TW592959B - Laminates, sealant films using the same, and containers using the same - Google Patents

Abstract

The present invention relates to laminates which, when used as a sealant film or a part of a container, can be easily peeled off; leave little residue on the surface onto which the laminates were applied; retain their peel strength during heating in the case in which the laminates are used for food packaging; and can be easily molded. The laminate is formed with a resin composition layer prepared from propylene-ethylene-butene terpolymers, low-density polyethylene, and a linear low-density polyethylene; and a layer prepared from propylene polymers. As the linear low-density polyethylene, and instead of the linear low-density polyethylene, a linear low-density polyethylene prepared using metallocene or single-site catalysts can be used. The present invention also relates to sealant films and containers using the laminates of the present invention. The sealant films and containers can be manufactured at low cost.

Description

592959 V. Description of the invention (1) Technical field of the invention The present invention relates to a food container, a medical container, and the like, which are easy to open after peeling, and the peeling surface has excellent appearance after heat treatment such as boiling treatment. ≫ Laminates, sealing films, and containers with excellent container moldability. Known technology has traditionally been used for various types of food packaging materials or medical packaging because of its low price, heat resistance, chemical resistance, and easy heat sealability. Material 〇 In food packaging, aluminum foil or vinylidene chloride resin and ethylene-vinyl acetate copolymer resin saponification are used as the gas barrier layer. In combination with a polyamide resin layer and a polyester resin layer, a heat-sealing layer is used. Polyolefin resin such as polypropylene or polyethylene A method for producing a sealing film 5 is known, such as a method in which a resin composition obtained by mixing polypropylene and polyethylene is used as a sealing layer, and a method in which a resin obtained by graft polymerization of styrene is used for a polyolefin-based resin. The combined cover material sealing film can be used in polypropylene blending with ethylene-propylene_polyethylene copolymer copolymer or ethylene-butene M J \ ΝN copolymer copolymer, or a mixture of polypropylene and polyethylene. A mixture of ethylene-vinyl acetate copolymer and other polyolefins is used as a sealing layer. Recently, rice containers are heated by electric cookers at home. Due to the popularity of outdoor activities, campsites and other places use warm water to eat. In particular, outdoor activities such as camping often use warm water to the container one by one. 3- Heating can be used. 妖妖 J \\\ However, in the temperature 592959 V. Description of the invention (3) issued by Yue Yue. However, the above habits It is known that the composite film is easy to open and inferior, and a residual film or a pull line may occur after peeling, which makes the appearance of the peeling surface poor. Due to the narrow heat sealing temperature range, the peeling strength is unstable, and there is a problem of poor container moldability. In addition, there is a problem that the sealing strength decreases during heating and the contents leak out. The present invention has been made in view of this situation, and an object thereof is to provide a laminated body, a sealing film, and a container that are easy to open, have a good appearance on the peeling surface, and have no decrease in sealing strength during heat treatment, and improved container moldability. Means for Solving the Problems The present inventors have repeatedly studied the results, and found that the use of a laminated body containing a layer containing a specific resin composition and a layer consisting of a propylene-ethylene random copolymer can solve the above-mentioned object, and the specific resin composition The layer, a linear low-density polyethylene layer made of a metallocene catalyst and a single-sided catalyst, and a laminated body made of it can solve the above problems and finally complete the present invention. That is, the present invention relates to a laminate, a sealing film, and a container as shown in the following items 1 to 13. 1. A laminated body comprising 55 to 85% by mass of a propylene-ethylene-butene terpolymer (al), 10 to 35% by mass of a low fasting polyethylene (b), and 5 to 20% by mass of a linear low A layer [(A 1) layer] of a resin composition composed of a density polyethylene (cl) (where (al) + (b) + (ci) = 100% by mass)) and a propylene-based polymer (dl) Layer [(B1) layer]. 2. The laminated body as described in item 1 wherein the propylene polymer (dl) is selected as 592959 V. Description of the invention (4) From propylene homopolymer, propylene-α-olefin random copolymer, and block polypropylene At least one resin or a mixture of two or more resins. 3. The laminated body as described in item 1 or 2, wherein the C-C-B-C-D fine binary copolymer (a 1) is a crystallization peak temperature (Tcp) measured using a differential scanning calorimeter (DSC). It is 75 to 90 ° C, and the crystal energy (ΔΗ) is 55 to 80 J / g. 4. The laminate according to any one of items 1 to 3, wherein the propylene-ethylene-butene terpolymer (a 1) is a propylene content of 96 to 72% by mass, an ethylene content of 1 to 10% by mass, and butene Copolymer with -1 content of 3 to 18% by mass. 5. The laminated body as described in any one of items 1 to 4 wherein the density of the linear low density polyethylene (cl) is 0.91 5 to 0.93 5 g / cm3, and the melt flow rate is 0.5 to 15 g / 10 minutes. 6. The laminated body according to any one of items 2 to 5, wherein the content of the propylene-?-Olefin random copolymer in the layer (B1) exceeds 70% by mass. 7 · —Laminates comprising 30 to 60% by mass of a propylene-ethylene-butene terpolymer (a2), 5 to 25% by mass of a low density polyethylene (b), and 20 to 40% by mass of a metal A layer of a resin composition made of a linear low-density polyethylene (c2) (where (a2) + (b) + (c2,) = 100% by mass) made of a metallocene catalyst or a single-sided catalyst [ A 2) layer], and a layer made of a linear low-density polyethylene (d2) made of a metallocene catalyst or a single-sided catalyst [(B2) layer] 〇8. The layered body as described in item 7, Among them, the propylene-ethylene-butene terpolymer (a 2) was measured using a differential scanning calorimeter (DSC), and the crystallization peak temperature (Tcp) was 75 to 90 ° C, and the crystallization energy (ΛΗ) was 55 to 80 J / g. 9. The laminated body as described in item 7 or 8, wherein propylene-ethylene-butene three 592959 V. Description of the invention (5) Metapolymer (a2) propylene content 96 ~ 72 mass%, ethylene content 1 ~ 10 mass %, Butene-1 copolymer having a content of 3 to 18% by mass. 10. The laminated body according to any one of items 7 to 9, wherein the (c2) component of the (A2) layer and the (d2) component of the (B2) layer have a density of 0.900 to 0.940 g / cm3, and the melt flow rate is 0. 5 to 20 g / 10 minutes. 1 1. A sealing film characterized in that, in the laminated body carried in any one of items 1 to 10, (A 1) layer or (A2) layer of the laminated body is used as a sealing layer. 12. An easy-opening laminated body, characterized in that: the laminated body carried in any one of items 1 to 10, or the (B1) layer or (B2) layer of the sealing film carried in item 11, having ( The side of the A1) layer or the (A2) layer, or the opposite side, has at least one layer selected from the group consisting of aluminum foil, metal vapor-deposited film, silicon oxide vapor-deposited film, vinylidene chloride resin layer, ethylene-ethyl acetate copolymer resin saponified resin layer , A polyamide resin layer, a polyester resin layer, a polycarbonate resin, and an oxygen absorber layer. 