Adhesive resin composition and laminate

Abstract

To provide an adhesive resin composition which is excellent in high speed moldability and long run property in a single layer or multilayer laminate molding, and has good adhesion between metal and a resin.SOLUTION: An adhesive resin composition contains the following components (A), (B-1), (B-2), (C) and (D). Component (A): modified propylene-based polymer having a melt flow rate (MFR) of 0.1-200 g / 10 min, component (B-1): propylene-based polymer having a melting point of 120°C or higher, component (B-2): propylene-based polymer having a melting point of lower than 120°C, and a percentage content of a propylene unit of 70-93 mol%, and a percentage content of an α-olefin unit other than ethylene and / or propylene of 30-7 mol%, component (C): ethylene-α-olefin copolymer having a percentage content of an ethylene unit of 60-95 mol% and a percentage content of an α-olefin unit other than ethylene of 40-5 mol%, and component (D): low density polyethylene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive resin composition that is excellent in high-speed formability and long-run properties in laminate molding and has good adhesion to metals and resins, and to a laminate using the adhesive resin composition. [Background technology]

[0002] Laminated laminates are widely used as exterior materials in applications where protecting the contents or maintaining quality is important or in fields where design is required, such as packaging materials for food and pharmaceuticals, outer packaging materials for secondary batteries, insulating films, decorative films, etc. Such laminates generally have substrate layers and resin layers made of different materials, and since the adhesive strength between the layers is poor, adhesive resin layers are interposed between the layers, and the layers are laminated together by the adhesive strength of the adhesive resin layer.

[0003] For laminating multiple layers such as a substrate layer / adhesive resin layer / resin layer, methods such as extrusion lamination, heat lamination, dry lamination, wet lamination, and co-extrusion are used. Among these, extrusion lamination is preferably used because it does not use organic solvents that have a high environmental impact, has high production speed, can laminate coatings over a wide area, and has a uniform coating thickness.

[0004] However, in extrusion lamination, a molten material containing an adhesive resin layer is laminated at high speed onto the surface of an already solidified substrate layer, so the adhesive strength between the substrate layer and the adhesive resin layer is not necessarily high. Here, the molten material containing the adhesive resin layer is, for example, a single layer of an adhesive resin composition or a multi-layer of an adhesive resin composition and other resins. As a result, the resulting laminate has problems such as peeling at the interface between the substrate layer and the adhesive resin layer. In contrast, if the extrusion speed during extrusion lamination is slowed down in order to improve the adhesion between the substrate layer and the adhesive resin layer, the high-speed formability that is a characteristic of extrusion lamination is significantly impaired.

[0005] Patent Document 1 discloses an adhesive resin composition that solves these problems and has good adhesion to a substrate layer and is suitable for high-speed extrusion lamination. The adhesive resin composition contains a modified propylene polymer (A), a propylene polymer (B) that satisfies certain conditions (an MFR of 5 to 30 g / 10 min measured at 230°C under a load of 2.16 kg and a heat of fusion of 20 mJ / mg or less, determined from an integrated value over the range of 80 to 170°C in DSC), and a low-density polyethylene (C) in specific proportions, and has an unsaturated carboxylic acid component content of 0.1% by mass or more. Furthermore, Patent Document 2 describes a modified polypropylene composition containing the following components (A) to (D) in specific proportions as an adhesive resin composition that has excellent high-speed extrusion laminate moldability, and when used as an adhesive layer in a laminate, has good adhesion to a base layer, and can maintain good adhesion to the base layer even under high-temperature and high-humidity environments. Component (A): Polypropylene resin containing the following component (a): Component (a): A modified polypropylene resin modified with an unsaturated carboxylic acid or its derivative. polypropylene Component (B): A copolymer containing 80 to 95% by weight of monomer units based on propylene, ethylene, and and / or the content of monomer units based on α-olefins other than propylene is 20 to 5% by weight Propylene copolymer (however, the content of propylene-based monomer units and ethylene and / or the total content of monomer units based on α-olefins other than propylene is 10 0% by weight.) Component (C): A copolymer having an ethylene-based monomer unit content of 76 to 90% by weight and an α-olefin copolymer. Ethylene-α-olefin copolymers with a content of 24-10% by weight of monomer units based on ethylene. (However, the content of ethylene-based monomer units and α-olefin-based monomer units The total of the contents of is 100% by weight.) Component (D): Polyethylene resin [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-135488 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-188662 Summary of the Invention [Problem to be solved by the invention]

[0007] When adhesive resin compositions are melt-molded at high temperatures to improve their adhesion to metals, resins, etc., the resin deteriorates, resulting in the formation of discoloration (thermal discoloration or carbonization of the adhesive resin composition) and lumps (crosslinking of the adhesive resin composition), which significantly impair the appearance of the resulting laminate. Furthermore, at high temperatures, thermal stability decreases, and discoloration forms on the lip of the extruder or the outlet of the molten resin film, called a T-die connected to the extruder, making it impossible to perform high-temperature melt molding continuously over long periods of time, resulting in a problem of poor long-run performance.

[0008] In extrusion lamination molding using a T-die, the melt containing the adhesive resin layer extruded from the T-die is stretched in the air gap between the T-die exit and the cooling roll, resulting in a neck-in phenomenon in which the width of the melt narrows. As a result, the thickness of the edges of the melt becomes thicker than that of the center. If the neck-in of the adhesive resin composition contained in the melt is large, not only will a laminate with a uniform thickness not be obtained, but the laminate may also become misaligned or wrinkled during winding. Furthermore, the amount of laminate that needs to be trimmed increases, resulting in poor yield and increased processing problems such as edge folds and cuts. In order to improve neck-in, a technique of improving the melt elasticity of the adhesive resin composition is often used. However, increasing the melt elasticity can cause the problem of the molten material breaking when stretched. The limit take-up speed at which the molten material breaks when stretched is called draw-down, and an adhesive resin composition with a small draw-down, i.e., an adhesive resin composition with poor draw-down properties, has poor productivity. Therefore, an adhesive resin composition that satisfies both neck-in and draw-down properties, i.e., good high-speed moldability, is required.

[0009] Regarding these required properties, the resin composition described in Patent Document 1 has excellent adhesion to the substrate layer in a laminate obtained by high-speed molding, but may have poor long-run properties. Also, the resin composition described in Patent Document 2 has excellent adhesion to the substrate layer in a laminate obtained by high-speed molding and has small neck-in during high-speed molding, but has poor drawdown properties, and both have room for improvement.

[0010] An object of the present invention is to provide an adhesive resin composition that is excellent in high-speed formability and long-run properties in single-layer or multi-layer laminate molding and has good adhesion to metals and resins, and a laminate using the adhesive resin composition. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that the above-mentioned problems can be solved by an adhesive resin composition containing: component (A): a modified propylene polymer having a melt flow rate (MFR; JIS K7210, 180°C, 2.16 kg load) of 0.1 to 200 g / 10 min; component (B-1): a propylene polymer having a melting point of 120°C or higher as measured by DSC; component (B-2): a propylene polymer having a melting point of less than 120°C as measured by DSC and having a content of 70 to 93 mol% of monomer units based on propylene and a content of 30 to 7 mol% of monomer units based on ethylene and / or an α-olefin other than propylene; component (C): an ethylene-α-olefin copolymer having a content of 60 to 95 mol% of monomer units based on ethylene and a content of 40 to 5 mol% of monomer units based on an α-olefin other than ethylene; and component (D): a low-density polyethylene, thereby completing the present invention.

[0012] That is, the present invention provides the following.

[0013] [1] An adhesive resin composition comprising the following components (A), (B-1), (B-2), (C) and (D): Component (A): A modified propylene polymer having a melt flow rate (MFR; JIS K7210, 180°C, 2.16 kg load) of 0.1 to 200 g / 10 min. Component (B-1): A propylene polymer having a melting point of 120°C or higher as measured by DSC. Component (B-2): A propylene-based polymer having a melting point of less than 120°C as measured by DSC, a content of monomer units based on propylene of 70 to 93 mol%, and a content of monomer units based on ethylene and / or an α-olefin other than propylene of 30 to 7 mol%. Component (C): Ethylene-α-olefin copolymer having a content of ethylene-based monomer units of 60 to 95 mol% and a content of monomer units based on α-olefins other than ethylene of 40 to 5 mol%. Component (D): Low-density polyethylene

[0014] [2] The adhesive resin composition according to [1], wherein the component (A) is a modified propylene polymer that satisfies the following conditions 1 and 2: Condition 1: A modified propylene polymer modified with an unsaturated carboxylic acid and / or a derivative thereof, the modification rate being 0.1 to 2.0% by mass Condition 2: Melting point measured by DSC is 60 to 170°C

[0015] [3] The adhesive resin composition according to [1] or [2], containing 15 to 49 mass% of component (B-1), 15 to 49 mass% of component (B-2), and 15 to 49 mass% of component (C), relative to 100 mass% of the total of components (B-1), (B-2), and (C).

