Hot-melt laminated film

Abstract

Provided is a polyethylene-based laminated film suitable for use in packaging bags and the like, which is excellent in tearability while maintaining excellent properties such as mechanical strength and anti-blocking, and which is further improved in mechanical strength such as Young's modulus while maintaining excellent properties such as anti-blocking, and which is excellent in lamination strength with an outer layer-side film and also excellent in anti-blocking while maintaining excellent properties such as sealing strength and impact resistance. This problem is solved by a laminated film having (A) a heat-fusible layer, (B) an intermediate layer, and (C) a laminated layer each containing a linear low-density polyethylene derived from petroleum, and containing a bio-based polyethylene derived from plants in at least one of the (A) heat-fusible layer, (B) intermediate layer, and (C) laminated layer.

Description

Technical Field

[0001] The first invention of this application relates to polyethylene-based laminated films, and more specifically, to laminated films suitable for use as packaging films such as tear-off bags and zipper bags, especially those with excellent tear resistance and reduced environmental impact due to the use of plant-derived resins.

[0002] The second invention of this application relates to polyethylene-based laminated films, and more specifically, to laminated films suitable for use as packaging films, especially those with excellent strength (Young's modulus) and reduced environmental impact through the use of plant-derived resins.

[0003] The third invention of this application relates to a polyethylene-based laminated film, and more specifically, to a laminated film suitable for use as a packaging film, which has excellent lamination strength and anti-caking properties with the outer side film, and whose environmental impact is reduced by using resins derived from plants. Background Technology

[0004] Packaging bags made by heat-sealing multilayer plastic films are widely used to contain various contents such as food, beverages, detergents, shampoos, and cosmetics. Various polyethylene-based laminated films with a three-layer structure, consisting of a heat-sealing layer laminated from the inner side, an intermediate layer, and a base film laminated on the outer side, have been proposed as the inner layer of the heat-sealing portion of such multilayer plastic films (see, for example, Patent Document 1). These laminated films are designed to have suitable characteristics from the viewpoints of sealing strength, impact resistance, and anti-caking properties.

[0005] As an important type of packaging bag, there are tear-off bags and zipper bags. In tear-off bags and zipper bags, the bag is usually torn when opened, so the film needs to have moderate tearability (not too high tear strength).

[0006] Furthermore, it has been proposed that polyethylene-based laminated films with a three-layer structure, consisting of a heat-sealing layer laminated from the inner side, an intermediate layer, and a substrate film (substrate layer) laminated on the outer side, be used as the inner layer of the heat-sealing portion of a plastic multilayer film (see, for example, Patent Document 1). These laminated films are designed to have suitable characteristics from the viewpoints of sealing strength, impact resistance, and anti-caking properties, but when used in applications such as stand-up pouches, there is a strong demand for laminated films with higher mechanical strength.

[0007] In addition, various polyethylene-based laminated films with a three-layer structure, consisting of a heat-sealing layer laminated from the innermost side, an intermediate layer, and a substrate film (substrate layer) laminated on the outer side, have been proposed as the inner layer of the heat-sealing portion of a plastic multilayer film (see, for example, Patent Document 1). These laminated films are designed to have suitable characteristics from the viewpoints of sealing strength, impact resistance, and anti-caking properties, but in recent years there has been a demand for improved lamination strength of the outer layer films and further improvements in anti-caking properties.

[0008] [Existing Technical Documents]

[0009] [Patent Literature]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2005-14461. Summary of the Invention

[0011] [The problem that the invention aims to solve]

[0012] In view of the above-mentioned technical background, the purpose of the first invention of this application is to provide a polyethylene-based laminated film suitable for use in packaging bags and the like, which has excellent tear resistance while maintaining excellent mechanical strength, anti-caking properties and other properties.

[0013] In view of the above-mentioned technical background, the object of the second invention of this application is to provide a laminated film suitable for use in packaging bags and the like, which further improves mechanical strength such as Young's modulus while maintaining excellent properties such as anti-caking properties.

[0014] In view of the above-mentioned technical background, the purpose of the third invention of this application is to provide a polyethylene-based laminated film suitable for use in packaging bags, etc., which has excellent lamination strength with the outer side film and excellent anti-caking properties while maintaining excellent sealing strength, impact resistance and other excellent properties.

[0015] [Technical means used to solve the problem]

[0016] Through careful investigation, the inventors discovered that in a laminated film having a heat-fusion layer, an intermediate layer, and a laminated layer respectively containing linear low-density polyethylene from petroleum, adding low-density polyethylene from biomass to at least one of these layers results in appropriate tear strength, enabling the production of packaging bags with excellent tear resistance, thus completing the first invention of this application.

[0017] In other words, the first invention of this application relates to: [1]

[0019] A laminated membrane comprising: a (1A) heat-fusion layer, a (1B) intermediate layer and a (1C) laminate layer, each containing linear low-density polyethylene derived from petroleum, wherein at least one of the (1A) heat-fusion layer, the (1B) intermediate layer and the (1C) laminate layer contains more than 3% by mass of biopolymer polyethylene derived from plants.

[0020] The following [2] to [7] are all preferred embodiments or implementations of the first invention of this application. [2]

[0022] The laminated film as described in [1], wherein the heat of fusion ΔH from 0°C to 130°C, calculated from the melting curve obtained by DSC determination, is 135 to 164 J / g. [3]

[0024] The laminated membrane as described in [1] or [2], wherein the molecular weight distribution Mw / Mn of the aforementioned plant-derived biopolymer polyethylene is 3.5 or higher. [4]

[0026] The laminated film as described in any one of [1] to [3] has a (1D) substrate layer on the side of the (1C) laminate layer, directly or across the bonding layer. [5]

[0028] A packaging bag comprising a laminated film as described in any one of [1] to [4]. [6]

[0030] The packaging bag described in [5] is a tear-open packaging bag. [7]

[0032] The packaging bag described in [5] is a zippered packaging bag.

[0033] Through careful investigation, the inventors discovered that in a laminated film having a heat-fusion layer, an intermediate layer, and a laminated layer respectively containing linear low-density polyethylene from petroleum, the Young's modulus is significantly improved by adding low-density polyethylene from biomass to the intermediate layer, thus completing the second invention of this application.

[0034] That is, the second invention of this application relates to: [8]

[0036] A laminated membrane comprising: a (2A) heat-fusion layer, a (2B) intermediate layer and a (2C) laminate, each containing linear low-density polyethylene derived from petroleum, wherein the (2B) intermediate layer contains biopolymer polyethylene derived from plants.

[0037] The following [9] to

[14] are all preferred embodiments or implementations of the second invention of this application. [9]

[0039] The laminated film as described in [8], wherein the heat of fusion ΔH from 0°C to 130°C, calculated from the melting curve obtained by DSC determination, is 135 to 164 J / g.

[10]

[0041] The laminated membrane as described in [8] or [9], wherein the molecular weight distribution Mw / Mn of the aforementioned plant-derived biopolymer polyethylene is 3.5 or higher.

[11]

[0043] The laminated film as described in any one of [8] to

[10] , wherein the (2A) heat-fusion layer, the (2B) intermediate layer and the (2C) laminated layer all contain biopolymer polyethylene derived from plants.

[12]

[0045] The laminated film as described in any one of [8] to

[11] has a (2D) substrate layer on the side of the (2C) laminate layer, directly or across the bonding layer.

[13]

[0047] A packaging bag comprising a laminated film as described in any one of [8] to

[12] .

[14]

[0049] A stand-up pouch comprising a laminated film as described in any one of [8] to

[12] .

[0050] Through careful investigation, the inventors discovered that in a laminated film having a heat-fusion layer, an intermediate layer, and a laminated layer respectively containing linear low-density polyethylene from petroleum, the lamination strength is significantly improved and the anti-caking property is also improved by adding linear low-density polyethylene from biomass to at least one of these layers, thus completing the third invention of this application.

[0051] That is, the third invention of this application relates to:

[15]

[0053] A laminated film comprising: a (3A) heat-fusion layer, a (3B) intermediate layer and a (3C) laminate layer respectively containing linear low-density polyethylene derived from petroleum, wherein at least one of the (3A) heat-fusion layer, the (3B) intermediate layer and the (3C) laminate layer contains at least 3% by mass of bio-based linear low-density polyethylene derived from plants.

[0054] The following

[16] to

[20] are all preferred embodiments or implementations of the third invention of this application.

[16]

[0056] The laminated film as described in

[15] , wherein the (3C) laminate contains at least 3% by mass of biogenic linear low-density polyethylene derived from plants.

[17]

[0058] The laminated film as described in

[15] or

[16] , wherein the heat of fusion ΔH from 0°C to 130°C, calculated from the melting curve obtained by DSC determination, is 135 to 164 J / g.

[18]

[0060] The laminated film as described in any one of

[15] to

[17] , wherein the molecular weight distribution Mw / Mn of the aforementioned biopolymer linear low-density polyethylene derived from plants is 3.5 or more.

[19]

[0062] The laminated film as described in any one of

[15] to

[18] has a (3D) substrate layer on the side of the (3C) laminate layer, directly or across the bonding layer.

[20]

[0064] A packaging bag comprising a laminated film as described in any one of

[15] to

[19] .

[0065] [The effects of the invention]

[0066] The laminated film of the first invention of this application maintains the excellent properties of conventional polyethylene laminated films such as mechanical strength and anti-caking properties, while significantly improving tear resistance and reducing the environmental impact during its manufacturing process. It has high practical value and surpasses the limits of prior art, making it suitable for various applications, including packaging bags with tear-off closures and zipper closures.

[0067] The laminated film of the second invention of this application maintains the excellent properties of conventional polyethylene laminated films such as anti-caking properties, while significantly increasing the Young's modulus and reducing the environmental impact during its manufacturing process. It has high practical value and surpasses the limits of prior art, making it suitable for use in various applications, including packaging bags such as stand-up pouches.

[0068] The laminated film of the third invention of this application maintains the excellent properties of conventional polyethylene laminated films such as sealing strength and impact resistance, while significantly improving the lamination strength and reducing the environmental impact during its manufacturing process. It has high practical value and is suitable for use in various applications, including packaging bags, at a level that surpasses the limits of prior art. Detailed Implementation

[0069] The following describes in detail the various embodiments of the first invention of this application.

[0070] The first invention of this application is a laminated film comprising: a (1A) heat-fusion layer, a (1B) intermediate layer and a (1C) laminated layer respectively containing linear low-density polyethylene derived from petroleum, wherein at least one of the (1A) heat-fusion layer, the (1B) intermediate layer and the (1C) laminated layer contains more than 3% by mass of biopolymer polyethylene derived from plants.

[0071] That is, the laminated film of the first invention of this application contains linear low-density polyethylene derived from petroleum in each of the layers of (1A) heat-fusion layer, (1B) intermediate layer and (1C) laminated layer.

[0072] Furthermore, the laminated film of the first invention of this application contains a predetermined amount of plant-derived biopolymer polyethylene in at least one of the (1A) heat-fusion layer, (1B) intermediate layer and (1C) laminated layer.

[0073] Linear low-density polyethylene derived from petroleum

[0074] The linear low-density polyethylene derived from petroleum used in the first invention of this application is a homopolymer of ethylene manufactured using petroleum as a raw material, or a copolymer of ethylene and α-olefin manufactured using petroleum as a raw material, and can be synthesized by commonly known manufacturing methods.

[0075] α-Olefins can be compounds having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc., and mixtures thereof may also be used. α-Olefins are more preferably compounds having 4, 6, or 8 carbon atoms, or mixtures thereof, such as 1-butene, 1-hexene, 1-octene, or mixtures thereof.

[0076] Linear low-density polyethylene derived from petroleum is available for commercial sale, such as 2040F (C6-LLDPE, MFR; 4.0, density; 0.918 g / cm³) manufactured by Ube-Maruzen Polyethylene Co., Ltd. 3 ).

[0077] The density of linear low-density polyethylene derived from petroleum is preferably 0.905 to 0.935 g / cm³. 3 The preferred value is 0.915 to 0.930 g / cm³. 3 The preferred MFR is 0.5 to 6.0 g / 10 min, and more preferably 2.0 to 4.0 g / 10 min.

[0078] The molecular weight distribution (expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn): Mw / Mn) of linear low-density polyethylene derived from petroleum is preferably from 1.5 to 4.0, more preferably from 1.8 to 3.5. This Mw / Mn ratio can be determined by gel permeation chromatography (GPC).

[0079] The linear low-density polyethylene derived from petroleum, from the endothermic curve measured by a differential scanning calorimeter (DSC) at a heating rate of 10°C / min, has one or more sharp peaks. The highest temperature of these peaks, i.e. the melting point, is preferably between 95 and 140°C, and more preferably between 105 and 130°C.

[0080] Linear low-density polyethylene derived from petroleum can be manufactured using conventionally known methods, employing catalysts such as multi-site catalysts like Ziegler catalysts or single-site catalysts like metallocene catalysts. From the viewpoint of obtaining linear low-density polyethylene capable of forming films with narrow molecular weight distributions and high strength, the use of single-site catalysts is preferred.

[0081] The aforementioned single-active-site catalyst is a catalyst capable of forming uniform active species, typically modulated by contacting a metal aromatic transition metal compound or a non-metal aromatic transition metal compound with an activation auxiliary catalyst. Compared to multi-active-site catalysts, single-active-site catalysts are preferred because their active site structure is uniform, allowing for the polymerization of high-molecular-weight polymers with highly uniform structures. Metal aromatic catalysts are particularly preferred. A metal aromatic catalyst is a catalyst comprising: a transition metal compound of Group IV of the periodic table containing a ligand with a cyclopentadienyl skeleton, an auxiliary catalyst, an optional organometallic compound, and a support.

[0082] In the aforementioned transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton, the cyclopentadienyl skeleton refers to cyclopentadienyl, substituted cyclopentadienyl, etc. The substituted cyclopentadienyl group has at least one substituent selected from hydrocarbon groups having 1 to 30 carbon atoms, silyl, silyl-substituted alkyl, silyl-substituted aryl, cyano, cyanoalkyl, cyanoaryl, halogen, haloalkyl, halosilyl, etc. The substituted cyclopentadienyl group may have two or more substituents. Furthermore, the substituents may bond to each other to form a ring, such as an indenyl ring, a fluorenyl ring, an azulenyl ring, or its hydride. The ring formed by the bonding of substituents to each other may also have substituents on each other.

[0083] Among transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton, examples of which include zirconium, titanium, and hafnium, are particularly preferred. This transition metal compound typically has two ligands with a cyclopentadienyl skeleton, and these ligands are preferably bonded to each other via crosslinking groups. Examples of crosslinking groups include substituted silylenes (1 to 4 carbon atoms), dialkylsilylenes, diarylsilylenes, dialkylgermanium, diarylgermanium, etc. Substituted silylenes are preferred.

[0084] Among transition metal compounds in Group IV of the periodic table, ligands other than those with a cyclopentadienyl skeleton can be representatively listed as: hydrogen, hydrocarbon groups with 1 to 20 carbon atoms (alkyl, alkenyl, aryl, alkylaryl, aralkyl, polyalkenyl, etc.), halogens, methylalkyl, methylaryl, etc.

[0085] The aforementioned transition metal compounds comprising a ligand having a cyclopentadienyl skeleton in Group IV of the periodic table may use one or more mixtures as catalyst components.

[0086] Auxiliary catalysts refer to those that can effectively transform transition metal compounds of Group IV in the periodic table into polymerization catalysts, or those that can balance the ionic charges of the activated state on the catalyst. Examples of auxiliary catalysts include: benzene-soluble aluminoxanes or benzene-insoluble organoaluminoxanes, ion-exchangeable layered silicates, boron compounds, ionic compounds composed of cations with or without active hydrogen groups and non-coordinate anions, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing fluorine groups.

[0087] Transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton can be used as supports for inorganic or organic compounds. The support is preferably a porous oxide of inorganic or organic compound, specifically including: ion-exchangeable layered silicates such as montmorillonite, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or mixtures thereof.

[0088] In addition, the organometallic compounds that may be used include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Among these, organoaluminum compounds are suitable.

[0089] Linear low-density polyethylene derived from petroleum can be used alone or in combination of two or more. Furthermore, it can also be used in conjunction with other polymers, primarily other vinyl polymers.

[0090] Without prejudice to the purpose of the first invention of this application, linear low-density polyethylene derived from petroleum may be optionally formulated with a variety of commonly known additives typically added to olefin polymers, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, anti-caking agents, lubricants, etc.

[0091] Plant-derived biopolymer polyethylene

[0092] The plant-derived biopolymer polyethylene used in the first invention of this application is polyethylene obtained by polymerizing ethylene manufactured using plants as raw materials.

[0093] In the first invention of this application, the aforementioned biopolymer polyethylene derived from plants may be any one of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, with low-density polyethylene or linear low-density polyethylene being more preferred, and low-density polyethylene being particularly preferred.

[0094] Plant-derived polyethylene is available commercially, and products such as those manufactured and sold by Braskem can be used. Specifically, SL218 and SPB681 are suitable.

[0095] The plant-derived biopolymer polyethylene used in the first invention of this application is produced by polymerizing monomers containing ethylene derived from biomass. The ethylene derived from biomass is preferably ethylene obtained by the manufacturing method described below, but is not limited thereto. Furthermore, since the monomers using ethylene derived from biomass are the raw material, the polymerized polyethylene is derived from biomass. The raw material monomers of polyethylene may not contain 100% by mass of ethylene derived from biomass, and may contain raw material monomers that are not derived from biomass or are other than ethylene.