1 3 · A container characterized by using the sealing film described in Item 11 or the easily-openable laminated body described in Item 12. Detailed description of preferred specific examples_ Among the resin compositions constituting the (A1) layer and (A2) layer in the present invention, the propylene-ethylene-butene terpolymer (al) (a2) [hereinafter sometimes referred to as PEB, Or (a 1) component or (a2) component] is a copolymer mainly composed of propylene, ethylene and butene-1, and is usually a resin obtained by a multi-stage copolymerization method. The p E B used in the present invention can be measured by a differential scanning calorimeter (D S C) with a crystallization peak temperature (Tcp) of 75 to 90 ° C and a crystallization energy (ΔΗ) of 55 to 80 J / g. Tcp is preferably 78 ~ 88 ° C ', 80 ~ 87 ° C is particularly preferred. Tcp is 592959 V. Description of the invention (6) 7 When the temperature is below 5 ° C, the heat seal strength increases, and it is difficult to obtain stable heat seal strength. On the other hand, when it exceeds 90 ° C, it has poor compatibility with the other components constituting the (A1) layer and (A2) layer, and it is difficult to exhibit low-temperature heat-sealability. problem. △ Η is preferably from 58 to 78 J / g, particularly from 60 to 75 J / g. △ Η When it is 5 5 J / g or less, the heat-sealing layer becomes thin, and no matter whether the heat-sealing strength is unstable or the heat-sealing strength becomes high, the openability tends to deteriorate. On the other hand, when it exceeds 800 J / g, the low-temperature heat-sealability and the appearance of the heat-seal peeled surface after peeling tend to deteriorate. The melting point (Tmp) is not particularly limited, but is preferably in the range of 125 to 145 t. Here Tcp and △ Η can accurately weigh about 3 to 5 mg of sample, set it in DSC, raise the sample temperature to 2 3 (TC, hold for 5 minutes, and then cool down to 30 ° C at 20 ° C / minute.) The composition ratio of PEB can be a propylene content of 96 to 72% by mass, an ethylene content of 1 to 10% by mass, and a butene-1 content of 3 to 18% by mass. The propylene content is preferably 95.3 to 75% by mass. Particularly preferred is 94.5 to 77% by mass. Ethylene content is preferably 1.2 to 8% by mass, particularly 1.5 to 7% by mass. Butene-1 content is preferably 3.5 to 17% by mass, especially 4.0 to 16 mass ° / 〇 is preferable. When the propylene content is 72% by mass or less, the sealing strength is weak, and content leakage is likely to occur. On the other hand, when it exceeds 96% by mass, 'low-temperature sealing performance is deteriorated, sealing strength is weakened, and content is liable to occur. Leakage of materials. When the ethylene content is 1% by mass or less, the low-temperature heat-sealability tends to deteriorate. On the other hand, when it exceeds 10% by mass, the easy-openability tends to be impaired. Butene-1 content is 3% by mass or less When it is easy to open, there is a tendency to deteriorate, 592959 V. Description of the invention (7) When it exceeds 18% by mass, the low-temperature heat-sealability tends to deteriorate. Examples of PES products on the market include the products of Saroma Corporation (trade name Adoxan Prex), and the products of Choso Corporation (trade name Koji Sobo The low density polyethylene (b) [hereinafter referred to as LDPE or single (b) component] used in the present invention is not particularly limited, but the density measured according to JIS K 7 1 1 2 D method is 0.910 ~ 0.9 25g / cm3, the melt flow rate (hereinafter referred to as MFR) measured in accordance with JIS K 7210 test condition 4 is preferably 20g / 10 minutes or less. The density is preferably 0.912 ~ 0.924g / cm3, especially 0.915 ~ 0.923g / cm3 is preferred. The MFR is preferably 5 g / 10 minutes or less, especially 0.1 to 2.0 g / 10 minutes. The linear low density polyethylene (cl) used in the present invention [hereinafter referred to as LLDPE or single name (cl) Ingredients] are copolymers of ethylene and one or more selected from C3-C12 α-olefins. Specific examples of the α-olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1 · Hexyl, 1-octyl, 1-decyl, 1-dodecane. Among these α-olefins, 1-butene, 1-hexene and 1-octene are preferred. Α- in the copolymer Composition ratio of olefins It is usually less than 30 mol%, preferably 1-20 mol%. The density of the LLDPE used in the present invention measured according to the JIS K 71 12 D method is usually 0.915 to 0.935 g / cm3, and 0.918 to 0.933 g / cm3 is preferred, especially 0.920 to 0.931 g / cm3. When the density is less than 0.915 g / cm3, the easy-opening property tends to deteriorate. On the other hand, the compatibility with other components exceeding 0.93 5 g / cm3, the appearance of the laminate, low-temperature heat-sealability, and line-sealability tend to deteriorate. In addition, MRF is measured according to JIS K 7210 test condition 4, usually 0.s 592959 V. Description of the invention (8) ~ 15g / 10 minutes, preferably 1 ~ 12g / 10 minutes, especially 1.5 ~ 10 g / 10 minutes is appropriate. The linear low-density polyethylene (C2) used in the (A2) layer of the present invention [hereinafter also referred to as (c2) component] and the linear low-density polyethylene (d2) used in the (B2) layer (hereinafter also referred to as (d2) component), It is a linear low-density polyethylene (hereinafter also referred to as mLLFPE) made using a metallocene catalyst or a single-sided catalyst. The metallocene catalyst referred to herein is, for example, < < Second generation polymer industrialization technology using metallocene catalyst > > (Harada Tetsuya, Kushiko Corporation, p. 13, 994), or < < High functionalization of olefin-based and styrene-based resins > > (Technical Information Association, p. 13, 2000) and other representative definitions, as generally defined here, there are hafnium, titanium, A catalyst consisting of a complex of a metal atom and a compound having at least one cyclopentadiene ring, that is, a cyclopentadienyl germanium salt. Catalysts include boron compounds such as triphenyl (hydroxyphenyl) borate, ginseng (pentafluorophenyl) (4-hydroxyphenyl) borate, and aluminol institutes such as methylaluminum aluminate. Limited to this. Furthermore, a certain metallocene catalyst is representative of a single-sided catalyst. Hereinafter, the metallocene catalyst referred to in the present invention means a metallocene catalyst and / or a single-sided catalyst. mLLDPE has a copolymer of ethylene and one or more selected from CVCua-olefins. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4 • methyl-1-pentene, 1-hexene, bustene, 1-decene, 1-dodecene, etc. . Preferred among these α-olefins are 1-butene, 1-hexene, and N octene. ^-The composition ratio of the olefin in the copolymer is usually 30 mol% or less, and 1-20 mol% is preferred. The density of m LLD ΡΕ used in the present invention is measured according to the JIS K 7 1 1 2 D method, -10- 592959 V. Description of the invention (9) Usually 0.9 00 to 0.940 g / cm3, and 0.910 to 0.93 5 g / cm3 is preferred, and 0.915 to 0.93 0g / cm3 is particularly preferred. When the density is 0.900 g / cm3 or less, the easy-opening property tends to deteriorate. On the other hand, when it exceeds 0.940 g / cm3, the compatibility with other components, the appearance of the laminate, low-temperature heat-sealability, and peeling appearance tend to deteriorate. MkF measured in accordance with JIS K 72 10 test condition 4 is usually 0.5 to 20 g / 10 minutes, preferably 1 to 15 g / 10 minutes, especially 1.5 to 10 g / l.