[0016] [4] The adhesive resin composition according to any one of [1] to [3], wherein the content of component (A) is 10 to 60 mass% relative to 100 mass% of the total of components (A), (B-1), (B-2), (C) and (D).

[0017] [5] The adhesive resin composition according to any one of [1] to [4], wherein the propylene polymer of component (B-1) has an MFR (JIS K7210, 230°C, 2.16 kg load) of 0.5 to 50 g / 10 min.

[0018] [6] The adhesive resin composition according to any one of [1] to [5], wherein the propylene polymer of component (B-2) has an MFR (JIS K7210, 230°C, 2.16 kg load) of 0.5 to 50 g / 10 min.

[0019] [7] The ethylene-α-olefin copolymer of component (C) has an MFR (JIS K7210, 190°C, 2.16 kg load) of 0.5 to 50 g / 10 min and a density (JIS K7112) of 0.90 g / cm 3 The adhesive resin composition according to any one of [1] to [6] below.

[0020] [8] The adhesive resin composition according to any one of [1] to [7], wherein the component (D) is a high-pressure low-density polyethylene.

[0021] [9] The adhesive resin composition according to any one of [1] to [8], wherein the component (D) is contained in an amount of 1 to 30 mass% relative to 100 mass% of the total of the components (A), (B-1), (B-2), (C) and component (D).

[0022]

[10] A laminate having a substrate layer, a layer made of the adhesive resin composition according to any one of [1] to [9], and a resin layer.

[0023]

[11] The laminate according to

[10] , wherein the substrate layer, the adhesive resin composition layer, and the resin layer are laminated in this order.

[0024]

[12] The laminate according to

[10] or

[11] , wherein the substrate layer is a film of metal or resin.

[0025]

[13] The laminate according to

[12] , wherein the substrate layer is a metal film, and the metal is aluminum, nickel, copper, or an alloy thereof.

[0026]

[14] The laminate according to any one of

[10] to

[13] , wherein the resin layer is a propylene-based polymer layer. [Effects of the Invention]

[0027] According to the present invention, it is possible to provide an adhesive resin composition that has excellent high-speed formability and long-run properties in single-layer or multi-layer laminate molding and has good adhesion to metals and resins, and a laminate using the adhesive resin composition. Furthermore, according to the present invention, a laminate is provided using this adhesive resin composition, which is excellent in reliability, productivity and quality stability. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will be described in detail below. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not go beyond the gist of the present invention. The present invention can be implemented by modifying it as desired within the scope of the gist of the present invention. In the present invention, when "~" is used to express a numerical value or a physical property value, the values ​​before and after the "~" are included.

[0029] In the present invention, the melt flow rate (MFR), melting point, and density of the resin are values ​​measured as follows.

[0030] <mfr> The MFR of the modified propylene polymer of component (A) described below is measured in accordance with JIS K7210 at a temperature of 180°C, a load of 2.16 kg, and for 10 minutes. The MFR of the propylene polymer of component (B-1) and the propylene polymer of component (B-2) is measured in accordance with JIS K7210 at a temperature of 230°C, a load of 2.16 kg, and for 10 minutes. The MFR of the ethylene-α-olefin copolymer of component (C) and the low-density polyethylene of component (D) is measured in accordance with JIS K7210 at a temperature of 190°C, a load of 2.16 kg, and for 10 minutes. The MFR of the adhesive resin composition of the present invention is measured in accordance with JIS K7210 under conditions of a temperature of 230° C., a load of 2.16 kg, and a time of 10 minutes.

[0031] <Melting point> It is measured using a differential scanning calorimeter (DSC). After first raising the temperature to 200°C to erase the thermal history, the temperature is lowered to 40°C at a rate of 10°C / min, and then raised again at a rate of 10°C / min. The temperature at the top of the endothermic peak is taken as the melting point (°C). The unit is °C.

[0032] <density> Measured by the underwater displacement method in accordance with JIS K7112. Standardized to JIS.

[0033] The content of each monomer unit constituting the copolymer, for example, the content of the propylene unit of the propylene copolymer of component (B-2) or the ethylene-α-olefin copolymer of component (C) described below, or the content of each structural unit of other copolymerization components, can be determined by nuclear magnetic resonance spectroscopy or infrared spectroscopy. Here, the term "monomer unit" refers to a repeating unit derived from a raw material monomer of the copolymer and introduced into the copolymer.

[0034] [Adhesive resin composition] The adhesive resin composition of the present invention (hereinafter sometimes referred to as the "resin composition of the present invention") is characterized by containing at least the following components (A), (B-1), (B-2), (C), and (D) as resin components. In the present invention, the term "resin component" refers to the following components (A) to (D) and resins other than the components (A) to (D) as other components described below that are used as needed. Component (A): A modified propylene polymer having a melt flow rate (MFR; JIS K7210, 180°C, 2.16 kg load) of 0.1 to 200 g / 10 min. Component (B-1): A propylene polymer having a melting point of 120°C or higher as measured by DSC. Component (B-2): A propylene-based polymer having a melting point of less than 120°C as measured by DSC, a content of monomer units based on propylene of 70 to 93 mol%, and a content of monomer units based on ethylene and / or an α-olefin other than propylene of 30 to 7 mol%. Component (C): Ethylene-α-olefin copolymer having a content of ethylene-based monomer units of 60 to 95 mol% and a content of monomer units based on α-olefins other than ethylene of 40 to 5 mol%. Component (D): Low-density polyethylene

[0035] <Mechanism> The adhesive resin composition of the present invention can have sufficient adhesion to the substrate layer by containing the modified propylene polymer as component (A). The propylene polymer of component (B-2) and the ethylene-α-olefin copolymer of component (C) have excellent wettability and affinity with the base layer, which works to increase adhesion even during high-speed molding or under low-heat conditions. The propylene polymer of component (B-1) increases the cohesive strength of the adhesive resin composition layer after cooling and solidification, further increasing the durable adhesive strength. The low-density polyethylene of component (D) increases the melt elasticity of the adhesive resin composition, and the inclusion of component (D) reduces necking during high-speed extrusion lamination molding, making it possible to obtain a laminate with a stable film thickness. Furthermore, the modified propylene polymer of component (A) has a specific melt flow rate, which not only provides excellent high-speed extrusion moldability but also acts to improve the dispersibility of component (A) in the matrix composed of components (B-1) and (B-2). Furthermore, component (B-2) contains a predetermined proportion of ethylene units or α-olefin units other than propylene units as copolymerizable monomers, thereby improving the compatibility between component (B-1) and component (C), and component (C) contains a predetermined proportion of α-olefin units other than ethylene units as copolymerizable monomers, thereby improving the compatibility between component (B-2) and component (D). This improves the compatibility of components (A) to (D) contained in the adhesive resin composition and suppresses the generation of die buildup, resulting in excellent long-run properties and stable adhesion.

[0036] <Component (A)> Component (A) is a modified propylene polymer having a melt flow rate (MFR; JIS K7210, 180°C, 2.16 kg load) of 0.1 to 200 g / 10 min. The modified propylene polymer of component (A) is preferably a modified polypropylene obtained by grafting at least one unsaturated carboxylic acid and / or its derivative onto polypropylene (propylene polymer).

[0037] The lower limit of the MFR of component (A) is preferably 0.5 g / 10 min or more, more preferably 1 g / 10 min or more, from the viewpoint of wettability to the base layer, that is, adhesiveness. The upper limit of the MFR of component (A) is preferably 190 g / 10 min or less, more preferably 180 g / 10 min or less, from the viewpoint of dispersibility in a matrix composed of components (B-1) and (B-2).