[0096] There are no particular limitations on the method for producing bioethylene, which serves as a raw material for plant-based bioethylene, and it can be obtained by methods generally known in the past. An example of a method for producing bioethylene is described below.

[0097] Bio-ethylene can be produced from bio-ethanol as a raw material. Fermented ethanol derived from plant materials is particularly preferred. The plant material is not particularly limited and can be any plant known in the conventional sense. Examples include corn, sugarcane, sugar beets, and cassava.

[0098] In the first invention of this application, "biomass-derived fermented ethanol" refers to ethanol obtained by contacting ethanol-producing microorganisms or products derived from their crushed form with a carbon-source-containing culture broth obtained from plant materials, followed by purification. The purification of ethanol from the culture broth can be achieved using conventionally known methods such as distillation, membrane separation, and extraction. Examples include adding benzene or cyclohexane and performing azeotropic distillation, or removing water through membrane separation.

[0099] In order to obtain bio-ethylene, this stage can be further refined to reduce the total amount of impurities in the ethanol to less than 1 ppm.

[0100] When ethylene is obtained from ethanol via dehydration, a catalyst is typically used. There are no particular limitations on the catalyst, and conventionally known catalysts can be used. A fixed-bed flow reaction process that facilitates the separation of the catalyst and products is advantageous, with γ-alumina being a preferred example.

[0101] Since this dehydration reaction is endothermic, it is usually carried out under heating conditions. The heating temperature is not limited if the reaction is carried out at a commercially useful rate, but is preferably 100°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher. There is no particular upper limit, but from the viewpoint of energy balance and equipment, is preferably 500°C or lower, and even more preferably 400°C or lower.

[0102] There is no particular limitation on the reaction pressure, but a pressure above atmospheric pressure is preferred to facilitate subsequent gas-liquid separation. Industrially, a fixed-bed flow reaction that facilitates catalyst separation is more suitable, but liquid-phase suspension bed, fluidized bed, etc., are also possible.

[0103] In the dehydration reaction of ethanol, the yield is influenced by the amount of water contained in the ethanol supplied as a raw material. Generally, when carrying out a dehydration reaction, anhydrous is preferred considering the efficiency of water removal. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that the formation of other olefins, especially butene, tends to increase when water is absent. This can be presumed to be because if a small amount of water is not present, it may be impossible to suppress the dimerization of the dehydrated ethylene. The lower limit of the permissible water content must be 0.1% by mass or more, preferably 0.5% by mass or more. There is no particular upper limit, but from the viewpoint of mass and heat balance, it is more preferably 50% by mass or less, especially 30% by mass or less, and more preferably 20% by mass or less.

[0104] By performing the dehydration reaction of ethanol in this manner, a mixture of ethylene, water, and a small amount of unreacted ethanol is obtained. Since ethylene is a gas at room temperature and below approximately 5 MPa, water and ethanol can be removed from this mixture by gas-liquid separation to obtain ethylene. This method can be carried out using generally known methods.

[0105] The ethylene obtained through gas-liquid separation is further distilled. Apart from the operating pressure being above atmospheric pressure, there are no special restrictions on the distillation method, operating temperature, and residence time.

[0106] When the raw material is biomass-derived fermented ethanol, the resulting ethylene contains trace amounts of carbon dioxide gas, which is an impurity introduced during the ethanol fermentation process, such as ketones, aldehydes, and esters, and their decomposition products. It also contains nitrogen-containing compounds, such as amines and amino acids, which are enzyme decomposition products and impurities, and their decomposition products, such as ammonia. Since these trace impurities may cause problems in the manufacture or use of polyethylene, they can be removed through purification. The purification method is not particularly limited and can be carried out using methods generally known in the past. Suitable purification operations include, for example, adsorption purification. The adsorbent used is not particularly limited and can be any adsorbent generally known in the past. A material with a high surface area is preferred, and the type of adsorbent should be selected according to the type and amount of impurities in the ethylene obtained from the dehydration reaction of biomass-derived fermented ethanol.

[0107] Alternatively, the purification of impurities in ethylene can also be performed using caustic water treatment. When caustic water treatment is performed, it is preferable to do so before adsorption purification. In this case, a water removal treatment must be applied after caustic treatment and before adsorption purification.

[0108] Monomers used as raw materials for plant-derived biopolymer polyethylene may contain more ethylene and / or α-olefins from fossil fuels, or more α-olefins from biomass.

[0109] The number of carbon atoms in the aforementioned α-olefins is not particularly limited, and typically 3 to 20 carbon atoms can be used, with butene, hexene, or octene being more preferred. This is because butene, hexene, or octene can be produced by polymerizing ethylene, which is derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyolefins have alkyl groups as branched structures, and compared to simple linear polyolefins, they can be configured as polyolefins rich in flexibility.

[0110] The aforementioned polyethylene is preferably an ethylene homopolymer. This is because, theoretically, it can be manufactured using ethylene derived from biomass, with 100% biomass-derived components.

[0111] The concentration of ethylene derived from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is determined by radiocarbon dating. 14 C) is the value obtained by measuring the carbon content from biomass. It is well known that carbon dioxide in the atmosphere contains a certain proportion (105.5 pMC). 14 C, therefore, plants that grow by absorbing carbon dioxide from the atmosphere, such as corn. 14 The carbon content is also approximately 105.5 pMC. Furthermore, it contains almost no carbon in fossil fuels. 14 C is also known. Therefore, by determining the carbon atoms contained in all the carbon atoms in polyethylene... 14 The ratio of C can be used to calculate the ratio of carbon from biomass. In the first invention of this application, when polyethylene is... 14 The content of C is set as P 14C In this case, the carbon content P from biomass bio The following methods can be used to obtain it.

[0112] P bio (%) = P 14C / 105.5×100

[0113] In the biopolymer polyethylene used in the first invention of this application, theoretically, if all ethylene from biopolymer is used as the raw material for polyethylene, the concentration of ethylene from biopolymer is 100%, and the biopolymer degree of the polyethylene is 100%. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biopolymer is 0%, and the biopolymer degree of the polyethylene is 0%.

[0114] In the first invention of this application, the biomass of the biopolyethylene does not need to be 100%. This is because even if raw materials from biomass are used in a portion of the biopolyethylene, the amount of fossil fuel used can be reduced compared to the past.

[0115] In the biopolymer polyethylene used in the first invention of this application, the polymerization method containing monomers derived from biopolymer ethylene is not particularly limited, and can be carried out by methods generally known in the art. The polymerization temperature or polymerization pressure can be appropriately adjusted according to the polymerization method or polymerization apparatus. There are also no particular limitations on the polymerization apparatus, and conventionally known apparatus can be used.

[0116] For example, polymerization methods for monomers containing ethylene, as described below, can be applied.

[0117] The polymerization method for biopolymer polyethylene can be appropriately selected according to the type of polyethylene being polymerized, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE), depending on their density or branching. For example, it is preferable to use multi-active-site catalysts such as Chigler catalysts or Phillips Catalyst catalysts, or single-active-site catalysts such as metal aromatic catalysts, as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0118] From the viewpoint of obtaining biopolymer polyethylene with a wide molecular weight distribution and excellent flexibility or formability, it is preferable to use multi-active-site catalysts such as Chigler catalysts and Philipp catalysts.

[0119] Preferred Chigler catalysts may be those commonly known for their use in the coordination polymerization of ethylene and α-olefins, such as catalysts containing titanium compounds and organoaluminum compounds, catalysts composed of titanium halide compounds and organoaluminum compounds, and catalysts composed of solid catalyst components such as titanium, magnesium, and chlorine and organoaluminum compounds. More specifically, such catalysts can be exemplified as: a catalyst composed of a catalyst component (a) obtained by reacting a titanium compound with an alcohol pretreatment product of anhydrous magnesium dihalide and an organometallic compound, and an organometallic compound (b); a catalyst composed of a catalyst component (A) obtained by reacting magnesium metal with an organic hydroxide or an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of transition metals, and an aluminum halide, and an organometallic compound catalyst component (B); a catalyst composed of a solid catalyst component (A) obtained by reacting (i) metallic magnesium with an organic hydroxide, an oxygen-containing organic compound of magnesium, and a halogenated compound, (ii) an oxygen-containing organic compound of transition metals and a halogenated compound, (iii) a reactant obtained by reacting a silicon compound, and (iv) an aluminum halide compound, and an organometallic compound catalyst component (B), etc.

[0120] In addition, the Philips catalyst can be the Philips catalyst commonly known for its use in the coordination polymerization of ethylene and α-olefins, such as a catalyst system containing chromium compounds such as chromium oxide, specifically exemplified by catalysts in which chromium compounds such as chromium trioxide and chromate are supported on solid oxides such as silica, alumina, silica-alumina, and silica-titanium oxide.

[0121] There are no particular limitations on the density of plant-derived biopolymer polyethylene, but a density of 0.905 to 0.935 g / cm³ is preferred. 3 The preferred value is 0.915 to 0.930 g / cm³. 3 In other words, plant-derived biopolymer polyethylene is preferably low-density polyethylene or linear low-density polyethylene.

[0122] There are no particular restrictions on the MFR of plant-derived biopolymer polyethylene. From the viewpoint of formability, it is more preferably 0.3 to 15.0 g / 10 min, more preferably 1.0 to 12.0 g / 10 min, more preferably 1.5 to 10.0 g / 10 min, and especially preferably 2.0 to 9.0 g / 10 min.

[0123] There are no particular limitations on the molecular weight distribution of plant-derived biopolymer polyethylene. From the viewpoint of flexibility and formability, the molecular weight distribution (expressed as the ratio of weight-average molecular weight: Mw to number-average molecular weight: Mn: Mw / Mn) is preferably 3.5 or higher, particularly preferably 3.8 to 9.0, and more preferably in the range of 4.0 to 8.6. This Mw / Mn can be determined by gel permeation chromatography (GPC), and more specifically, by the method described, for example, in the embodiments of this application.

[0124] Furthermore, the plant-derived biopolymer polyethylene has one or more sharp peaks obtained from the endothermic curve measured by a differential scanning calorimeter (DSC) at a heating rate of 10°C / min. The highest temperature of this peak, i.e. the melting point, is preferably 95 to 140°C, and more preferably in the range of 100 to 135°C.

[0125] Plant-derived biopolymers can be used alone or in combination with two or more. Furthermore, they can also be used in combination with other polymers, primarily based on other vinyl polymers.

[0126] Without prejudice to the purpose of the first invention of this application, various commonly known additives, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, anti-caking agents, and lubricants, may be optionally incorporated into the plant-derived biopolymer polyethylene.

[0127] The laminated film of the first invention of this application has (1A) a heat-fusion layer, (1B) an intermediate layer and (1C) a laminated layer as described below.

[0128] (1A) the heat-fused layer, (1B) the intermediate layer, and (1C) the laminate all contain the aforementioned linear low-density polyethylene derived from petroleum. By including the aforementioned linear low-density polyethylene derived from petroleum in (1A) the heat-fused layer, (1B) the intermediate layer, and (1C) the laminate, sufficient lamination strength between each layer can be achieved. Furthermore, this is also advantageous from the perspective of the productivity and cost of the laminated film.

[0129] (1A) Thermal fusion layer

[0130] The heat-sealing layer (1A) constituting the laminated film of the first invention of this application is often configured as the innermost layer and fused with other films when the laminated film of the first invention of this application is used to form a packaging bag. Therefore, it is preferable to use a low-melting-point resin in a manner that obtains high sealing strength. For example, by setting the ethylene content of linear low-density polyethylene derived from petroleum to a low level, the melting point of the heat-sealing layer (1A) can be reduced. More specifically, it is preferable to set the ethylene content of linear low-density polyethylene derived from petroleum to 10% by mass or less, more preferably to 7% by mass or less, and even more preferably to 5% by mass or less.

[0131] When the ethylene content of linear low-density polyethylene derived from petroleum must be increased due to reasons such as the need to improve the strength of the membrane or the necessity of using materials common to other layers, a low-melting-point resin can be added to the (1A) heat-fusion layer. Furthermore, when biodegradable polyethylene derived from plants is added to the (1A) heat-fusion layer, a low-melting-point biodegradable polyethylene derived from plants can also be added.

[0132] Other low-melting-point resins mentioned above include: high-pressure low-density polyethylene, ethylene-α-olefin random copolymers and other ethylene polymers with relatively low density; aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosin, styrene resins, coumarone-indene resins and other adhesive resins.

[0133] From the viewpoint of heat-sealing properties, the content of linear low-density polyethylene derived from petroleum in the (1A) heat-fusion layer is preferably 50% by mass or more, more preferably 55% to 99% by mass, and especially preferably 65% ​​to 95% by mass.

[0134] From the viewpoint of tear resistance, etc., the content of plant-derived biopolymer polyethylene in the (1A) heat-fusion layer is preferably 1% by mass or more, more preferably 5 to 40% by mass, and especially preferably 7 to 30% by mass.

[0135] (1A) There is no particular limitation on the thickness of the heat-sealing layer. From the viewpoint of heat sealing, it is preferred to be 5 μm or more, and even more preferred to be 10 μm or more.

[0136] On the other hand, from the viewpoint of membrane strength, a thickness of 30 μm or less is preferred, and a thickness of 20 μm or less is even more preferred.

[0137] Without prejudice to the purpose of the first invention of this application, various commonly known additives that are usually added to polyolefins, such as anti-caking agents, lubricants, antioxidants, weather stabilizers, antistatic agents, antifogging agents, etc., may be optionally incorporated into the heat-fused layer.

[0138] Anti-caking agents include: silica, talc, clay, calcium carbonate, synthetic zeolite, starch, alumina, acrylic resin, methacrylic resin, silicone resin, polytetrafluoroethylene resin, etc.

[0139] In addition, examples of lubricants include: palmitamide, stearamide, rhodiola, oleamide, mustardamide, oleopalatamide, stearapalatamide, methylene bis-stearamide, methylene bis-oleamide, ethylene bis-oleamide, ethylene bis-mustardamide, and other amides; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; hydrogenated castor oil, etc.

[0140] (1B) Intermediate layer

[0141] Of the layers constituting the laminated film of the first invention of this application, the (1A) heat-sealing layer is preferably designed to obtain an appropriate sealing strength, and the (1C) laminating layer is preferably designed with consideration of the lamination strength with the (1D) substrate layer, etc. In contrast, since the (1B) intermediate layer has relatively fewer restrictions, it can be designed to impart desired physical properties and performance, such as mechanical properties, to the laminated film of the first invention of this application as a whole. In this case, it is more preferable to set the thickness of the (1B) intermediate layer to be greater than the thickness of the (1A) heat-sealing layer and the thickness of the (1C) laminating layer, and more preferably to be greater than the sum of the thicknesses of the (1A) heat-sealing layer and the (1C) laminating layer.

[0142] More specifically, (1B) the thickness of the intermediate layer is preferably 10 μm or more, more preferably 15 μm or more, and especially preferably 30 μm or more.

[0143] On the other hand, from the viewpoint of heat sealing, the thickness of the (1B) intermediate layer is preferably 150 μm or less, more preferably 130 μm or less, more preferably 100 μm or less, and especially preferably 90 μm or less.

[0144] For example, from the viewpoint of achieving high mechanical strength for the laminate as a whole, (1B) the intermediate layer is preferably made of a resin with high mechanical strength in a high proportion. For example, a resin with a high molecular weight and a narrow molecular weight distribution is selected as linear low-density polyethylene derived from petroleum, and more preferably, this content is set to be relatively high.

[0145] From this perspective, the content of linear low-density polyethylene derived from petroleum in the (1A) heat-fusion layer is preferably 50% by mass or more, more preferably 75% to 100% by mass, even more preferably 85% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0146] Furthermore, the molecular weight distribution of the linear low-density polyethylene derived from petroleum is preferably 4.0 or less, and particularly preferably 3.0 or less. Similarly, the molecular weight of the linear low-density polyethylene derived from petroleum is preferably 20,000 or more, especially preferably 25,000 or more, more preferably 50,000 or more, and particularly preferably 70,000 or more.

[0147] From the viewpoint of improving the flexibility or impact resistance of the laminate as a whole, (1B) the intermediate layer is preferably made of a resin with high flexibility or high impact resistance in a high proportion. For example, a resin with high flexibility or high impact resistance can be selected as linear low-density polyethylene derived from petroleum, and this content is further set to be relatively high.

[0148] Furthermore, by adding an elastomer or rubber component to the (1B) intermediate layer, the softness or impact resistance of the (1B) intermediate layer can be improved, thereby enhancing the overall softness or impact resistance of the laminate. Examples of elastomers or rubber components include ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-propylene-butene copolymers, etc., and the amount added can be set to 1 to 30% by mass, preferably 5 to 10% by mass.

[0149] (1C) laminate

[0150] The (1C) laminate layer constituting the laminated film of the first invention of this application may optionally or as desired be laminated with other layers, starting with the (1D) substrate layer described later.

[0151] Therefore, the (1C) laminate is preferably designed with consideration of the bonding strength with other layers.