Minutes are appropriate. The composition ratio of the above components in the (A1) layer of the present invention is (al) component 55 to 85% by mass, (b) component 10 to 36% by mass, and (cl) component 5 to 20% by mass [where & 1) + (131) + ((^) = 100% by mass). (Al) The content is preferably 60 to 80% by mass, and more preferably 65 to 75% by mass. (B) The content is 13 to 30% by mass. 15 to 25 mass% is preferred, and (cl) is preferably 8 to 18 mass%, particularly preferably 10 to 16 mass%.

(a 1) When the content is less than 55% by mass, the sealing properties of the inclusions, the low-temperature heat-sealing properties, and the compatibility with other components are poor, so it is not suitable. On the other hand, if it exceeds 85% by mass, the easy-opening property is inferior, which is not suitable. Regarding the component (b), when the content is 15 mass% or less, the easy-opening property is poor, so it is not good. On the other hand, when it exceeds 35% by mass, the laminated body may break or gel, which may increase fisheye holes and impair the appearance, so it is not good. Regarding the (cl) component, when the content is 5 mass% or less, the easy-opening property is inferior, which is not preferable. On the other hand, if it exceeds 20% by mass, the heat-sealed part is drawn and the appearance of the peeled surface is deteriorated. The propylene polymer (dl) [hereinafter also referred to as (dl) component] used in the (B1) layer of the present invention is composed of propylene homoene, propylene-α-olefin random copolymer, and block-11-592959. V. Invention Note (1〇) Polypropylene is better, and it can be used in combination of two or more kinds. Among them, a balance between heat-sealability and heat resistance is preferred. The propylene-^-smoke-like random copolymer is preferred. The content of the propane-α-carbon-burning random copolymer in the (B1) layer is preferably more than 70% by mass, and more preferably, it is composed of a propylene-α-olefin random copolymer alone. (dl) The MFR measured in accordance with JIS K 7210 test condition 14 is usually 3-15 g / 10 minutes, preferably 4-13 g / 10 minutes, and particularly preferably 6-13 g / 10 minutes. When the MFR is less than 3 g / 10 minutes, the heat-sealing strength becomes stronger, and the easy-opening property becomes worse. When co-extruded with the (A 1) layer, the interface between the layers is easily disordered, and flow mottles such as flow marks are liable to occur. On the other hand, if it exceeds 15 g / 10 minutes, the appearance of the peeled surface after peeling tends to deteriorate. The propylene homopolymer has a higher stereoregularity as measured by 13C-NMR with a cis-linking tertiary component ratio of 96% or more. . Propylene-α-olefin random copolymer (hereinafter also referred to as RPP), there are random copolymers of propylene and C2-C12 (except C3) α-olefin. The α-olefin includes ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1.pentene, 4-methyl-1-pentene, and 4-dimethyl-1- Pentene, vinylcyclopentane, vinylcyclohexane and the like. These α-olefins may be used singly or in combination of two or more kinds other than 1-butene. Of these α-olefins, ethylene is preferred. The α-olefin content is usually 3 to 8% by mass, preferably 3.2 to 7.0% by mass, and particularly preferably 3.5 to 6.0% by mass. When the α · olefin content is 3% by mass or less, low-temperature heat-sealability tends to be difficult to exhibit. On the other hand, when it exceeds 8% by mass, in the sealing film using the layer (A1) of the laminated body of the present invention as a sealing layer described later, the sealing film flows, the sealing layer becomes thin, and the heat-sealing strength decreases. Sealing-12-592959 5. Description of the invention (11) The flowing parts of the layers are fused with each other, and problems such as the inability to peel off the heat-sealed portion tend to occur. Block polypropylene (hereinafter also referred to as BPP) contains 70 to 95% by mass of polypropylene segments, and 5 to 30% by mass of propylene and C2_C12 (except C3) alpha-olefin copolymer pellets. / 〇. The polypropylene segment includes a propylene homopolymer, or a random copolymer of propylene and C2-C14 (except C3) α-olefins of 5 mass% or less. The copolymerization ratio of the α-olefin in the copolymer pellets is 5 to 40% by mass. The composition ratio of the above components in the layer (A2) of the present invention, (a2) is 30 to 60% by mass, (b) is 5 to 25% by mass, and (c2) is 20 to 40% by mass (of which (a2) + (b) + (c2) = 100% by mass). (A2) The content is preferably 35 to 58% by mass, and more preferably 40 to 55% by mass. (B) The content is preferably 10 to 23% by mass, and more preferably 12 to 20% by mass. The component (c2) is preferably 25 to 38% by mass, and more preferably 28 to 35% by mass. (a2) When the content is 30% by mass or less, the inclusions have poor sealing properties, low-temperature sealing properties, and compatibility with other components, so they are not good. On the other hand, when it exceeds 60 mass%, the easy-opening property is not good. Regarding the component (b), when the content is 5 mass% or less, the easy-opening property is inferior, which is not preferable. On the other hand, when it exceeds 25% by mass, the laminated body film is broken or gelled, and fisheye holes are increased, and the appearance is impaired, which is unfavorable. Regarding the component (c2), when the content is 20% by mass or less, the easy-opening property is inferior, which is not preferable. On the other hand, if it exceeds 40% by mass, the heat-sealed part will be drawn during peeling, and the appearance of the peeling surface will be deteriorated, which is not good. For the resins constituting the (A1) layer and the (A2) layer, and the (B1) layer and the (B2) layer of the present invention, other additives commonly used in thermoplastic resins may be appropriately blended within the range not detrimental to the purpose of the present invention, such as Antioxidants, weather resistance An-13- 592959 V. Description of the invention (12) Stabilizers, antistatic agents, slip agents, anti-blocking agents, anti-fogging agents, dyes, pigments, oils, tinctures, materials, etc., or others Thermoplastic resin. Taking specific examples of additives, the antioxidants include 2,5-bis (tertiary-butyl) hydroquinone, 