[0038] The MFR of the modified propylene polymer of component (A) can be controlled within the above range by adjusting the concentration of the radical generator, the reaction temperature, and the reaction time when the propylene polymer used as a raw material described below is used and an unsaturated carboxylic acid and / or a derivative thereof is graft-modified.

[0039] The propylene polymer used as a raw material for component (A) (hereinafter, sometimes referred to as "raw propylene polymer") is not limited as long as it has a propylene unit content of more than 50 mol%, i.e., a content of monomer units other than propylene of less than 50 mol%. Preferably, the content of monomer units other than propylene is 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

[0040] The raw propylene polymer is not particularly limited as long as it satisfies the above criteria. Examples include propylene homopolymers, propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-ethylene-1-butene copolymers, and propylene-4-methyl-1-pentene copolymers, which are copolymers of propylene with one or more α-olefins other than propylene, and copolymers of propylene with other vinyl monomers. In this specification, the term "α-olefin" in propylene-α-olefin copolymers refers to ethylene in a broad sense. The α-olefins other than propylene are not limited, but typically include ethylene and hydrocarbons having a double bond with 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms. Furthermore, "other vinyl monomers" are also not limited, but examples include vinyl acetate, vinyl alcohol, (meth)acrylic acid, (meth)acrylic acid alkyl esters, styrene, and styrene derivatives. Here, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid."

[0041] The raw material propylene polymer may be one of the above resins or a mixture of two or more of them.

[0042] The above-mentioned copolymers may be any of block copolymers, graft copolymers, and random copolymers.

[0043] Among these, propylene homopolymers, propylene-ethylene copolymers, and blends thereof are preferred as the raw propylene polymers.

[0044] The density of the raw material propylene polymer is 0.870 to 0.910 g / cm in order to provide excellent mechanical strength to the component (A). 3 It is preferable that the density is 0.885 to 0.905 g / cm 3 By adjusting the density of the raw material propylene polymer to fall within the above range, the mechanical strength of component (A) is improved, thereby increasing adhesiveness.

[0045] The MFR (230°C, load 2.16 kg) of the raw material propylene polymer is not particularly limited, but is usually 0.01 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min, and more preferably 0.5 to 15 g / 10 min. By setting the MFR to the above lower limit or higher, it is possible to prevent the cohesive force of the polymer from increasing alone, facilitate uniform mixing with other components, and suppress an increase in the energy load during production of the adhesive resin composition of the present invention. Furthermore, by setting the MFR to the above upper limit or lower, it is possible to control the fluidity of the adhesive resin composition of the present invention within a desired range, thereby maintaining excellent high-speed moldability and adhesiveness.

[0046] The melting point of the raw material propylene polymer, as measured by DSC, is preferably 40° C. or higher, more preferably about 55° C. or higher, and even more preferably 60° C. or higher, from the viewpoint of heat resistance. Also, from the viewpoint of adhesiveness, it is preferably 170° C. or lower, and more preferably 165° C. or lower.

[0047] The unsaturated carboxylic acid used for graft-modifying the raw material propylene polymer is preferably an α,β-ethylenically unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, or isocrotonic acid. Examples of derivatives of unsaturated carboxylic acids include acid anhydrides and carboxylic acid esters of these unsaturated carboxylic acids, and may also include derivatives such as acid halides, amides, and imides. Of these derivatives, acid anhydrides are preferred.

[0048] Among these, maleic acid and / or its anhydride are particularly suitable. A plurality of these compounds may be used in combination. Furthermore, vinyl silanes such as vinyltrimethoxysilane may also be used in combination with the unsaturated carboxylic acid and / or its derivative.

[0049] The graft modification to obtain the modified propylene polymer of component (A) may be performed by any known method, and may be performed by a reaction using heat alone, or may be performed by adding a known organic peroxide or the like that generates radicals during the reaction as a radical generator. Examples of the reaction method include a solution modification method in which the reaction is performed in a solvent and a melt modification method in which no solvent is used. Furthermore, other methods such as a suspension dispersion reaction method may also be used.

[0050] Examples of melt modification methods that can be used include a method in which a raw propylene polymer, an unsaturated carboxylic acid and / or a derivative thereof, and, if necessary, a radical generator described below are mixed in advance and then melt-kneaded in a kneader to cause a reaction, and a method in which a mixture of a radical generator and an unsaturated carboxylic acid and / or a derivative thereof is added to a raw propylene polymer molten in a kneader through an inlet to cause a reaction. Mixing is typically performed using a Henschel mixer, ribbon blender, V-type blender, or the like. Melt-kneading can typically be performed using a single-screw or twin-screw extruder, rolls, a Banbury mixer, a kneader, a Brabender mixer, or the like.

[0051] The solution modification method can be a method in which a raw material propylene-based polymer is dissolved in an organic solvent or the like, and a radical generator and an unsaturated carboxylic acid and / or a derivative thereof, which will be described later, are added thereto to carry out graft copolymerization. The organic solvent is not particularly limited, and examples of the organic solvent that can be used include alkyl-substituted aromatic hydrocarbons and halogenated hydrocarbons.

[0052] The blending ratio of the raw material propylene-based polymer and the unsaturated carboxylic acid and / or derivative thereof during graft modification is not limited, but it is desirable to blend the unsaturated carboxylic acid and / or derivative thereof in an amount of usually 0.01 to 30 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass per 100 parts by mass of the raw material propylene-based polymer.

[0053] Known radical generators can be used, including dialkyl peroxides, peroxy esters, diacyl peroxides, hydroperoxides, ketone peroxides, etc. Among these, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide are preferably used as dialkyl peroxides.

[0054] These radical generators can be appropriately selected depending on the type and MFR of the raw material propylene polymer, the type of unsaturated carboxylic acid and / or its derivative, reaction conditions, etc., and two or more types may be used in combination.

[0055] The amount of the radical generator to be added is not limited, but is usually 0.001 to 20 parts by mass, preferably 0.005 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the raw material propylene polymer.

[0056] The modification rate (graft rate) of the modified propylene polymer of component (A) with unsaturated carboxylic acid and / or its derivative is not limited, but is usually 0.1% by mass or more, preferably 0.15% by mass or more, more preferably 0.3% by mass or more, and is usually 2.0% by mass or less, preferably 1.8% by mass or less, more preferably 1.6% by mass or less. When the modification rate with unsaturated carboxylic acid and / or its derivative is equal to or greater than the lower limit, the adhesive resin composition of the present invention exhibits good adhesion to the substrate layer. When the modification rate is equal to or less than the upper limit, deterioration in thermal stability and compatibility with other components can be suppressed.

[0057] Here, the modification rate (graft rate) means the content of unsaturated carboxylic acid and / or its derivative components in a modified polyolefin, which is determined in advance as a standard sample by nuclear magnetic resonance measurement, and measured with an infrared spectrometer using a calibration curve created from the quantitative values. For example, the graft rate refers to the absorption characteristic of carboxylic acid and / or its derivatives in a sample press-molded into a sheet having a thickness of about 100 μm, specifically, 1900 to 1600 cm -1 The modification rate (graft rate) can be determined by measuring the carbonyl characteristic absorption (C=O stretching vibration band) of the unsaturated carboxylic acid and / or its derivative. Note that, in the modification with the unsaturated carboxylic acid and / or its derivative, 100% may not be subjected to the reaction, and unsaturated carboxylic acid and / or its derivative that has not reacted with the raw material propylene polymer may remain in the modified polypropylene. However, the modification rate (graft rate) in the present invention means the value measured by the above method.

[0058] The modified propylene polymer of component (A) can be treated to remove unreacted unsaturated carboxylic acid and / or its derivatives. Although the method for this treatment is not limited, a specific example is a method in which the modified propylene polymer is placed in a storage tank having a structure that allows gas to be blown in from the bottom of the device, the device is heated to about 100°C with a heater or thermal oil, and an inert gas such as nitrogen or air is blown in from the bottom of the device for 6 to 24 hours.

[0059] The melting point of the modified propylene polymer of component (A), as measured by DSC, is preferably 60° C. or higher, more preferably 65° C. or higher, and even more preferably 70° C. or higher, from the viewpoint of heat resistance. Also, from the viewpoint of adhesiveness, it is preferably 170° C. or lower, more preferably 165° C. or lower.

[0060] The modified propylene polymer of component (A) may be used alone or in combination of two or more starting propylene polymers having different copolymer component compositions or physical properties.