[0152] From this perspective, the linear low-density polyethylene derived from petroleum in the (1C) laminate is preferably selected from petroleum-derived linear low-density polyethylene with excellent affinity to other layers, including the (1D) substrate layer, and the content is preferably 40 to 99% by mass, and more preferably 70 to 95% by mass.

[0153] In addition, to further enhance the bonding strength with other layers, corona treatment, roughening treatment, and other treatments can be performed on the surface of the (1C) laminate (the side opposite to the surface of the (1B) intermediate layer).

[0154] On the other hand, from the viewpoint of anti-caking when storing the laminated film of the first invention of this application, (1C) the laminate may contain an anti-caking agent.

[0155] Powdered silica can be suitable as an anti-caking agent, preferably synthetic silica. From the viewpoint of uniformly dispersing powdered silica in the (1C) laminate, the powdered silica can be dispersed in a resin with excellent compatibility with the petroleum-derived linear low-density polyethylene constituting the (1C) laminate, for example, dispersed in low-density polyethylene to form a masterbatch, which is then added to the petroleum-derived linear low-density polyethylene. Furthermore, without prejudice to the purpose of the first invention of this application, a lubricant (slip agent) may optionally be incorporated into the laminate.

[0156] Examples of lubricants include: palmitamide, stearamide, rhodiola, oleamide, mustardamide, oleopalatamide, stearapalatamide, methylene bis-stearamide, methylene bis-oleamide, ethylene bis-oleamide, ethylene bis-mustardamide, and other amides; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; and hydrogenated castor oil.

[0157] (1C) There is no particular limitation on the thickness of the laminate, but from the viewpoint of lamination processability, it is more preferably 5 μm or more, and especially preferably 10 μm or more.

[0158] On the other hand, from the viewpoint of membrane strength, it is more preferably 30 μm or less, and more preferably 20 μm or less.

[0159] laminated membrane

[0160] The laminated film of the first invention of this application comprises: a (1A) heat-fusion layer, a (1B) intermediate layer, and a (1C) laminate layer, each containing linear low-density polyethylene derived from petroleum. In the laminated film of the first invention of this application, it is more preferable that the (1C) laminate layer and the (1A) heat-fusion layer are laminated with the (1B) intermediate layer in between, but other layers may also be present.

[0161] The laminated film of the first invention of this application can be formed using various generally known film forming methods, such as: a method of forming a laminated film by first forming a (1C) layer, an intermediate layer, and a (1A) heat-fused layer separately, and then bonding the films together to form a laminated film; a method of forming a laminated film by extruding a (1C) layer onto an intermediate layer after obtaining a composite film composed of an intermediate layer (1B) and a heat-fused layer (1A) using a multilayer mold; a method of forming a laminated film by extruding a (1A) layer onto an intermediate layer (1B) using a multilayer mold; or a method of forming a laminated film composed of an (1C) layer, an intermediate layer (1B), and a heat-fused layer (1A) using a multilayer mold, etc.

[0162] In addition, various generally known film forming methods can be used, specifically including die casting film forming method and blown film forming method.

[0163] The laminated film and each layer constituting the laminated film of the first invention of this application may be an unstretched film (non-stretched film) or a stretched film.

[0164] The thickness of each layer of the laminated film of the first invention of this application is not particularly limited, but is usually 3 μm or more, more preferably 5 to 150 μm, and even more preferably in the range of 5 to 90 μm.

[0165] The thickness of the laminated film of the first invention of this application is not particularly limited, but from the viewpoint of ensuring practical strength, it is generally 20 μm or more, more preferably 25 μm or more, and especially preferably 30 μm or more. On the other hand, from the viewpoint of having practical flexibility after being laminated with the (1D) substrate layer, it is generally 200 μm or less, more preferably 180 μm or less, and especially preferably 150 μm or less.

[0166] The laminated film of the first invention of this application contains more than 3% by mass of plant-derived biopolymer polyethylene in at least one of the (1A) heat-fusion layer, (1B) intermediate layer and (1C) laminated layer.

[0167] By containing more than 3% by mass of plant-derived biopolymer polyethylene in at least one of the (1A) heat-fusion layer, (1B) intermediate layer and (1C) laminated layer, the laminated film of the first invention of this application significantly improves tear resistance while maintaining the excellent properties of conventional polyethylene laminated films such as mechanical strength and anti-caking properties, thereby achieving remarkable technical effects.

[0168] As described above, in the laminated film of the first invention of this application, by adding a predetermined amount of plant-derived biopolymer polyethylene to any layer constituting the laminated film, the tear resistance is significantly improved. On the other hand, the reduction in mechanical strength is suppressed. For example, the yield point stress is not only almost the same as that in the case where biopolymer polyethylene is not added, but is also increased. Therefore, for example, when the laminated film of the first invention of this application is used in packaging bags, the ease of opening can be significantly improved without compromising the strength of the packaging bag.

[0169] The content of plant-derived biopolymer polyethylene is preferably 6% by mass or more, and particularly preferably 12% by mass or more.

[0170] There is no particular upper limit to the content of plant-derived biopolymer polyethylene, but from the viewpoint of tear resistance and film strength, it is generally preferred to be 6% by mass or more, and particularly preferred to be 12% by mass or more.

[0171] The laminated film of the first invention of this application only needs to contain more than 3% by mass of plant-derived biopolymer polyethylene in at least one of the (1A) heat-fusion layer, (1B) intermediate layer and (1C) laminated layer. From the perspective of greatly improving tear resistance, it is more preferred that the (1B) intermediate layer contains more than 3% by mass of plant-derived biopolymer polyethylene.

[0172] It is particularly preferred that all layers of (1A) the heat-fusion layer, (1B) the intermediate layer and (1C) the laminate contain more than 3% by mass of plant-derived biopolymer polyethylene.

[0173] The content of plant-derived biopolymer polyethylene can be appropriately increased or decreased, for example, by adjusting the formulation of the resin composition during the manufacture of each layer.

[0174] The content of plant-derived biopolymer polyethylene in each layer of the manufactured membrane can be measured, for example, by radiocarbon dating (RTA). 14 C) The determination measures the content of biomass-derived carbon in the membrane and calculates it from the result of this determination and the content of biomass-derived carbon in the plant-derived biopolyethylene.

[0175] The laminated membrane of the first invention of this application contains more than 3% by mass of biopolymer polyethylene derived from plants in at least one of the (1A) heat-fusion layer, (1B) intermediate layer and (1C) laminated layer, which can reduce the amount of fossil fuel used in manufacturing and reduce the environmental impact.

[0176] The biomass of laminated membranes can be calculated by weighting the biomass of each layer by the weight of each layer.

[0177] The biomass of the laminated membrane can be adjusted by changing the biomass of each layer, and the biomass of each layer can be adjusted by changing the biomass and amount of the resin used in each layer.

[0178] The biomass of the laminated film of the first invention of this application is preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0179] The higher the biomass of the laminated membrane of the first invention of this application, the better. There is no particular upper limit. In terms of its relationship with the physical properties or cost of the membrane, it is usually below 60% by mass, and in most cases below 30% by mass.

[0180] The heat of fusion ΔH of the laminated film of the first invention of this application, calculated from the melting curve obtained by DSC measurement from 0°C to 130°C, is preferably 135 to 164 J / g.

[0181] By keeping the heat of melting ΔH between 0°C and 130°C within the aforementioned range, the tear resistance of the laminated film can be further improved effectively.

[0182] The determination of the melting curve by DSC and the calculation of the heat of fusion ΔH from 0°C to 130°C in the melting curve can be performed by conventionally known methods, and more specifically, by the methods described in the embodiments of this application.

[0183] The heat of fusion ΔH at 0°C to 130°C is preferably 135 to 164 J / g, and more preferably 140 to 164 J / g.

[0184] The heat of fusion ΔH from 0°C to 130°C can be reduced by adding components other than petroleum-derived linear low-density polyethylene to decrease the crystallinity of the film. Preferably, plant-derived biopolymer polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, etc., are added as components other than petroleum-derived linear low-density polyethylene.

[0185] The laminated film of the first invention of this application may be an extended film or a non-extended film. From the viewpoint of improving mechanical properties, an extended film is preferred, and a biaxially extended film is particularly preferred.

[0186] Dual-axis extension can be achieved by appropriately employing methods such as successive dual-axis extension, synchronous dual-axis extension, and multi-stage extension.

[0187] The conditions for biaxial stretching can be listed as the manufacturing conditions of commonly known biaxially stretched films. For example, in the successive biaxial stretching method, the longitudinal stretching temperature is set to 100°C to 145°C and the stretching ratio is set to a range of 4 to 7 times. The transverse stretching temperature is set to 150°C to 190°C and the stretching ratio is set to a range of 8 to 11 times.

[0188] (1D) Substrate layer

[0189] As desired, the laminated film of the first invention of this application can be laminated on the (1C) laminate layer and the (1D) substrate layer.

[0190] (1D) There are no particular limitations on the substrate layer, and it is suitable for use, for example, films commonly used in plastic packaging bags.

[0191] Preferred materials for the (1D) substrate layer include, for example, polyolefins such as crystalline polypropylene, crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly4-methylpentene-1, low-density polyethylene, medium-density polyethylene, or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ion-crosslinked olefin copolymers (ionomers); aromatic ethylene copolymers such as polystyrene and styrene-butadiene copolymers; halogenated ethylene polymers such as polyvinyl chloride and dichloroethylene resin; nitrile polymers such as acrylonitrile-styrene copolymer and acrylonitrile-styrene-butadiene copolymer; polyamides such as nylon 6, nylon 66, p-xylene-hexamethylenediamide, or m-xylene-hexamethylenediamide; polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate; various polycarbonates; and thermoplastic resins such as polyoxymethylene and polyacetals. In addition, when the contents of the package are sensitive to oxygen, a film coated with metal oxides or other organic compounds or a layer made of ethylene-vinyl alcohol copolymer (EVOH) resin can be provided on the above-mentioned film.

[0192] Plastic films made of these materials can be used unstretched, or uniaxially or biaxially stretched.

[0193] (1D) The substrate layer can be a single layer or two or more of these plastic films. In addition, one or more of these plastic films can be bonded to metal foil such as aluminum, paper, Cellophane, etc.

[0194] Preferred (1D) substrate layers include, for example, single-layer films composed of stretched nylon films or stretched polyester films; double-layer films composed of polyolefin films such as low-density polyethylene or polypropylene and PET; and triple-layer films composed of PET / nylon / polyethylene. When manufacturing these laminated films, adhesives or anchoring agents (also known as adhesion promoters) may optionally be present between the layers. Furthermore, an ink layer that expresses a design aesthetic may also be provided.

[0195] There are no particular limitations on the method of laminating the (1D) substrate layer onto the (1C) laminate layer. For example, the (1D) substrate layer can be directly laminated onto the (1C) laminate layer by means of extrusion lamination. Alternatively, the (1D) substrate layer can be laminated onto the (1C) laminate layer in the presence of an adhesive, such as by dry lamination. Commonly used adhesives such as urethane adhesives, acid-modified polyolefin adhesives, polyester adhesives, polyether adhesives, and polyamide adhesives can be used.

[0196] (1D) The thickness of the substrate layer can be set arbitrarily, typically selected from 5 to 50 μm, and more preferably from the range of 10 to 30 μm.

[0197] The laminated film of the first invention of this application and the laminated film on which the (1C) laminate layer of the laminated film of the first invention of this application is laminated with the (1D) substrate layer are laminated, are suitable for use in various applications, and are particularly suitable for use as packaging materials.

[0198] When used as packaging material, a packaging bag can be formed by heat-sealing the laminated films together or the laminated films with other films on the heat-sealing layer (1A).

[0199] In the case of tear-off bags, ziplock bags, etc., since the bag will tear when opened, the laminated film of the first invention of this application, whose tear resistance has been greatly improved, is particularly suitable.

[0200] There are no particular restrictions on the contents of these packaging bags; they can be used to store ingredients such as fruits and vegetables, processed foods, medicines, and hygiene products.

[0201] The following describes in detail the various embodiments of the second invention of this application.

[0202] The second invention of this application is a laminated film comprising: a (2A) heat-fusion layer, a (2B) intermediate layer and a (2C) laminated layer respectively containing linear low-density polyethylene from petroleum, wherein the (2B) intermediate layer contains biopolymer polyethylene from plants.

[0203] That is, the laminated film of the second invention of this application contains linear low-density polyethylene derived from petroleum in each of the layers of (2A) the heat-fusion layer, (2B) the intermediate layer and (2C) the laminated layer.

[0204] Furthermore, the laminated film system of the second invention of this application contains at least a predetermined amount of plant-derived biopolymer polyethylene in the intermediate layer (2B).

[0205] Linear low-density polyethylene derived from petroleum

[0206] The petroleum-derived linear low-density polyethylene used in the second invention of this application is a homopolymer of ethylene manufactured using petroleum as a raw material, or a copolymer of ethylene and α-olefins manufactured using petroleum as a raw material, and may be a petroleum-derived linear low-density polyethylene synthesized by commonly known manufacturing methods.

[0207] α-Olefins can be compounds having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc., and mixtures thereof may also be used. α-Olefins are more preferably compounds having 4, 6, or 8 carbon atoms, or mixtures thereof, such as 1-butene, 1-hexene, 1-octene, or mixtures thereof.

[0208] Linear low-density polyethylene derived from petroleum is available for commercial sale, such as 2040F (C6-LLDPE, MFR; 4.0, density; 0.918 g / cm³) manufactured by Ube-Maruzen Polyethylene Co., Ltd. 3 ).

[0209] The density of linear low-density polyethylene derived from petroleum is preferably 0.905 to 0.935 g / cm³. 3 The preferred value is 0.915 to 0.930 g / cm³. 3 The preferred MFR is 0.5 to 6.0 g / 10 min, and more preferably 2.0 to 4.0 g / 10 min.

[0210] The molecular weight distribution (expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn): Mw / Mn) of linear low-density polyethylene derived from petroleum is preferably from 1.5 to 4.0, more preferably from 1.8 to 3.5. This Mw / Mn ratio can be determined by gel permeation chromatography (GPC).

[0211] The linear low-density polyethylene derived from petroleum, from the endothermic curve measured by a differential scanning calorimeter (DSC) at a heating rate of 10°C / min, has one or more sharp peaks. The highest temperature of these peaks, i.e. the melting point, is preferably between 95 and 140°C, and more preferably between 105 and 130°C.

[0212] Linear low-density polyethylene derived from petroleum can be manufactured using conventionally known methods, employing catalysts such as multi-site catalysts like Chigler catalysts or single-site catalysts like metal-aromatic catalysts. From the viewpoint of obtaining linear low-density polyethylene capable of forming films with narrow molecular weight distribution and high strength, the use of single-site catalysts is preferred.

[0213] The aforementioned single-active-site catalyst is a catalyst capable of forming uniform active species, typically modulated by contacting a metal aromatic transition metal compound or a non-metal aromatic transition metal compound with an activation auxiliary catalyst. Compared to multi-active-site catalysts, single-active-site catalysts are preferred because their active site structure is uniform, allowing for the polymerization of high-molecular-weight polymers with highly uniform structures. Metal aromatic catalysts are particularly preferred. A metal aromatic catalyst is a catalyst comprising: a transition metal compound of Group IV of the periodic table containing a ligand with a cyclopentadienyl skeleton, an auxiliary catalyst, an optional organometallic compound, and a support.

[0214] In the aforementioned transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton, the cyclopentadienyl skeleton refers to cyclopentadienyl, substituted cyclopentadienyl, etc. The substituted cyclopentadienyl group has at least one substituent selected from hydrocarbon groups having 1 to 30 carbon atoms, silyl, silyl-substituted alkyl, silyl-substituted aryl, cyano, cyanoalkyl, cyanoaryl, halogen, haloalkyl, halosilyl, etc. The substituted cyclopentadienyl group may have two or more substituents. Furthermore, the substituents may bond to each other to form a ring, such as an indene ring, afluorene ring, an azurite ring, or its hydride. The ring formed by the bonding of substituents to each other may also have substituents in each other.

[0215] Among transition metal compounds of Group IV of the periodic table containing ligands having a cyclopentadienyl skeleton, examples of which include zirconium, titanium, and hafnium, with zirconium and hafnium being particularly preferred. This transition metal compound typically has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other via a crosslinking group. Examples of crosslinking groups include substituted silanes (1 to 4 carbon atoms), dialkylsilanes, diarylsilanes, diarylsilanes, dialkylgermaniums, diarylgermaniums, etc., substituted germaniums, etc. Substituted silanes are more preferred.

[0216] Among transition metal compounds in Group IV of the periodic table, ligands other than those with a cyclopentadienyl skeleton can be representatively listed as: hydrogen, hydrocarbon groups with 1 to 20 carbon atoms (alkyl, alkenyl, aryl, alkylaryl, aralkyl, polyalkenyl, etc.), halogens, methylalkyl, methylaryl, etc.

[0217] The aforementioned transition metal compounds comprising a ligand having a cyclopentadienyl skeleton in Group IV of the periodic table may use one or more mixtures as catalyst components.

[0218] Auxiliary catalysts refer to those that can effectively transform transition metal compounds of Group IV in the periodic table into polymerization catalysts, or those that can balance the ionic charges in the activated state on the catalyst. Examples of auxiliary catalysts include: benzene-soluble aluminum oxanes or benzene-insoluble organoaluminooxy compounds, ion-exchangeable layered silicates, boron compounds, ionic compounds composed of cations with or without active hydrogen groups and non-coordinate anions, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing fluorine groups.