2,6-bis (tertiary-butyl) p-cresol, 4,4'-thiobis (6-tri Butyl sulfide) '2,2-methylene bis (4-methyl-6-tertiary butyl phenol), octadecyl-3- (3', 5 | -di (tertiary butyl) _1 '_Hydroxyphenyl) propionate, 4,4, _thiobis (6-butylphenol), UV absorber includes ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-Hydroxy-5-methylphenyl) benzotriazole, 2-hydroxy-4-octyloxybenzophenone, plasticizers include dimethyl phthalate, diethyl phthalate, wax, mobile Paraffin wax, phosphate ester, and antistatic agents include isopentaerythritol monostearate, sorbitol monopalmitate, sulfated oleic acid, polyethylene oxide, carbon wax, and lubricants include ethylene distearate. Ammonium amine, butyl stearate, etc. The coloring agents are carbon black, phthalocyanine, quinacridone, indolin, azo pigments, phthalic oxide, iron oxide, etc. The materials are glass fiber, asbestos, mica. , Wollastonite, calcium silicate, aluminum silicate, calcium carbonate, etc. In addition, to the extent that the effect of the present invention is not hindered, various other polymer compounds may be mixed. The method for compounding the resin composition used for the (A1) layer and the (A2) layer in the present invention is not particularly limited, and a known method can be used. For example, a mixing roll, a Banbury black mixer, and a mixer such as a Hengshi, a shaker, a belt mixer, etc. are used to mix the ingredients and then use an extruder to granulate. The components (al), (b), (cl), or (a2), (b), (c2) can also be directly supplied to the forming machine by dry mixing. In addition, the components used in the (B1) layer and the (B2) layer can also be mixed with the (A1) layer and the (A2) layer. The laminated body comprising (A1) layer and (B1) layer, or the laminated body comprising (A2) layer and (B2) -14-592959 V. Description of the invention The laminated body of (13) layer can be co-extruded, for example, Co-extrusion lamination method and other known extrusion lamination forming method and forming mechanism. The sealing film of the present invention is composed of a sealing layer and a supporting layer. The features of the present invention are (A1) layer and (A2) layer of the laminated body as the sealing layer, and (B1) layer and (B2) layer as the supporting layer. The thickness of the sealing film of the present invention is usually 20 to 70 μm, preferably 25 to 60 μm, and more preferably 30 to 55 μm. When the thickness is 20 μm or less, impact resistance, heat-sealing strength, and water vapor permeability are poor, so it is not good. On the other hand, when it exceeds 70 μm, the easy-opening property is poor and poor. The thickness ratio of (A1) layer and (B1) layer, (A1) layer / (B1) layer = 2/8 to 8/2, preferably 1.5 / 8.5 to 8.5 / 1.5, and 1/9 to 9 / 1 is better. The thickness ratio of (A2) layer and (B2) layer, usually (A2) layer / (B2) layer = 2/8 to 8/2, preferably 1.5 / 8.5 to 8.5 / 1.5, and 1/9 to 9 / 1 is better. Regarding the layer structure, (A1) layer / (B1) layer, and (A2) layer / (B2) layer two kinds of two layers, and (A1) layer / (B1) layer / (A1) layer; and (A2) Layers / (B2) layers / (A2) layers are preferred. The easy-opening laminated body of the present invention is characterized in that 'the (B1) layer or (B2) layer of the laminated body or the sealing film of the present invention has a side or opposite side of the (A1) layer or (A2) layer, and the layer is selected from aluminum foil , Metal vapor-deposited film, silicon oxide vapor-deposited film, vinylidene chloride resin layer, ethylene-vinyl acetate copolymer resin saponified resin layer, polyamide resin layer, polyester resin layer, polycarbonate resin layer, and oxygen absorbent The layer comprises at least one layer (c). Among them, a case, a metal vapor-deposited film, a silicon oxide vapor-deposited film, a vinylidene chloride resin layer, an ethylene-vinyl acetate copolymer resin saponified resin layer 'can be used as the gas barrier layer. -15- 592959 V. Description of the invention (14) The oxygen absorber layer includes a layer containing iron oxide. The easily-openable laminated body of the present invention can be obtained by laminating (C) on the laminated body or the sealing film of the present invention with or without an adhesive using a known dry laminating machine. The container of the present invention is characterized by using the sealing film of the present invention or an easily-openable laminate. The container includes a self-supporting pouch container such as a pouch container, a stand-up pouch, and the like, and a container in which a sealing film or an easily-openable laminated body of the present invention is used as a lid material for a concave resin container. Concave resin containers have multilayer sheets made of polypropylene or polyethylene, adhesive resins and ethylene-vinyl acetate saponification resin, polypropylene or polyethylene, multilayer resins made of adhesive resin and vinylidene chloride resin Sheet, sheet made of resin such as polypropylene or polyethylene, adhesive resin, ethylene-vinyl acetate saponified resin, and oxygen absorbent, and formed by vacuum forming and compression forming. When these concave resin containers are connected to the (A 1) layer and (A2) layer 'series resin container of the laminated body, sealing film, or easy-opening laminated body of the present invention, the temperature can be from 12 to 25 (rc It is made by heat-sealing from 0.1 to 20 seconds. In addition, the heat-sealing form used in the container of the present invention is wire seal, flat seal, roll seal, etc. The flat seal can obtain a beautiful appearance of the peeling surface, stable heat seal strength, and heat seal temperature. The width is wide, and the characteristics of the peeling surface of the sealing film and the easy-opening laminate of the present invention can be fully obtained. The multilayer, sealing film or easy-opening laminate of the present invention can be used as a cover material of the container of the present invention. The present invention The container is easy to open, and has excellent peeling surface appearance and container moldability. It can be used as a food container such as a tofu container, a rice container, or a medical container. In particular, the container is easy to open and has a good peeling surface appearance, and is suitable for use as a food container. -16-592959