[0061] <Component (B-1)> The propylene polymer of component (B-1) is a propylene polymer having a melting point of 120°C or higher as measured by DSC. A melting point of 120°C or higher for component (B-1) improves crystallinity and mechanical strength, enhances the cohesive force of the adhesive resin composition layer after cooling and solidification, and enables high durable adhesive strength to be obtained. The melting point of the propylene polymer of component (B-1) is preferably 125°C or higher. However, an excessively high melting point reduces uniform mixing with other components, and therefore the melting point of the propylene polymer of component (B-1) is preferably 175°C or lower.

[0062] The propylene polymer of component (B-1) may contain an α-olefin such as ethylene or 1-butene, or other monomer units other than α-olefins. Specific examples of other monomers include the "other vinyl monomers" in the propylene polymer raw material of component (A). Among these, propylene homopolymers, propylene-ethylene copolymers, and blends thereof are preferably used as the propylene polymer of component (B).

[0063] When the propylene-based polymer of component (B-1) is a propylene-α-olefin copolymer, materials capable of achieving the above-mentioned melting point include highly crystalline materials, specifically those in which the propylene unit content in the copolymer is higher than the α-olefin content. The copolymerization ratio of propylene and α-olefin in the copolymer is preferably 60 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more, where the sum of the propylene unit content and the content of monomer units based on α-olefin is taken as 100 mol%. If the propylene unit content is above the above-mentioned lower limit, the copolymer has high mechanical strength and maintains adhesiveness. On the other hand, the upper limit of the propylene unit content is not particularly limited, but is usually less than 100 mol%.

[0064] The density of the propylene polymer of component (B-1) is not limited, but is usually 0.880 g / cm 3 If the density of the propylene polymer is equal to or higher than the above lower limit, the adhesiveness to the substrate layer at high temperatures, i.e., the heat resistance, can be prevented from decreasing. There is no upper limit to the density of the propylene polymer of component (B), but it is usually 0.910 g / cm. 3 The following is the result.

[0065] The MFR (230°C, load 2.16 kg) of the propylene polymer of component (B-1) is preferably 0.5 to 50 g / 10 min. By setting the MFR of the propylene polymer of component (B-1) to the above upper limit or less, the melt elasticity of component (B-1) can be maintained, and excellent moldability can be obtained when it is made into an adhesive resin composition. On the other hand, by setting the MFR to the above lower limit or more, compatibility with other components becomes good. The MFR of component (B) is more preferably 0.5 to 35 g / 10 min.

[0066] Component (B-1) is available as a commercially available product, such as "Novatec (registered trademark)" and "Wintec (registered trademark)" manufactured by Japan Polypropylene Corporation, "Moplen (registered trademark)," "Metocene (registered trademark)," and "Adflex (registered trademark)" manufactured by Basel Chemicals, Inc., or the "Tafmer (registered trademark)" series manufactured by Mitsui Chemicals, Inc.

[0067] These propylene polymers of component (B-1) may be used alone or in combination of two or more different copolymerization component compositions and physical properties.

[0068] <Component (B-2)> The propylene polymer of component (B-2) is a propylene copolymer having a melting point of less than 120°C as measured by DSC, a content of propylene-based monomer units of 70 to 93 mol%, and a content of ethylene and / or monomer units of α-olefins other than propylene of 30 to 7 mol%. By using a component (B-2) having a melting point of less than 120°C, it becomes easier to improve adhesion even during high-speed molding or under low-heat conditions.

[0069] The melting point of the propylene polymer of component (B-2) is preferably 100°C or lower. However, if the melting point is too low, not only will the compatibility with component (B-1) decrease, but the cohesive strength will also decrease, resulting in poor adhesiveness of the adhesive resin composition. The melting point of the propylene polymer of component (B-2) is preferably 40°C or higher.

[0070] The copolymerization ratio of propylene and α-olefins other than ethylene and / or propylene in the propylene-based polymer of component (B-2), where the sum of the content of monomer units based on propylene and the content of monomers based on α-olefins other than ethylene and / or propylene is 100 mol %, is preferably 75 to 92 mol % propylene and 25 to 8 mol % ethylene and / or propylene, and more preferably 80 to 90 mol % propylene and 20 to 10 mol % ethylene and / or propylene. When the proportion of monomer units based on propylene is equal to or less than the upper limit, the wettability and affinity of component (B-2) with the substrate layer are enhanced, i.e., the adhesive resin composition has high adhesiveness. Furthermore, compatibility with component (C) is enhanced, resulting in high-speed moldability and long-run properties. When the proportion of monomer units based on propylene is equal to or greater than the lower limit, compatibility with component (B-1) is enhanced, resulting in high-speed moldability and long-run properties.

[0071] The α-olefins other than propylene and ethylene that can be used as raw materials for the propylene polymer of component (B-2) are not limited, and examples include α-olefins having about 4 to 10 carbon atoms, such as 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene. The propylene polymer of component (B-2) may contain other monomer units besides the α-olefins, and specific examples of such other monomers include the "other vinyl monomers" in the raw material propylene polymer of component (A).

[0072] The MFR (230°C, load 2.16 kg) of the propylene polymer of component (B-2) is preferably 0.5 to 50 g / 10 min. By setting the MFR of the propylene polymer of component (B-2) to the above upper limit or less, the melt elasticity of component (B-2) can be maintained, and excellent moldability can be obtained when it is made into an adhesive resin composition. On the other hand, by setting the MFR to the above lower limit or more, compatibility with other components becomes good. The MFR of component (B-2) is more preferably 0.5 to 35 g / 10 min.

[0073] The density of the propylene polymer of component (B-2) is not limited, but is usually 0.895 g / cm 3 If the density of the propylene polymer is equal to or less than the above lower limit, the adhesion to the substrate layer can be improved. There is no lower limit for the density of the propylene polymer of component (B-2), but it is usually 0.860 g / cm. 3 The following is the result.

[0074] Component (B-2) is available as a commercially available product, such as "Versyfy (registered trademark)" manufactured by Dow or "Vistamaxx (registered trademark)" manufactured by ExxonMobil.

[0075] These propylene polymers of component (B-2) may be used alone or in combination of two or more different copolymerization component compositions and physical properties.

[0076] <Ingredient (C)> The ethylene-α-olefin copolymer of component (C) has a content of ethylene-based monomer units of 60 to 95 mol % and a content of monomer units based on α-olefins other than ethylene of 40 to 5 mol %.

[0077] The copolymerization ratio of ethylene to α-olefin other than ethylene in the ethylene-α-olefin copolymer of component (C) is preferably 65 to 90 mol % ethylene and 35 to 10 mol % α-olefin other than ethylene, where the sum of the content of ethylene-based monomer units and the content of monomers based on α-olefin other than ethylene is 100 mol %. When the proportion of ethylene-based monomer units is below the upper limit, the wettability and affinity of component (C) with the substrate layer are enhanced, i.e., the adhesive resin composition has high adhesiveness. Furthermore, compatibility with component (B-2) is enhanced, resulting in high-speed moldability and long-run properties. When the proportion of ethylene-based monomer units is above the lower limit, compatibility with component (D) is enhanced, resulting in high-speed moldability and long-run properties.

[0078] The α-olefins other than ethylene that can be used as raw materials for the ethylene-α-olefin copolymer (C) are not limited, and examples thereof include α-olefins having approximately 3 to 10 carbon atoms, such as propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene. The ethylene-α-olefin copolymer of component (C) may contain other monomer units besides the α-olefins, and specific examples of such other monomers include the "other vinyl monomers" in the raw material propylene polymer of component (A).

[0079] The density of the ethylene-α-olefin copolymer of component (C) is not limited, but is preferably 0.90 g / cm 3 is less than or equal to 0.890 g / cm 3 If the density of component (C) is equal to or less than the above lower limit, the adhesion to the substrate layer can be improved. There is no lower limit for the density of the ethylene-α-olefin copolymer of component (C), but it is usually 0.855 g / cm 3 That's all.

[0080] The MFR (190°C, load 2.16 kg) of the ethylene-α-olefin copolymer of component (C) is preferably 0.5 to 50 g / 10 min. By setting the MFR of the ethylene-α-olefin copolymer of component (C) to the above upper limit or less, the melt elasticity of component (C) can be maintained, and excellent moldability can be obtained when it is made into an adhesive resin composition. On the other hand, by setting the MFR to the above lower limit or more, compatibility with other components can be improved. The MFR of component (C) is more preferably 0.5 to 35 g / 10 min.