[0219] Transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton can be used as supports for inorganic or organic compounds. The support is preferably a porous oxide of inorganic or organic compound, specifically including: ion-exchangeable layered silicates such as montmorillonite, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof.

[0220] In addition, the organometallic compounds that may be used include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Among these, organoaluminum compounds are suitable.

[0221] Linear low-density polyethylene derived from petroleum can be used alone or in combination of two or more. Furthermore, it can also be used in conjunction with other polymers, primarily other vinyl polymers.

[0222] Without prejudice to the purpose of the second invention of this application, the linear low-density polyethylene derived from petroleum may be optionally formulated with a variety of commonly known additives typically added to olefin polymers, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, anti-caking agents, lubricants, etc.

[0223] Plant-derived biopolymer polyethylene

[0224] The plant-derived biopolymer polyethylene used in the second invention of this application is polyethylene obtained by polymerizing ethylene manufactured using plants as raw materials.

[0225] In the second invention of this application, the above-mentioned biopolymer polyethylene derived from plants can be any one of high-density polyethylene, low-density polyethylene and linear low-density polyethylene, more preferably low-density polyethylene or linear low-density polyethylene, and especially preferably low-density polyethylene.

[0226] Plant-derived polyethylene is available commercially, and products such as those manufactured and sold by Braskem can be used. Specifically, SL218 and SPB681 are suitable.

[0227] The plant-derived biopolymer polyethylene used in the second invention of this application is produced by polymerizing monomers containing ethylene derived from biomass. The ethylene derived from biomass is preferably ethylene obtained by the manufacturing method described below, but is not limited thereto. Furthermore, since the monomers using ethylene derived from biomass are the raw material, the polymerized polyethylene is derived from biomass. The raw material monomers of polyethylene may not contain 100% by mass of ethylene derived from biomass, and may contain raw material monomers that are not derived from biomass or are other than ethylene.

[0228] There are no particular limitations on the method for producing bioethylene, which serves as a raw material for plant-based bioethylene, and it can be obtained by methods generally known in the past. An example of a method for producing bioethylene is described below.

[0229] Bio-ethylene can be produced from bio-ethanol as a raw material. Fermented ethanol derived from plant materials is particularly preferred. The plant material is not particularly limited and can be any plant known in the conventional sense. Examples include corn, sugarcane, sugar beets, and cassava.

[0230] In the context of the second invention of this application, "biomass-derived fermented ethanol" refers to ethanol obtained by contacting ethanol-producing microorganisms or products derived from their crushed material with a carbon-source-containing culture broth obtained from plant materials, followed by purification. The purification of ethanol from the culture broth can be achieved using conventionally known methods such as distillation, membrane separation, and extraction. Examples include adding benzene or cyclohexane and performing azeotropic distillation, or removing water through membrane separation.

[0231] In order to obtain bio-ethylene, this stage can be further refined to reduce the total amount of impurities in the ethanol to less than 1 ppm.

[0232] When ethylene is obtained from ethanol via dehydration, a catalyst is typically used. There are no particular limitations on the catalyst, and conventionally known catalysts can be used. A fixed-bed flow reaction process that facilitates the separation of the catalyst and products is advantageous, with γ-alumina being a preferred example.

[0233] Since this dehydration reaction is endothermic, it is usually carried out under heating conditions. The heating temperature is not limited if the reaction is carried out at a commercially useful rate, but is preferably 100°C or higher, particularly 250°C or higher, and more preferably 300°C or higher. There is no particular upper limit, but from the viewpoint of energy balance and equipment, is preferably 500°C or lower, particularly 400°C or lower.

[0234] There is no particular limitation on the reaction pressure, but a pressure above atmospheric pressure is preferred to facilitate subsequent gas-liquid separation. Industrially, a fixed-bed flow reaction is more suitable for easy catalyst separation, but liquid-phase suspension bed, fluidized bed, etc. are also possible.

[0235] In the dehydration reaction of ethanol, the yield is influenced by the amount of water contained in the ethanol supplied as a raw material. Generally, when carrying out a dehydration reaction, anhydrous is preferred considering the efficiency of water removal. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that the formation of other olefins, especially butene, tends to increase when water is absent. This can be presumed to be because if a small amount of water is not present, it may be impossible to suppress the dimerization of the dehydrated ethylene. The lower limit of the permissible water content must be 0.1% by mass or more, preferably 0.5% by mass or more. There is no particular upper limit, but from the viewpoint of mass and heat balance, it is more preferably 50% by mass or less, especially 30% by mass or less, and more preferably 20% by mass or less.

[0236] By performing the dehydration reaction of ethanol in this manner, a mixture of ethylene, water, and a small amount of unreacted ethanol is obtained. Since ethylene is a gas at room temperature and below approximately 5 MPa, water and ethanol can be removed from this mixture by gas-liquid separation to obtain ethylene. This method can be carried out using generally known methods.

[0237] The ethylene obtained through gas-liquid separation is further distilled. Apart from the operating pressure being above atmospheric pressure, there are no special restrictions on the distillation method, operating temperature, and residence time.

[0238] When the raw material is biomass-derived fermented ethanol, the resulting ethylene contains trace amounts of carbon dioxide gas, which is an impurity introduced during the ethanol fermentation process, such as ketones, aldehydes, and esters, and their decomposition products. It also contains nitrogen-containing compounds, such as amines and amino acids, which are enzyme decomposition products and impurities, and their decomposition products, such as ammonia. Since these trace impurities may cause problems in the manufacture or use of polyethylene, they can be removed through purification. The purification method is not particularly limited and can be carried out using methods generally known in the past. Suitable purification operations include, for example, adsorption purification. The adsorbent used is not particularly limited and can be any adsorbent generally known in the past. A material with a high surface area is preferred, and the type of adsorbent should be selected according to the type and amount of impurities in the ethylene obtained from the dehydration reaction of biomass-derived fermented ethanol.

[0239] Alternatively, the purification of impurities in ethylene can also be performed using caustic water treatment. When caustic water treatment is performed, it is preferable to do so before adsorption purification. In this case, a water removal treatment must be applied after caustic treatment and before adsorption purification.

[0240] Monomers used as raw materials for plant-derived biopolymer polyethylene may contain more ethylene and / or α-olefins from fossil fuels, or more α-olefins from biomass.

[0241] The number of carbon atoms in the aforementioned α-olefins is not particularly limited; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being more preferred. This is because butene, hexene, or octene can be produced by polymerizing ethylene, which is derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyolefins have alkyl groups as branched structures, and compared to simple linear polyolefins, they can be configured as polyolefins rich in flexibility.

[0242] The aforementioned polyethylene is preferably an ethylene homopolymer. This is because, theoretically, it can be manufactured using ethylene derived from biomass, with 100% biomass-derived components.

[0243] The concentration of ethylene derived from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is determined by radiocarbon dating. 14 C) is the value obtained by measuring the carbon content from biomass. It is well known that carbon dioxide in the atmosphere contains a certain proportion (105.5 pMC). 14 C, therefore, plants that grow by absorbing carbon dioxide from the atmosphere, such as corn. 14 The carbon content is also approximately 105.5 pMC. Furthermore, it contains almost no carbon in fossil fuels. 14 C is also known. Therefore, by determining the carbon atoms contained in all the carbon atoms in polyethylene... 14 The ratio of C allows for the calculation of the ratio of carbon from biomass. In the second invention of this application, when polyethylene is... 14 The content of C is set as P 14C In this case, the carbon content P from biomass bio The following methods can be used to obtain it.

[0244] P bio (%) = P 14C / 105.5×100

[0245] In the biopolymer polyethylene used in the second invention of this application, theoretically, if all ethylene from biopolymer is used as the raw material for polyethylene, the concentration of ethylene from biopolymer is 100%, and the biopolymer degree of the polyethylene is 100%. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biopolymer is 0%, and the biopolymer degree of the polyethylene is 0%.

[0246] In the second invention of this application, the biomass degree of biopolymer does not need to be 100%. This is because even if raw materials from biomass are used in a portion of the biopolymer, the amount of fossil fuel used can be reduced compared to the past.

[0247] In the biopolymer polyethylene used in the second invention of this application, the polymerization method containing monomers derived from biopolymer ethylene is not particularly limited, and can be carried out by methods generally known in the art. The polymerization temperature or polymerization pressure can be appropriately adjusted according to the polymerization method or polymerization apparatus. There are also no particular limitations on the polymerization apparatus, and conventionally known apparatus can be used.

[0248] For example, polymerization methods for monomers containing ethylene, as described below, can be applied.

[0249] The polymerization method for biopolymer polyethylene can be appropriately selected according to the type of polyethylene being polymerized, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE), depending on their density or branching. For example, it is preferable to use multi-active-site catalysts such as Chigler catalysts or Philipp catalysts, or single-active-site catalysts such as metal aromatic catalysts, as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0250] From the viewpoint of obtaining biopolymer polyethylene with a wide molecular weight distribution and excellent flexibility or formability, it is preferable to use multi-active-site catalysts such as Chigler catalysts and Philipp catalysts.

[0251] Preferred Chigler catalysts may be those commonly known for their use in the coordination polymerization of ethylene and α-olefins, such as catalysts containing titanium compounds and organoaluminum compounds, catalysts composed of titanium halide compounds and organoaluminum compounds, and catalysts composed of solid catalyst components such as titanium, magnesium, and chlorine and organoaluminum compounds. More specifically, such catalysts can be exemplified as: a catalyst composed of a catalyst component (a) obtained by reacting a titanium compound with an alcohol pretreatment product of anhydrous magnesium dihalide and an organometallic compound, and an organometallic compound (b); a catalyst composed of a catalyst component (A) obtained by reacting magnesium metal with an organic hydroxide or an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of transition metals, and an aluminum halide, and an organometallic compound catalyst component (B); a catalyst composed of a solid catalyst component (A) obtained by reacting (i) metallic magnesium with an organic hydroxide, an oxygen-containing organic compound of magnesium, and a halogenated compound, (ii) an oxygen-containing organic compound of transition metals and a halogenated compound, (iii) a reactant obtained by reacting a silicon compound, and (iv) an aluminum halide compound, and an organometallic compound catalyst component (B), etc.

[0252] In addition, the Philips catalyst can be the Philips catalyst commonly known for its use in the coordination polymerization of ethylene and α-olefins, such as a catalyst system containing chromium compounds such as chromium oxide, specifically exemplified by catalysts in which chromium compounds such as chromium trioxide and chromate are supported on solid oxides such as silica, alumina, silica-alumina, and silica-titanium oxide.

[0253] There are no particular limitations on the density of plant-derived biopolymer polyethylene, but a density of 0.905 to 0.935 g / cm³ is preferred. 3 The preferred value is 0.915 to 0.930 g / cm³. 3 In other words, plant-derived biopolymer polyethylene is preferably low-density polyethylene or linear low-density polyethylene.

[0254] There are no particular restrictions on the MFR of plant-derived biopolymer polyethylene. From the viewpoint of formability, it is more preferably 0.3 to 15.0 g / 10 min, more preferably 1.0 to 12.0 g / 10 min, more preferably 1.5 to 10.0 g / 10 min, and especially preferably 2.0 to 9.0 g / 10 min.

[0255] There are no particular limitations on the molecular weight distribution of plant-derived biopolymer polyethylene. From the viewpoint of flexibility and formability, the molecular weight distribution (expressed as the ratio of weight-average molecular weight: Mw to number-average molecular weight: Mn: Mw / Mn) is preferably 3.5 or higher, particularly preferably 3.8 to 9.0, and more preferably in the range of 4.0 to 8.6. This Mw / Mn can be determined by gel permeation chromatography (GPC), and more specifically, by the method described, for example, in the embodiments of this application.

[0256] Furthermore, the plant-derived biopolymer polyethylene has one or more sharp peaks obtained from the endothermic curve measured by a differential scanning calorimeter (DSC) at a heating rate of 10°C / min. The highest temperature of this peak, i.e. the melting point, is preferably 95 to 140°C, and more preferably in the range of 100 to 135°C.

[0257] Plant-derived biopolymers can be used alone or in combination with two or more. Furthermore, they can also be used in combination with other polymers, primarily based on other vinyl polymers.

[0258] Without prejudice to the purpose of the second invention of this application, various commonly known additives, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, anti-caking agents, and lubricants, may be optionally incorporated into the plant-derived biopolymer polyethylene.

[0259] The laminated film of the second invention of this application has (2A) a heat-fused layer, (2B) an intermediate layer and (2C) a laminated layer as described below.

[0260] (2A) the heat-fused layer, (2B) the intermediate layer, and (2C) the laminate all contain the aforementioned linear low-density polyethylene derived from petroleum. By including the aforementioned linear low-density polyethylene derived from petroleum in (2A) the heat-fused layer, (2B) the intermediate layer, and (2C) the laminate, sufficient lamination strength between each layer can be achieved. Furthermore, this is also advantageous from the perspective of the productivity and cost of the laminated film.

[0261] (2A) Thermal fusion layer

[0262] The heat-sealing layer (2A) constituting the laminated film of the second invention of this application is often configured as the innermost layer and fused with other films when the laminated film of the second invention of this application is used to form a packaging bag. Therefore, it is preferable to use a low-melting-point resin in a manner that obtains high sealing strength. For example, by setting the ethylene content of linear low-density polyethylene from petroleum to a low level, the melting point of the heat-sealing layer (2A) can be reduced. More specifically, it is preferable to set the ethylene content of linear low-density polyethylene from petroleum to 10% by mass or less, more preferably to 7% by mass or less, and even more preferably to 5% by mass or less.

[0263] When the ethylene content of linear low-density polyethylene derived from petroleum must be increased due to reasons such as the need to improve the strength of the membrane or the necessity of using materials common to other layers, a low-melting-point resin can be added to the (2A) heat-fusion layer. Furthermore, when adding bio-polyethylene derived from plants to the (2A) heat-fusion layer, a low-melting-point bio-polyethylene derived from plants can also be added.

[0264] Other low-melting-point resins mentioned above include: high-pressure low-density polyethylene, ethylene-α-olefin random copolymers and other ethylene polymers with relatively low density; aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosin, styrene resins, coumarone-indene resins and other adhesive-improving resins.

[0265] From the viewpoint of heat-sealing properties, the content of linear low-density polyethylene derived from petroleum in the (2A) heat-fusion layer is preferably 50% by mass or more, more preferably 55% to 99% by mass, and especially preferably 65% ​​to 95% by mass.

[0266] From the viewpoint of rigidity, etc., the content of plant-derived biopolymer polyethylene in the (2A) heat-fusion layer is preferably 1% by mass or more, more preferably 5 to 40% by mass, and especially preferably 7 to 30% by mass.

[0267] (2A) There is no particular limitation on the thickness of the heat-sealing layer. From the viewpoint of heat sealing, it is preferred to be 5 μm or more, and even more preferably 10 μm or more.

[0268] On the other hand, from the viewpoint of membrane strength, a thickness of 30 μm or less is preferred, and a thickness of 20 μm or less is even more preferred.

[0269] Without prejudice to the purpose of the second invention of this application, various commonly known additives that are usually added to polyolefins, such as anti-caking agents, lubricants, antioxidants, weather stabilizers, antistatic agents, antifogging agents, etc., may be optionally incorporated into the heat-fused layer.

[0270] Anti-caking agents include: silica, talc, clay, calcium carbonate, synthetic zeolite, starch, alumina, acrylic resin, methacrylic resin, silicone resin, polytetrafluoroethylene resin, etc.

[0271] In addition, examples of lubricants include: palmitamide, stearamide, rhodiola, oleamide, mustardamide, oleopalatamide, stearapalatamide, methylene bis-stearamide, methylene bis-oleamide, ethylene bis-oleamide, ethylene bis-mustardamide, and other amides; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; hydrogenated castor oil, etc.

[0272] (2B) Intermediate layer

[0273] In the laminated film constituting the second invention of this application, the (2A) heat-sealing layer is preferably designed to obtain an appropriate sealing strength, and the (2C) laminating layer is preferably designed considering the lamination strength with the (2D) substrate layer, etc. In contrast, since the (2B) intermediate layer has relatively fewer restrictions, it can be designed to impart desired physical properties and performance, such as mechanical properties, to the laminated film of the second invention of this application as a whole. In this case, it is preferable to set the thickness of the (2B) intermediate layer to be greater than the thickness of the (2A) heat-sealing layer and the thickness of the (2C) laminating layer, and more preferably to be greater than the sum of the thicknesses of the (2A) heat-sealing layer and the (2C) laminating layer.

[0274] More specifically, the thickness of the intermediate layer (2B) is preferably 10 μm or more, more preferably 15 μm or more, and especially preferably 30 μm or more.

[0275] On the other hand, from the viewpoint of heat sealing, the thickness of the (2B) intermediate layer is preferably 150 μm or less, more preferably 130 μm or less, more preferably 100 μm or less, and especially preferably 90 μm or less.

[0276] For example, from the viewpoint of achieving high mechanical strength for the laminate as a whole, (2B) the intermediate layer is preferably made of a resin with high mechanical strength in a high proportion. For example, a resin with a high molecular weight and a narrow molecular weight distribution is selected as linear low-density polyethylene derived from petroleum, and more preferably, this content is set to be relatively high.