V. Description of the Invention (is) The present invention is described in detail by the following examples, but the present invention is not limited to these examples. The test methods and evaluation methods used in the examples are as follows. Peak junction temperature (Ted and crystallization energy (Λ H, DSC device: DSC7 type g compound manufactured by PERKIN-ELMER Co., Ltd. Mass: about 2 to 5 mg Measurement method: The sample is heated to a temperature of 230 ° C and held for 5 minutes 'Decrease the temperature at 20 ° C / min to obtain T cp and △ η. The heat seal strength is determined by using a tensile tester (RTA_ 100) manufactured by Oritech, and the speed is 3 00 mm / min. T-type peel strength. The appearance of the heat-sealed peeled surface is a test piece with a heat-sealed temperature of 1 80 ° C. The peeled surface after the seal strength measurement is visually observed, and the state of fluff or residual film is observed. The appearance is beautiful and no problem. 〇: The peeling part is slightly fluffy, and it can also be used. Scoring: ◎: Smooth and complete peeling. ○: Some film breaks during peeling. It can also be used. △: The film is broken during peeling and cannot be used. • 17-592959 V. Description of the invention (16) X: It is peeled into two layers. : (A 1) calendar component resin kl) component PEB1: from ethylene 1.5 Propylene-ethylene-butene-1 terpolymer (Tcp 84.5 ° C, AH63.1J / g, MFR5.3g / 10 minutes) composed of mass%, butene-1 4.5% by mass, and propylene content 93.5% by mass PEB2 : Propylene-ethylene-butene-1 terpolymer (Tcp 83.1. (: △ H 61.2J / g, MFR 7.2) consisting of 2% by mass of ethylene, butene-18% by mass, and 90% by mass of propylene g / 10 minutes) PEB3: Terpolymer composed of 0.5% by mass of ethylene, 0.5% by mass of butene-1, 99.0% by mass of propylene (Tcp 90.8 ° C, AH 92.8J / g, MFR 6.2g / l 0 minutes) (b) Ingredient LD1: Use low density polyethylene with a density of 0.918g / cm3 and MFR7.2g / 10 minutes. LD2: Use low density polymer with a density of 0.921g / cm3 and MFR 3.5g / 10 minutes. Ethylene. LD3: Low density polyethylene with a density of 0.922 g / cm3 and MFR 0.4 g / 10 minutes. PE1: High density polyethylene with a density of 0.95 8 g / cm3 and MFR 5.8 g / 10 minutes. (C 1 ) Ingredient LLD1M uses a density of 0.923 g / cm3 and MFR 0.5g / 10 minutes straight -18- 592959 V. Description of the invention (17) Low-density polyethylene glycol. LLD2: Use density 0.928g / cm3 and MFR 2.1g Low-density polyethene in 10 minutes. LLD 3: Use density 〇 918g / cm3 and MFR3.2g / 1〇 * bell linear low density polyethylene. @ 1) Layer composition tree 1 (dl) composition RPP1: A propylene-ethylene random copolymer having an ethylene content of 4.5% by mass and an MFR of 8.1 g / 10 minutes was used. RPP2: A propylene-ethylene random copolymer having an ethylene content of 3.5 mass% and an MFR of 6.2 g / 10 minutes was used. PP1: Propylene homopolymer with MFR 6.8 g / 10 minutes was used. BPP1: A block polypropylene having an ethylene-propylene random copolymer bomb content of 20% by mass and an MFR of 2.3 g / l for 10 minutes was used. (A 2) layer component resin (a2) component PEB1: from ethylene 2 mass. / 〇, butene- 丨 4.5% by mass, propylene 93 5 mass weight ° / 〇 propylene-ethyl-butane-butene-1 terpolymer (TCp 84.5 ° c, AH 63.1J / g, MFR 5.3g / 10 minutes) PEB2: 2% by mass of ethylene, butene; [8% by mass, 90% by mass of propane. Composition of propylene-ethene-butene · 1 terpolymer (T cp 8 3.1 ° C, AH 61.2J / g, MFR 7.2g / 10 minutes) PEB3: 4% by weight of ethylene, butene-i A propylene-ethylene-butene-1 terpolymer (Tcp 81, -19- 592959) composed of 15 mass% and propylene content (%). Jade, description of the invention (18) ΔΗ 63.8J / g, MFR 6.8g / 10 minutes) PEB4: propylene-ethylene-butene-1 terpolymer composed of 0.5% by mass of ethylene, 0.5% by mass of butene-1, and 99.0% by mass of propylene (Tcp 9.0.8 ° C, ΔΗ 92.8J / g, MFR 6.2g / 10 minutes) Ingredient LD1: Use low-density polyethylene with a density of 0.918g / cm3 and MFR 7.2g / 10 minutes. LD2: Use low density polyethylene with a density of 0.921g / cm3 and MFR3.5g / 10 minutes. LD3: A low-density polyethylene having a density of 0.922 g / cm3 and an MFR of 0.4 g / 10 minutes was used. PEI M uses high-density polyethylene with a density of 0.95 8 g / cm3 and MFR 5.8 g / 10 minutes. Composition LLD1: Use metallocene catalyst linear low-density polyethylene with a density of 0.922 g / cm3 and MFR 3.5 g / 10 minutes. LLD2 .. A metallocene catalyst-based linear low-density polyethylene with a density of 0.928 g / cni3 and MFR 7.5 g / 10 minutes was used. LLD3: Metallocene catalyst linear low-density polyethylene with a density of 914 g / cm3 and MFR of 1.5 g / 10 minutes. LLD4: A metallocene catalyst-based linear low-density polyethylene having a density of 0.922 g / cnl3 and an MFR of 4.5 g / 10 minutes was used. (B2) Layer formation (d2) Composition -20- 592959 V. Description of the invention (19) LLD1 ·· Use metallocene catalyst linear low-density polyethylene with a density of 0.922g / cm3 and MFR 3.5g / 10 minutes. LLD2: Metallocene catalyst linear low-density polyethylene with a density of 0.992 8 g / cm3 and MFR 7.5 g / 10 minutes. PE1: Use high-density polyethylene with a density of 0.95 5g / cm3 and MFR 8.2g / 10 minutes. PP1: A propylene homopolymer with MFR 7.8 g / 10 minutes was used. Examples 1 to 2 and Comparative Examples 1 to 1 4 The components of the (A1) and (A2) layers and the components of the (B1) and (B2) layers are shown in Tables 1 and 2 (A1) The types and blending amounts of the components of the layer or (Α2) layer and the components of the (B1) layer or (B2) layer are mixed with a vibrator, and then a biaxial extruder (type KK 37 manufactured by Kobe Steel) is used. Granulation was performed at a temperature of 190 to 2 at 10 ° C at a screw revolution of 250 rpm. Nine tablets each obtained from T indium molding were formed using a T-shaped mold forming machine (product of Toshiba Machinery Co., Ltd., 65ηιηιφ, mold width 1,300mm) at a mold temperature of 25 (TC. The layer structure was (A1) layers / ( B1) layer or (A2) layer / (B2) layer of two kinds of two-layer structure. The thickness of each layer is 7.5 μm for each layer of (A1) and (A2), and 42.5 μm for each layer of (B1) and (B2). Second, Each of the obtained T-shaped mold-laminated films and a biaxially-stretched polymer amine film with a thickness of 15 μm were laminated on the side of the (B1) layer or (B2) layer using a polyurethane-based adhesive by the dry lamination method. The test piece is used for the production, followed by a checkerboard pattern flat rod sealing mechanism that also has the first seal.