[0081] Component (C) is available as a commercially available product, and examples of commercially available products include the "Tafmer (registered trademark)" series manufactured by Mitsui Chemicals, Inc., the "Engage (registered trademark)" series manufactured by DOW, the "LUCENE (registered trademark)" series manufactured by LG Chem, and the "SOLUMER (registered trademark)" manufactured by SK Chem.

[0082] The ethylene-α-olefin copolymer of component (C) may be used alone or in combination of two or more copolymers with different copolymer component compositions or physical properties.

[0083] [Component (D)] The low-density polyethylene of component (D) is a component that imparts excellent neck-in properties to the adhesive resin composition when used in combination with components (A), (B-1), (B-2), and (C) of the present invention.

[0084] The low-density polyethylene of component (D) is preferably a high-pressure low-density polyethylene which has an excellent balance of adhesiveness and strength, and has a density of 0.860 to 0.930 g / cm 3 , especially 0.910~0.930g / cm 3 It is preferable that:

[0085] Furthermore, the physical properties of the low-density polyethylene of component (D) are not particularly limited, but the MFR (190°C, load 2.16 kg) is usually 1 g / 10 min or more, preferably 3 g / 10 min or more, and usually 30 g / 10 min or less, preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less. When the MFR of the low-density polyethylene is above the lower limit, dispersibility in the resin composition is good, and when it is below the upper limit, improved processability is obtained, and in either case, high-speed moldability tends to be excellent.

[0086] Component (D) is available as a commercially available product, such as the "Novatec (registered trademark)" series manufactured by Japan Polyethylene Corporation.

[0087] The low-density polyethylene of component (D) may be used alone or in combination of two or more types having different copolymerization component compositions or physical properties.

[0088] <Contents of component (A), component (B-1), component (B-2), component (C), and component (D)> The adhesive resin composition of the present invention preferably contains 15 to 49 mass% of component (B-1), 15 to 49 mass% of component (B-2), and 15 to 49 mass% of component (C), relative to 100 mass% of the total of components (B-1), (B-2), and (C). By setting the content of component (B-1) at or above the lower limit, the crystallinity and mechanical strength of the adhesive resin composition are increased, the cohesive force of the adhesive resin composition layer after cooling and solidification is increased, and high durable adhesive strength is achieved. By setting the content of component (B-1) at or below the upper limit, it is possible to prevent a decrease in adhesion during high-speed molding or under low heat conditions. By setting the content of component (B-2) and component (C) at or above the lower limit, excellent wettability and affinity with the substrate layer are achieved, and high adhesiveness is achieved even during high-speed molding or under low heat conditions. By setting the content of component (B-2) and component (C) at or below the upper limit, a decrease in cohesive strength is suppressed, and high mechanical strength can be maintained.

[0089] The content of component (A) in the total of 100% by mass of components (A), (B-1), (B-2), (C) and (D) is preferably 10 to 60% by mass. The content of component (A) reflects the amount of acid used for graft modification, but by keeping it below the above upper limit, it is easy to prevent side effects such as a reaction between moisture and functional groups due to moisture absorption, a decrease in adhesion, and increased foaming due to absorbed moisture. By keeping the content of component (A) above the above lower limit, it is easy to control the functional group concentration within a range sufficient to exhibit adhesion to the base layer. The content of component (A) is more preferably 10 to 50 mass% out of a total of 100 mass% of components (A), (B-1), (B-2), (C), and (D).

[0090] Furthermore, the content of component (D) is preferably 1 to 30 mass% relative to the total 100 mass% of components (A), (B-1), (B-2), (C) and (D), and the content of component (D) relative to the total 100 mass% of components (A), (B-1), (B-2), (C) and (D) is more preferably 5 to 20 mass%.

[0091] By setting the content of component (D) at or above the lower limit, excellent neck-in resistance and high-speed moldability tend to be maintained. Also, by setting the content of component (D) at or below the upper limit, the necessary amounts of other components can be secured, improving adhesion and long-run properties.

[0092] <Content of Unsaturated Carboxylic Acid Component in Adhesive Resin Composition> The adhesive resin composition of the present invention preferably contains 0.01% by mass or more of an unsaturated carboxylic acid component relative to 100% by mass of the total of the resin components.

[0093] The content of the unsaturated carboxylic acid component in the adhesive resin composition can be determined in the same manner as the modification rate of the modified propylene polymer of component (A) described above, or can be calculated from the modification rate (graft rate) of the modified propylene polymer of component (A) and the content of component (A) in the adhesive resin composition.

[0094] By setting the content of the unsaturated carboxylic acid component in the adhesive resin composition of the present invention to the above lower limit or more, sufficient adhesion to the substrate layer is easily obtained. However, if the content of the unsaturated carboxylic acid component is too high, the compatibility as an adhesive resin composition decreases. Therefore, from the viewpoint of achieving both adhesion and compatibility, the content of the unsaturated carboxylic acid component in 100% by mass of the resin component is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 1.2% by mass or less, and more preferably 1.0% by mass or less.

[0095] <Other ingredients> The adhesive resin composition of the present invention may contain additives, resins, etc. (hereinafter, sometimes referred to as "other components") in addition to the above-mentioned components (A) to (D), as long as the effects of the present invention are not significantly impaired. The other components may be used alone or in any combination and ratio of two or more.

[0096] The additives that can be used in the adhesive resin composition of the present invention are not limited, but specific examples include heat stabilizers, weather stabilizers (antioxidants, light stabilizers, UV absorbers, etc.), flame retardants, antiblocking agents, slip agents, antistatic agents, fillers (inorganic and / or organic fillers, etc.), processing aids, plasticizers, nucleating agents, impact modifiers, compatibilizers, catalyst residue neutralizers, carbon black, and colorants (pigments, dyes, etc.). When these additives are used, their content is not limited, but is generally 0.01% by mass or more, preferably 0.2% by mass or more, and generally 5% by mass or less, preferably 2% by mass or less, based on the adhesive resin composition.

[0097] The adhesive resin composition of the present invention may also contain a tackifier as another component. Examples of tackifiers include amorphous resins that are solid at room temperature, such as petroleum resins, rosin resins, terpene resins, and hydrogenated versions of these. However, containing a large amount of tackifier in a resin composition may cause smoke generation during molding or reduce heat resistance. Therefore, even when a tackifier is used, its content in the resin composition is preferably 30% by mass or less, more preferably 20% by mass or less. The adhesive resin composition of the present invention, even without a tackifier, has excellent low-temperature processability, and when used as an adhesive layer in a laminate, it exhibits good adhesion to a substrate layer and can maintain good adhesion to the substrate layer even under high-temperature and high-humidity conditions.

[0098] Examples of the petroleum resin include aliphatic petroleum resins, aromatic petroleum resins, copolymers thereof, and hydrogenated products thereof. Examples of the petroleum resin skeleton include C5 resins, C9 resins, C5 / C9 copolymer resins, cyclopentadiene resins, polymers of vinyl-substituted aromatic compounds, copolymers of olefins and vinyl-substituted aromatic compounds, copolymers of cyclopentadiene compounds and vinyl-substituted aromatic compounds, and hydrogenated products thereof. The rosin resin is a natural resin containing abietic acid as a main component, and examples thereof include natural rosin, polymerized rosin derived from natural rosin, stabilized rosin obtained by disproportionating or hydrogenating natural rosin or polymerized rosin, unsaturated acid-modified rosin obtained by adding unsaturated carboxylic acids to natural rosin or polymerized rosin, natural rosin ester, modified rosin ester, and polymerized rosin ester. Examples of the terpene resin include aromatic terpene resins such as polyterpene resins and terpene phenol resins, aromatic modified terpene resins, and hydrogenated products thereof.