[0277] From this perspective, the content of linear low-density polyethylene derived from petroleum in the (2A) heat-fusion layer is preferably 50% by mass or more, more preferably 75% to 100% by mass, even more preferably 85% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0278] Furthermore, the molecular weight distribution of the linear low-density polyethylene derived from petroleum is preferably 4.0 or less, and particularly preferably 3.0 or less. Similarly, the molecular weight of the linear low-density polyethylene derived from petroleum is preferably 20,000 or more, especially preferably 25,000 or more, more preferably 50,000 or more, and particularly preferably 70,000 or more.

[0279] From the viewpoint of improving the flexibility or impact resistance of the laminate as a whole, (2B) the intermediate layer is preferably made of a resin with high flexibility or high impact resistance in a high proportion. For example, a resin with high flexibility or high impact resistance can be selected as linear low-density polyethylene derived from petroleum, and this content is further set to be relatively high.

[0280] Furthermore, by adding an elastomer or rubber component to the (2B) intermediate layer, the softness or impact resistance of the (2B) intermediate layer can be improved, thereby enhancing the overall softness or impact resistance of the laminate. Examples of elastomers or rubber components include ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-propylene-butene copolymers, etc., and the amount added can be set to 1 to 30% by mass, preferably 5 to 10% by mass.

[0281] (2C) laminate

[0282] The (2C) laminate layer constituting the laminated film of the second invention of this application may optionally or as desired be laminated with other layers, starting with the (2D) substrate layer described later.

[0283] Therefore, the (2C) laminate is preferably designed with consideration of the bonding strength with other layers.

[0284] From this perspective, the linear low-density polyethylene derived from petroleum in the (2C) laminate is preferably selected from petroleum-derived linear low-density polyethylene with excellent affinity to other layers, including the (2D) substrate layer, and the content is preferably 40 to 99% by mass, and more preferably 70 to 95% by mass.

[0285] In addition, to further enhance the bonding strength with other layers, corona treatment, roughening treatment, and other treatments can be applied to the surface of the (2C) laminate (the side opposite to the surface of the (2B) intermediate layer).

[0286] On the other hand, from the viewpoint of anti-caking when storing the laminated film of the second invention of this application, the (2C) laminate may contain an anti-caking agent.

[0287] Powdered silica can be suitable as an anti-caking agent, preferably synthetic silica. From the viewpoint of uniformly dispersing powdered silica in the (2C) laminate, the powdered silica can be dispersed in a resin with excellent compatibility with the petroleum-derived linear low-density polyethylene constituting the (2C) laminate, for example, dispersed in low-density polyethylene to form a masterbatch, which is then added to the petroleum-derived linear low-density polyethylene. Furthermore, without prejudice to the purpose of the second invention of this application, a lubricant (slip agent) may optionally be incorporated into the laminate.

[0288] Examples of lubricants include: palmitamide, stearamide, rhodiola, oleamide, mustardamide, oleopalatamide, stearapalatamide, methylene bis-stearamide, methylene bis-oleamide, ethylene bis-oleamide, ethylene bis-mustardamide, and other amides; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; and hydrogenated castor oil.

[0289] (2C) There is no particular limitation on the thickness of the laminate, but from the viewpoint of lamination processability, it is more preferably 5 μm or more, and especially preferably 10 μm or more.

[0290] On the other hand, from the viewpoint of membrane strength, it is more preferably 30 μm or less, and more preferably 20 μm or less.

[0291] (2A) the heat-fused layer, (2B) the intermediate layer, and (2C) the laminate may contain various additives and fillers other than petroleum-derived linear low-density polyethylene (and, where present, plant-derived biopolymer polyethylene), such as heat stabilizers, antioxidants, light stabilizers, antistatic agents, anti-caking agents, lubricants, nucleating agents, flame retardants, pigments, dyes, calcium carbonate, barium sulfate, magnesium hydroxide, mica, talc, clay, antibacterial agents, and antifogging agents, provided that the purpose of the second invention of this application is not violated. Furthermore, other thermoplastic resins, thermoplastic elastomers, rubbers, hydrocarbon resins, petroleum resins, etc., may also be formulated within the scope of the second invention of this application.

[0292] laminated membrane

[0293] The laminated film of the second invention of this application comprises: a (2A) heat-fusion layer, a (2B) intermediate layer, and a (2C) laminate layer, each containing linear low-density polyethylene derived from petroleum. In the laminated film of the second invention of this application, it is more preferable that the (2C) laminate layer and the (2A) heat-fusion layer are laminated with the (2B) intermediate layer in between, but other layers may also be present.

[0294] The laminated film of the second invention of this application can be formed using various generally known film forming methods, such as: a method of forming a laminated film by first forming a (2C) layer, an intermediate layer, and a (2A) heat-fused layer separately, and then bonding the films together; a method of forming a laminated film by extruding a (2C) layer onto an intermediate layer after obtaining a composite film composed of an intermediate layer (2B) and a heat-fused layer (2A) using a multilayer mold; a method of forming a laminated film by extruding a (2A) layer onto an intermediate layer after obtaining a composite film composed of an intermediate layer (2C) layer and an intermediate layer (2B) using a multilayer mold; or a method of forming a laminated film composed of an intermediate layer (2C) layer, an intermediate layer (2B), and a heat-fused layer (2A) using a multilayer mold, etc.

[0295] In addition, various generally known film forming methods can be used, specifically including die casting film forming method and blown film forming method.

[0296] The laminated film and each layer constituting the laminated film of the second invention of this application may be an unstretched film (non-stretched film) or a stretched film.

[0297] The thickness of each layer of the laminated film of the second invention of this application is not particularly limited, but is usually 3 μm or more, more preferably 5 to 150 μm, and even more preferably in the range of 5 to 90 μm.

[0298] The thickness of the laminated film of the second invention of this application is not particularly limited. From the viewpoint of ensuring practical strength, it is generally 20 μm or more, more preferably 25 μm or more, and especially preferably 30 μm or more. On the other hand, from the viewpoint of having practical flexibility after being laminated with a (2D) substrate layer, it is generally 200 μm or less, more preferably 180 μm or less, and especially preferably 150 μm or less.

[0299] The laminated film of the second invention of this application contains plant-derived biopolymer polyethylene in the (2B) intermediate layer. By containing plant-derived biopolymer polyethylene in the (2B) intermediate layer, the laminated film of the second invention of this application significantly improves the Young's modulus while maintaining the excellent properties of conventional polyethylene-based laminated films, such as anti-caking properties. Because the Young's modulus of the laminated film of the second invention of this application is significantly improved, it is particularly advantageous for applications requiring high mechanical strength, such as stand-up pouches.

[0300] (2B) The content of plant-derived biopolymer polyethylene in the intermediate layer is preferably 3% by mass or more, more preferably 4.4% by mass or more, more preferably 10% by mass or more, and especially preferably 15% by mass or more.

[0301] (2B) There is no particular upper limit to the content of plant-derived biopolymer polyethylene in the intermediate layer. From the viewpoint of bag rupture resistance, it is generally preferred to be 50% by mass or less, more preferably 30% by mass or less, and especially preferably 20% by mass or less.

[0302] The laminated film of the second invention of this application only needs to contain plant-derived biopolymer polyethylene in the (2B) intermediate layer. However, from the viewpoint of further improving the Young's modulus and further reducing the environmental impact, it is more preferable to also contain plant-derived biopolymer polyethylene in the (2A) heat-fused layer and / or the (2C) laminated layer. It is particularly preferred that all layers of the (2A) heat-fused layer, (2B) intermediate layer and (2C) laminated layer contain plant-derived biopolymer polyethylene.

[0303] The content of plant-derived biopolymer polyethylene in (2A) the heat-fusion layer and / or (2C) the laminate is preferably 10% by mass or more, and particularly preferably 20% by mass or more.

[0304] There is no particular upper limit to the content of plant-derived biopolymer polyethylene in (2A) the heat-fusion layer and / or (2C) the laminate layer. From the viewpoint of bag rupture resistance, it is generally 50% by mass or less, more preferably 30% by mass or less, and especially preferably 25% by mass or less.

[0305] The content of plant-derived biopolymer polyethylene in the laminated film of the second invention of this application is preferably 6% by mass or more, and particularly preferably 12% by mass or more.

[0306] The content of plant-derived biopolymer polyethylene in the laminated film of the second invention of this application has no particular upper limit, but from the viewpoint of tear resistance and film strength, it is generally preferred to be less than 30% by mass.

[0307] The content of plant-derived biopolymer polyethylene can be appropriately increased or decreased, for example, by adjusting the formulation of the resin composition during the manufacture of each layer.

[0308] The content of plant-derived biopolymer polyethylene in each layer of the manufactured membrane can be measured, for example, by radiocarbon dating (RTA). 14 C) The determination measures the content of biomass-derived carbon in the membrane and calculates it from the result of this determination and the content of biomass-derived carbon in the plant-derived biopolyethylene.

[0309] The laminated membrane of the second invention of this application contains biopolymer polyethylene derived from plants in the (2B) intermediate layer (and more preferably the (2A) heat-fusion layer and / or (2C) laminated layer), which can reduce the amount of fossil fuel used in manufacturing and reduce the environmental impact.

[0310] The biomass of laminated membranes can be calculated by weighting the biomass of each layer by the weight of each layer.

[0311] The biomass of the laminated membrane can be adjusted by changing the biomass of each layer, and the biomass of each layer can be adjusted by changing the biomass and amount of the resin used in each layer.

[0312] The biomass of the laminated film of the second invention of this application is preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0313] The higher the biomass of the laminated membrane of the second invention of this application, the better. There is no particular upper limit. In terms of its relationship with the physical properties or cost of the membrane, it is usually below 60% by mass, and in most cases below 30% by mass.

[0314] The heat of fusion ΔH of the laminated film of the second invention of this application, calculated from the melting curve obtained by DSC measurement from 0°C to 130°C, is preferably 135 to 164 J / g.

[0315] By keeping the heat of fusion ΔH between 0°C and 130°C within the above range, the Young's modulus of the laminated film can be further improved effectively.

[0316] The determination of the melting curve by DSC and the calculation of the heat of fusion ΔH from 0°C to 130°C in the melting curve can be performed by conventionally known methods, and more specifically, by the methods described in the embodiments of this application.

[0317] The heat of fusion ΔH at 0°C to 130°C is preferably 135 to 164 J / g, and more preferably 140 to 164 J / g.

[0318] The heat of fusion ΔH from 0°C to 130°C can be reduced by adding components other than petroleum-derived linear low-density polyethylene to decrease the crystallinity of the film. Preferably, plant-derived biopolymer polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, etc., are added as components other than petroleum-derived linear low-density polyethylene.

[0319] The laminated film of the second invention of this application may be an extended film or a non-extended film. From the viewpoint of improving mechanical properties, an extended film is preferred, and a biaxially extended film is particularly preferred.

[0320] Dual-axis extension can be achieved by appropriately employing methods such as successive dual-axis extension, synchronous dual-axis extension, and multi-stage extension.

[0321] The conditions for biaxial stretching can be listed as the manufacturing conditions of commonly known biaxially stretched films. For example, in the successive biaxial stretching method, the longitudinal stretching temperature is set to 100°C to 145°C and the stretching ratio is set to a range of 4 to 7 times. The transverse stretching temperature is set to 150°C to 190°C and the stretching ratio is set to a range of 8 to 11 times.

[0322] (2D) Substrate Layer

[0323] As desired, the laminated film of the second invention of this application can be laminated on the (2C) laminate layer and the (2D) substrate layer.

[0324] (2D) There are no particular limitations on the substrate layer, and it can be suitable for use, for example, films commonly used in plastic packaging bags.

[0325] Preferred materials for the (2D) substrate layer include, for example, polyolefins such as crystalline polypropylene, crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly4-methylpentene-1, low-density polyethylene, medium-density polyethylene, or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ion-crosslinked olefin copolymers (ionomers); aromatic ethylene copolymers such as polystyrene and styrene-butadiene copolymer; halogenated ethylene polymers such as polyvinyl chloride and dichloroethylene resin; nitrile polymers such as acrylonitrile-styrene copolymer and acrylonitrile-styrene-butadiene copolymer; polyamides such as nylon 6, nylon 66, p-xylene-hexamethylenediamide, or m-xylene-hexamethylenediamide; polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate; various polycarbonates; and thermoplastic resins such as polyoxymethylene and polyacetals. In addition, when the contents of the package are sensitive to oxygen, a film coated with metal oxides or other organic compounds or a layer made of ethylene-vinyl alcohol copolymer (EVOH) resin can be provided on the above-mentioned film.

[0326] Plastic films made of these materials can be used unstretched, or uniaxially or biaxially stretched.

[0327] (2D) The substrate layer can be a single layer or two or more of these plastic films can be stacked. In addition, one or more of these plastic films can be bonded to metal foil such as aluminum, paper, Cellophane, etc.

[0328] Preferred (2D) substrate layers include, for example, single-layer films composed of stretched nylon films or stretched polyester films; double-layer films composed of polyolefin films such as low-density polyethylene or polypropylene and PET; and triple-layer films composed of PET / nylon / polyethylene. When manufacturing these laminated films, adhesives or anchoring agents may optionally be intermediaries between the layers. Furthermore, an ink layer that expresses a design aesthetic may also be provided.

[0329] There are no particular limitations on the method of laminating the (2D) substrate layer onto the (2C) laminate layer. For example, the (2D) substrate layer can be directly laminated onto the (2C) laminate layer by means of extrusion lamination. Alternatively, the (2D) substrate layer can be laminated onto the (2C) laminate layer in the presence of an adhesive, such as by dry lamination. Commonly used adhesives such as urethane adhesives, acid-modified polyolefin adhesives, polyester adhesives, polyether adhesives, and polyamide adhesives can be used.

[0330] (2D) The thickness of the substrate layer can be set arbitrarily, typically selected from 5 to 50 μm, and more preferably from the range of 10 to 30 μm.

[0331] The laminated film of the second invention of this application, and the laminated film on which the (2C) laminate layer of the laminated film of the second invention of this application is laminated with the (2D) substrate layer, are suitable for use in various applications, and are particularly suitable for use as packaging materials.

[0332] When used as packaging material, the laminated films are heat-sealed together or with other films on the heat-sealing layer (2A) to form a packaging bag.

[0333] The laminated film of the second invention of this application has an increased Young's modulus, so such packaging bags are easy to stand up, and can be used as stand-up pouches for example.

[0334] The contents of a packaging bag that uses the laminated film of the second invention of this application are preferably a stand-up pouch. There are no particular restrictions on the contents, but it is particularly suitable for containing, for example, liquid medicines, or cosmetics such as liquid detergents and fabric softeners, or liquid foods such as espresso, or powders such as detergents, sugar, pepper, and salt.

[0335] The following describes in detail the various embodiments of the third invention of this application.

[0336] The third invention of this application is a laminated film comprising: a (3A) heat-fusion layer, a (3B) intermediate layer and a (3C) laminated layer respectively containing linear low-density polyethylene derived from petroleum, wherein at least one of the (3A) heat-fusion layer, the (3B) intermediate layer and the (3C) laminated layer contains at least 3% by mass of bio-based linear low-density polyethylene derived from plants.

[0337] That is, the laminated film of the third invention of this application contains linear low-density polyethylene derived from petroleum in each of the layers of the (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminate.

[0338] Furthermore, the laminated film of the third invention of this application contains a predetermined amount of bio-linear low-density polyethylene derived from plants in at least one of the (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminated layer.

[0339] Linear low-density polyethylene derived from petroleum

[0340] The petroleum-derived linear low-density polyethylene used in the third invention of this application is a homopolymer of ethylene manufactured using petroleum as a raw material, or a copolymer of ethylene and α-olefins manufactured using petroleum as a raw material, and may be petroleum-derived linear low-density polyethylene synthesized by commonly known manufacturing methods.

[0341] α-Olefins can be compounds having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc., and mixtures thereof may also be used. α-Olefins are more preferably compounds having 4, 6, or 8 carbon atoms, or mixtures thereof, such as 1-butene, 1-hexene, 1-octene, or mixtures thereof.

[0342] Linear low-density polyethylene derived from petroleum is available for commercial sale, such as 2040F (C6-LLDPE, MFR; 4.0, density; 0.918 g / cm³) manufactured by Ube-Maruzen Polyethylene Co., Ltd. 3 ).

[0343] The density of linear low-density polyethylene derived from petroleum is preferably 0.905 to 0.935 g / cm³. 3 The preferred value is 0.915 to 0.930 g / cm³. 3 The preferred MFR is 0.5 to 6.0 g / 10 min, and more preferably 2.0 to 4.0 g / 10 min.

[0344] The molecular weight distribution (expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn): Mw / Mn) of linear low-density polyethylene derived from petroleum is preferably from 1.5 to 4.0, more preferably from 1.8 to 3.5. This Mw / Mn ratio can be determined by gel permeation chromatography (GPC).

[0345] The linear low-density polyethylene derived from petroleum, from the endothermic curve measured by a differential scanning calorimeter (DSC) at a heating rate of 10°C / min, has one or more sharp peaks. The highest temperature of these peaks, i.e. the melting point, is preferably between 95 and 140°C, and more preferably between 105 and 130°C.

