8.

11. The laminate according to claim 10, comprising a base layer and a layer made of the resin composition laminated on at least one surface of the base layer.

12. The laminate according to claim 11, wherein the substrate layer has an inorganic compound vapor deposition layer or a metal layer on the surface of the substrate layer on which the resin composition is laminated.

13. The laminate according to claim 12, wherein the inorganic compound vapor-deposited layer is an aluminum vapor-deposited layer.

14. The laminate according to claim 12, wherein the metal layer is an aluminum layer.

Images