[0099] The resins used as other components are not limited, but examples thereof include polyphenylene ether resins, polycarbonate resins, polyamide resins such as nylon 66 and nylon 11, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, styrene resins such as polystyrene, cyclic polyolefin resins, and acrylic / methacrylic resins such as polymethyl methacrylate resins. However, in order to effectively obtain the effects of the present invention due to the adhesive resin composition of the present invention containing the above-mentioned components (A) to (D), the content of resins other than components (A) to (D) contained in 100% by mass of all resin components in the adhesive resin composition of the present invention is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

[0100] <Method for producing adhesive resin composition> The adhesive resin composition of the present invention can be obtained by mixing the above-mentioned components in a predetermined ratio. The mixing method is not particularly limited as long as the raw material components are uniformly dispersed. That is, the raw material components described above can be mixed simultaneously or in any order to obtain a composition in which the components are uniformly dispersed. For more uniform mixing and dispersion, it is preferable to melt-mix predetermined amounts of the raw material components. For example, the raw material components of the resin composition of the present invention may be mixed in any order and then heated, or all of the raw material components may be mixed while being melted sequentially, or a mixture of the raw material components may be pelletized or melt-mixed during molding to produce the desired molded product.

[0101] The adhesive resin composition of the present invention can be prepared by various known methods, such as mixing predetermined amounts of the above-mentioned raw material components using a tumbler blender, V blender, ribbon blender, Henschel mixer, etc., and then melt-kneading and granulating or pulverizing the mixture using a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, etc. The temperature during melt-kneading may be any temperature at which at least one of the raw material components is in a molten state, but a temperature at which all of the components used are melted is usually selected, and the melt-kneading is generally carried out in the range of 150 to 300°C.

[0102] The adhesive resin composition of the present invention does not need to be used as an independent raw material as long as it contains at least the above-mentioned components (A) to (D). That is, a resin composition that already contains two or more of these components can be used as a raw material, or a molded product made of a resin composition can be crushed and used as a raw material. Furthermore, if a raw material that is already a resin composition does not contain all of the components constituting the present invention, only the missing components can be supplemented as raw materials.

[0103] <Physical Properties of Adhesive Resin Composition> The melt flow rate (MFR; JIS K7210, 230°C, 2.16 kg load) of the adhesive resin composition of the present invention is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, and even more preferably 1 g / 10 min or more, from the viewpoint of moldability, while from the viewpoint of mechanical strength, it is preferably 200 g / 10 min or less, more preferably 100 g / 10 min or less, and even more preferably 50 g / 10 min or less.

[0104] Furthermore, from the viewpoint of heat resistance, the melting point of the adhesive resin composition of the present invention is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher. On the other hand, from the viewpoint of adhesiveness, the melting point of the adhesive resin composition of the present invention is usually 170° C. or lower.

[0105] <Molded Articles of Adhesive Resin Composition> There is no limitation on the molded articles obtainable from the adhesive resin composition of the present invention, and various extrusion molded articles and injection molded articles can be obtained. In addition, the adhesive resin composition of the present invention can be used alone to form molded articles such as single-layer sheets, but since the adhesive resin composition of the present invention has excellent adhesion to various metals and resins described below, it is suitably used as an adhesive layer for laminates using these as substrates.

[0106] [Laminate] The laminate using the adhesive resin composition of the present invention includes a laminate having at least a layer made of the adhesive resin composition of the present invention and a substrate layer, with the substrate layer being in contact with one or both sides of the adhesive resin layer of the present invention. A resin layer may also be laminated. It may also be a laminate in which a substrate layer, an adhesive resin layer, and a resin layer are laminated in this order. This laminate may be a laminate of three or more layers including a layer structure other than these three layers, as long as the substrate layer, adhesive resin layer, and resin layer are laminated in this order. Examples of the laminate include a laminate sheet and a laminate film. Here, "sheet" and "film" both mean a planar molded product and are synonymous.

[0107] The material constituting the substrate layer of the laminate of the present invention is not limited, but specific examples include a metal or resin film or sheet. Furthermore, the layer configuration of the layer made of the adhesive resin composition of the present invention and the substrate layer is not limited, but it is preferable that these layers are adjacent to each other.

[0108] When the substrate layer is a metal film or sheet, the metal constituting the metal film or sheet is not limited, but specifically includes aluminum, nickel, copper, stainless steel, cobalt, iron, zinc, lead, titanium, carbon steel, or alloys thereof, with aluminum, nickel, copper, or alloys thereof being preferred.

[0109] When the substrate layer is a resin film or sheet, the resin constituting the resin film or sheet is not limited, but specifically, thermoplastic resins such as olefin polymers and olefin elastomers including ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, poly4-methyl-1-pentene, polycarbonate resins, polyamide resins such as polyamide 6, polyamide 66, polyamide 6-66, and polyamide 12, polyester resins and polyester elastomers such as polyethylene terephthalate and polybutylene terephthalate, styrene resins and styrene elastomers, and acrylic resins are preferably used.

[0110] Two or more of these substrate layers may be laminated.

[0111] The form of the substrate layer is not limited to a film or a sheet, and may be a woven fabric or a nonwoven fabric. The substrate layer may have a single-layer structure or a multi-layer structure. The method for producing a multi-layer substrate is not particularly limited, and examples thereof include a co-extrusion film method, a dry lamination method, a wet lamination method, a hot-melt lamination method, an extrusion lamination method, and a thermal lamination method.

[0112] The resin constituting the resin layer is not limited, and specific examples include the components (A), (B-1), (B-2), (C), and (D) of the present invention and the resins listed as other components in the resin composition of the present invention described above. However, from the viewpoint of excellent co-extrudability with the resin composition of the present invention, an olefin polymer is preferred, and a propylene polymer containing propylene units as the main component is particularly preferred. Here, a propylene polymer containing propylene units as the main component means that, among the monomers constituting the propylene polymer, propylene units are contained in the largest amount, by mass.

[0113] The laminate of the present invention may have any layer provided thereon in addition to the layer made of the adhesive resin composition of the present invention, the substrate layer, and the layer made of a resin.

[0114] Various known methods can be used to produce the laminate of the present invention, but lamination molding is particularly suitable. Lamination methods include extrusion lamination, in which a molten resin film extruded from a T-die is continuously coated and pressure-bonded onto the surface of a previously produced substrate, and thermal lamination, in which a film previously formed and solidified by a T-die is thermally pressure-bonded. Lamination is usually performed on one side of the substrate, but can also be performed on both sides if necessary.

[0115] In the lamination molding, not only one type of substrate layer is used as a film in advance, but also two or more types of films may be used. In this case, they may be molded by simultaneous lamination, or one substrate may be used in advance to form a laminate, and then the other substrate may be laminated to this. In addition, the resin to be laminated is not limited to being one type, and two or more types may be co-extruded.

[0116] When the laminate of the present invention is obtained by stretching, after stretching as described above, heat setting may be performed or the product may be produced without heat setting. If heat setting is not performed, the laminate can be used as a shrink film because the stress is released by heating the laminate thereafter and the laminate has the property of shrinking.

[0117] The laminate thus produced can be further subjected to various film processing treatments such as metal deposition, corona discharge treatment, and printing.

[0118] In the laminate of the present invention, the thickness of the layer made of the adhesive resin composition of the present invention is not particularly limited and can be set as desired depending on the layer structure, application, shape of the final product, required physical properties, etc., but is usually 0.1 to 200 μm, preferably 0.3 to 100 μm, and more preferably 0.5 to 50 μm.

[0119] The adhesive resin composition of the present invention exhibits excellent high-speed moldability and long-run properties, and high adhesion to metals, resins, etc., and therefore the laminate of the present invention using this composition can be suitably used as a body material, frame material, cylindrical material, packaging material, etc. in transportation equipment such as automobiles and aircraft, home appliances, the electronics field, and the robot field. [Example]

[0120] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that the values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limit values ​​in the embodiments of the present invention, and a preferred range may be defined by a combination of the above-mentioned upper or lower limit values ​​and the values ​​in the following examples or values ​​between the examples.

[0121] [Measurement and evaluation method] The raw materials used in the following examples and comparative examples, and the methods for measuring and evaluating the resulting adhesive resin compositions and laminates are as follows.

[0122] (1) Graft ratio Pellets of the modified propylene polymer or the adhesive resin composition were press-molded (230°C) into a film having a thickness of 100 μm, and the graft ratio was calculated by infrared absorption spectroscopy using an FT-IR device (JASCO FT / IR610, manufactured by JASCO Corporation) according to the method described above. The graft ratio of the adhesive resin composition corresponds to the content of the unsaturated carboxylic acid component in the adhesive resin composition.