[0346] Linear low-density polyethylene derived from petroleum can be manufactured using conventionally known methods, employing catalysts such as multi-site catalysts like Chigler catalysts or single-site catalysts like metal-aromatic catalysts. From the viewpoint of obtaining linear low-density polyethylene capable of forming films with narrow molecular weight distribution and high strength, the use of single-site catalysts is preferred.

[0347] The aforementioned single-active-site catalyst is a catalyst capable of forming uniform active species, typically modulated by contacting a metal aromatic transition metal compound or a non-metal aromatic transition metal compound with an activation auxiliary catalyst. Compared to multi-active-site catalysts, single-active-site catalysts are preferred because their active site structure is uniform, allowing for the polymerization of high-molecular-weight polymers with highly uniform structures. Metal aromatic catalysts are particularly preferred. A metal aromatic catalyst is a catalyst comprising: a transition metal compound of Group IV of the periodic table containing a ligand with a cyclopentadienyl skeleton, an auxiliary catalyst, an optional organometallic compound, and a support.

[0348] In the aforementioned transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton, the cyclopentadienyl skeleton refers to cyclopentadienyl, substituted cyclopentadienyl, etc. The substituted cyclopentadienyl has at least one substituent selected from hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl-substituted alkyl groups, silyl-substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups, halosilyl groups, etc. The substituted cyclopentadienyl may have two or more substituents; furthermore, the substituents may bond to each other to form a ring, such as an indene ring, afluorene ring, an azurite ring, or its hydride. The ring formed by the bonding of substituents to each other may also have substituents in each other.

[0349] Among transition metal compounds of Group IV of the periodic table containing ligands having a cyclopentadienyl skeleton, examples of which include zirconium, titanium, and hafnium, with zirconium and hafnium being particularly preferred. This transition metal compound typically has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other via a crosslinking group. Examples of crosslinking groups include substituted silanes (1 to 4 carbon atoms), dialkylsilanes, diarylsilanes, diarylsilanes, dialkylgermaniums, diarylgermaniums, etc., substituted germaniums, etc. Substituted silanes are more preferred.

[0350] Among transition metal compounds in Group IV of the periodic table, ligands other than those with a cyclopentadienyl skeleton can be representatively listed as: hydrogen, hydrocarbon groups with 1 to 20 carbon atoms (alkyl, alkenyl, aryl, alkylaryl, aralkyl, polyalkenyl, etc.), halogens, methylalkyl, methylaryl, etc.

[0351] The aforementioned transition metal compounds comprising a ligand having a cyclopentadienyl skeleton in Group IV of the periodic table may use one or more mixtures as catalyst components.

[0352] Auxiliary catalysts refer to those that can effectively transform transition metal compounds of Group IV in the periodic table into polymerization catalysts, or those that can balance the ionic charges in the activated state on the catalyst. Examples of auxiliary catalysts include: benzene-soluble aluminum oxanes or benzene-insoluble organoaluminooxy compounds, ion-exchangeable layered silicates, boron compounds, ionic compounds composed of cations with or without active hydrogen groups and non-coordinate anions, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing fluorine groups.

[0353] Transition metal compounds of Group IV of the periodic table containing ligands with a cyclopentadienyl skeleton can be used as supports for inorganic or organic compounds. The support is preferably a porous oxide of inorganic or organic compound, specifically including: ion-exchangeable layered silicates such as montmorillonite, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof.

[0354] In addition, the organometallic compounds that may be used include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Among these, organoaluminum compounds are suitable.

[0355] Linear low-density polyethylene derived from petroleum can be used alone or in combination of two or more. Furthermore, it can also be used in conjunction with other polymers, primarily other vinyl polymers.

[0356] Without prejudice to the purpose of the third invention of this application, the linear low-density polyethylene derived from petroleum may optionally be formulated with a variety of commonly known additives typically added to olefin polymers, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, anti-caking agents, lubricants, etc.

[0357] Biopolymer linear low-density polyethylene derived from plants

[0358] The bio-based linear low-density polyethylene used in the third invention of this application is a linear low-density polyethylene obtained by polymerizing ethylene manufactured using plants as raw materials.

[0359] In the third invention of this application, the above-mentioned bio-based linear low-density polyethylene derived from plants is linear low-density polyethylene, which, as described below, is polymerized by polymerizing monomers containing ethylene derived from biomass.

[0360] Therefore, apart from linear low-density polyethylene formed by polymerizing monomers containing ethylene from biomass, it is more preferable that the other products have the same physical properties as conventional linear low-density polyethylene.

[0361] For example, the “linear low-density polyethylene” in this application is preferably an ethylene-based (co)polymer having 10 to 30 SCBs (side chains with 1 to 5 carbons; also known as “short chain branches”) per 1000 carbons.

[0362] Plant-derived biopolymer linear low-density polyethylene (BLD) is commercially available, such as the BLD manufactured and sold by Braskem. Specifically, model SL218 is suitable.

[0363] The bio-based linear low-density polyethylene used in the third invention of this application is produced by polymerizing monomers containing ethylene derived from biomass. The ethylene derived from biomass is preferably obtained by the manufacturing method described below, but is not limited thereto. Furthermore, since the monomers using ethylene derived from biomass are the raw materials, the polymerized linear low-density polyethylene is derived from biomass. The raw material monomers of the linear low-density polyethylene may not contain 100% by mass of ethylene derived from biomass, and may contain raw material monomers that are not derived from biomass or are other than ethylene.

[0364] There are no particular limitations on the method for producing bioethylene, which serves as a raw material for bio-based linear low-density polyethylene derived from plants, and it can be obtained by methods generally known in the past. An example of a method for producing bioethylene is described below.

[0365] Bio-ethylene can be produced from bio-ethanol as a raw material. Fermented ethanol derived from plant materials is particularly preferred. The plant material is not particularly limited and can be any plant known in the conventional sense. Examples include corn, sugarcane, sugar beets, and cassava.

[0366] In the context of the third invention of this application, "biomass-derived fermented ethanol" refers to ethanol obtained by contacting ethanol-producing microorganisms or products derived from their crushed form with a carbon-source-containing culture broth obtained from plant materials, followed by purification. The purification of ethanol from the culture broth can be achieved using conventionally known methods such as distillation, membrane separation, and extraction. Examples include adding benzene or cyclohexane and performing azeotropic distillation, or removing water through membrane separation.

[0367] In order to obtain bio-ethylene, this stage can be further refined to reduce the total amount of impurities in the ethanol to less than 1 ppm.

[0368] When ethylene is obtained from ethanol via dehydration, a catalyst is typically used. This catalyst is not particularly limited and can be any conventionally known catalyst. A fixed-bed flow reaction process that facilitates the separation of the catalyst and products is more advantageous, with γ-alumina being a preferred example.

[0369] Since this dehydration reaction is endothermic, it is usually carried out under heating conditions. The heating temperature is not limited if the reaction is carried out at a commercially useful rate, but is preferably 100°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher. There is no particular upper limit, but from the viewpoint of energy balance and equipment, is preferably 500°C or lower, and even more preferably 400°C or lower.

[0370] There is no particular limitation on the reaction pressure, but a pressure above atmospheric pressure is preferred to facilitate subsequent gas-liquid separation. Industrially, a fixed-bed flow reaction is more suitable for easy catalyst separation, but liquid-phase suspension bed, fluidized bed, etc. are also possible.

[0371] In the dehydration reaction of ethanol, the yield is influenced by the amount of water contained in the ethanol supplied as a raw material. Generally, when carrying out a dehydration reaction, anhydrous is preferred considering the efficiency of water removal. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that the formation of other olefins, especially butene, tends to increase when water is absent. This can be presumed to be because if a small amount of water is not present, it may be impossible to suppress the dimerization of the dehydrated ethylene. The lower limit of the permissible water content must be 0.1% by mass or more, preferably 0.5% by mass or more. There is no particular upper limit, but from the viewpoint of mass and heat balance, it is more preferably 50% by mass or less, especially 30% by mass or less, and more preferably 20% by mass or less.

[0372] By performing the dehydration reaction of ethanol in this manner, a mixture of ethylene, water, and a small amount of unreacted ethanol is obtained. Since ethylene is a gas at room temperature and below approximately 5 MPa, water and ethanol can be removed from this mixture by gas-liquid separation to obtain ethylene. This method can be carried out using generally known methods.

[0373] The ethylene obtained through gas-liquid separation is further distilled. Apart from the operating pressure being above atmospheric pressure, there are no special restrictions on the distillation method, operating temperature, and residence time.

[0374] When the raw material is biomass-derived fermented ethanol, the resulting ethylene contains trace amounts of carbon dioxide gas, which is an impurity introduced during the ethanol fermentation process, such as ketones, aldehydes, and esters, and their decomposition products. It also contains nitrogen-containing compounds, such as amines and amino acids, which are enzyme decomposition products and impurities, and their decomposition products, such as ammonia. Since these trace impurities may cause problems in the manufacture or use of polyethylene, they can be removed through purification. The purification method is not particularly limited and can be carried out using methods generally known in the past. Suitable purification operations include, for example, adsorption purification. The adsorbent used is not particularly limited and can be any adsorbent generally known in the past. A material with a high surface area is preferred, and the type of adsorbent should be selected according to the type and amount of impurities in the ethylene obtained from the dehydration reaction of biomass-derived fermented ethanol.

[0375] Alternatively, the purification of impurities in ethylene can also be performed using caustic water treatment. When caustic water treatment is performed, it is preferable to do so before adsorption purification. In this case, a water removal treatment must be applied after caustic treatment and before adsorption purification.

[0376] Monomers used as raw materials for bio-based linear low-density polyethylene derived from plants may contain more ethylene and / or α-olefins derived from fossil fuels, or more α-olefins derived from biomass.

[0377] The number of carbon atoms in the aforementioned α-olefins is not particularly limited; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being more preferred. This is because butene, hexene, or octene can be produced by polymerizing ethylene, which is derived from biomass. Furthermore, by containing such α-olefins, the linear low-density polyethylene polymerized has alkyl groups as branched structures, and compared to simple linear polyethylene, it can be configured as a polyethylene rich in flexibility.

[0378] From an environmental impact perspective, the aforementioned linear low-density polyethylene is preferably a copolymer of ethylene and an α-olefin derived from ethylene. This is because, theoretically, it can be manufactured using ethylene derived from biomass as a raw material, with 100% biomass-derived components.

[0379] The concentration of ethylene derived from biomass in the aforementioned linear low-density polyethylene (hereinafter sometimes referred to as "biomass content") is determined by radiocarbon dating. 14 C) is the value obtained by measuring the carbon content from biomass. It is well known that carbon dioxide in the atmosphere contains a certain proportion (105.5 pMC). 14 C, therefore, plants that grow by absorbing carbon dioxide from the atmosphere, such as corn. 14 The carbon content is also approximately 105.5 pMC. Furthermore, it contains almost no carbon in fossil fuels. 14C is also known. Therefore, by measuring the total carbon atoms contained in linear low-density polyethylene... 14 The ratio of C can be used to calculate the ratio of carbon from biomass. In the third invention of this application, in the linear low-density polyethylene... 14 The content of C is set as P 14C In this case, the carbon content P from biomass bio The following methods can be used to obtain it.

[0380] P bio (%) = P 14C / 105.5×100

[0381] In the bio-based linear low-density polyethylene used in the third invention of this application, theoretically, if all ethylene and α-olefins derived from biomass are used as raw materials for polyethylene, the concentration of ethylene from biomass is 100%, and the biomass degree of the bio-based linear low-density polyethylene is 100%. Furthermore, in fossil fuel-derived polyethylene manufactured solely from fossil fuel feedstocks, the concentration of ethylene from biomass is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0%.

[0382] In the third invention of this application, the biomass content of the bio-based linear low-density polyethylene does not need to be 100%. This is because even if raw materials from biomass are used in a portion of the bio-based linear low-density polyethylene, the amount of fossil fuel used can be reduced compared to the past.

[0383] In the bio-based linear low-density polyethylene used in the third invention of this application, the polymerization method containing monomers derived from biomass ethylene is not particularly limited, and can be carried out by methods generally known in the art. The polymerization temperature or polymerization pressure can be appropriately adjusted according to the polymerization method or polymerization apparatus. There are also no particular limitations on the polymerization apparatus, and conventionally known apparatus can be used.

[0384] For example, polymerization methods for monomers containing ethylene, as described below, can be applied.

[0385] The polymerization method for bio-based linear low-density polyethylene can be appropriately selected according to the density or branching of the desired linear low-density polyethylene. For example, it is more preferable to use multi-active-site catalysts such as Chigler catalysts and Philipp catalysts, or single-active-site catalysts such as metal aromatic catalysts, as polymerization catalysts, and carry out the polymerization in one or more stages through any one of gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0386] From the viewpoint of obtaining bio-based linear low-density polyethylene with a wide molecular weight distribution and excellent flexibility or formability, it is preferable to use multi-active-site catalysts such as Chigler catalysts and Philipp catalysts.

[0387] Preferred Chigler catalysts may be those commonly known for their use in the coordination polymerization of ethylene and α-olefins, such as catalysts containing titanium compounds and organoaluminum compounds, catalysts composed of titanium halide compounds and organoaluminum compounds, and catalysts composed of solid catalyst components such as titanium, magnesium, and chlorine and organoaluminum compounds. More specifically, such catalysts can be exemplified as: a catalyst composed of a catalyst component (a) obtained by reacting a titanium compound with an alcohol pretreatment product of anhydrous magnesium dihalide and an organometallic compound, and an organometallic compound (b); a catalyst composed of a catalyst component (A) obtained by reacting magnesium metal with an organic hydroxide or an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of transition metals, and an aluminum halide, and an organometallic compound catalyst component (B); a catalyst composed of a solid catalyst component (A) obtained by reacting (i) metallic magnesium with an organic hydroxide, an oxygen-containing organic compound of magnesium, and a halogenated compound, (ii) an oxygen-containing organic compound of transition metals and a halogenated compound, (iii) a reactant obtained by reacting a silicon compound, and (iv) an aluminum halide compound, and an organometallic compound catalyst component (B), etc.

[0388] In addition, the Philips catalyst can be the Philips catalyst commonly known for its use in the coordination polymerization of ethylene and α-olefins, such as a catalyst system containing chromium compounds such as chromium oxide, specifically exemplified by catalysts in which chromium compounds such as chromium trioxide and chromate are supported on solid oxides such as silica, alumina, silica-alumina, and silica-titanium oxide.

[0389] There are no particular limitations on the density of biopolymer linear low-density polyethylene derived from plants, but a density of 0.905 to 0.935 g / cm³ is preferred. 3 The preferred value is 0.915 to 0.930 g / cm³. 3 .

[0390] There are no particular limitations on the MFR of biopolymer linear low-density polyethylene derived from plants. From the viewpoint of formability, it is more preferably 0.3 to 15.0 g / 10 min, more preferably 1.0 to 12.0 g / 10 min, more preferably 1.5 to 10.0 g / 10 min, and especially preferably 2.0 to 9.0 g / 10 min.

[0391] There are no particular limitations on the molecular weight distribution of biopolymer linear low-density polyethylene derived from plants. From the viewpoint of flexibility and formability, the molecular weight distribution (expressed as the ratio of weight-average molecular weight: Mw to number-average molecular weight: Mn: Mw / Mn) is preferably 3.5 or higher, particularly preferably 3.8 to 9.0, and more preferably in the range of 4.0 to 8.6. This Mw / Mn can be determined by gel permeation chromatography (GPC), and more specifically, by the method described, for example, in the embodiments of this application.

[0392] Furthermore, the biomass linear low-density polyethylene derived from plants has one or more sharp peaks in the endothermic curve obtained from the differential scanning calorimeter (DSC) at a heating rate of 10°C / min. The highest temperature of this peak, i.e. the melting point, is preferably in the range of 95 to 140°C, and more preferably in the range of 100 to 135°C.

[0393] Biopolymer linear low-density polyethylene derived from plants can be used alone or in combination with two or more other polymers. Furthermore, it can also be used, primarily with other ethylene-based polymers, or in combination with other polymers, regardless of whether it is derived from plants.

[0394] Without prejudice to the purpose of the third invention of this application, various commonly known additives, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, anti-caking agents, and lubricants, may be optionally incorporated into the biopolymer linear low-density polyethylene derived from plants.

[0395] The laminated film of the third invention of this application has the following (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminated layer.

[0396] (3A) The heat-fused layer, (3B) The intermediate layer, and (3C) The laminate all contain the aforementioned linear low-density polyethylene derived from petroleum. By including the aforementioned linear low-density polyethylene derived from petroleum in (3A) The heat-fused layer, (3B) The intermediate layer, and (3C) The laminate in (3C) The lamination strength between each layer can be sufficiently achieved. Furthermore, this is also advantageous from the perspective of the productivity and cost of the laminated film.

[0397] (3A) Thermal fusion layer

[0398] The (3A) heat-sealing layer constituting the laminated film of the third invention of this application is often configured as the innermost layer and fused with other films when the laminated film of the third invention of this application is used to form a packaging bag. Therefore, it is preferable to use a low-melting-point resin in a manner that obtains high sealing strength. For example, by setting the ethylene content of linear low-density polyethylene derived from petroleum to a low level, the melting point of the (3A) heat-sealing layer can be reduced. More specifically, it is preferable to set the ethylene content of linear low-density polyethylene derived from petroleum to 10% by mass or less, more preferably to 7% by mass or less, and even more preferably to 5% by mass or less.