-21-592959 V. Description of the invention (20) and the second stage of the sealed line seal mechanism of the commercial Shikoku Chemical Machinery Co., Ltd. Desai Pod FS02 filling and sealing machine, the second stage of the seal rod and The first flat seal mechanism with the same checkerboard pattern, in a polypropylene container (three sides of 7cmx7cm, 3cm in height), at the flange portion of the container, each laminated film was heat-sealed at a pressure of 0.29 M pa The heat-sealing time is 1.5 seconds, and the heat-sealing temperature is 160 ° C, 180 ° C, and 200 ° C. The heat-sealing time is cut into 15mm width and used as a test piece for evaluating heat-sealing characteristics.

Evaluation of heat seal strength obtained by heat treatment Using the aforementioned container, a boiling treatment was performed at a temperature of 90t x 30 minutes. The flange portion of the container subjected to this heat treatment was cut out to a width of 15 mm, and the heat seal strength was measured. Evaluation of cooked leaks The container filled with the aforementioned rice was immersed in water, and the container was observed to see whether air bubbles had formed in the stomach to evaluate whether the heat-sealed part had leaked. The evaluation was based on visually observing the heat seal for leaks in 30 containers, which were divided into the following Ξ.

〇: No leakage at all △: 1 to 5 leaks X: 6 or more leaks The above results are shown in Tables 3 and 4. -22- 592959 V. Description of the invention (21) (B1) layer-constituting resin (dl mixed amount (% by mass)) ο (N — m type I _I (N (N (NQQQ μ-ί μ-3 μ —Ί ddd compounding amount (% by mass) ΟΟΟΟΟΟΟΟΟΟΟΟ ^^-, 02222222222 ^^ 2 2 100 100 100 100 100 100 100 ^ T'PhPhPhPhPhPh RPP1 RPP1 RPP1 RPP1 RPP2 RPP1 PP1 (A1) layer constituting resin (cl component blending amount (% by mass)) ^ OOWOOCNqoOOCNCNCNCNCNCNCN H rH 1-HH tH rH r-H ^ -H rH rH i-Hο mm ο ο ^ (^ \ J rH τ—Η Type LLD1 LLD1 LLD1 LLD2 LLD3 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD1 LLD2 LLD1 LLD1 LLD1 ⑼Composition of ingredients (mass%) oooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooomm丨 H r * H r * H t1H, H O'i r_H ν * Η τ ..... < ι 1 < t " * H Type QQQQQQQQQQQQQQQQQ m ΓΠ (Ν rH τ—Η QQQQQQ μ-) iJ μ -ί η-ί ι—) μ-ί (al relative amount (% by mass)) OOOOtnOOCNOOOOOOO or ^ oooo 卜 oovo 卜卜卜卜卜 卜卜 〇 tr > Ο Ο Ο Ο inch α 卜卜 00 〇Type PEB1 PEB1 PEB1 PEB2 PEB3 PEB1 PEB1 PEB1 PEB1 PEB1 PEB1 PEB1 PEB1 PEB1 PEB3 PEB1 PE1 PEB1 PEB1 PEB2 PEB1 RPP1 PP1 〇— (N m inch m * CN | C ^) Vs〇 ^^-OO r—Η ι—Η τ— (r— ^ * ζ = Γ7 * = 77 rzrr * z = T7 * = T7 * = T7 * = Γ7 * ==? " rrr? trr? t = T7 ^ j ^ i $ Ni§ \ i§ \ i§Ni§ \ ig \ i5 \ i§ \ i5 \ i§ \ i5 \ i§ \ i§ \ Compilation Compilation Compilation Compilation {| i (| 1; { | &|;i; | i; | ι;!; | ι; | ·; | ι; | ι; | ι; | ΐ (| ΐ (| ·; Comparative Example 1 Comparative Example i 2 Comparative Example 3 Comparative Example 4 Comparative example 5 Comparative example 6 Comparative example 7 -23- 592959 V. Description of the invention (22) < N «_§ 001 ooi ooiooi ooi001 001 ~~ ^ 001 001 001 001 001 001 001 001 001 § 001 (% * M )_ring

Idd 5ΤΊ i cm ιατι ιατι (Ncm IIQTI ιατι ST! I cm ST! STI ιατι ιατι ιατι ιατι ιατι ιατι ιατι I Φ) Chain (q) ss Negotiated fsrslv) (% * M) &n_o; (Nm (N0o O 0000) inch-inch mmm rn