[0123] (2) Density, MFR, melting point The density, MFR, and melting point were measured by the methods described above. In addition, when the adhesive resin composition and the comparative example contained multiple resins or multiple modified propylene polymers, the melting point or MFR of the composite thereof was measured.

[0124] In the evaluations of (3) to (6) below, a laminate film obtained by extrusion lamination molding using pellets of the adhesive resin composition obtained in each example was used.

[0125] <Extrusion lamination molding> An extrusion laminating apparatus (manufactured by Sumitomo Heavy Industries Modern Co., Ltd.) equipped with a T-die and equipped with two 40 mm diameter extruders A and B was used. The obtained adhesive resin composition was supplied to extruder A, and a propylene-based polymer (PH943B manufactured by SunAllomer Co., Ltd.) was supplied to extruder B. A distribution block was set so that the layer of adhesive resin composition from extruder A was disposed on the side of the metal aluminum film described below, which was provided as a base layer. The temperatures of the resins extruded in two layers were both set to 255 to 270°C, and extrusion film formation was performed with an air gap of 120 mm, a cooling roll surface temperature of 20°C, a die width of 360 mm, a die lip opening of 0.7 mm, and a take-up speed of 50 m / min, with the extrusion rate adjusted so that the coating thickness of the adhesive resin composition layer was 20 μm and the coating thickness of the propylene-based polymer layer was 20 μm. A laminated film was obtained in which the base layer, the layer of adhesive resin composition, and the layer of propylene-based polymer were laminated in this order. Furthermore, at the same extrusion rate, the take-up speed was set to 100 m / min., and films were formed so that the adhesive resin composition layer had a coating thickness of 10 μm and the propylene-based polymer layer had a coating thickness of 10 μm, thereby obtaining a laminated film in which the substrate layer, adhesive resin composition layer, and propylene-based polymer layer were laminated in this order. As the substrate layer, a metal aluminum film, Alpet 12-50 (manufactured by Panac Corporation, thickness: 62 μm) (hereinafter referred to as "metal (aluminum)") was used so that the aluminum surface was in contact with the layer of the adhesive resin composition.

[0126] (3) Adhesion strength with metal aluminum The laminated film obtained above was cut into 15 mm wide strips in the extrusion direction (MD) to prepare test pieces, and a T-peel test was performed at a speed of 300 mm / min in a constant temperature atmosphere of 23°C to measure adhesive strength. Here, adhesive strength refers to the adhesive strength at the interface between the metal (aluminum) and the adhesive resin composition layer. High adhesive strength is preferable, and a strength of 2 N / min or more was considered to be sufficient for practical use.

[0127] (4) High-speed molding (neck-in) Under the above extrusion lamination conditions, the width of the adhesive resin composition layer / propylene-based polymer-containing resin layer in the obtained laminate film of base material layer / adhesive resin composition layer / propylene-based polymer was measured, and the difference between the die width (effective width: 360 mm) and the width of the resin layer, i.e., the value obtained by subtracting the width of the resin layer from the effective width, was taken as the neck-in value. A small neck-in value was considered good, and a value of 150 mm or less was considered acceptable.

[0128] (5) High-speed formability (drawdown ability) Under the above extrusion lamination molding conditions, the take-up speed was increased from 50 m / min to confirm the limit speed at which the molten resin film broke or the edge of the resin film began to flow unstably. A higher limit speed was considered good, and a speed of 100 m / min or higher was considered acceptable.

[0129] (6) Long-term availability Under the above-mentioned extrusion laminate molding conditions, the temperature of the resins extruded in the two layers was both set to 295 to 305°C, the screw rotation speeds of extruders A and B were both set to 150 rpm, and the melts of the resins constituting the adhesive resin composition layer and the propylene-based polymer layer were continuously extruded for 30 minutes with a die width of 360 mm and a die lip opening of 0.7 mm, and then the die lip on the adhesive resin composition layer side was observed. After 30 minutes, cases where deposits such as die resin and discoloration had occurred on the die lip surface were marked with "X", and cases where no deposits had occurred were marked with "O".

[0130] [raw materials] In the following Examples and Comparative Examples, the raw materials used in producing adhesive resin compositions are as follows.

[0131] <Component (A): Modified propylene polymer> (A)-1 As the modified propylene polymer (A)-1, a commercially available propylene-ethylene polymer [density: 0.87 g / cm 3 A modified propylene polymer [modification rate (graft rate): 1.1 mass%, MFR (180°C, load 2.16 kg): 11 g / 10 min, melting point: 66°C] obtained by graft-modifying a propylene-based polymer having a molecular weight of 2.0 g / 10 min (MFR: 230°C, load 2.16 kg): 2.0 g / 10 min, melting point: 59°C, propylene unit content: 84 mol%, ethylene unit content: 16 mol%) with maleic anhydride was used. (A)-2 As the modified propylene polymer (A)-2, a commercially available propylene-ethylene copolymer [density: 0.89 g / cm 3 A modified propylene polymer [modification rate (graft rate): 0.9 mass%, MFR (180°C, load 2.16 kg): 160.0 g / 10 min), melting point: 128°C] obtained by graft-modifying a propylene-based polymer having a polymeric olefin copolymer (polymerizable copolymer) of propylene (230°C, load 2.16 kg): 6.0 g / 10 min, melting point: 128°C, propylene unit content: 93 mol%, ethylene unit content: 7 mol%) with maleic anhydride was used. (A)-3 As the modified propylene polymer (A)-3, a commercially available propylene homopolymer [density: 0.90 g / cm 3 A modified propylene polymer [modification rate (graft rate): 1.3 mass%, MFR (180°C, load 2.16 kg): 192.0 g / 10 min), melting point: 157°C] obtained by graft-modifying a propylene-based polymer having a molecular weight of 1.30 g / 10 min, MFR (230°C, load 2.16 kg): 0.6 g / 10 min, melting point: 161°C) with maleic anhydride was used. (A)'-4 As a comparative modified propylene polymer (A)'-4, a commercially available propylene homopolymer [density: 0.90 g / cm 3 A modified propylene polymer [modification rate (graft rate): 2.2 mass%, MFR (180°C, load 2.16 kg): 283.0 g / 10 min), melting point: 164°C] obtained by graft-modifying a propylene-based polymer having a molecular weight of 1.01 g / 10 min and a melting point of 165°C with maleic anhydride was used. (A)'-5 As a comparative modified propylene polymer (A)'-5, a commercially available propylene homopolymer [density: 0.90 g / cm 3 A modified propylene polymer [modification rate (graft rate): 2.5 mass%, MFR (180°C, load 2.16 kg): 450.0 g / 10 min), melting point: 153°C] obtained by graft-modifying a propylene-based polymer having a molecular weight of 1.01 g / 10 min and a melting point of 165°C with maleic anhydride was used.

[0132] <Component (B-1): Propylene polymer with a melting point of 120°C or higher> (B-1)-1 Propylene-based polymer (B-1)-1 is a propylene-ethylene random copolymer [density: 0.90 g / cm 3 , MFR (230°C, load 2.16 kg): 30.0 g / 10 min, melting point: 142°C] was used. (B-1)-2 As the propylene polymer (B-1)-2, a propylene-ethylene random copolymer [Adflex (registered trademark) V109F manufactured by Basel, density: 0.88 g / cm 3 , MFR (230°C, load 2.16 kg): 12.0 g / 10 min, melting point: 143°C] was used. (B-1)-3 As the propylene polymer (B-1)-3, a propylene-ethylene-butene random copolymer [Tafmer (registered trademark) PN2070, manufactured by Mitsui Chemicals, Inc., density: 0.87 g / cm 3 , MFR (230°C, load 2.16 kg): 7.0 g / 10 min, melting point: 160°C] was used. (B-1)-4 As the propylene polymer (B-1)-4, a propylene-ethylene random copolymer [density: 0.90 g / cm 3 , MFR (230°C, load 2.16 kg): 7.0 g / 10 min, melting point: 135°C] was used. (B-1)-5 Propylene-based polymer B-1-5 is a propylene-ethylene block copolymer [density: 0.90 g / cm 3 , MFR (230°C, load 2.16 kg): 3.5 g / 10 min, melting point: 165°C] was used. (B-1)-6 As the propylene polymer (B-1)-6, a propylene homopolymer [Novatec (registered trademark) MA3Q manufactured by Japan Polypropylene Corporation, density: 0.90 g / cm 3 , MFR (230°C, load 2.16 kg): 10.0 g / 10 min, melting point: 160°C] was used.