[0399] When the ethylene content of petroleum-derived linear low-density polyethylene (LDPE) must be increased due to reasons such as the need to improve membrane strength or the necessity of using materials common to other layers, a low-melting-point resin can be added to the (3A) heat-fusion layer. Furthermore, when bio-based LDPE from plants is added to the (3A) heat-fusion layer, a low-melting-point bio-based LDPE from plants can also be added.

[0400] Other low-melting-point resins mentioned above include: high-pressure low-density polyethylene, ethylene-α-olefin random copolymers and other ethylene polymers with relatively low density; aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosin, styrene resins, coumarone-indene resins and other adhesive-improving resins.

[0401] From the viewpoint of heat-sealing properties, the content of linear low-density polyethylene derived from petroleum in the (3A) heat-fusion layer is preferably 50% by mass or more, more preferably 55% to 99% by mass, and especially preferably 65% ​​to 95% by mass.

[0402] (3A) There is no particular limitation on the thickness of the heat-sealing layer. From the viewpoint of heat sealing, it is preferred to be 5 μm or more, and even more preferred to be 10 μm or more.

[0403] On the other hand, from the viewpoint of membrane strength, a thickness of 30 μm or less is preferred, and a thickness of 20 μm or less is even more preferred.

[0404] Without prejudice to the purpose of the third invention of this application, various commonly known additives that are usually added to polyolefins, such as anti-caking agents, lubricants, antioxidants, weather stabilizers, antistatic agents, antifogging agents, etc., may be optionally incorporated into the heat-fused layer.

[0405] Anti-caking agents include: silica, talc, clay, calcium carbonate, synthetic zeolite, starch, alumina, acrylic resin, methacrylic resin, silicone resin, polytetrafluoroethylene resin, etc.

[0406] In addition, examples of lubricants include: palmitamide, stearamide, rhodiola, oleamide, mustardamide, oleopalatamide, stearapalatamide, methylene bis-stearamide, methylene bis-oleamide, ethylene bis-oleamide, ethylene bis-mustardamide, and other amides; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; hydrogenated castor oil, etc.

[0407] (3B) Intermediate layer

[0408] In the laminated film constituting the third invention of this application, the (3A) heat-sealing layer is preferably designed to obtain an appropriate sealing strength, and the (3C) laminating layer is preferably designed considering the lamination strength with the (3D) substrate layer, etc. In contrast, since the (3B) intermediate layer has relatively fewer restrictions, it can be designed to impart desired physical properties and performance, such as mechanical properties, to the laminated film of the third invention of this application as a whole. In this case, it is more preferable to set the thickness of the (3B) intermediate layer to be greater than the thickness of the (3A) heat-sealing layer and the thickness of the (3C) laminating layer, and more preferably to be greater than the sum of the thicknesses of the (3A) heat-sealing layer and the (3C) laminating layer.

[0409] More specifically, the thickness of the (3B) intermediate layer is preferably 10 μm or more, more preferably 15 μm or more, and especially preferably 30 μm or more.

[0410] On the other hand, from the viewpoint of heat sealing, the thickness of the (3B) intermediate layer is preferably 150 μm or less, more preferably 130 μm or less, more preferably 100 μm or less, and especially preferably 90 μm or less.

[0411] For example, from the viewpoint of achieving high mechanical strength for the laminate as a whole, (3B) the intermediate layer is preferably made of a resin with high mechanical strength in a high proportion. For example, a resin with a high molecular weight and a narrow molecular weight distribution is selected as linear low-density polyethylene derived from petroleum, and more preferably, this content is set to be relatively high.

[0412] From this perspective, the content of linear low-density polyethylene derived from petroleum in the (3A) heat-fusion layer is preferably 50% by mass or more, more preferably 75% to 100% by mass, even more preferably 85% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0413] Furthermore, the molecular weight distribution of the linear low-density polyethylene derived from petroleum is preferably 4.0 or less, and particularly preferably 3.0 or less. Similarly, the molecular weight of the linear low-density polyethylene derived from petroleum is preferably 20,000 or more, especially preferably 25,000 or more, more preferably 50,000 or more, and particularly preferably 70,000 or more.

[0414] From the viewpoint of improving the flexibility or impact resistance of the laminate as a whole, (3B) the intermediate layer is preferably made of a resin with high flexibility or high impact resistance in a high proportion. For example, a resin with high flexibility or high impact resistance can be selected as linear low-density polyethylene derived from petroleum, and this content is further set to be relatively high.

[0415] Furthermore, by adding an elastomer or rubber component to the (3B) intermediate layer, the softness or impact resistance of the (3B) intermediate layer can be improved, thereby enhancing the overall softness or impact resistance of the laminate. Examples of elastomers or rubber components include ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-propylene-butene copolymers, etc., and the amount added can be set to 1 to 30% by mass, preferably 5 to 10% by mass.

[0416] (3C) laminate

[0417] The (3C) laminates constituting the laminated film of the third invention of this application may optionally or as desired be laminated with other layers, starting with the (3D) substrate layer described later.

[0418] Therefore, the (3C) laminate is preferably designed with consideration of the bonding strength with other layers.

[0419] From this perspective, the linear low-density polyethylene derived from petroleum in the (3C) laminate is preferably selected from petroleum-derived linear low-density polyethylene with excellent affinity to other layers, including the (3D) substrate layer, and the content is preferably 40 to 99% by mass, and more preferably 70 to 95% by mass.

[0420] In addition, to further enhance the bonding strength with other layers, corona treatment, roughening treatment, and other treatments can be performed on the surface of the (3C) laminate (the side opposite to the surface of the (3B) intermediate layer).

[0421] On the other hand, from the viewpoint of anti-caking when storing the laminated film of the third invention of this application, the (3C) laminate may contain an anti-caking agent.

[0422] Powdered silica can be suitable as an anti-caking agent, preferably synthetic silica. From the viewpoint of uniformly dispersing powdered silica in the (3C) laminate, the powdered silica can be dispersed in a resin with excellent compatibility with the petroleum-derived linear low-density polyethylene constituting the (3C) laminate, for example, dispersed in low-density polyethylene to form a masterbatch, which is then added to the petroleum-derived linear low-density polyethylene. Furthermore, without prejudice to the purpose of the third invention of this application, a lubricant (slip agent) may optionally be incorporated into the laminate.

[0423] Examples of lubricants include: palmitamide, stearamide, rhodiola, oleamide, mustardamide, oleopalatamide, stearapalatamide, methylene bis-stearamide, methylene bis-oleamide, ethylene bis-oleamide, ethylene bis-mustardamide, and other amides; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; and hydrogenated castor oil.

[0424] (3C) There is no particular limitation on the thickness of the laminate, but from the viewpoint of lamination processability, it is more preferably 5 μm or more, and especially preferably 10 μm or more.

[0425] On the other hand, from the viewpoint of membrane strength, it is more preferably 30 μm or less, and more preferably 20 μm or less.

[0426] (3A) the heat-fused layer, (3B) the intermediate layer, and (3C) the laminate may contain various additives and fillers other than petroleum-derived linear low-density polyethylene (and, where present, biomass-derived linear low-density polyethylene), such as heat stabilizers, antioxidants, light stabilizers, antistatic agents, anti-caking agents, lubricants, nucleating agents, flame retardants, pigments, dyes, calcium carbonate, barium sulfate, magnesium hydroxide, mica, talc, clay, antibacterial agents, antifogging agents, etc., provided that the purpose of the third invention of this application is not violated. Furthermore, other thermoplastic resins, thermoplastic elastomers, rubbers, hydrocarbon resins, petroleum resins, etc., may also be formulated within the scope of the third invention of this application.

[0427] laminated membrane

[0428] The laminated film of the third invention of this application comprises: a (3A) heat-fusion layer, a (3B) intermediate layer, and a (3C) laminate layer, each containing linear low-density polyethylene derived from petroleum. In the laminated film of the third invention of this application, it is more preferable that the (3C) laminate layer and the (3A) heat-fusion layer are laminated with the (3B) intermediate layer in between, but other layers may also be present.

[0429] The laminated film of the third invention of this application can be formed using various generally known film forming methods, such as: a method of forming a laminated film by first forming a (3C) layer, an intermediate layer, and a (3A) heat-fused layer separately, and then bonding the films together; a method of forming a laminated film by using a multilayer mold to obtain a composite film composed of an intermediate layer (3B) and a heat-fused layer (3A), and then pressing the (3C) layer onto the intermediate layer (3B); a method of forming a laminated film by using a multilayer mold to obtain a composite film composed of an intermediate layer (3C) layer and an intermediate layer (3B), and then pressing the (3A) heat-fused layer onto the intermediate layer (3B); or a method of forming a laminated film composed of an intermediate layer (3C) layer, an intermediate layer (3B), and a heat-fused layer (3A) using a multilayer mold, etc.

[0430] In addition, various generally known film forming methods can be used, specifically including die casting film forming method and blown film forming method.

[0431] The laminated film and each layer constituting the laminated film of the third invention of this application may be an unstretched film (non-stretched film) or a stretched film.

[0432] The thickness of each layer of the laminated film of the third invention of this application is not particularly limited, but is usually 3 μm or more, more preferably 5 to 150 μm, and even more preferably in the range of 5 to 90 μm.

[0433] The thickness of the laminated film of the third invention of this application is not particularly limited. From the viewpoint of ensuring practical strength, it is generally 20 μm or more, more preferably 25 μm or more, and especially preferably 30 μm or more. On the other hand, from the viewpoint of having practical flexibility after being laminated with a (3D) substrate layer, it is generally 200 μm or less, more preferably 180 μm or less, and especially preferably 150 μm or less.

[0434] The laminated film of the third invention of this application contains at least 3% by mass of bio-linear low-density polyethylene derived from plants in at least one of the (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminated layer.

[0435] By including at least 3% by mass of bio-based linear low-density polyethylene derived from plants in at least one of the (3A) heat-fusion layer, (3B) intermediate layer, and (3C) laminated layer, the laminated film of the third invention of this application significantly improves the lamination strength with the (3D) substrate layer while maintaining the excellent properties of conventional polyethylene-based laminated films, such as mechanical strength and anti-caking properties, thus achieving remarkable technical effects. Furthermore, even with such a significant improvement in lamination strength with multiple layers, surprisingly, the anti-caking properties between the laminated films of the third invention of this application can be maintained at the same level as conventional products.

[0436] The content of biopolymer linear low-density polyethylene derived from plants is preferably 6% by mass or more, and particularly preferably 12% by mass or more.

[0437] There is no particular upper limit to the content of biopolymer linear low-density polyethylene derived from plants, but from the viewpoint of tear resistance and film strength, it is generally preferred to be 6% by mass or more, and particularly preferred to be 12% by mass or more.

[0438] The laminated film of the third invention of this application only needs to contain more than 3% by mass of bio-linear low-density polyethylene derived from plants in at least one of the (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminated layer. From the perspective of greatly improving the laminated strength, it is more preferable that all layers of the (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminated layer contain more than 3% by mass of bio-linear low-density polyethylene derived from plants.

[0439] The content of biopolymer linear low-density polyethylene derived from plants can be appropriately increased or decreased, for example, by adjusting the formulation of the resin composition during the manufacture of each layer.

[0440] The content of plant-derived linear low-density polyethylene in each layer of the manufactured membrane can be measured, for example, by radiocarbon dating (RTA). 14 C) The determination measures the content of biomass-derived carbon in the membrane and calculates it from the result of this determination and the content of biomass-derived carbon in the plant biomass linear low-density polyethylene.

[0441] The laminated membrane of the third invention of this application contains bio-based linear low-density polyethylene derived from plants in at least one of the (3A) heat-fusion layer, (3B) intermediate layer and (3C) laminated layer, which can reduce the amount of fossil fuel used in manufacturing and reduce the environmental impact.

[0442] The biomass of laminated membranes can be calculated by weighting the biomass of each layer by the weight of each layer.

[0443] The biomass of the laminated membrane can be adjusted by changing the biomass of each layer, and the biomass of each layer can be adjusted by changing the biomass and amount of the resin used in each layer.

[0444] The biomass of the laminated film of the third invention of this application is preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0445] The higher the biomass of the laminated membrane of the third invention of this application, the better. There is no particular upper limit. In terms of its relationship with the physical properties or cost of the membrane, it is usually below 60% by mass, and in most cases below 30% by mass.

[0446] The heat of fusion ΔH of the laminated film of the third invention of this application, calculated from the melting curve obtained by DSC measurement from 0°C to 130°C, is preferably 135 to 164 J / g.

[0447] By keeping the heat of melting ΔH between 0°C and 130°C within the above range, the lamination strength between the laminated film and the substrate layer can be further and more effectively improved.

[0448] The determination of the melting curve by DSC and the calculation of the heat of fusion ΔH from 0°C to 130°C in the melting curve can be performed by conventionally known methods, and more specifically, by the methods described in the embodiments of this application.

[0449] As described above, the heat of fusion ΔH at 0°C to 130°C is preferably 135 to 164 J / g, and more preferably 140 to 164 J / g.

[0450] The heat of fusion ΔH from 0°C to 130°C can be reduced by adding components other than petroleum-derived linear low-density polyethylene to decrease the crystallinity of the film. Preferably, plant-derived biopolymer polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, etc., are added as components other than petroleum-derived linear low-density polyethylene.

[0451] The melting point of the laminated film of the third invention of this application, as determined by DSC, corresponding to the maximum peak value, is preferably greater than 114°C.

[0452] By ensuring that the melting point, which corresponds to the maximum peak value, is within the aforementioned range, the lamination strength between the laminated film and the substrate layer can be further and more effectively improved.

[0453] The melting point is preferably above 115°C, and even more preferably above 116°C.

[0454] The laminated film of the third invention of this application may be an extended film or a non-extended film. From the viewpoint of improving mechanical properties, an extended film is preferred, and a biaxially extended film is particularly preferred.

[0455] Dual-axis extension can be achieved by appropriately employing methods such as successive dual-axis extension, synchronous dual-axis extension, and multi-stage extension.

[0456] The conditions for biaxial stretching can be listed as the manufacturing conditions of commonly known biaxially stretched films. For example, in the successive biaxial stretching method, the longitudinal stretching temperature is set to 100°C to 145°C and the stretching ratio is set to a range of 4 to 7 times. The transverse stretching temperature is set to 150°C to 190°C and the stretching ratio is set to a range of 8 to 11 times.

[0457] (3D) Substrate Layer

[0458] As desired, the laminated film of the third invention of this application can be laminated on the (3C) laminate layer and the (3D) substrate layer. In the third invention of this application, a significant effect is achieved by greatly improving the lamination strength with the (3D) substrate layer.

[0459] The lamination strength can be determined using methods generally known in the art. More specifically, for example, in a (3C) laminate of a laminate, after being laminated with a (3D) substrate layer, the sample can be cut into strips 15 mm wide, and then the (3D) substrate layer and the laminate can be peeled apart at an extension speed of 100 mm / min. The strength of the peeled surface is then measured for evaluation. More specifically, this can be done using the method described in the embodiments of this application. The lamination strength at this time is preferably 3 (N / 15 mm) or more, and particularly preferably 5 (N / 15 mm) or more.

[0460] There are no particular limitations on the (3D) substrate layer, and it can be suitable for use, for example, films commonly used in plastic packaging bags.

[0461] Preferred materials for the (3D) substrate layer include, for example, polyolefins such as crystalline polypropylene, crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly4-methylpentene-1, low-density polyethylene, medium-density polyethylene, or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ion-crosslinked olefin copolymers (ionomers); aromatic ethylene copolymers such as polystyrene and styrene-butadiene copolymer; halogenated ethylene polymers such as polyvinyl chloride and dichloroethylene resin; nitrile polymers such as acrylonitrile-styrene copolymer and acrylonitrile-styrene-butadiene copolymer; polyamides such as nylon 6, nylon 66, p-xylene-hexamethylenediamide, or m-xylene-hexamethylenediamide; polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate; various polycarbonates; and thermoplastic resins such as polyoxymethylene and polyacetals. In addition, when the contents of the package are sensitive to oxygen, a film coated with metal oxides or other organic compounds or a layer made of ethylene-vinyl alcohol copolymer (EVOH) resin can be provided on the above-mentioned film.

[0462] Plastic films made of these materials can be used unstretched, or uniaxially or biaxially stretched.

[0463] (3D) The substrate layer can be a single layer or two or more of these plastic films can be stacked. In addition, one or more of these plastic films can be bonded to metal foil such as aluminum, paper, cerova, etc.

[0464] Preferred (3D) substrate layers include, for example, single-layer films composed of stretched nylon films or stretched polyester films; double-layer films composed of polyolefin films such as low-density polyethylene or polypropylene and PET; and triple-layer films composed of PET / nylon / polyethylene. When manufacturing these laminated films, adhesives or anchoring agents may optionally be interposed between the layers. Furthermore, an ink layer that expresses a design aesthetic may also be provided.

[0465] There are no particular limitations on the method of laminating the (3D) substrate layer onto the (3C) laminate layer. For example, the (3D) substrate layer can be directly laminated onto the (3C) laminate layer by means of extrusion lamination. Alternatively, the (3D) substrate layer can be laminated onto the (3C) laminate layer in the presence of an adhesive, such as by dry lamination. Commonly used adhesives such as urethane adhesives, acid-modified polyolefin adhesives, polyester adhesives, polyether adhesives, and polyamide adhesives can be used.