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TH (Nmmmmrn (Nmmr-Hcn QQQQQQQQQQQQ oooo ^ noooo ^ nooo inch i〇 inch τ ~ Ι r—H r—H rH r—H rH r—H (" N) (" S ^ pQmmpQpqphpPhpPwpPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhpPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPhwPqPqwPqwpqwpqwpqwpqwqpqwqpqwpqwpqwpqwpqwpqwpqwpqwpqwp cmIs inch cm ιατι (Ncm ιατι ι cm

OOOOOOO inchcn (N (N (N (N (N mmN iH mmm QQQ pq QQQ _1 ^ h-1 Ph ^ U ^ 1 oamo 〇〇o (N rn ^ r) i〇m in t—H t--H rH r—H i—H PQ PQ pq Ph PQ pq rn w pq ω Ph pq pq ω Ph Pl Pl Ph Ph Ph Pl 2 ^ 1 ^ π Mf 镒 ugly 0-1 ^ 00 Marina 镒 qq1HISIS ^ lwIs · ® s & 61 Pei Mss i 91 earthquake® -24- 592959 V. Description of the invention (23) Leakage 000000000000000 < 〇 <] 〇 < 0 X χ < < <] Kaifeng Property X < 1 XX < < < Appearance of peeling surface ◎ ◎ 〇 ◎◎◎◎◎◎◎ <] 〇 > < 〇X <] XX <] XX side ίί 6 6 5 g touch e 200 ° C 10.6 11.0 7.6 11.4 11.1 10.1 11.8 6.8 10.2 9.1 9.5 11.4 10.5 6.5 17.5 (N m 〇〇 ^ (N 〇〇〇'〇 ^ 〇〇ι > 180 ° C r ^^ (NjT ^ 〇〇v〇0 〇t〇 ^ OOCNO (NO ^^ t οο ^^ 〇αΝ〇ν〇〇〇〇〇〇〇 ^^^ ηηr—H r * H rH r—H r * H t—H 00 m (N (N » 〇inch inch o ^ ^ rn cn ^ 160 ° C 9.6 10.3 6.2 10.4 9.4 9.2 10.4 1 6.2 9.4 8.6 8.2 7.4 6.9 6.1 14.3 in irj oo (N (N (NH rH heat seal strength (N / 15mm width) 200 ° C 11.2 11.9 8.6 12. 5 11.8 10.8 13.1 7.8 10.4 9.8 10.2 14.3 13.8 8.1 8.6 3.1 32.6 26.4 42.3 24.5 22.4 34.6 180 ° C 10.9 11.4 8.2 12.1 11.2 10.4 12.6 7.3 10.2 9.5 9.8! 12.1 11.5 7.8 6.8 2.2 18.0 15.2 19.8 16.8 15.2 4.5! 160 ° C inch —〇〇r ^ (N — m «O00 (Nr ^ 00 inch (N (N Or ^ c ^^ oOr-ivdasO ^ aNododvood rH tH rH i-1 r— < 〇〇〇〇 (Sj CO i ~ l CvJ Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 1 COMPARATIVE EXAMPLE 2 COMPARATIVE EXAMPLE 3 COMPARATIVE EXAMPLE 4 COMPARATIVE EXAMPLE 5 COMPARATIVE EXAMPLE 6 Specific Example i 7 -25- 592959 V. Description of the Invention (24) Leakage 000000000000000 < 1OX <] XXXXX Openability ◎ ◎◎◎◎◎◎◎◎ 〇〇 < 1 X 0 XX < 1 XX appearance of peeling surface ◎◎◎◎◎◎◎◎◎ XXXXXX side * N 1 You $ m 200 ° C ^ 4 i 1 i ， H f 4 r1 H v H f%) »i ， r * H fO 2 inch 2 n ^ n 180 ° C (N inch… heart―a inch inch m — τ * Η rH rH rH r * HH r * H rH t * H ^ CN i-ι ^ ― 'Ο 160 ° C OmcN ^ OO ^ cN ^ nv ^ rO r * H rH rH H r-Η rH i—H • rH r—H rH 〇 Heat seal strength (N / 15mm width) 200 ° C OOC ^ O ^ mONOOOOOO ^ OVO ^ D iH y—i (NJ (N) r—ti—H (Nj t—ti—ir—H (S) g 00 ^ ^ ^ m 00 180 ° C m oo. (Nm bu ^ noo ^ o inch. r «H rH τ ~ Η (N) r ~ < r ~ li ~ H (N) (NJ g inch JQ ... 2 one inch 160 ° C (N. inch 〇〇— (N and W inch (N ^ O inch H ^ · Η rH r ~ H rH τ * Η 2 rn (N ON 't-η (N tv〇 卜 〇〇〇〇〇— (Nm inch i " «H i ~ t ι« · η t * h fs ^ (N | CS (N (N CN (N (N Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kuang Han Kuang Fa IK {$ (| «(| B (|« (IK | B (IK IK IK IK {_ Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example π Comparative Example 12 Comparative Example 14 Comparative Example 14 • 26- 592959 V. Description of the Invention (25) Effect of the Invention The laminated body and the sealing film of the present invention have easy-opening properties and a peeling surface Excellent appearance 'The heating cooking seal strength will not decrease, and the container has excellent moldability. The container of the present invention has easy opening and sealing ability, and after peeling off one week after the passage ± 4 rrfe A, the appearance is excellent. , The sealed post will not leak and is cheap.