[0133] <Component (B-2): Propylene-based polymer with a melting point of less than 120°C> (B-2)-1 As the propylene polymer (B-2)-1, a propylene-ethylene random copolymer [density: 0.87 g / cm 3 , MFR (230°C, load 2.16 kg): 8.0 g / 10 min, melting point: 59°C, propylene unit content: 84 mol%, ethylene unit content: 16 mol%] was used. (B-2)-2 Propylene-based polymer (B-2)-2 is a propylene-ethylene random copolymer [density: 0.87 g / cm 3 , MFR (230°C, load 2.16 kg): 2.0 g / 10 min, melting point: 67°C, propylene unit content: 84 mol%, ethylene unit content: 16 mol%] was used. (B-2)'-3 As a comparative propylene polymer (B-2)'-3, a propylene-ethylene random copolymer [density: 0.90 g / cm 3 , MFR (230°C, load 2.16 kg): 2.0 g / 10 min, melting point: 125°C, propylene unit content: 96 mol%, ethylene unit content: 4 mol%] was used.

[0134] <Component (C): Ethylene-α-olefin copolymer> (C)-1 Ethylene-α-olefin copolymer (C)-1: ethylene-octene random copolymer [density: 0.88 g / cm 3 , MFR (190°C, load 2.16 kg): 18.0 g / 10 min, melting point: 76°C, ethylene unit content: 89 mol%, octene unit content: 11 mol%] was used. (C)-2 Ethylene-α-olefin copolymer (C)-2: ethylene-1-butene random copolymer [density: 0.89 g / cm 3 , MFR (190°C, load 2.16 kg): 2.0 g / 10 min, melting point: 76°C, ethylene unit content: 82 mol%, 1-butene unit content: 18 mol%] was used. (C)-3 As the ethylene-α-olefin copolymer (C)-3, an ethylene-1-butene random copolymer [Tafmer® A4085S, manufactured by Mitsui Chemicals, Inc., density: 0.88 g / cm 3 , MFR (190°C, load 2.16 kg): 3.6 g / 10 min, melting point: 67°C, ethylene unit content: 90 mol%, 1-butene unit content: 10 mol%] was used. (C)'-4 For comparison, ethylene-α-olefin copolymer (C)'-4 was prepared from ethylene-1-hexene random copolymer [density: 0.92 g / cm 3 , MFR (190°C, load 2.16 kg): 2.0 g / 10 min, melting point: 124°C, ethylene unit content: 99 mol%, 1-hexene unit content: 1 mol%] was used.

[0135] <Component (D): Low-density polyethylene> (D)-1 As low-density polyethylene, high-pressure low-density ethylene homocopolymer [density: 0.92 g / cm 3 , MFR (190°C, load 2.16 kg): 4.0 g / 10 min, melting point: 105°C] was used.

[0136] <Additives> (X)-1: BASF phosphorus-based antioxidant "IRGAFOS (registered trademark) 168" (X)-2: BASF phenolic antioxidant "IRGANOX (registered trademark) 1010" (Y)-1: Hydrotalcite compound "DHT4A" manufactured by Kyowa Chemical Industry Co., Ltd.

[0137] [Example 1] <Production of Adhesive Resin Composition> As shown in Table 1, 30 parts by mass of (A)-1, 20 parts by mass of (B-1)-1, 20 parts by mass of (B-2)-1, 20 parts by mass of (C)-1, 10 parts by mass of (D)-1, 0.1 parts by mass of (X)-1, 0.1 parts by mass of (X)-2, and 0.15 parts by mass of (Y)-1 were dry-blended and mixed, and the mixture was melt-kneaded using a single-screw extruder (IKG, PSM50-32(1V), D=50 mmφ, L / D=32) at a set temperature of 180 to 210°C, a screw rotation speed of 40 to 70 rpm, and an extrusion rate of 15 to 40 kg / h. Pellets of the adhesive resin composition were obtained by strand cutting. The obtained pellets of the adhesive resin composition were evaluated for the above-mentioned (1) to 6). The evaluation results are shown in Table 1.

[0138] [Comparative Examples 1 and 2] Pellets of adhesive resin composition were obtained in the same manner as in Example 1, except for the formulation shown in Table 1. The evaluations (1) to (6) were carried out in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0139] [Examples 2 to 8, Comparative Examples 3 to 12] Pellets of adhesive resin compositions were obtained in the same manner as in Example 1 except for the formulations shown in Tables 2 to 4, and the above evaluations (1) to (6) were carried out in the same manner as in Example 1. The evaluation results are shown in Tables 2 to 4.

[0140] [Table 1]

[0141] [Table 2]

[0142] [Table 3]

[0143] [Table 4]

[0144] [Evaluation results] Tables 1 to 4 show that the laminate films containing layers of the adhesive resin compositions obtained using Examples 1 to 8, which are specific examples of the adhesive resin composition of the present invention, are excellent in high-speed formability and long-run properties, and also in adhesion to aluminum. In contrast, the adhesive resin compositions of Comparative Examples 1 to 12, which do not satisfy the requirements of the present invention, are poor in any of high-speed formability, long-run properties, and adhesion to aluminum.< / mfr>

Claims

1. An adhesive resin composition comprising the following components (A), (B-1), (B-2), (C) and (D): The composition contains 15 to 49 mass% of component (B-1), 15 to 49 mass% of component (B-2), and 15 to 49 mass% of component (C) relative to 100 mass% of the total of components (B-1), (B-2), and (C), the content of component (A) is 10 to 60% by mass, relative to 100% by mass of the total of components (A), (B-1), (B-2), (C), and (D); An adhesive resin composition comprising 1 to 30 mass% of component (D) relative to 100 mass% of the total of components (A), (B-1), (B-2), (C) and component (D). Component (A): A modified propylene polymer having a melt flow rate (MFR; JIS K7210, 180°C, 2.16 kg load) of 0.1 to 200 g / 10 min. Component (B-1): A propylene polymer having a melting point of 120°C or higher as measured by DSC. Component (B-2): A propylene-based polymer having a melting point of less than 120°C as measured by DSC, a content of monomer units based on propylene of 70 to 93 mol%, and a content of monomer units based on ethylene and / or an α-olefin other than propylene of 30 to 7 mol%. Component (C): an ethylene / α-olefin copolymer having a content of ethylene-based monomer units of 60 to 95 mol % and a content of monomer units based on an α-olefin other than ethylene of 40 to 5 mol %. Component (D): Low-density polyethylene

2. 2. The adhesive resin composition according to claim 1, wherein the component (A) is a modified propylene polymer that satisfies the following conditions 1 and 2: Condition 1: A modified propylene polymer modified with an unsaturated carboxylic acid and / or a derivative thereof, the modification rate being 0.1 to 2.0% by mass Condition 2: Melting point measured by DSC is 60 to 170°C

3. 3. The adhesive resin composition according to claim 1, wherein the propylene polymer of component (B-1) has an MFR (JIS K7210, 230°C, 2.16 kg load) of 0.5 to 50 g / 10 min.

4. The adhesive resin composition according to any one of claims 1 to 3, wherein the propylene polymer of component (B-2) has an MFR (JIS K7210, 230°C, 2.16 kg load) of 0.5 to 50 g / 10 min.

5. The ethylene-α-olefin copolymer of component (C) has an MFR (JIS K7210, 190°C, 2.16 kg load) of 0.5 to 50 g / 10 min and a density (JIS K7112) of 0.90 g / cm ３ The adhesive resin composition according to any one of claims 1 to 4, wherein:

6. 6. The adhesive resin composition according to claim 1, wherein component (D) is a high-pressure low-density polyethylene.

7. A laminate having a substrate layer, a layer made of the adhesive resin composition according to any one of claims 1 to 6, and a resin layer.

8. The laminate according to claim 7 , wherein the substrate layer, the layer made of the adhesive resin composition, and the resin layer are laminated in this order.

9. The laminate according to claim 7 or 8, wherein the substrate layer is a film of metal or resin.

10. 10. The laminate according to claim 9, wherein the substrate layer is a metal film, and the metal is aluminum, nickel, copper, or an alloy thereof.

11. The laminate according to any one of claims 7 to 10, wherein the resin layer is a propylene-based polymer layer.

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