[0466] The thickness of the (3D) substrate layer can be set arbitrarily, typically selected from 5 to 50 μm, and more preferably from the range of 10 to 30 μm.

[0467] The laminated film of the third invention of this application, and the laminated film on which a (3D) substrate layer is laminated on the (3C) laminate layer of the laminated film of the third invention of this application, are suitable for use in various applications, and are particularly suitable for use as packaging materials.

[0468] When used as packaging material, the laminated films are heat-sealed together or with other films on the (3A) heat-sealing layer to form a packaging bag.

[0469] The laminated film of the third invention of this application has a (3D) substrate layer laminated on the (3C) laminate layer. Due to its strong lamination strength, it rarely peels off during manufacturing and use. Therefore, it is suitable for use as packaging material in a wide range of applications in combination with various (3D) substrate layers.

[0470] There are no particular limitations on the contents that should be contained in the packaging bag using the laminated film of the third invention of this application, but it is particularly suitable for containing ingredients such as fruits and vegetables, prepared foods, liquid medicines, or cosmetics such as liquid detergents and fabric softeners, or liquid foods such as espresso, liquid or powdered detergents, and powders such as sugar, pepper, and salt.

[0471] [Example]

[0472] The first to third inventions of this application are described in detail below with reference to embodiments / comparative examples. Furthermore, the first to third inventions of this application are not limited to the following embodiments in any sense.

[0473] The evaluation of the physical properties and characteristics of the embodiments / comparative examples of the first invention of this application is carried out by the following methods.

[0474] (1) Molecular weight distribution (Mw / Mn)

[0475] After pretreating the polymer sample under the following conditions, the molecular weight was determined by GPC, and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) was set as the molecular weight distribution.

[0476] i) Preprocessing

[0477] 20 mL of the mobile phase (o-dichlorobenzene) for GPC determination was added to the sample (30 mg) and dissolved by vibration at 145 °C. The resulting solution was then hot-filtered through a sintered filter with a pore size of 1.0 μm and then provided for GPC determination.

[0478] ii) GPC

[0479] Apparatus: Tosoh Corporation, HLC-8321 gel permeation chromatography system

[0480] Tube string: Made by Tosoh Corporation, 7.5mm inner diameter × 30cm, 4 pieces (2 pieces of TSKgel GMH6-HT and 2 pieces of TSKgel GMH6-HTL)

[0481] Column temperature: 140℃

[0482] Detector: Differential refractometer

[0483] Flow rate: 1 mL / min

[0484] Sampling interval: 0.5 seconds

[0485] (2) Heat of fusion

[0486] Using a TA Instruments Q100 differential scanning calorimeter (DSC), approximately 5 mg of sample was weighed. According to JIS K7121, under the condition of nitrogen inflow rate of 50 mL / min, the temperature was increased from 25 °C to 250 °C at a heating rate of 10 °C / min, and the thermal melting curve was measured. Then, the heat of melting of the sample was determined from the obtained thermal melting curve.

[0487] (3) Elongation strength (yield point stress)

[0488] Using a Tensilon universal testing machine (A&D Corporation, RTG1210), a 15mm wide membrane specimen was stretched at an ambient temperature of 23°C along the main stretching direction (main contraction direction) and a right angle. The clamping distance was set to 50mm, and the stretching speed was 300mm / min. Stretching stress-strain curves were then generated. The first maximum point of the stretching stress-strain curve was used as the yield point stress (unit: MPa).

[0489] (4) Tear strength

[0490] Using a light-load tear tester manufactured by Toyo Seiki Co., Ltd., the tear strength of the laminated films obtained in the examples and comparative examples in the MD and TD directions was measured under the conditions of a temperature of 23±3℃ and a humidity of 50±5%RH.

[0491] (Comparative Example a1)

[0492] The components constituting each layer were supplied to each extruder according to the formulation shown in Table 1, and a laminated film with (1A) a heat-fused layer, (1B) an intermediate layer, and (1C) a laminated layer was produced by the T-die method. Since no plant-derived biopolymer polyethylene was used, the biopolymer content was 0% by mass.

[0493] The heat of fusion, tensile strength (yield point stress), and tear strength of the fabricated membrane were evaluated. The results are shown in Table 1.

[0494] (Examples a1 to a12)

[0495] Except for using plant-derived biopolymer polyethylene and changing the resin composition as shown in Table 1, the laminated film was prepared in the same manner as in Comparative Example a1, and the heat of melting, elongation strength (yield point stress), and tear strength were evaluated. The results are shown in Table 1.

[0496] The details of each component listed by abbreviation in the resin composition column of Table 1 of the first invention of this application are as follows.

[0497] ·LLDPE(1)

[0498] Linear low-density polyethylene derived from petroleum

[0499] MFR (2.16kg, 190℃): 2.3g / 10min

[0500] Density: 918 kg / m³ 3

[0501] Molecular weight distribution (Mw / Mn): 2.52

[0502] ·Bioplastic PE(1)

[0503] Plant-derived bio-low-density polyethylene

[0504] MFR (2.16kg, 190℃): 3.8g / 10min

[0505] Density: 922 kg / m³ 3

[0506] Molecular weight distribution (Mw / Mn): 5.88

[0507] [Table 1]

[0508]

[0509] The evaluation of the physical properties and characteristics of the embodiments / comparative examples / reference examples of the second invention of this application is carried out by the following methods.

[0510] (1) Molecular weight distribution (Mw / Mn)

[0511] After pretreating the polymer sample under the following conditions, the molecular weight was determined by GPC, and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) was set as the molecular weight distribution.

[0512] i) Preprocessing

[0513] 20 mL of the mobile phase (o-dichlorobenzene) for GPC determination was added to the sample (30 mg) and dissolved by vibration at 145 °C. The resulting solution was then hot-filtered through a sintered filter with a pore size of 1.0 μm and then provided for GPC determination.

[0514] ii) GPC

[0515] Apparatus: Tosoh Corporation, HLC-8321 gel permeation chromatography system

[0516] Tube string: Made by Tosoh Corporation, 7.5mm inner diameter × 30cm, 4 pieces (2 pieces of TSKgel GMH6-HT and 2 pieces of TSKgel GMH6-HTL)

[0517] Column temperature: 140℃

[0518] Detector: Differential refractometer

[0519] Flow rate: 1 mL / min

[0520] Sampling interval: 0.5 seconds

[0521] (2) Heat of fusion

[0522] Using a TA Instruments Q100 differential scanning calorimeter (DSC), approximately 5 mg of sample was weighed. According to JIS K7121, under nitrogen flow rate of 50 mL / min, the temperature was increased from 25 °C to 200 °C at a heating rate of 10 °C / min, and the thermal melting curve was measured. The heat of crystallization of the sample was then determined from the obtained thermal melting curve.

[0523] (3) Young's Modulus

[0524] Long strips (length: 150 mm, width: 15 mm) were cut from the membrane along both the longitudinal (MD) and transverse (TD) axes to serve as test pieces. An elongation test was conducted using an A&D Corporation RTG1210 stretching tester with a fixture spacing of 100 mm and a crosshead speed of 5 mm / min, and the Young's modulus (MPa) was determined. The measured value was the average of five tests.

[0525] (Comparative Example b1)

[0526] The components constituting each layer are supplied to each extruder according to the formulation shown in Table 2, and a laminated film is produced by the T-compression molding method, consisting of a (2A) hot-melt layer, a (2B) intermediate layer, and a (2C) laminated layer, all composed of the same layers shown in Table 2. Since no plant-derived biopolymer polyethylene is used, the biopolymer content is 0% by mass.

[0527] The heat of fusion and Young's modulus of the fabricated membrane were evaluated. The results are shown in Table 2.

[0528] (Refer to Examples b2 to b5 and Examples b1 to b8)

[0529] Except for using plant-derived biopolymer polyethylene and changing the resin composition as shown in Table 2, the laminated film was prepared in the same manner as in Comparative Example b1, and the heat of melt and Young's modulus were evaluated. The results are shown in Table 2.

[0530] The details of each component listed by abbreviation in the resin composition column of Table 2 of the second invention of this application are as follows.

[0531] ·LLDPE(2)

[0532] Linear low-density polyethylene derived from petroleum

[0533] MFR (2.16kg, 190℃): 2.3g / 10min

[0534] Density: 918 kg / m³ 3

[0535] Molecular weight distribution (Mw / Mn): 2.52

[0536] ·Bioplastic PE(2)

[0537] Plant-derived bio-low-density polyethylene

[0538] MFR (2.16kg, 190℃): 3.8g / 10min

[0539] Density: 922 kg / m³ 3

[0540] Molecular weight distribution (Mw / Mn): 5.88

[0541] [Table 2]

[0542]

[0543] The evaluation of the physical properties and characteristics of the embodiments / comparative examples of the third invention of this application is carried out by the following methods.

[0544] (1) Molecular weight distribution (Mw / Mn)

[0545] After pretreating the polymer sample under the following conditions, the molecular weight was determined by GPC, and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) was set as the molecular weight distribution.

[0546] i) Preprocessing

[0547] 20 mL of the mobile phase (o-dichlorobenzene) for GPC determination was added to the sample (30 mg) and dissolved by vibration at 145 °C. The resulting solution was then hot-filtered through a sintered filter with a pore size of 1.0 μm and then provided for GPC determination.

[0548] ii) GPC

[0549] Apparatus: Tosoh Corporation, HLC-8321 gel permeation chromatography system

[0550] Tube string: Made by Tosoh Corporation, 7.5mm inner diameter × 30cm, 4 pieces (2 pieces of TSKgel GMH6-HT and 2 pieces of TSKgel GMH6-HTL)

[0551] Column temperature: 140℃

[0552] Detector: Differential refractometer

[0553] Flow rate: 1 mL / min

[0554] Sampling interval: 0.5 seconds

[0555] (2) Melting point and heat of fusion

[0556] Using a TA Instruments Q100 differential scanning pyrolysis (DSC) instrument, approximately 5 mg of sample was weighed. According to JIS K7121, under the condition of nitrogen inflow rate of 50 mL / min, the temperature was increased from 25 °C to 200 °C at a heating rate of 10 °C / min, and the thermal melting curve was measured. Then, the melting point (Tm) and heat of fusion of the sample were determined from the obtained thermal melting curve.

[0557] (3) Agglomeration strength

[0558] According to ASTM D1893-67, the (3A) heat-fused layers of overlapping laminates are measured against each other.

[0559] (4) Lamination strength

[0560] A 15-micron thick nylon film (manufactured by Toyobo Co., Ltd., trade name: Harden) was used as the (3D) substrate layer. An adhesive (made by Mitsui Chemicals Co., Ltd., a mixture of Takelac / Takenate = A310 / A3 in ethyl acetate) was then applied to the side surface of the (3C) laminate of the laminate used as the test sample, and bonded to the (3D) substrate layer using a manual laminator. The sample was cut into 15-mm wide strips, and a peel opening was formed between the laminate used as the test sample and the (3D) substrate layer. The substrate and sealant were then peeled using a Tensilon universal testing machine (manufactured by A&D Co., Ltd., RTG1210), and the strength of the extended peel surface was measured at an extension speed of 100 mm / min. This strength was set as the lamination strength (N / 15 mm).

[0561] (Comparative Example c1)

[0562] The components constituting each layer are supplied to each extruder according to the formulation shown in Table 3, and a laminated film is produced by the T-compression molding method, consisting of a (3A) hot-melt layer, a (3B) intermediate layer, and a (3C) laminated layer with the resin composition shown in Table 3, also composed of the layers shown in Table 3. Since no bio-based linear low-density polyethylene from plants is used, the biomass degree is 0% by mass.

[0563] The melting point, heat of fusion, agglomeration strength, and lamination strength of the fabricated membrane were evaluated. The results are shown in Table 3.

[0564] (Examples c1 to c8)

[0565] Except for using bio-derived linear low-density polyethylene from plants and changing the resin composition as shown in Table 3, the laminated film was prepared in the same manner as in Comparative Example c1, and the melting point, heat of fusion, agglomeration strength, and lamination strength were evaluated. The results are shown in Table 3.

[0566] The details of each constituent component, referred to by abbreviation in the resin composition column of Table 3 of the third invention of this application, are as follows.

[0567] ·LLDPE(3)

[0568] Linear low-density polyethylene derived from petroleum

[0569] MFR (2.16kg, 190℃): 2.3g / 10min

[0570] Density: 918 kg / m³ 3

[0571] Molecular weight distribution (Mw / Mn): 2.52

[0572] ·Bioplastic PE(3)

[0573] Biopolymer linear low-density polyethylene derived from plants

[0574] MFR (2.16kg, 190℃): 2.3g / 10min

[0575] Density: 916 kg / m³ 3

[0576] Molecular weight distribution (Mw / Mn): 4.12

[0577] [Table 3]

[0578]

[0579] [Industry applicability]

[0580] The laminated film of the first invention of this application maintains the excellent properties of conventional polyethylene laminated films, such as mechanical strength, and significantly improves the tear resistance when used in packaging bags such as tear-off bags and zipper bags. It also reduces the environmental impact during its manufacturing process. With these properties, it has high practical value and is particularly suitable for use in packaging bags such as tear-off bags and zipper bags. It has extremely high applicability in various fields of agriculture, food processing, distribution, and food delivery industries.

[0581] The laminated film of the second invention of this application maintains the excellent properties of conventional polyethylene laminated films, and significantly improves mechanical properties such as Young's modulus, which are important for use in packaging bags such as stand-up pouches. It also reduces the environmental impact during its manufacturing process. With these high-level and practically valuable properties, it is particularly suitable for use in packaging bags such as stand-up pouches and has extremely high applicability in various fields such as agriculture, food processing, distribution, and food delivery industries.

[0582] The laminated film of the third invention of this application maintains the excellent properties of conventional polyethylene laminated films, and significantly improves the lamination strength with the outer layer, while also reducing the environmental impact during its manufacturing. It possesses high-value practical properties at a high level, making it particularly suitable for use in packaging bags and other applications. It has extremely high applicability in various fields of agriculture, food processing, distribution, and food service industries.

Claims

1. A packaging bag composed of laminated films, comprising: a (1A) heat-sealing layer, a (1B) intermediate layer, and a (1C) laminate layer, each containing linear low-density polyethylene derived from petroleum, wherein, The laminated film contains at least 3% by mass of plant-derived low-density polyethylene in at least one of the (1A) heat-fused layer, (1B) intermediate layer and (1C) laminated layer, the biomass of the laminated film is 5 to 30% by mass, and the packaging bag is a tear-off packaging bag or a zippered packaging bag.

2. The packaging bag according to claim 1, wherein the heat of fusion ΔH of the aforementioned laminated film, calculated from the melting curve obtained by DSC measurement, is 135 to 164 J / g from 0°C to 130°C.

3. The packaging bag according to claim 1 or 2, wherein the molecular weight distribution Mw / Mn of the aforementioned plant-derived biodegradable low-density polyethylene is 3.5 or higher.

4. The packaging bag according to claim 1 or 2, wherein the aforementioned laminated film has a (1D) substrate layer on the side of the (1C) laminated layer, directly or through the adhesive layer.

5. A stand-up pouch comprising a laminated film, wherein the laminated film comprises: a (2A) heat-sealing layer, a (2B) intermediate layer, and a (2C) laminated layer, each comprising linear low-density polyethylene derived from petroleum, wherein, The aforementioned (2A) heat-fusion layer, (2B) intermediate layer and (2C) laminate all contain bio-based low-density polyethylene derived from plants, and the bio-based degree of the aforementioned laminated film is 5 to 10.3 by mass.

6. The stand-up pouch according to claim 5, wherein the heat of fusion ΔH of the aforementioned laminated film, calculated from the melting curve obtained by DSC measurement, from 0°C to 130°C, is 135 to 164 J / g.

7. The stand-up pouch according to claim 5 or 6, wherein the molecular weight distribution Mw / Mn of the aforementioned plant-derived biomass low-density polyethylene is 3.5 or higher.

8. The stand-up pouch according to claim 5 or 6, wherein the aforementioned laminated film has a (2D) substrate layer on the side of the (2C) laminated layer, directly or across the adhesive layer.

9. A laminated film comprising: a (3A) heat-fusion layer, a (3B) interlayer, and a (3C) laminate, each containing linear low-density polyethylene derived from petroleum, wherein, (3C) The laminate contains at least 3% by mass of bio-based linear low-density polyethylene derived from plants, and the biomass of the aforementioned laminate is 5 to 10.2% by mass.

10. The laminated film according to claim 9, wherein the (3A) heat-fused layer and / or the (3B) intermediate layer further contain at least 3% by mass of bio-linear low-density polyethylene derived from plants.

11. The laminated film according to claim 9 or 10, wherein the heat of fusion ΔH calculated from the melting curve obtained by DSC determination from 0°C to 130°C is 135 to 164 J / g.

12. The laminated film according to claim 9 or 10, wherein the molecular weight distribution Mw / Mn of the aforementioned biopolymer linear low-density polyethylene derived from plants is 3.5 or more.

13. The laminated film according to claim 9 or 10, wherein a (3D) substrate layer is provided directly or across the bonding layer on the side of the (3C) laminate layer.

14. A packaging bag comprising a laminated film according to any one of claims 9 to 13.

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