-27,

Claims (1)

Sixth, the scope of patent application No. 9 1 1 22 1 20 "Laminated body, sealing film and container" patent case (revised on March 12, 1993) Λ scope of patent application: 1. A laminated body, including 55 ~ 85 Mass% propylene-ethylene-butene terpolymer U1), 10 to 35 mass% low density polyethylene (b), and 5 to 20 mass% linear low density polyethylene (cn (where (al) + (b ) + (cl) zi 100% by mass) The layer [(A 1) layer] of the resin composition and the layer [(B1) layer] containing a propylene polymer (dl). 2 · If you apply for a patent The laminated body according to the first item, wherein the propylene-based polymer (d 1) is at least one resin or two selected from the group consisting of a propylene homopolymer, propylene-0-ene, a random copolymer, and a block polypropylene. A mixture of resins and above. 3. The laminated body according to item 1 or 2 of the scope of patent application, wherein the propylene-ethylene-butene terpolymer (a 1) is measured using a differential scanning calorimeter (DSC). The peak temperature (T cp) is 7 5-9 0 ° C, and the crystallization energy (△ Η) is 5 5-8 0 J / g. 4. For example, the laminated body of item 1 or 2 of the scope of patent application, where The olefin-ethylene-butene terpolymer (a 1) is a copolymer having a propylene content of 96 to 72% by mass, an ethylene content of 1 to 10% by mass, and a butene-1 content of 3 to 18% by mass. 5 · If applying for a patent The laminated body in the range 1 or 2, wherein the density of the linear low-density polyethylene (cl) is 0.991 5 to 0.93 5 g / cm3, and the melt flow rate is 0.5 to 15 g / 10 minutes. 6 . For example, the laminated body of item 1 or 2 of the scope of patent application, wherein the content of the propylene-α-olefin random copolymer in the (B 1) layer exceeds 70% by mass. Includes 30 to 60% by mass of propylene-ethylene-butene copolymer U2), 5 to 25% by mass of low density polyethylene (b), and 20 to 40% by mass using metallocene catalysts or one side A layer of a resin composition [(A2) layer made of a linear low-density polyethylene (c 2) made of a catalyst (where (a 2) + (b) + (c 2) = 100% by mass)) ], And a layer [(B2) layer] made of a linear low-density polyethylene (d2) using a metallocene catalyst or a single-sided catalyst. 8 · The laminated body according to item 7 in the scope of patent application, wherein the crystallization peak temperature (T cp) of the propylene-ethylene-butene copolymer (a 2) measured by a differential scanning calorimeter (DSC) is 7 From 5 to 90 ° C, the crystallization energy (△ η) is 5 5 to 8 0 J / g. 9. The laminated body according to item 7 or 8 of the scope of patent application, wherein the propylene-ethylene-butene terpolymer (a2) is a propylene content of 96 to 72% by mass, an ethylene content of 1 to 10% by mass, and butene-1 Copolymer with a content of 3 to 18% by mass. 1 〇 If the laminated body of item 7 or 8 of the scope of patent application, wherein the density of the component (c2) of the (a 2) layer and the component (d2) of the (B2) layer are 0.900 to 0.940 g / cm 3 0.5 ~ 20g / 10 minutes. 1 1 · A sealing film, which is characterized in that, in the laminated body according to any one of claims 1 to 10 of the application scope, the (A1) layer or (A2) layer of the laminated body is used as a sealing layer. 1 2. An easy-opening laminated body, characterized in that the laminated body as in any one of claims 1 to 10 in the scope of patent application, or the sealing film contained in item 11 in the scope of patent application (B1) Layer or (B2) layer with (A1) layer or (A2) layer on the side or opposite side, with at least one layer selected from the group consisting of aluminum foil, metal vapor-deposited film, silicon oxide vapor-deposited film, vinylidene chloride resin layer, ethylene-ethyl acetate Ester 592959 6. Patent application scope Copolymer resin saponified resin layer, polyamide resin layer, polyester resin layer, polycarbonate resin layer and oxygen absorber layer. 13. A container characterized by using a sealing film such as the scope of application for item 11 of the patent application or an easily-openable laminate as described in the scope of application for patent application 12.